Atkins' Physical Chemistry Solution Manual (7th Ed)

Student Solutions Manual to Accompany
Quanta, Matter,
and Change
A molecular approach to physical chemistry
Charles Trapp, Marshall Cady, Carmen Giunta

STUDENT SOLUTIONS MANUAL FOR
QUANTA, MATTER, AND CHANGE:
A MOLECULAR APPROACH TO PHYSICAL CHEMISTRY
C. A. Trapp
Professor of Chemistry, University of Louisville,
Louisville, Kentucky, USA
M. P. Cady
Professor of Chemistry,
Indiana University Southeast, New Albany Indiana , USA
C. Giunta
Professor of Chemistry,
Le Moyne College, Syracuse, NY, USA
OXFORD
UNIVERSITY PRESS
OXFORD
UNIV E RSI TY PRESS
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OX2 6DP, United Kingdom
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in the UK and in certain other countries.
© C. A. Trapp, M. P. Cady, and C. Giunta, 2009
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First printing
ISBN: 978-0-1995-5907-7
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ISBN-10: 1-4292-2375-8 ISBN-13: 978-1-4292-2375-1
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Preface
This manual provides detailed solutions to all of the end-of-chapter (a) Exercises, and to the odd-numbered
Discussion Questions and Problems in Quanta, Matter, and Change.
The solutions to some of the Exercises and many of the Problems in this manual relied heavily on the
mathematical, graphical, and molecular modeling software that is now generally accessible to physical
chemistry students. The availability of the software makes it possible to create and solve problems that can
realistically mimic scientific research. Many of the problems specifically requested the use of such software,
and, indeed, would have been almost unsolvable otherwise. We used the following software for many of the
solutions in this manual: Excel™ for spreadsheet calculations and graphing, and Mathcad™ for mathematical
calculations and the plotting of the results. When a quantum chemical calculation or molecular modeling
process was called for, we usually provided the solution with PC SpartanTM because of its common availability.
However, the majority of the Exercises and many of the Problems can still be solved with a modem hand-held
scientific calculator.
In general we adhered rigorously to the rules for significant figures in displaying the final answers. However,
when intermediate answers are shown, they are often given with one more figure than would be justified by the
data. These excess figures are indicated with an overline.
The solutions were carefully cross-checked for errors not only by us, but very thoroughly by Valerie Walters,
who also made many helpful suggestions for improving the solutions. We would be grateful to any readers who
bring any remaining errors to our attention.
We warmly thank our publishers, especially Jonathan Crowe and Jessica Fiorillo, and also Samantha
Calamari, for their patience in guiding this complex, detailed project to completion.
C. T.
M. C.
C.G.
Contents
Fundamentals 5 The chemical bond 102
PART1 Quantum theory 15 Answers to discussion questions 102

Solutions to exercises 104
1 The principles of quantum theory 17 Solutions to problems 110
Solutions to numerical problems 110
Answers to discussion questions 17 Solutions to theoretical problems 124
Solutions to exercises 18 Solutions to applications 128
Solutions to problems 26
Solutions to numerical problems 26 6 Computational chemistry 132
Solutions to theoretical problems 28
Solutions to applications 31 Answers to discussion questions 132
2 Nanosystems 1 : motion in one dimension 33
Answers to discussion questions 33
Solutions to applications 154
Solutions to theoretical problems 45 7 Molecular symmetry 156
3 Nanosystems 2: motion in several Solutions to exercises 156
dimensions 55 Solutions to problems 162
Solutions to numerical problems 62 8 Molecular assemblies 176

PART2 Atoms, molecules, and Solutions to numerical problems 185
assemblies 77 Solutions to applications 193
4 Atomic structure and atomic spectra 79

9 Solids 196
Answers to discussion questions 79 Answers to discussion questions 196

Solutions to exercises 80 Solutions to exercises 198
Solutions to problems 88 Solutions to problems 207
Solutions to numerical problems 88 Solutions to numerical problems 207
Solutions to theoretical problems 92 Solutions to theoretical problems 210
Solutions to applications 98 Solutions to applications 221
viii CONTENTS
PART3 Molecular spectroscopy 225 15 The second law of thermodynamics 352

10 Rotational and vibrational spectra 227
Answers to discussion questions 227 Solutions to problems 364
Solutions to exercises 228 Solutions to numerical problems 364
Solutions to problems 236 Solutions to theoretical problems 374
Solutions to numerical problems 236 Solutions to applications 382
16 Physical equilibria 385
11 Electronic spectroscopy 251
Answers to discussion questions 251 Solutions to exercises 386
Solutions to exercises 253 Solutions to problems 395
Solutions to problems 261 Solutions to numerical problems 395
Solutions to numerical problems 261 Solutions to theoretical problems 401
Solutions to theoretical problems 265 Solutions to applications 406
12 Magnetic resonance 271 17 Chemical equilibrium 411

PART4 Molecular PART5 Chemical dynamics 439

thermodynamics 289
18 Molecular motion 441
13 The Boltzmann distribution 291
Answers to discussion questions 291 Solutions to exercises 443
Solutions to exercises 292 Solutions to problems 454
Solutions to problems 304 Solutions to numerical problems 454
Solutions to numerical problems 304 Solutions to theoretical problems 459
14 The first law of thermodynamics 314 19 Chemical kinetics 469
Answers to discussion questions 314 Answers to discussion quest1o~s 469

Solutions to numerical problems 326 Solutions to numerical problem> 479
Solutions to theoretical problems 335 Solutions to theoretical pr 486
i·~--. .. .. ~,.,.
.... . .
.. • • ~ ' d
·~ "!'~
I;;;.· . , , ._ .·. ·-~.

CONTENTS ix
20 Molecular reaction dynamics 492 21 Catalysis 512

Solutions to theoretical problems 506 Solutions to theoretical problems 526
STUDENT SOLUTIONS MANUAL FOR
QUANTA, MATTER, AND CHANGE:
A MOLECULAR APPROACH TO PHYSICAL CHEMISTRY
Fundamentals
Exercises
F.1 Atoms
F1 .1 (a) The nuclear atomic model consists of atomic number Z protons concentrated along with all atomic
neutrons within the nucleus, an extremely small central region of the atom. Z electrons occupy
atomic orbitals, which are voluminous regions of the atom that describe where electrons are likely
to be found with no more than two electrons in any orbital. The electrostatic attraction binds the
negatively charged electrons to the positively charged nucleus, and the so-called strong interaction
binds the protons and neutrons within the nucleus.
The atomic orbitals are arranged in shells around the nucleus, each shell being characterized by a
principal quantum number, n = 1, 2, 3, 4 .... A shell consists of n2 individual orbitals, which are
grouped together into n subshells. The subshells, and the orbitals they contain, are denoted s, p, d, and f.
For all neutral atoms other than hydrogen, the subshells of a given shell have slightly different energies.
F1 .2(a) Example Element Ground-state Electronic Configuration
(a) Group 2 Ca, calcium [Ar]4s2

(b) Group 7 Mn, manganese [Ar]3d 54s 2
(c) Group 15 As, arsenic [Ar]3d I04s 24p 3
F1 .3(a) (a) chemical formula and name: Mgeh, magnesium chloride

ions: Mg 2+ and er
oxidation numbers of the elements: magnesium, +2; chlorine, -1
(b) chemical formula and name: FeO, iron(II) oxide

ions: Fe2+ and 0 2-
oxidation numbers of the elements: iron, +2; oxygen, -2
(c) chemical formula and name: Hg 2eh, mercury(!) chloride

ions: er and Hg/ + (a polyatomic ion)
oxidation numbers of the elements: mercury, +1; chlorine, -1
F1 .4(a) Metals conduct electricity, have luster, and are malleable and ductile.
Nonmetals do not conduct electricity and are neither malleable nor ductile.
Metalloids typically have the appearance of metals but behave chemically like
nonmetals.
2 STUDENT SOLUTIONS MANUAL FOR QUANTA, MATIER, AND CHANGE
IA
I 2
HA
3
1118
4
IVB
5
VB
6
VlB
7
VllB
8
VIIIB
9
VIHB
lO
VIIIB
II
18
I 12
llB
13
IllA
14
!VA
15
VA
16
VIA
l7
VllA
18
VlllA
I 2
H Periodic Table of the Elements He
1.008 4.003
3 4 s 6 7 8 9 IO
Li Be B c N 0 F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
II 12 13 14 15 16 17 18
Na Mg Al Si p s Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti v Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 SI 52 53 54
Rb Sr y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) IOI.I 102.9 106.4 107.9 11::!.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta w Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.l 197.0 :?00.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89
Fr Ra Ac
(223) 226 (227)
58 59 60 61 62 63 64 65 66
Ce Pr Nd Pm Sm Eu Gd Tb Dy
140.l 140.9 144.2 145 150.4 152.0 157.3 158.9 162.5
90 91 92 93 94 95 96 97 98
Th Pa u Np Pu Am Cm Bk Cf
232.0 (231) 238.0 237 (244) (243) (247) (247) (251)
F.2 Molecules
F2.1 (a) A single bond is a shared pair of electrons between adjacent atoms within a molecule while a
multiple bond involves the sharing of either two pairs of electrons (a double bond) or three pairs of
electrons (a triple bond).
F2.2(a) (a) Sulfite anion, S0 32- 2-

:0
.. I ..
[
..
:o--s--o: .. .. ]
Alternatively, resonance structures may be drawn and, if desired, formal charges (shown in circles
below) may be indicated.
·a·. 0·. O". 0· .

.. e ·1~e ..e12-
..-.. r .. e I ...e12---- r .._I ...
e e12-~ r .. e I_·
e .. 12-
.. .. ..
r :o-s-o: .. .. ..
:o-s-o: .. .. ..
:O-s-o: :o-s-o:
.. .. ..
(b) Xenon tetrafluoride, XeF4 ..

•F •
· 1 / " ·..
: F--Xe---F :
··./I
• : F :
(c) White phosphorus, P4

FUNDAMENTALS 3
F2.3(a) Valence-shell electron pair repulsion theory (VSEPR theory) predicts molecular shape with the
concept that regions of high electron density (as represented by single bonds, multiple bonds, and lone
pairs) take up orientations around the central atom that maximize their separation. The resulting
positions of attached atoms (not lone pairs) are used to classify the shape of the molecule. When the
central atom has two or more lone pairs, the molecular geometry must minimize repulsion between the
relatively diffuse orbitals of each lone pair. Furthermore, it is assumed that the repulsion between a
lone pair and a bonding pair is stronger than the repulsion between two bonding pairs, thereby making
bond angles smaller than the idealized bond angles that appear in the absence of a lone pair.
F2.4(a) Molecular shape and polyatomic ion shape are predicted by drawing the Lewis structure and
applying the concepts of VSEPR theory.
(a) PCl3
Cl--P-CI
Lewis structure: I
Cl
Orientations caused by repulsions between one lone pair and three bonding pairs:
Molecular shape: trigonal pyramidal and bond angles somewhat smaller than 109.5°
(b) PC1 5
Cl Cl
Lewis structure: Cl "'p/ Cl
I
Cl
Orientations caused by repulsions between five bonding pairs (no lone pair):
Cl
Cl~~-CI
Cl~I
Cl
Molecular shape: trigonal bipyramidal with equatorial bond angles of 120° and axial bond
angles of 90°
(c) XeF2
Lewis structure:
."" /·.
F--xe-F
I
Orientations caused by repulsions between three lone pairs and two bonding pairs:
F
.
·~xe--:
I
.~I
F
Molecular shape: linear with a 180° bond angle
4 STUDENT SOLUTIONS MANUAL FOR QUANTA, MATTER, AND CHANGE
(d) XeF4
·~ /·.
Lewis structure: F-Xe-F
F
I "F
Orientations caused by repulsions between two lone pairs and four bonding pairs:
Molecular shape: square planar with 90° bond angles
F2.5(a) (b) P - H Nonpolar or weakly polar. (c) 3+ 3-

N-O
F2.6(a) (a) C0 2 is a linear, nonpolar molecule.
(b) S02 is a bent, polar molecule.
(c) N20 is a linear, polar molecule.
(d) SF4 is a seesaw molecule, and it is a polar molecule.
F2.7(a) In the order of increasing dipole moment: C0 2 , N20 , SF4 , S0 2
F.3 Bulk matter
F3.1 (a) The solid phase of matter has a shape that is independent of the container it occupies. It has a
density compatible with the close proximity of either its constituent elemental atoms or its
constituent molecules, and consequently it has low compressibility. Constituent atoms, or
molecules, are held firmly at specific lattice sites by relatively strong net forces of attraction
between neighboring constituents. Solids may be characterized by terms such as brittle, ductile,
tensile strength, toughness, and hardness.
A liquid adopts the shape of the part of the container that it occupies; it can flow under the influence
of gravitational attraction to occupy any shape. Like a solid, it has a density caused by the close
proximity of either its constituent elemental atoms or its constituent molecules, and it has low
compressibility. Liquids can flow because the constituent atoms or molecules have enough average
kinetic energy to overcome the attractive forces between neighboring constituents, thereby making
it possible for constituents to slip past immediate neighbors. This causes constituents to be placed
randomly in contrast to the orderly array in crystals. Liquids are characterized by terms such as
surface tension, viscosity, and capillary action. Liquids within a vertical, narrow tube exhibit a
meniscus that is either concave up or concave down depending on the nature of the attractive or
repulsive forces between the liquid and the material of the tube.
Gases have no fixed shape or volume. They expand to fill the container. The constituent molecules
move freely and randomly. A perfect gas has a total molecular volume that is negligibly small
compared to the container volume, and because of the relatively large average distance between
molecules, intermolecular attractive forces are negligibly small. Gases are compressible.
F3.2(a) (a) Mass is an extensive property.

(b) Mass density is an intensive property.
(c) Temperature is an intensive property.
(d) Number density is an intensive property.
FUNDAMENTALS 5
F3.3(a) (a) n= ~ = 25.0 g( 1

mo! ) = lo.543 moll [P.l]
M 46.069 g
6 0221 1023
(b) N = nNA = 0.543 mo1 ( · x molecules ] = l3.27xl0 23 molecules I
mo!
18.015g) ~
F3.4(a) (a) m=nM=lO.Omol ( =~ [P.l]
mo!
(b) weight= F gravityonEanh = m g Eanh
= (180. g)x(9.81 m s-2 )x (~)

1000 g
=1.77 kg m s-2 = JI.77 NI
F mg
F3.5(a) p=-=-
A A
2 2
(
= 65kg)x(9.8lms- ) ( 1 cm J = 4.3xl0 4 N m-2 = 4.3xl04 Pa ( ~lb)
150 cm 2 10-4 m 2 10 5 Pa
= lo.43 bar I
1
F3.6(a) 0.43 bar( atm ) = lo.42 atml
1.01325 bar
5
1325
F3.7(a) (a) 1.45 atm(l.0 xl0 PaJ = li.47Xl0 5 Pal
1 atm
(b) 1.45 atm(l.01325 bar)= II.47 barl

1 atm
F3.8(a) T I K =B I °C + 273.15 = 37.0 + 273.15 = 310.2 [P.2]
IT=310.2 Kl
F3.9(a) To devise an equation relating the Fahrenheit and Celsius scales requires that consideration be given
to both the degree size and a common reference point in each scale. Between the normal freezing
point of water and its normal boiling point, there is a degree scaling of 100°C and 180°F. Thus, the
scaling ratio is 5°C per 9°F. A convenient reference point is provided by the normal freezing point
of water, which is 0°C and 32°F. So to calculate the Celsius temperature from a given Fahrenheit
temperature, 32 must be subtracted from the Fahrenheit temperature (OF) followed by scaling to the
Celsius temperature (8) with the ratio 5°C I 9°F.
I(} I °C = %X(BFI 0
P - 32) or BFI 0 P = %X(} I °C + 321
BF/ 0 P = ;%' xB /°C + 32 = %x78.5+32=173
l(}F = 173 opl
F3.10(a) 110 kPa x (7.0+273.15)K) = I105 kPa I

[ (20.0+273.15) K
mRT
F3.11 (a) pV = nRT [F.3] = - -
M
M = mRT = pRT where p is the mass density

pV p
(3.710 kg m-3 )(8.314 J K- 1 mor 1 )(773.15 K)

= 3 = 0.256 kg mol-I = 256 g mor 1
93 .2x10 Pa
The molecular mass is eight times as large as the atomic mass of sulfur (32.06 g mor 1), so the
molecular formula is ~.
1
F3.12(a) n=22 g x ( mo! J =0.73 mo!
30.07 g
1 1
=nRT F =(0.73mol)(8.314JK- mol- )(298.15K)( cmJ J
3
p V [ · ] 1000. cm3 10-6 m3
= l.8 x l0 6 Pa= li.8 MPal
F3.13(a) ~' = 1.0 mole and nH, = 2.0 mole
1 1
_ nN, RT _ (1.0mol)(8.314JK- mo1- )(278.15K)( dm 3 J-1 5 I
PN2 - [F.3] - 3 3 3
- 2.3x10 Pa
V 10.0 dm 10- m
Since there are twice as many moles of hydrogen as nitrogen, the hydrogen partial pressure must be
twice as large.
5
PH 2 = l4.6xl0 5 Pal P = PN2 +PH 2 [F.4] = l6.9xl0 Pal
F.4 Thermodynamic properties
F4.1 (a) t:,,.T = t:,,.U [F.5] = lOO. J = 127.2 Kor 27.2 °CI
C 3.67 J K- 1
1
F4.2(a) n = 100. g x( mo! J = 0.483 mo!
207.2 g
t:,,.U = Ct:,,.T [F.5] = nCmt:,,.T
= (0.483 mo!)( 26.44 J K- 1 mol- 1 )(10.0K)=1128 JI
F4.3(a)
F4.4(a)
FUNDAMENTALS 7
F4.5(a) Dividing eqn. F.7 by the number of moles n and using the molar properties (intensive) Hm, Um, and
Vm yields the equation
Hm -Um= pVm
Substitution of the perfect gas eos, pVm =RT, yields
H m-Um= RT= (8.3145 J moi- 1 K- 1)x(298K)=12.48 kJ mo1- 1I
F4.6(a)
_ _
H m Um-PVm [F.7]-
·
- _
5
_ pM _ (1.00xl0 Pa )x( 207.2 g mol- ') (10-6 m 3
-L826Jmol.
)-I _,I
p 11 .350 g cm 3 cm 3
F4.7(a)
F4.8(a) S Fe(3000 K ) > S Fe(300 K)
F4.9(a) The second law of thermodynamics states that any spontaneous (that is, natural) change in an
isolated system is accompanied by an increase in the entropy of the system. This tendency is
expressed commonly by saying that the natural direction of change is accompanied by dispersal of
energy from a localized region to a less organized form.
F4.1 O(a) In a state of dynamic equilibrium, which is the character of all chemical equilibria, the forward and
reverse reactions are occurring at the same rate and there is no net tendency to change in either
direction. Examples:
2 S0 2(g) + 0 2(g) ~ 2 S0 3(g) Addition of oxygen shifts the equilibrium to the right. An increase
in pressure also shifts it to the right so as to reduce the number of moles of gas.
CaC0 3(s) ~ CaO(s) + C0 2(g) Addition of carbon dioxide shifts the equilibrium to the left. An
increase in pressure also shifts it to the left so as to reduce the number of moles of gas.
CO(g) + H 20(g) ~ C0 2(g) + H 2(g) Addition of carbon monoxide shifts the equilibrium to the
right. An increase in pressure has no effect on the equilibrium because there are equal numbers of
moles of gas on left and right.
F.5 The relation between molecular and bulk properties
F5.1 (a) Quantized energies are certain discrete values that are permitted for particles confined to a region of space.
19
F5.2(a) M = Eupper -E10wer = 1 eV = 1.6022xl0- J
(a)
(b)
Hupper = e - llE / kT = e-(1.6022xl0-19 i)t{(l.381xl0-23 JK-l)x(3000 KJ} = l2.092 x 10-2 I
Hlower
F5.3(a) lim(Hupper)=lim(e-w*r) [F.9]=e- =0

T ->0
Hlower T ->0
In the limit of the absolute zero of temperature all particles occupy the lower state. The upper state
is empty.
F5.4(a) M = Eupper - E 10wer = vhc = ( 2500 cm- ')( 6.626x 10-34 J s )( 3.000xl0 10 cm s- 1) = 4.970x10- 20 J
Hupper = e-llE t klT [F. ] = e-(4.97oxw-20 i)1{(us1x10-23 J K-1)x(293 KJ} = 14 .631 x l0-6 1
9
Hlower
The ratio Huppe/ Hiower is so small that the population of the upper level is approximately zero.
8 STUDENT SOLUTIONS MANUAL FOR QUANTA, MATTER. AND C'-'-
FS.S(a) Kinetic molecular theory, a model for a perfect gas. as .. ume. that the molecules, imagined as
particles of negligible size, are in ceaseless, random motion and do not interact except during their
brief collisions.
F5.6(a) Molecules can survive for long periods without undergoing chemical reaction at low temperatures
when few molecules have the requisite speed and corresponding kinetic energy to promote
excitation and bond breakage during collisions.
2
F5.7(a) Vmeanoc(T / M)" [F.11]
Vmean (T2) (T2/ M)l/2 =(T2J112

12
VmeaJz;) (I; ! M}' I;
112
Vmean (313 K) =(313 K) =l1.07I
Vmean (273K) 273K
2
F5.8(a) Vmean oc (T / M)' [F.11]
12
vmea0 (N 2) = ( 44.0gmor:J ' =11.2 5 1
vmean ( co2) 28.0 g mor
F5.9(a) A gaseous argon atom has three translational degrees of freedom (the components of motion in the
x, y, and z directions). Consequently, the equipartition theorem assigns a mean energy of 3/ 2kT to
each atom. The 'molar internal energy is
um= f NAkT = f RT [F.10] = +(8.3145 J mor 1 K-I )(298 K) = 3.72 kJ mor 1
1 3 72
U = nUm = mM- 1Um = (5.0 g)( mo! J( · kJ) = I0.47 kJJ
39.95 g mo!
FS.1 O(a) (a) A gaseous linear carbon dioxide molecule has three quadratic translational degrees of freedom
(the components of motion in the x, y, and z directions) but it has only two rotational quadratic
degrees of freedom because there is no rotation along the internuclear line. There is a total of
five quadratic degrees of freedom for the molecule. Consequently, the equipartition theorem
assigns a mean energy of 5/ 2kT to each molecule. The molar internal energy is
um= f NAkT = f RT [F.10] = f(8.3145 J mol-I K- 1)(293 K) = 6.09 kJ mor 1
1
U = nU"' = mM- Um = (10.0 g{ ~4~0~ J( 6 ·:0 ~1 ) = ll.38 kJJ
(b) A gaseous, nonlinear methane molecule has three quadratic translational degrees of freedom
(the components of motion in the x, y, and z directions) and three quadratic rotational degrees of
freedom . Consequently, the equipartition theorem assigns a mean energy of 6/ikT to each
molecule. The molar internal energy is
Um =%NAkT = 3RT [F.IO] = 3(8.3145 J mol- 1 K- 1)(293 K) = 7.31 kJ mol- 1
7 31
U = nUm = mM- 1Um = (10.0 g)( l mo! J( · kJ)=14.56 kJI
16.04 g mo!
FUNDAMENTALS 9
F5.11 (a) See Exercise F5 .9( a) for the description of the molar internal energy of argon.
F5.12(a) See Exercise F5.10(a) for the description of the molar internal energies of carbon dioxide and
methane.
(a) Um =%RT for carbon dioxide
(b) Um = 3RT for methane
F.6 Particles
F6.1(a) a = dvldt = g so dv = g dt . The acceleration of free fall is constant near the surface of the Earth.
f"(I)
J.,=0 dv =
r=, g dt
!=0
v(t) =gt
(a) v(l.O s)=(9.81 ms-2 )x(l.O s)=l9.81 ms- 1 1
(b) v(3.0 s) = (9.81 m s-2 )x(3.0s)=129.4 m s- 1 I
~ =tmv2 =t(0.0010kg)x(29.4ms- 1 }2 =I0.43JI
F6.2(a) The terminal velocity occurs when there is a balance between the force exerted by the electric
field and the force of frictional drag. It will be in the direction of the field and have the
magnitude Sterminal·
ze£ = 6Jrr/Rsterminal
ze&
sterminal =1U/
-- R6
F6.3(a) x(t) = A sin( (t){) + B cos( (t){)
dx =Adsin((t){) +Bdcos((t){) =Ax(cocos((t){))+Bx(-cosin(ta))

dt dt dt
= Acocos(ta)- Bcosin( (t){)
IO STUDENT SOLUTIONS MANUAL FOR QUANTA, MATIER, AND CHANGE
2
d x =Aw dcos(wt) Bw dsin(wt)
dt 2 dt dt
= Awx ( -wsin( wt))- Bwx ( wcos( wt))
= -w2 (Asin(wt)+ Bcos(wt)) = -w2 x where w= (k I m )112
d
m dt x
2
2 = -mw x = -m x m x = -kx
2 (k)
This confirms that x(t) satisfies the harmonic oscillator equation of motion.
F6.4(a) The harmonic oscillator solution x(t) =A sin( wt) has the characteristics
x(t) = Asin(wt)+Bcos(wt)
dx
v(t) = - = Awcos(wt)
dt
x min =x(t=nn l w, n=0, 1,2... )=0 and x max = x(t=(n+1)n ! w, n=0,1,2 ... )=A
At Xmin the harmonic oscillator restoration force (Hooke's law, -kx) is zero, and consequently, the
harmonic potential energy, V, is a minimum that is taken to equal zero while kinetic energy, Ek> is a
maximum. As kinetic energy causes movement away from Xmin• kinetic energy continually converts
to potential energy until no kinetic energy remains at Xmax where the restoration force changes the
direction of motion and the conversion process reverses. We may easily find an expression for the
total energy E(A) by examination of either Xmin or Xmax ·
Analysis using Xm;n:
2 2
E = E k. max = .!.m
2 v max = .!.mA
2 w 2
where w= (k I m) 112 or mw2 = k
We begin the analysis that uses Xm ax by deriving the expression for the harmonic potential energy.
dV = -Fxdx [F.20] = kx dx (i.e., Fx = -kx; Exercise F6.3a)
r x> dV = r kxdx
2 2 2
V(x) = tkx Thus, vmax = V(xm.J = 1kA and IE= vmax = tkA I
F6.5(a) The electron acceleration is caused by the centripetal electrostatic force of attraction of the
positively charged nucleus for the negatively charged electron. The force and its resultant
acceleration always point from the electron to the nucleus. A path of constant radius r is possible
only when the electron speed v creates a centrifugal force, mv2/r, that exactly balances the
centripetal force. The magnitude of the centripetal acceleration is found by equating the force of
Newton' s second law of motion and the centrifugal force.
mv 2
F=ma=--
r
v 2 ( 2188xl03 m s- 1 )2
a= - = = 9.0xl0 22 m s-2
r 53xl0- 12 m
F6.6(a) The relationship between angular velocity w and the speed of an electron in a stable circular path
(i.e., an "orbit" of radius r) is found by recognizing that, when the electron travels through one
orbit, it traverses 2n radians while traveling the distance 2nr. Thus,
w= vx(2n / 2nr) = v I r
FUNDAMENTALS 11
2
J=lm=(mr )x(;) =mrv [F.15]
= (9.10938xl0-3 1 kg)x( 53x10- 12 m )x( 2188xl0 3 m s- 1 )
= 1.lxl0-34 kg m2 s- 1 = 1.lxl0-34 J s
2
= ( 1.1x10-34 J s) x ( ; ) 1i where 1i = h I 21£
34 2
=(l.lxl0- Js)x( 1£_ )n=ll.onl
6.63x10 34 J s
F6.7(a) w = t kx 2 where x = R - R. is the displacement from equilibrium
(a) w=t(450Nm- 1 )x(1ox10- 12 mf =2.25x10-20 Nm= l2.25x10-20 JI
(b) w=t(450Nm- 1 )x(2ox10- 12 m}2 =9.00x10-20 Nm= 19.00xl0-20 JI
F6.8(a)
t mv 2 = efirp or V =
(
2emfirp)"
v = 2(1.6022x10- c)x(1ooxl0
( 9.10938xl0-3 1 kg
19 3
v)]" 2
8(c
= 1.88xl0 -
vJ"
kg
2
= 1.88xl0 8 (
-
kg
J J"
2
(kg~: s-
2
=1.ssx10 8
2
J" =li.ssx1os ms- 1 1
, E =Ek = efirp = ex(lOO kV)= 1100 keVI
F6.9(a) The work needed to separate two ions to infinity is identical to the Coulomb potential drop that
occurs when the two ions are brought from an infinite separation, where the interaction potential
equals zero, to a separation of r.
In a vacuum:
w=-V=-( q1q2
4JtG0 r
J [F.24]=-((e)x(-e)J=~
4JtG r 4JtG r 0 0
19 2
(1.6022xl0- c)
=----------,...-------~
41t(8.85419x10- 12 r 1
C2 m- 1 )x(2oox10- 12 m)
In water:
2
w = -V = -( q1q 2 ) [F.24] = -(( e )x (-e) J = ___![__ = e [F.25] where £, = 78 for water at 25°C
4JtGr 4JtGr 4JtGr 4JtG,&0 r
2
i.6022x10- 19 c )
( I I
----------- -- -2 - -1 - - = L 124 8 x 1 0-20 J
41t(78)x(8.85419xl0- r C m- )x(20ox10- m)
12 1
F6.10(a) We will model a solution by assuming that the LiH pair consists of the two point charge ions Li+
and H-. The electric potential will be calculated along the line of the ions.
19
l.6022xl0- C ( 1 1 )
rp= 4tr(8.85419xl0- 12 r 1 C 2 m- 1 ) 2oox10- 12 m 150x10- 12 m
= -2.40 J c- 1 = -2.40 c v c- 1 = l-2.40 vi

F6.11 (a) We will assume that the electric circuit has a negligibly small heat capacity so that the water
receives all of the electrically generated heat energy.
11UH,o =energy dissipated by the electric circuit
=I 11rp l1t [F.30)
= (2.23 A)x(15.0 V)x(720 s) = 24. lxl0 3 C s- 1 Vs= 124.1 kJI
11UH,o = (nC!1T)H,o [F.5)
11T =
11U
H,O /1UH,O 24.lxl0 3 J
(nC)H,o (mC I M)H,o (200 g)x( 75.3 J K- 1 mor 1 ) I (18.02 g mor 1 )
= 28.8K=128.8 °cl
F.7 Waves
2
1
F7.1(a) Ji=_!_ [F.33)= 9
(io- mJ=ll.69xl0 4 cm- 11
A, 590xl0- m cm
v=~
8
[F.31]= 3 .00xl0 ms-I =5.08xl0 14 s- 1 =l5 .08x10 14 Hzl
A, 590x10-9 m
F7.2(a) cH o = !!..._ [F.32) = 3.00xlOs m s-1 = l2.26x10s m s-1I

' n, 1.33
A=~v [F.33)= 25001cm _1( 10

106
F7.3(a) 2
µmJ=14.00 µml
cm
v = ~ [F.31) = 3.00xl0 ms-' = 7.50xl0 13 s- 1 = l7.50xl0 13 Hzl

8
A, 4.00xl0-6 m
F7.4(a) (a) j(x) = cos(2nx/},) where).= 1 cm (See Figure F. l : - - - - - - - .)
(b) j(x) = cos(2n:x/). + cp) where cp = nl3 (See Figure F.l: _______________ .)
FUNDAMENTALS 13
-0.5
-1'--~----'---'-->.IL~~~~L-~----.-'-....:...._-'>!L~~~__J
0 0. 5 1.5
x / cm FigureF.1
F7.5(a) f (x, t) =cos{ 2trvt-(2tr I A-)x}
of = -2;rv sin { 2trvt - (2tr I A, )x}

ot
2
0 f =-(2;rv) 2 cos{2trvt-(2tr I A-)x}
-
2
ot
2
=-(2;rv) f
of = -( -2tr I A,) sin {2trvt - (2tr I A,)x} = ( 2tr I A,) sin {2trvt - (2tr I A, )x}
OX
2
0f
-
2
= -(2tr I A, ) cos{2trvt-(2tr I A-)x}
OX 2
=-(2tr / -1)2f
2
0f 2
c 2- 2 =-(2trc / -1) f
OX
2
=-(2;rv) f
Inspection of the simplified equations for o 2f I ot 2 and c 2 (o 2 f I ox 2 ) reveals that they are equal.
Consequently, we conclude thatf(x,t) satisfies the wave equation.
F.8 Units
3
F8.1 (a) 1.45cm3 =1.45 (10- 2 m) = l1.45xl0--{j m 3 I
~)x( ~g _~mm )
3
1 1 3 3
F8.2(a) ( 11.2 cm J x( =lll.2x10 kgm- 1
10 g 10
2 3 3
F8.3(a) Pa=Nm- =(Nm)m- =Jm- =lm-3 1
J J J J
23 1
kT (1.38lxl0- J K- )x(298 K) I _I
F8.4(a) - - - -34- - - - - -10- - = 1 _207.2 cm 1 .
he ( 6.626xl0- J s )x( 2.998xl0 cm s- )
3
)x(~)
3
44 1 1
F8.5(a) 8.3l )x( Pa m )x( atm = lo.08206 atm dm 3 K- 1 moi- 1I
( K mol J 101325 Pa 10-1 m
F8.6(a) (1 dmJ atm)x(10-1 m)J x(l01325 Pa)x(-J-)=1101.325 Jj

elm 1 atm Pam3
2 c2 1 (kg m2 s-2) 2
F8.7(a) (a) Base unit of~= ( _ _ ) ( ) = (J m- )x = lkg m s- 1
Eor c2 J I m I x m2 J
2 2
= (J m- 1)x(kg ~
2
(b) Unit of __i__2 = C1
8
- ) =kg m s-2 = lliJ
E0 r (C
2
r 1 m- )x( m2 )
PART 1 Quantum theory
1 The principles of
quantum theory
Answers to discussion questions
01 .1 At the end of the nineteenth century and the beginning of the twentieth, there were many
experimental results on the properties of matter and radiation that could not be explained on the
basis of established physical principles and theories. Here we list only some of the most significant.
(1) The photoelectric effect revealed that electromagnetic radiation, classically considered to be a wave,
also exhibits the particle-like behavior of photons. Each photon is a discrete unit, or quantum, of
energy that is absorbed during collisions with electrons. Photons are never partially absorbed. They
either completely give up their energy or they are not absorbed. The energy of a photon can be
calculated if either the radiation frequency or wavelength is known: Ephoton =hv = hcl.J...
(2) Absorption and emission spectra indicated that atoms and molecules can only absorb or emit discrete
packets of energy (i.e., photons). This means that an atom or molecule has specific, allowed energy
levels, and we say that their energies are quantized. During a spectroscopic transition the atom or
molecule gains or loses the energy till by either absorption of a photon or emission of a photon,
respectively. Thus, spectral lines must satisfy the Bohr frequency condition: AB= hv.
(3) Neutron and electron diffraction studies indicated that these particles also possess wave-like
properties of constructive and destructive interference. The joint particle and wave character of
matter and radiation is called wave-particle duality. The de Broglie relation, Ade Broglie= hip,
connects the wave character of a particle (Ade Broglie) with its particulate momentum (p ).
Evidence that resulted in the development of quantum theory also included:
(4) The energy density distribution of blackbody radiation as a function of wavelength.
(5) The heat capacities of monatomic solids such as copper metal.
01 .3 If the wavefunction describing the linear momentum of a particle is precisely known, the particle
has a definite state of linear momentum; but then according to the uncertainty principle (eqn. l.19a),
the position of the particle is completely unknown. Conversely, if the position of a particle is
precisely known, its linear momentum cannot be described by a single wavefunction. Rather, the
wavefunction is a superposition of many wavefunctions, each corresponding to a different value for
the linear momentum. All knowledge of the linear momentum of the particle is lost when its
position is specified exactly. In the limit of an infinite number of superposed wavefunctions, the
wavepacket illustrated in text Fig. 1.17 turns into the sharply spiked packet shown in Fig. 1.16. But
the requirement of the superposition of an infinite number of momentum wavefunctions in order to
locate the particle means a complete lack of knowledge of the momentum.
01 .5 By wave-particle duality we mean that in some experiments an entity behaves as a wave while in
other experiments the same entity behaves as a particle. Electromagnetic radiation behaves as a
wave in reflection and refraction experiments but it behaves as particulate photons in absorption and
emission spectroscopy. Electrons behave as waves in diffraction experiments but as particles in the
photoelectric effect. Consequences are especially important for small fundamental particles like
electrons, atoms, and molecules. It is not possible to precisely specify complementary observables
like position and momentum for fundamental particles. It is also impossible to specify the
simultaneous energy and timing of an event. Rather, the multiplied uncertainties of complementary
observables must always be greater than, or equal to, 1i I 2 (i.e., the Heisenberg uncertainty
principle of eqns. l.19a and 1.23). Quantum theory shows that, because of wave-particle duality, it
is necessary to specify the wavefunction of fundamental particles and to use Postulates 1-V of the
text to interpret their behavior and observable properties.
01 .7 (a) The eigenvalue equation Qlj/ = OJlf/ provides the relation between the operator for an
observable (fl) and the value of the observable (w). Whenever the system is described by a
wavefunction If/, which is an eigenfunction of fl, the outcome of a measurement of the
observable Q will be the eigenvalue w. This is Postulate IV of the text.
(b) Should the system wavefunction be a superposition of eigenfunctions ( eqn. 1.14, If/= ~:Cklf/k) the
probability of observing the eigenvalue wk is proportional to lel. This is Postulate Vkofthe text.
Solutions to exercises
he
E1.1(a) till=hv [1.1]=-
IL
34 8 1
= (6.626xl0- J s)x(2.998xl0 ms- )=1 . xl0_19 JI
3 37
590xl0-9 m
E1 .2(a) till = hv = h I T where the period T equals 1I v ( T = 1I v)
(a) till= 6.626xlo-34 J s = 3.3x10-20 J = J33 zJI

2ox10- 15 s
1
This corresponds to NA x(3 .3xl0-20 J)=120. kJmo1- I
6 626 10 34 1
(b) till= · x - s = l3.3xl0-34 JI, lo.20 nJ mo1- 1I
2.0 s
This is much too small to be measurable, thereby, demonstrating that for practical purposes the
energy of a macroscopic object is a non-quantized, continuous variable.
112
E1 .3(a) v={ ~e xEk }
<P = 2.14eV = (2.14)x(l.602xl0- 19 J) = 3.43xl0- 19 J
34 1
(a)
8
he= (6.626 x 10- Js) x (2.998 x 10 ms - ) = 3.4 2 x 10-19 1
IL 580 x 10-9 m
The photon energy is very nearly equal to the value of the work~fu_n_c_ti_on_._ _ _ _ _ _ _~
Consequently, if photoejection occurs, the electrons will have Ino kinetic energy and zero speed I·
- 34 8 -I
he (6.626 x 10 Js) x (2.998 x 10 ms ) -I9
(b) - = 9
= 7.95xl0 J
IL 250 x 10- m
19
Ek = ~ mv 2 = (7 .95 - 3.43) x 10- 19 J = 4.52x10- J = J0.452 aJI
v= 2Ek 1/2 = ( (2)x(4.52xl0- 19 J) JJ/2 =1 996 kms-il

( m ) 9.109xl0-31 kg
THE PRINCIPLES OF QUANTUM THEORY 19
E1 .4(a) <P = he _E
A, k
34 8
he (6 .626 x l0- Js) x (2.998 x l0 ms- ') ( l.602x10- 19 J )
<P=--Ek = (2.lleV) x
A, 465 x l0-9 m eV
= 8.92 x 10-20 J
The maximum wavelength needed for photoejection leaves the electron with zero kinetic energy. If the
wavelength is longer, the radiation has insufficient energy for photoejection. If the absorbed wavelength
is shorter, the electron will have a non-zero kinetic energy after photoejection. In the former case,
A, =-=
he (6.626 x l0-
34
Js)x(2 .998 x l0 ms-' )
8
--<i
=2 .23xl0 m= 2 .23 µm
I I
max <P 8.92 x 10- 20 J
E1 .5(a)
l he 2
Ek = -mev = hv-<P = - -<P [1.2]
2 A-
or
he 1
<P=---mv 2
A- 2 e or v= {(~Jx(~ -<JJ )r 2
he 1
A, 2
34
e
9
- -
8
(6.626 x l0- Js) x (2 .998 x l0 ms- ' )
<P = ---m v2 = - - - - - - - - - ---
165xl0- m
..!..( 9.l 09x 10- 3!
2
kg) x( l.24x 10 6 m s- 1 r
= 5.04 x l0-' 9 J
2
v={(~)x( he -<JJ)}"
34 8
= {( 2 Jx( (6.626 x l0- Js) x (2.998 x l0 ms-') S.0 4 x 10_,91J}'
me A- 9.109 x l0- 31kg 265 x !0-9 m
=17.35 x l0 ms-'
5
I
1 2 he 1 2
E1 .6(a) Ebi nding -E
- photon
-Ek -hv--mv
- 2 e ----mv
- A 2 e
34 8
E . . =he _..!_m v2 (6.626 x l0- Js) x (2.998 x l0 ms-' ) 1 ( 9 .l 09 xlo-3 ' kg)x( 2 .l 4 x 10 1 ms- 1)2
binding A, 2 e l 50xl 0-12 m 2
= (l.12 x l0- 15 J) x( leV _ ) =16 .96 keVI without a relativist mass correction.
I .602 x l0 19 J
Note: The photoelectron is moving at 7.1 % of the speed of light. So, in order to calculate a more accurate
value of the binding energy, it would be necessary to use the relativistic mass in place of the rest mass.
= me = 9.l09 x l0-31 kg = 9 13 10-31 k

m 112 112 · x g
7 8
(1-( v!e )2} (1-(2.14 x l0 ms- ' / 2.998xl0 ms-' f)
34 8
he 1 (6.626 x l0- Js) x (2 .998 x l0 ms-' ) 1( _ )( _ )2
Eb. d. =---m v 2 = 12 - - 9.13 x l0 31 kg x 2.14xl0 7 ms 1
'" mg A, 2 e 150 x lo- m 2
=(l.12 x l0- 15 J) x( leV _ ) =16.96keVlwiththerelativisticmasscorrection.

l.602 x l0 19 J
The relativistic mass correction did not make a difference in this exercise.
he NAhe
E1 .?(a) E = hv = T ' E(per mole)= NAE= -A,-
he = (6.62608 x I 0- 34 J s) x (2.99792x 108 ms _,)= l .986 x 10- 25 J m
NA he= (6.02214 x l0 23 mor' )x(l .986 x l0- 25 Jm) = 0.1196 J m mo1- 1
Thus, E= l.986 x lo-2sJm E( ) 0.1196Jmmor'

permo 1e = A,
A,
ENT SOLUTIONS MANUAL FOR -
We can therefore tne following table.
1
E/J El (kJ mor )
1a16:W 3.20 x 10- 19 193

(b) 570 3.49 x 10- 19 210
(c) 380 5.23 x 10- 19 315
E1 .8(a) Power is energy per unit time; hence
E
N = ~[P =power in watts, 1W=1 J s- 1) = p).,
!:it hv he
p)., (P I W)x(J./ nm)s- 1

= 1 = -'----'---'------'--
(6.626x10-34 J s)x(2.998xl0 ms- )8
l.99xl0- 16
Ei
= 5.03xl0 15 (P I W)x(J. / nm)s- 1
(a) N I !:it= (5 .03xl015)x (10)x(590s- 1) = j3.0x 1019 s- 1j
(b) N I !:it= (5.03 xl0 15)x (250)x(590s- 1) = j7.4x 10 20 s- 1j
h h
E1 .9(a) J.=-=- [1 .3)
p mv
(a)
For a macroscopic object (e.g. , 2 g) the de Broglie wavelength is much too small to be observed. Its
particulate character predominates and energy levels are extraordinarily close, thereby producing an
apparent continuum of possible energies.
E.
(b) J.= 6.626x10-34 Js =113x10-36ml
(2.0xl0-3 kg)x(2.5x105 m s- 1) ·
(c) A= 6.626xlo-34Js =1997 ml

(4.003)x(l.6605xl0-27 kg)x(lOOOm s- 1) · p
COMMENT. The wavelengths in (a) and (b) are smaller than the dimensions of any known particle,
whereas the wavelength in (c) is comparable to atomic dimensions.
Question. For stationary particles, v = 0, corresponding to an infinite wavelength. What meaning

can be ascribed to this result?
E1 .1 O{a) )., = !!... = }!_ [1.3)

p mv
v=_!!___= 6.626x10-34 Js =l7.27x106 ms-1j

m.J. {9.109xl0-31 kg)x(10ox10- 12 m)
The accelerating potential difference needed to provide this speed is
E = 2I m.v 2
V=-k
e e
=
t(9.109xl0-
31
kg)x(7.27xl0 m s-
6 1
f (1-c-v) =@..Yj
~
19
1.602xl0- C J
Low-energy electron diffraction (LEED) uses a beam of electrons of a well-defined low energy
(typically in the range 20-200 eV) incident to a single crystal with a well-ordered surface structure
in order to generate a back-scattered electron diffraction pattern.
l/ 2
1 he 2hc
E1 .11 (a) Ek =-me v =hv= -A,
2
2
or
(m.A- J
v= - -
1/ 2
2(6.626xl0-
34
Js)x(2.998xl0 ms-
8 1
) I -j
V = 31 9
= 1. 71X10 6 mS I
( ( 9.109x10- kg) x ( 150x 10- m) ]
E1 .12(a) The time-independent wavefunction in three-dimensional space is a function of x, y, and z so we

write !f!(X, y, z) or !f!(r). The infinitesimal space element is dr = dxdydz with each variable ranging
from -oo to +oo. The time-independent wavefunction is said to be a stationary state.
It is reasonable to expect that in some special cases the probability densities in each of the three
independent directions should be mutually independent. This implies that the probability density for
the time-independent wavefunction !f!(r) should be the product of three probability densities, one for
2 2
each coordinate: 11f1(r)l oc IXCx)l x IYCY)l 2 x IZ(z)l 2 . Subsequently, we see that the wavefunction is
the product of three independent wavefunctions in such a special case and we write !f!(r) oc X(x) x
Y(y) x Z(z). Such a wavefunction is said to exhibit the separation of variables.
For the special case of a particle free to move in a cube of volume L 3, we may generalize the
wavefunction provided in Example 1.4 of the text, X ( x) µ sin ( J'CX I L), to Y(y) oc sin(7Z)l/L) and Z(z) oc
sin(7CZ/L) and conclude that !f!(r) oc sin(n:x/L) x sin(7Z)l/L) x sin(7CZ/L). Alternatively, for a particle free to
move in a rectangular parallelepiped of sides Lx, Ly and L,, !f!(r) oc sin(n:xlLx) x sin(7l)llLy) x sin(7CZ/Lz).
Remarkably, when the potential energy term of the harniltonian is either zero or a constant value throughout
space, the time-independent wavefunction does not depend upon the particle mass! Mass does appear in
both the kinetic energy operator and eigenvalues of operators that contain the kinetic energy operator.
Similarly, electrical charge does not appear in the time-independent wavefunction in this particular case.
E1 .13(a) An isolated, freely moving hydrogen atom is expected to have a translational, time-independent
wavefunction that is a function of the center-of-mass coordinates Xem• Yem• and Zem• so we write
lf!em(Xem• Yem• Zem) or lf!em(rcm) with each variable ranging from -oo to +oo. The infinitesimal space
element for the center of mass variables is drcm= dxemdYemdzem·
The hydrogen atom also has variables x, y, and z, which are the Cartesian coordinates of the electron
with respect to the center-of-mass of the hydrogen atom. The electronic wavefunction can be
written as lf/ei(x, y, z) or lf/ei(r) with each variable ranging from -oo to +oo.
In general we expect that the total wavefunction is the product lf/emCrem) x lf/ei(r). (See El.12a.)
Furthermore, we expect that there are special cases for which the translational wavefunction
exhibits the separation of variables: lf/em(rcm) oc Xem(Xem) x YCYem) x Zem(Zem). The electronic
wavefunction does not exhibit the separation of Cartesian variables because the electrostatic
potential between the electron and nucleus is proportional to l!r, which cannot be written as a sum
of separate terms in the variables x, y, and z.
E1 .14(a) An isolated, freely moving hydrogen atom is expected to have a translational, time-independent
wavefunction that is a function of the center-of-mass coordinates Xem• Yem• and Zem• so we write
lf!cm(Xem• Yem• Zem) or lf!cm(rcm) with each variable ranging from -oo to + oo. The infinitesimal space
element for the center of mass variables is drem = dxemdYemdzem·
The hydrogen atom also has variables r, e,

and rp. These are the spherical polar coordinates of the
electron with respect to the center-of-mass of the hydrogen atom. The electronic wavefunction can
be written as l/fei(r, e,
rp) with the variables lying in the ranges 0 ~ rp ~ 2tr, 0 ~ B ~tr, and
0 ~ r ~ oo (see text Figs. 3.12 and 3.13). Furthermore, the infinitesimal space element is dr =
dxdydz = ? sine drdBdrp.
In general we expect that the total wavefunction is the product l/fcm(Tcm) x l/fei(r, B, rp). (See El.12a.)
Furthermore, we expect that there are special cases for which the translational wavefunction
exhibits the separation of variables: l/fcm(Tcm) oc Xcm(Xcm) x Y(ycm) x Zcm(Zcm). In Chapter 4 you will
discover that the electronic wavefunction also exhibits the separation of spherical polar coordinates
because the electrostatic potential between the electron and nucleus is proportional to llr.
E1 .15(a) The normalized wavefunction has the form l/f( rp) =Neill' where N is the normalized constant.
f2" •
1 'I' 'I' drp = 1 [1.6)
E1 .16(a) lfl(rp) = (1/2n)"2 eill' so llfl(rp)l 2 = (1/2n) e-i1P eill' = l/2n. Thus, the probability of finding the atom in an
infinitesimal volume element at any angle is l(l/2n) d~.
1 )112 .
E1 .17(a) The normalized wavefunction is 'I'= ( tr e'IP
2
3Jr/2 •
Probability that tr I 2 ~ rp ~ 3tr I 2 = 'I' 'I' drp [Postulate II]
iJr/2
= - 1 ) i3Jr/2e-•1Pe•1P
. . drp= ( - 1 ) i3Jr/2drp
( 2 2
2tr "' 2tr "'
= (-1 2tr
)fPl1P=JJr12 =
\P=Jf/2 2tr
(-1
)x(3tr _tr)
2 2
JTI
l1J
E1 .1 S(a) £ = fi2 = J;; + fJ! =_!!__(~) _!!__(~) [LllJ

k 2m 2m 2m ox 2m ay2 2
y x
E1 .19(a) Let a and b be any real or complex number and let j(x) be defined as f (x) = ae 2ix +be-iix. Then
d/ = 2iae 2 ix - 2ibe -2ix
dx
~ =(2i) 2
ae 2ix +(2i/ be-2ix =-4{ae 2ix +be- 2ix)
=-4/(x)
j(x) is an eigenfunction of the operator d2/d.x2 • The eigenvalue is BJ.
i/a
E1 .20(a) (a) ~ = ( ik) e;1a Thus, eikx is an eigenfunction of d/d.x. The eigenvalue is~
d.x
de ax' 2 2
(b) - - = ( 2a.x) e"" Thus, eax is not an eigenfunction of d/d.x.
dx
(c) d.x = 1 Thus, x is not an eigenfunction of d/dx.

d.x
2
(d) dx = 2x Thus, x 2 is not an eigenfunction of d/dx.
d.x
d(ax+b)
(e) - - - = a Thus, ax + b is not an eigenfunction of d/dx.
d.x
(f) dsin(x
- -- +3a) .(x + 3a ) ts
- =cos ( x + 3a )Th us, sm . not an e1gen
. f unct10n
. of d/dx.
d.x
E1 .21 (a) f
If/; and lf/j are orthogonal if If/;. lf/j d r = 0 [ 1. 16].
Where n :t= m and both n and m are integers,
£Lsin(n7rx I L)xsin(m7rx I L) dx = [sin(7r(n-m)x

(
! L)
2Jr n - m) I L
sin((n+m)x ! L)lx=L
2Jr ( n + m) I L
x=O
= sin(Jr(n-m)) _ sin(7r(n+m)) { sin(O) sin(O) }

27r(n-m) ! L 2Jr(n+m) ! L 27r(n-m) ! L 27r(n+m) ! L
=0 because the sine of an integer multiple of Jr equals zero.
Thus, the functions sin(nJrx I L) and sin(mJrx I L) are orthogonal in the region 0 ~ x ~ L.
E1 .22(a) If/; and lf/j are orthogonal if f If/;. lf/j d r = 0 [ 1.16].
f"( e;qi )' x e2;qi d<p = f" e-iqi x e2;qi d<p = f" e;qi d<p = Te;qi 1::~"
=~ ( e2" ; - e0 ) =~ ( e 2"; -1) = ~(cos(2tr)- isin(2tr)-l) = ~(1-0-1) = 0
1 1 1 I
0
(The Euler identity e = cos(a)-isin(a) has been used in the math manipulations.)
;
Thus, the functions eiqi and e 2iqi are orthogonal in the region 0 ~ <p ~ 2tr.
E1 .23(a) The normalized form of this wavefunction is
2 )!/2
lj/(x)= ( L sin(2trx ! L) (See Self-test 1.4)
The expectation value of the electron position is
(x ) = r If/. x If/ d.x [l.15b] = (±)r x sin

2
(2~x ) dx
rX2 XSin ( ~X) COS( ~X ) ]x=L
4 4
2
=[1:} 4- 81' 1L 8(21' 1L)' ,,,
= (~)x[L2 Lsin(4tr) cos(4 -1~- Oxsin(O) cos }] (2) (L

2
)
L 4 8tr I L 8 Jr I L ) 2 4 8tr I L 8 Jr I L) 2
= L x 4
=~
E1 .24(a) The normalized form of this wavefunction is
2 )112
lj/(x)= ( L sin(nx! L) (See Example 1.4)
112
L
d: : = ( 2 ) ( Z ) cos(nxl L)
The expectation value of the electron momentum is
=( T)(i r ~) 2
( LLIf/. cos(~) dx = ( T)(i )( ~) LLsin (~)cos(~) dx
=( ~2) r sin (~)cos ( ~) dx
2
= ( !!___)x [sin
iL 2
(
2n I L
T)ix=L = ( !!___) x[sin2 (n)
iL2 2n I L
2
sin ( 0))=(-iL
2;r I L
h ) x ( O+O )
2
IAl
=&J
x=O
E1 .25(a) Let/and g be functions of x and examine the integral [J' (- ;: ! 2 J g dx. Integrate successively
by parts (see Justification 1.1) and use the fact that these functions must be well behaved at the
boundaries (i.e. , they equal zero at infinity in either direction) .
2 2 2 2
[ f • ( - 2m
;i2 dx
d2Jg ( fi
dx = - 2m J [ f • ( dx fi J [
d 2 J g dx =( - 2m f • ( dx
d ) dg
dx dx
Thus
'
[! • ( -2m
-dxd2
1i2 -J g dx = { ( g • ( -2m
1i2
2
- d2-J f
dx 2
dx }'
This is exactly the criterion that a hermitian operator must satisfy [1.13], so we conclude that the
kinetic energy operator is hermitian.
E1 .26(a) A quick examination of its expectation value reveals that it is complex because the expectation
values of both position and momentum are real. All observables must be real.
Also, x and Px are complementary observables so they cannot be simultaneously known.

The hermiticity of the operator may also be checked using the fact the both the position and linear
momentum operators are hermitian.
f
fg(.X+i,&J f dr= g(x) f dr+i g(,&J f dr f
={f1(.x) g Mr +i{fg(ftx) / Mr
={f1(.x) g drr -i' {fg(ftx) / drr
= { f/ (x-i,&J g drr
This is not the relationship required by eqn. 1.13 so we conclude that the operator is not hermitian
and cannot correspond to an observable.
E1 .27(a) flp "'O.OlOOpercent ofp0 =Po x(l.OOxl0-4) = mPvx(l.OOxI0-4) (p0 = mPv)

34
~q "'_!___ [l.1 9a]"' l.055xl0- J s
2flp (2) x (1.673x10-27 kg)x (6.1x10 6 m s- 1)x (1.00x 10-4)
11
"'5.2x10- m "'\52 pm\
E1 .28(a) The minimum uncertainty in position and momentum is given by the uncertainty principle in the
form flp~q ?.J.2 n [l.19a] with the choice of the equality. The uncertainty in momentum is
flp=m~v so
(a) ~v . =-n-= l.055xl0_34 Js =II 1x10-2s ms -11

mm 2m~q (2)x(0.500kg)x(l.Oxl0-6 m) .
(b) ~ =-n-= l.055xl0-34 Js =\1x10-21 ml

qmin 2m~v (2)x(5.0xl0-3 kg)x(lxl0-5 ms- 1)
COMMENT. These uncertainties are extremely small; thus, the ball and bullet are effectively classical
particles.
Question. If the ball were stationary (no uncertainty in position) the uncertainty in speed would be
infinite. Thus, the ball could have a very high speed, contradicting the fact that it is stationary. What
is the resolution of thjs apparent paradox?
E1 .29(a) (a) [.X,y] = xy-yx = xy-xy = [Q]
a2 a2
because - - = - - for all well-behaved functions.
dxdy dydx
(c) [x,p,] = x(~j__)-(~j__)x = i ~ -(~)- (~vgi = [!fil

I dX I dX ;Kfax) I yax)
(d) [.x2 ,ftx ]=x2(~j__)-(~j__)x2

dX dX
= x2(~ _ 2~n _ x2(~ =~
I/{iax) I/{iax) I
(e) [ XA" pA] -- X"( -fzi dX

' x
- - (fz
j dX
a) a)
- - X"-~'
- X n-
j dX
nx"--
- -
j
fz - ~n
X -
j dX
-I- n IX. n-1,.I1
rt
Solutions to problems
Solutions to numerical problems
P1.1 l/f= (2)L 1/ 2

. trx
smL and 2
I// =-sm -
2 .
L
2 trx
L
The probability P that the particle will be found in the region between a and b is the integral
summation of all the probabilities of finding the particle within infinitesimally small volume
elements within the region (l/f2 m according to Postulate II).
P(a,b) = l l/f m 2
[Section 1.5, Postulate II]
= ~ rsin 2
7 m= ~x(%- 4~ sin 2 ~x I~: = (f- 2~ sin 2 ~x I~:
= b - a __l_(sin 2trb -sin 2tra )
L 2tr L L
L =10.0 nm
1 (sin C21r) x ( 5.05)

P(4.95 nm,5.05 nm)= O.lO - - . -'---'----'---'-
(2tr) x ( 4.95) )
(a) sm
10.0 2tr 10.0 10. 0
= 0.010+0.010=10.0201
1 2 9 5
(b) P(7.95 nm,9.05 nm)= l.IO - - (sin ( 1r)x( .0 ) s. m
(2tr)x(7.95))
----
10.0 2tr 10.0 10.0
= 0.110-0.063 = lo.0471
(c) P( 9 .90 nm, lO.O nm)= 0.10 __

1 (sin (2tr)x(10.0) sin (2tr)x(9.90))
10.0 2tr 10.0 10.0
= 0.010-0.009993 = l1x10-6 I
(d) P(O nm,5.0 nm)= P(5.0 nm,10.0 nm)=~ [bysyrnmetry]
(e) 1 -L
P ( -L 2 ) =--- . 4tr . 2tr) =&.&li
1 1 ( sm--sm- 17\Zil
3 '3 3 2tr 3 3
P1 .3 The normalization constant for this wavefunction is

1/ 2
1/ 2
N=
[ r l
x' xx' dx ]
[1.4]=
(,,
~
l
so the normalized wavefunction is
2
5 ) 11 2
l/f= ( - x
trs
Consequently, P =Yi when IQ= 7r I l115j

P1 .5 The normalization constant for this wavefunction is
1/2 [ ]1 /2 1/2
N=
(
1
f'<"'xe-""" dq> ] r dq>
[l.4]= _1_ = _1
(2,,J
so the normalized wavefunction is
P1 .7 The most probable location occurs when the probability density, JtpJ 2 , is a maximum. Thus, we wish
to find the value x =Xmax such that dJtpJ /dx =0.
2
If/( x) = Nxe-l-1 20'-

lv I= N x2e-J-id-
1
dlvl I dx = N 1{2xe-J-tt?- -( 2x3 I d) e-J-tt?- } = 2N2x{ l -x2 I d} e-J-tt?-

The above derivative equals zero when the factor 1- x2 Id equals zero so we conclude that kmax = ~.
P1 .9 The expectation value of the commutator is
f
([.X, ,VJ)= lf/· [.X, fa]lf/dr
First evaluate the commutator acting on the wavefunction. The commutator of the position and
momentum operators is defined as
[
'] nd nd
x p =xp-px=xx-----x
A AA AA
, i dx i dx ,
so the commutator acting on the wavefunction is
Evaluating this expression yields
'"'( a )1/2 e -ax/2

A pA] If/ = in
[ x,
which is just in times the original wavefunction. Putting this result into the expectation value yields
([x,p])= [ (a) 11 2 e-ax 12 (in)(a) 11 2 e-ax 12 dx=ian [ e-axdx
([.X, ,VJ)= ianx ~; [ = [!!J.
Note: Although the commutator is a well-defined and useful operator in quantum mechanics, it does
not correspond to an observable quantity. Thus one need not be concerned about obtaining an
imaginary expectation value.
Solutions to theoretical problems
P1.11 Time-independent SchrOdinger equation of a single particle: (-~~+

2m d.x
v)lf/ =Elf/ [1.7]
(a)
2 2
tz d
(b)
( - 2m d.x2 If/ = Elf/
)
(c) F = c (a constant) implies that V =-ex because F = -dV/dx.

2 2
tz - d- e x )
-- If/= Elf/
( 2m dx
2
P1.13 (i) [ A,B] =AB-BA =-(BA-AB)=-[ B,A]

(ii) [ A,B+c] =AB+ AC-BA-CA= AB-BA+AC-CA =[ A,B]+[ A,c]
(iii) [ A2,BJ= A2B-BA 2=(A 2B-ABA)+( ABA-BA2)=A( AB-BA)+( AB-BA)A
=A[ A,BJ+[ A,B]A
P1.15 (a) Since the relevant Heisenberg uncertainty principle is /}.pxfu"?.fin [l.19a], knowledge of the
values of both positions x and Px simultaneously is restricted to non-zero uncertainties. However, if
the uncertainty in one of these observables is very large, the uncertainty in the other can be small.
The value of an observable can be known exactly in the case for which its complementary
observable is completely uncertain. Non-complementary observables, like Px and y, can be
simultaneously measured without the restrictions that the uncertainty principle implies.
(b) The three components of momentum (p., py, pz) commute with each other, so they are not
complementary and they may be simultaneously measured without the restrictions that the
uncertainty principle implies.
(c) The operators for kinetic energy and potential energy do not commute (see Self-test 1.13), so in
general they cannot be measured without the restrictions that the uncertainty principle implies.
[v£] =~(d2v
'
+1 dv ~)
2m d.x2 d.x d.x
k
However, the general form of the uncertainty principle, ~.qti.q "?.fil([.q,4J)I [1.23],
indicates special cases for which uncertainty restrictions will not occur. These include the case
for which
(i) dV/d.x =0 and (ii) jd2V +2dV ~\=0

\ d.x2 d.x d.x I
(d) The general form of the uncertainty principle indicates that ~µ!ill= _!:!!_(ft,)
(see Example
2me
1.10) so in general, electric dipole moment and energy cannot be measured without uncertainty
restrictions. However, in the special case for which (ft,)= 0 there will be no restriction on the
simultaneous determination of them even though the corresponding operators are complementary.
J
(e) Since [ x,Ek =in ftx (see Example 1.10), the general uncertainty principle indicates that
m
Position and kinetic energy are complementary observables. However, in the special case for which
(ftx) = 0 there will be no restriction on the simultaneous determination of them.
3
P1.17 (a) i(x 3 -kx) = (- x) -k(-x) = - x 3 +kx = -l x (x3 -kx)
x 3 - kx is an eigenfunction of i. Its eigenvalue is OJ
(b) i (cos(kx)) =cos(-kx) = cos(kx)
cos(kx) is an eigenfunction of i. Its eigenvalue is E!J
2
(c) i (x 2 + 3x- l) = (-x ) + 3 (-x )-1 = x 2 -3x-1
x 2 + 3x -1 is not an eigenfunction of i
P1.19
and the unnormalized wavefuction is If/= (cos z)ei1cr + (sinz)e-i1cr = c1eih +c2 e-i1cr
P1.21
(i) The normalized wavefunction (see Pl.12) is

112
200 1
If/= N( 2-_!_) e-'' where N = ( - - 3 )
a0 7ra0
- 41r(4
- -3
ao
r 3 -4r
- +r-
ao
4 5
2 ) e - 2rl aod r
ao
; 2)-- -
\r
4
31
ao
r( 4r 4- -
4r
ao
+ - a2 e
o
5 6
r ) -2r1a0 d _ 4 5 (4x4! 4x5! 6!)
r--a3 ao - 25 - - 26 +-21
o
= l9a I 21
0
2
112
1200 1
(ii) The normalized wave function (see Pl.12) is If/= Nrsin Bcost/J e-' where N = ( - -- 5 )
321ra0
P1.23 For the hermitian operator f2: (f2 2 ) =fl;/ fl 21j/dr = fIf/*Qfllj/dr = { J( fllj/ r fllj/drr
The integrand on the far right is a function times its complex conjugate, which must always be a real,
positive number. When this type of integrand is integrated over real space, the result is always a real,
positive number. Thus, the expectation value of the square of a hermitian operator is always positive.
P1.25 A-)- 8JChc ( 1 )

P( - ;.s ehcWT -l
(a) A plot of Planck's spectral energy density at 298 K is shown in Figure 1.1.
TI1e Planck Distribution

T=298K
0.4
0.3
p (A.)
kg·tn- 2 ·s- 1
0.2
0.1
10 15 20 25
µm Figure 1.1
(b) ~i2l P (A) = ~i2l { 8~7c ( e hc l JT _ J} = ~i2l { 8~~c ( ehc~m ) }
In the l"nrut
. as"--+
j 0 , ehc/J.kT --+ oo more rapidly than ).5 --+ 0. Hence, p--+ Oas).--+ O. To see this
in a series of mathematical manipulations, let a = hclkT and examine the denominator of the
above expression in the limit as ). --+ 0.
11
limp( A-)= 8Jrhclim{-h} = 8Jrhclim{ 1 } = 8Jrhclim{-l-} }.
}.--.O }.--.O A e a }.--.O eln}.' ea/}. }.--.O e }. ln}.' e a
11
=8Jrhclim{-~- , -} ;. =8Jrhclim{
11 11
1 } }. =8Jrhclim{ 1 } }.
eln}. e•
J.--.O }.--.O lim (tn}.") }.--.O lim (1n.<')
e}.--.o e• e.<--.o e•
= 8JChc lim { ~ }
}.--.O e e
!/ }.
= 8JChc lim
}.--.O
{
+
e e•
}1/ }.
= 8JChc Jim
{
}.--.o e•
_l_} 1/ }.
= 8JChc Jim{-1-}
}.--.O e a/ ;.
=Jim{
;.__,
8Jrhc} = 0
e hc ! UT
0
(c) As ). increases, hc/J.kT decreases, and at very long wavelength hc!J.kT « 1. Hence we can
expand the exponential in a power series. Let x = hc!J.kT. Then
e x = l +x+ -x
1 2 + -I x 3 + ...
l
2! 3!
p= 8~~c
"
[ 1 1I
I+x+Lix + x + .. ·-1
2 3
31
limp = 8JChc
<--.~
5
).
[-+ 1- J (-1- )-
1 x- I
= 8JChc 8JCkT
). 5 he/ J.kT - ~
This is the Rayleigh-Jeans law.
Solutions to applications
8 1
he ( 6.626xl0-34 J s )x( 2.998xl0 m s- )
P1.27 26
Amax = SkT [Pl. ] = 5x(1.38lxl0-23 J K- 1 )x(5800 K)
= 4.96xl 0-7 m =1496 nm, blue-green I(See text Fig. F.11.)
P1.29 The superpositions of cosine functions of the form cos(nx) can be chosen with n equal to any
integer between 1 and m. For convenience, x can be examined in the range between -tr I 2
and tr I 2 The normalization constant for each function is determined by integrating the function
squared over the range of x [l.4]. Using Mathcad to perform the integration, we find
1· 1·
2 · cos ( tr · n) · sin ( tr · n) + tr · n
t 2
( cos(n · x)) 2 dx ~ -1 · --...:..::...---'----'---__;,_ _
2 n
When n is an even integer, sin ( trn I 2) = 0, and when n is an odd integer, cos ( trn I 2) = 0.
2
Consequently, when n is an integer, the above integral equals tr I 2 and we select ( 2 I tr )1' as the
normalization constant for the function cos(nx). The normalized function is </f._.n, x). The
superposition, l/f(m, x), is the sum of these cosine functions from n = 1 to n = m. Since the cosine
2
functions are orthogonal, l/f(m, x) has a normalization constant equal to (1 I m )11 • The Mathcad
probability density plots of Figure 1.2 show vJ(m, x) against x form = 1, 3, and 10.
</J(n,x) := ( ~ J·
_l
cos(n,x) ljl(m,x) := ( m
1 )t~</J(n,x)
m
x := - ; ' - ; +0.001. . . ~
Probability Density Plots
~x) 4 '
1j1(3. x)'
3
ljl (IO ,x)'
01-..."'"""~;:,,... .....:..L____;.,L__L__lL__-'>...;=l.....C.:.:::s;,........-1
-1 -0.5 0.5
x
Figure 1.2
Examination of the probability density plots reveals that, when the superposition has few terms, the
particle position is ill-defined. There is a great uncertainty in knowledge of position. When many
terms are added to the superposition, the uncertainty narrows to a small region around x = 0. A plot
with m greater than 10 will further confirm this conclusion.
Each function in the superposition has been assigned a weight equal to the normalization constant (l/m) 112•
This means that each cosine function in the superposition has an identical probability contribution to the
expectation value for momentum (see Justification 1.4). Each cosine function contributes with a probability
equal to l/m. Furthermore, each cosine function represents a particle momentum that is proportional to the
argument n (see Example 1.5). The Figure 1.3 Mathcad plot of momentum probability against momentum,
as represented by n, is an interesting contrast to the plot of probability density against position.
Variables needed for the Mathcad plot: n := 1...12 Prob(n,m) :=if( n $; m, ~ ,0)
Momcntrnn Probability, Prob(n,m),against Momcnttun n
I I I I I
0.8 - -
Prob( n , 1) 0.6 -
Prob ( n ,5)
Prob (n , 10) _ _
04
0.2- ... .. . . .... .... . .. . . . . . .
I I ·. , I .~
4 10 12
n Figure 1.3
The momentum probability plot shows momentum probabilities for superpositions of m = 1, 5, and 10
terms. When there are many terms in the superposition, the range of possible momentum is very broad even
though the range of observed positions becomes narrow. Position and momentum are complementary
variables. As location becomes more precise with the superposition of many functions, precise knowledge
of momentum decreases. This illustrates the Heisenberg uncertainty principle ( l. l 9a and 1.23].
The plot of probability density against position clearly indicates that the superposition is
symmetrical around the point x = 0. Consequently, the expectation position for all superpositions is
=
x 0. The expectation value for position is independent of the number of terms in the superposition.
The square root of the expectation value of x 2 is called the root-mean-square value of x, Xnns· The
Figure 1.4 Mathcad plot of Xnns against m indicates that this expectation value depends upon the
number of terms in the superposition. However, it does appear to very slowly converge to a very
small value (zero?) when the superposition contains many functions.
m := 1. . . 50
Root-Mean-Square Position
02
10 20 30
m Figure 1.4
Nanosystems 1· motion in
2 one dimension
02.1 In quantum mechanics, particles are said to have wave characteristics. The fact of the existence of
the particle then requires that the wavelengths of the waves representing it be such that the wave
does not experience destructive interference upon reflection by a barrier or in its motion around a
closed loop. This requirement restricts the wavelength to values A,= 2 I nxL, where Lis the length
of the path and n is a positive integer. Then using the relations A= h I p and E = p 2 I 2m , the
energy is quantized at E = n 2h 2 I 8mL2 • This derivation applies specifically to the particle in a box.
The derivation is similar for the particle on a ring (see Section 3.3); the same principles apply.
02.3 The lowest energy level possible for a confined quantum mechanical system is the zero-point energy,
and zero-point energy is not zero energy. The system must have at least that minimum amount of
energy even at absolute zero. The physical reason is that if the particle is confined, its position is not
completely uncertain, and therefore its momentum and hence its kinetic energy cannot be exactly zero.
We have already seen zero-point energy in the particle in a box and the harmonic oscillator.
02.5 Macroscopic synthesis and material development always contain elements of molecular
randomness. Crystal structures are never perfect. A product of organic synthesis is never absolutely
free of impurities, although impurities may be at a level that is lower than measurement techniques
make possible. Alloys are grainy and slightly non-homogeneous within any particular grain.
Furthermore, the random distribution of atomic/molecular positions and orientations within and
between macroscopic objects causes the conversion of energy to non-useful heat during
manufacturing processes. Production efficiencies are difficult to improve. Nanometer technology on
. the 1 nm to 100 nm scale may resolve many of these problems. Self-organization and production
processes by nanoparticles and nanomachines may be able to exclude impurities and greatly
improve homogeneity by effective examination and selection of each atom/molecule during
nanosynthesis and nanoproduction processes. Higher efficiencies of energy usage may be
achievable as nanomachines produce idealized materials at the smaller sizes and pass their products
to larger nanomachines for production of larger scale materials.
The directed, non-random use of atoms and molecules by nanotechniques holds the promise of the
production of smaller transistors and wires for the electronics and computer industries. Unusual
material strengths, optical properties, magnetic properties, and catalytic properties may be
achievable. Higher efficiencies of photoelectronic conversion would be a boon to mankind. There is
hope that science will devise nanoparticles that destroy pathogens and repair tissues. See Impact 2.1
for discussion of examination of atom positions on a macroscopic surface by scanning probe
microscopy and for the current nanotechnological method for positioning atoms on a surface. See
Impact 3.1 for discussion of nanoquantum dots that have unusual optical and magnetic properties.
02.7 The particle in a box can serve as a model for many kinds of bound particles. Perhaps most relevant to
chemistry, it is a model for 7t-electrons in linear systems of conjugated double bonds. See Example
2.1, in which it is the basis for estimating the absorption wavelength for an electronic transition in the
linear polyene ~-carotene. More crudely yet more fundamentally, it can provide order-of-magnitude
excitation energies for bound particles such as an electron confined to an atom-sized box
around a nucleus or even for a nucleon confined to a nucleus-sized box. The harmonic oscillator
serves as the first approximation for describing molecular vibrations. The excitation energies for
stretching and bending bonds are manifested in infrared spectroscopy.
E2.1 (a) If the wavefunction is an eigenfunction of an operator, the corresponding eigenvalue is the value of
the corresponding observable (Section 1.7, Postulate IV). Applying the linear momentum operator
p= T! ( eqn. 1.10) to the wavefunction yields
so the wavefunction is an eigenfunction of the linear momentum; thus, the value of the linear
momentum is the eigenvalue
1ik = l.0546xl0-34 J sx3 m- 1 = 13xl0-34 kg m s- 1 I

' 1i2 d2
Similarly, applying the kinetic energy operator Ek= - m dx2 (eqn. 1.11) to the wavefunction
yieldsO 2
so the wavefunction is an eigenfunction of this operator as well; thus, its value is the eigenvalue
34 1 2
(1.0546xl0- J sx3 m- ) = lsxl0_ 38 JI
2x9.llxl0-31 kg
E2.2(a) (a) An electron accelerated through a potential difference of 1.0 V acquires a kinetic energy of
1.0 eV. That is the definition of the electronvolt. The wavefunction for such a particle is (eqn.
2.2 with B =0 because the particle is moving toward positive x)
lf/k =I Aeikx I
The index k is given by the relationship
1i2k2
Ek =--=1.0 eV
2m
12
k = (2mEk)1 = (2x9.l lxl0-31 kgxl.O eVxl.602xl0- 19 J ev- 1 )1 12
Thus
ti l.0546xl0-34 J s
= ls .lxl0 9 m- 1 I
(b) Here Ek= 10 keV, so
(2x9.llxl0- 31 kgxl0xl0 3 eVxl.602xl0- 19 J eV- 1 ) 112

1.0546x10-34 J s
= ls.1x10
11
m- 1 I
2h2
E2.3(a) E = _n_ [2.6a]
2
8mJ
34 2
(6.626xl0- Js) = 6.0lxl0_20 J
8(9.l lxl0-31 kg)x(l.Ox10-9 m) 2
NANOSYSTEMS 1: MOTION IN ONE DIMENSION 35
The conversion factors required are

1 eV = l.602xl0- 19 l ; 1 cm- 1 = l.986xl0-23 l; I eV = 96.485 kl moi- 1
2 2
h 3h - -20
(a) E 2 -£1 =(4-1)-- 2
= - -2 =(3)x(6.02x10 l)
8meL 8mcL
= li.sx10- 19 ll, lu evl, l9.lxl0 3 cm- 1 I, lux10 2 kl mo1- 1 I

2
(b) E6 -E5 =(36-25)~= llh 2 =(ll)x(6.02x10-20 l)
8mJ 8meL
= l6.6 x l0- 19 ll, 14.1 eVI, l3.3xl0 4 cm- 1 I, l4.0xl0 2 kl mo1- 1 I
COMMENT. The energy level separations increase as n increases.
E2.4(a) The wavefunctions are
The required probability is
where Lix = 0.02L and the function is evaluated at x = L/2.
(a)
2
Pi= ( z }in ( ~ Jx o.02L = lo.o41
(b) Pi= ( z}in 2 (2; 2

Jx 0.02L = ( z}in nx0.02L = [Qj
E2.5(a) The wavefunction for a particle in the state n = l in a square-well potential is
V/1 =(zf n; J si{ [2.6b]
. f
The expectatwn value o the momentum operator, p = i dx , is
, n ct .
The expectation value of the momentum squared operator, fi = -n 2 ~, is

dx
(p 2)-- - -2nL
2
r·{TCXJ
Sl -
L
2
-dS I·{TCXJctx-(2n
dx 2
- -
L
-
L
2
Jx (TCJ
-
L
2
r. sm 2(TCXJdx
-
L
Use Jcsin 2 ax)dx = _::2 _ -4a1- sin 2ax with a = rt/L. Thus
COMMENT. The expectation value of p is zero because on average the particle moves to the left as
often as the right.
E2.6(a) The zero-point energy is the ground-state energy; that is, with n = 1,
n1h2 h1
E = - -2 [2.6a]=--2
8m.L 8mJ
Set this equal to the rest energy mec 2 and solve for L:
h
so L = - 1-12- -
8 m.c
In absolute units, the length is
L= 6.63xlo-34 J s = 8.58x10-13 m = 0.858 pm

8112 x(9.l lxl0- 31 kg)x(3.00xl0 8 m s- 1)
In terms of the Compton wavelength of an electron, ~ = }!__,

m.c
L = ~2 1
8
I
E2.7(a)
P(x) oc
2 . 2( L
lj/3 oc sm 3nx )
The maxima and minima in P(x) correspond to dP(x) = 0.

dx
dP(x)
- dlj/- oc
- oc -
2
• (-
sm 3nx
- ) cos ( -
3nx) . --
- oc sm (6nx) [2sinacosa = sin2a]
dx dx L L L
sin B= 0 when ()equals an integer times rt:
6nx_ , "ior ,_0, 1, 2, ... , which

- n Jr n -
. corresponds to _n'L x-
,<
, n _ 6.
L 6
n' = 0, 2, 4, and 6 correspond to minima in r. leaving n' = 1, 3, and 5 for the maxima; that is,
LL 5L
x= - - and -
6' 2 6
2
COMMENT. Maxima in lf/ correspond to maxima and minima in lfl itself, so one can also solve this
exercise by finding all points where d If/ = 0.

dx
E2.8(a) The transmission probability (eqn. 2.17) depends on the energy of the tunneling particle relative to
the barrier height(£= EIV = 1.5 eV/(2.0 eV) = 0.75), on the width of the barrier (L = 100 pm), and
on the decay parameter of the wavefunction inside the barrier (.tj, where
{2m(V-E)} 112 {2x9.1 lxl0-31 kgx(2.0-l.5) eVxl.602xl0- 19 J eV- 1}112

1\=-'--------'-
1i 1.0546xl0-34 Js
= 3.6 x l0 9 m- 1
We note that 1\L = 3.6 x l0 9 m- 1xlOOxl0- 12 m = 0.36 is not large compared to 1, so we must use
eqn. 2. l 7(a) for the transmission probability.
1 1
(e ..L-e-1<L )2}- { (eo36 _e-036 )2 }-
T= 1+ = 1+ =I0.81
{ 16£(1- £) 16x 0.75 x (1- 0.75)
E2.9(a) The zero-point energy of a harmonic oscillator is (eqn. 2.23)
[ . = l.0546xl0-34 J s x ( 155 Nm- 1 )1/2

2 211
2 1.67x10-27 kg
E2.1 O(a) The difference in adjacent energy levels is
k )l/2
M = Eu+i - Eu = hOJ [2.22) = n( m [2.21)
2 2
f:..£) 25 ( 4 s2x10-21 J ) = 278 kg s-2 =1278 N m- 1I
( n = (l.33xl0- kg)x l.055xl0
Hence k = m - · _
Js 34
E2.11 (a) The requirement for a transition to occur is that M(system) =£(photon),
where M(system) = nOJ [2.22)
he
and £(photon)= hv = -
A,
112
Therefore, -he = -hOJ = ( - h ) x ( -k )
A, 27r 27r m
A,= 27re( m)112 = (27r) x(2.998xl os m s-1)x[1.673x10-211 kgl112

k 855Nm-
= 2.63xl0--{;m = 12.63 µml
E2.12(a) A, = 27re ( :
112
r 2
[E2. ll a]
12 112
Since A oc m , Anew= i A01d = (2 )x(2.63µm)=13.72 µml
E2.13(a) The SchrOdinger equation for the linear harmonic oscillator is
n_2 d2VJ" 1 2
----
2
+- kx VJ"= EVJ" [2.20)
2m dx 2
The ground-state wavefunction to be tested is
Vl"o = Noe-x' 12a' [2.25a]
with a= ( ~: r 4
[2.24); so k= m~4 (a)
Performing the operations,
dVJ"o =
dx
(--1a2 x) ur
'f'O
2
c1x2
1 1
d VJ"o =(-- x)x(-- x)x11r
a2 a2 'f'o
+(--a2 11r
1
'f'o a4 l 11r =(i._ __
)=i._11, __
'f'o
l )11r
a2 'f'o a4 a2 'f'o
Substituting into the SchrOdinger equation,
which implies
E0 = -n2 (~--1 J+_!_kx2 (b)

2m a 4 a 2 2
But £ 0 is a constant, independent of x; therefore the terms that contain x must drop out, which is
possible only if
-n 2 i
---+-k=O
4
2ma 2
which is consistent with k = ~ as in (a). What is left in (b) is
n2 1
Eo=--=-nw
2ma 2 2
ma
[ using OJ= (m
2
k )1/ p,2
and k = ma4
l
1
Therefore, 1fJO is a solution of the SchrOdinger equation with energy - nw.
2
E2.14(a) The harmonic oscillator wavefunctions have the form
lf/v(x) = NvHv(y)exp ( -
1
y
2 •
with y
x
=a and a=
n2Jl/4 [2.24]
mk
2 ) (
The exponential function approaches zero only as x approaches ±oo, so the nodes of the
wavefunction are the nodes of the Hermite polynomials.
4
H 4 (y)=l6y - 48y2+12=0 [Table2.l]
Dividing through by 4 and letting z = y2, we have a quadratic equation 4z 2 - l 2z + 3 = 0.
-b±-Jb2 -4ac 12±'112 2 -4x4x3 3±16

So z=
2a 2x4 2
and
Evaluatin
y =±~3±216 and
x=+J¥J
the result numerically yields z = 0.275 or 2.72, so y = ±0.525 or ±1.65 . Therefore,
x = 0.525aor ±l.65a.
COMMENT. Numerical values could also be obtained graphically by plotting H,(y).
E2.15(a) The harmonic oscillator wavefunctions have the form
lf/v(x) = NVHV(y)exp(-~ y2) with y =; and a= ( ; : r4
[2.24]
so the wavefunction in question is
Normalization requires
l= [lf/2 *1f/2dx= [lf/22ady= [(N2(4y2-2)e-l 12

f ady
=4N/a [(4y 4 -4/+l)e-/ dy

To evaluate the integral, note that the integrand is even, so the integral is twice the integral from
zero to infinity of the same function. Use
r oY
2ne-ay'd = 1·3···(2n-l)t
!JI 2•+1 a n a
and
ro
e-a/ dy--
- 1 -
2 a
t
Thus 3£ £ r=
1=8N/a 4x-3- - 4 x 2- + - = 8N/avtt £)
2 [ 2 2
and N = 1
2 (8a)112,.114
Confirming orthogonality amounts to demonstrating that
The integral in question is
= 8N4 N 2 a J~ (4y4 -12y 2 + 3)(2y2 -l)e-r' dy
= 8N4 N 2 a J~ (8y6 -28y 4 +18y 2 -3)e-/ dy
=8N4 N 2 a ( 8x 15 -28x 3 +18x"22-3x

1 r=
1) vtt
24 23 2
The terms in parentheses, _!2 _ ~ + 2_ _ ~ , do indeed add up to zero, making the integral vanish, as
2 2 2 2
required.
E2.16(a) The effective mass is
mAme mc1mc1 mc 34.9688 uxl.66054xl0-27 kg u- 1

µ= = = - 1= -----------"---
mA +m8 mc 1+mc1 2 2
26
= 2.90335xl0- kg
The difference in adjacent energy levels, which is equal to the energy of the photon, is
M = nw [2.22) = hv
so, in terms of wavenumbers,
k )1/2 ii= ll..(!:...)112 = _ l (!:...)1/2

n( m (2.21) = hcii and
he m 2ttc m
1/2
ii= 1 329 N m-1 = ls65 cm-1 I
2ttx2.998xl0 10 cm s- 1 ( 2.90335xl0-26 kg )
E2.17(a) Justification 2.2 analyzes the classical turning points of the hannonic oscillator. In terms of the
dimensionless variable y, the turning points are Ytp = ±(2v + 1) 112 • The probability of extension
beyond the classical turning point is
"6 SIUDENT SOLUTIONS MANUAL FOR QUANTA, MATIER, AND CHANGE
For v = 1, H 1(y) = 2y and N 1 = ( - -11-2

1 )l/2
2a7r
Use integration by parts:
Judv = uv- Jvdu

2
where u = y, dv = y e-y dy
so
and
The remaining integral can be expressed in terms of the error function:
2 f~ e-y2 dy
erf z = 1-----vz
1C z
-'
i3'" e
~ 1f112(1-erf 3112)
so Y dy = - - - - - -
2
Finally, using erf 3 112 = 0.986,
p = 1f-112 ( 3112e-3 + 1f 112 (l-2erf 3112) ) = /0.0561
COMMENT. This is the probability of an extension greater than the positive classical turning point. There
is an equal probability of a compression smaller than the negative classical turning point, so the total
probability of finding the oscillator in a classically forbidden region is [D] .
COMMENT. Note that molecular parameters such as m and k do not enter into the calculation .
E2.18(a) Mean kinetic and potential energies are related by
2(E k) = b( V) , where V = axb . [2.30]
So for V ex: xb, we have 2(Ek) = 3(V), or kEk) = 3(V)/~ .
E2.19(a) The perturbation is
,1
H <l = V(x) =-£sin (21fx
L )
The first-order correction to the ground-state energy, E 1, is [2.34]
112 112
fL (O)
EI(l) -_ Jo1//1
*H
'(I)
1//1
(O) d x -
- -
fl( 2 )
Jo L Sill
. (L
1CX ) £Sill
. (L21CX )( 2 )
L Sill
. (1CX)
L dx
E (I)
1
_ -2£
- -
L
il . ( 1CX ) . ( 21CX) dx
o
Sill 2 -
L
Sill - -
L
Notice that the sin 2 term is symmetric about the midpoint of the r~ion of integration while the sin
term is antisymmetric. Therefore, the integral vanishes, and 1> = lQJ . Er
1 -r-----i::o--~=----ir--=---'""""o--r-----r-----,
0.8 +---~--+---~-t-----+--'"""-"""----+--r------...--i
0.6 +-----+--~..,____ __.,.___ _ _--+--------+-~-+--.--i---i
0.4 +--~--t7"'----__,r----'lo,------+-----------t
0.2 -t-7'----:;7"''----t-----j--T----t----'----t~~----j
0-1'---=-'-----+--------lf---..+----+-----+--___::""'---,I
-0.2 + - - - - - + - - - - - _ _ , f - - - -- - - + - - - - - + - - ---,<'---l
-0.4 +-----+-----__,f--_.,...,,--.,__,r-+-----+--~,,__-;
-0.6 +-----+-----__,f-.=~=;o=+----'lo~----+-~,,__--;
-0.8 +-----+-----__,f-------+----"----+~,,___ _-;
-1 -1-------+--- -----lf-------+--..::::..-.....,.._ _ _ _--l
0 0.2 0.4 0.6 0.8
x/L Figure2.1
E2.20(a) The perturbation is
if<1> = V(x) =-Ecos(2;x) (2;x)

The first-order correction to the ground-state energy, Ei. is [2.34]
12 112
EI( I) -_ LoL *H' oJ ,<oJdx- LoL
11, (o)
l"I 11
l"IL(2J - - - ' sm
• - (;rxJ
L
ECOS (2;rxJ(2J
-- -
LL
sm
•(;rxJdx
-
L
E,(I) -_ - - 2E LLsm. (ffxJ

- 2
cos (2JrxJdx
--
L o L L
Use the trigonometric identity
• 2
sm (trxJ
L = 1 - 1 cos (2;rxJ
L
2 2
So E,( I) =-LE{LLcos (2;rx)
L dx- LLcos (2;rx)
0
L dx } 0
2
dx =-+---
x sin2ax
Use
f cos ax
2
2 4a
for the second integral, so
E 1ol -_ -~{!:___ sm. (2;rx)

L 2;r
- - - -x- - L
L 2 8;r
. (4trx)~jl
sm - -
L
= _
2
m
0
E2.21 (a) The functional form of a linear slope that rises from O at x = o to Eat x =L is
flO >= V(x) = EX
L
The first-order correction to the ground-state energy, E,, is [2.34]
.C ::i ::NT SOL 1 S MANUAL FOR QUANTA, MATIER, AND CHANGE
.
xsm 2 ax
dx x
2
xsin2ax cos2ax
Use
f =-----
4 4a 8a 2
-_ ~
2 2
So E (I) -_ -2£2 IL xsm. 2(Jrx)dx
- -_ -2£2 (x
- - -xL
sm 2Jrx)
. (- L
- ---cos
2
(27rx)JIL
-- -
I L 0 L L 4 4Jr L 8Jr L 2
0
E2.22{a) The perturbation is
il 0l = V(x) = mgx
The first-order correction to the ground-state energy, £ 0, is [2.34]
E(I) llE(O) * ilOl11r<O

- foo 'f'O )dx = f oo N 0 e-x'12a' mgxN0 e-x'12a' dx
0 -
- 'f'O
-
COMMENT. The expression integrates to zero because the integrand is antisymmetric about the
midpoint of the region of integration (i.e., an odd function of x). The result should not be terribly
surprising, as the perturbation affects stretching and compressing the bond to an equal but opposite
degree.
E2.23{a) The second-order correction to the ground-state energy, £ 0 , is [2.35]
oo IJoo 11/0) * H(l)llE(O) dxl2

(2) - "'"'
_ .,, v 'f' 0
Eo - L..i E(O) - E(O)
v=l 0 v
where i l(ll = mgx, l/f~o) = NvHv(y)e-i 12 and Ev = (v+f)nw.

The denominator in the sum is
E (O) - E (O) = l nw-(v +

0 v 2
!) nw
2
= -vnw
The integral in the sum is
f~l/f~o) * il<nlfl6°)dx = [ NvHv(y)e-i 12mgxN0 e-i 12 dx
= mgNvNoa f~ H v(y)e-y212ye-y212dx
where we have used H 0(y) = 1 and y = x/a. Now notice that H 1(y) = 2y, so the integral can be
expressed as
f~l/f~o) * H(l)lflcio)dx = m~~oa f~ NvHJy)e-/12 N1H1 (y)e-/12dx

I
~ mgNoa f oo (OJ * (O)dx

- N _ lflv 1/11
2 I
Because the harmonic-oscillator wavefunctions are orthogonal, this integral vanishes unless v = 1.
In that case, the remaining integral is the normalization integral.
Using N 0 = ( ~ ) ~
1/2 ( )112 ( 2 Jl/4
, N1 = , a= !!:_ , and k = mw2, this result simplifies to
an 2an mk
£<2>
0 -
-
n1h2 3h 2
P2.1 E = - -2 [2.6a], E2-E1 =--2
8mL 8mL
We take m(0 2) = (32.000)x(l.6605xl0- 27 kg), and find
E -E = (3)x(6.626xl0-J4 J s)2 = li.24xl0-J9 JI

2 1
(8)x(32.00)x(l.6605xl0-27 kg)x(5.0x10-2 m) 2
n 2h 2 1
We set E = &ml2 = "ikT and solve for n.
h2 E2-E1
From above, - - 2 =- - = 4.13xl0-4° J; then
8mL 3
n 2 x(4.13xl0-4° J) = ( ~ )x(l.38lxl0-23 J K - 1)x(300 K) = 2.07x10-21 J
21 Jl/2
We find n= 2 .0?xlO- J =l2.2xl09 1
( 4.13xl0-4° J
At this level,
2 2 2
2 2 h h h
E - E = {n -(n -1) } x - - = (2n -1) x - - "' (2n) x - -
" n-I 8mL2 8ml2 8ml2
= (4.4xl0 9)x(4.13xl0-4° J) "'li.&xl0-30 JI [or 1.1 µJ mol- 1]
k)l/2
(µ [2.21 with µ in place of m]
P2.3 OJ=
The relationship between the oscillator frequency and the wavenumber of absorbed photons comes
from the fact that absorption occurs when Ephoton equals the difference between adjacent energy
levels:
hcv _
Ev+I - Ev = liOJ [2.22] = Ephoton = hv = hcv so OJ=-= 2ncv
Ii
44 STUDENT SOLUTIONS MANUAL FOR QUANTA, MATIER , AND CHANGE
We draw up the following table using isotope masses from a handbook.
IH35 Cl 1Hs1 Br IHl 27 1 12c1 60 14N160
vi m- 1 299000 265000 231000 217000 190400

27
10 m,lkg 1.6735 1.6735 1.6735 19.926 23 .253
27
10 m/ kg 58.066 134.36 210.72 26.560 26.560
k /(N m-') 516 412 314 1902 1595
Therefore, the order of stiffness is Im < HBr < HCl < NO < cg
P2.5 The probability is given by
P,, = ~If/" 2 Idx [Section 1.6, Postulate II]
Use the integral
. dx x sin 2ax
f sm 2 ax =-----
2 4a
-~
2
(a) - 2 J, sm
P --
" L o
ru
• 2( -
n7rx)
L
- dx-
--
2
x L . (-
2 ( ----sm
L 2 4Trn
27rnx))I
L
- L/ - -
2
0
COMMENT. The sine term vanishes at both limits of integration for all n.
L/ 4
(b) p = 3._{~-__i:_sin ( 2Trnx )} = 3._ {~-__i:_sin ( nff)} = ~--1 sin(nff)

" L 2 4Trn L I0
L 8 4Trn 2 4 2Trn 2
For even n, the sine term vanishes. The sine term is 1 for n = 1, 5, 9, and - 1 for n = 3, 7, 11, and so
on. Thus
t for even n
P,, = t- 2 ~" for n = 1, 5, 9, etc.
{i+i,;;;- for n = 3, 7, 11, etc.
(c) Here the interval of integration is small, so the integral is equal to the integrand evaluated at the
midpoint of the interval times the size of the interval:
2
P =- l L+Jx sm. 2( -n7rx)
- dx =-sm
2 . 2 4<5x. 2 ( -7rn)
( -7rn ) x 2ux=--sm
s:
n L ,L - Jx L L 2 L 2
Again, the sine term vanishes for even n; for odd n , squaring the sine term gives 1. So
0 for even n
P,, = 4<5x
{- - foroddn
L
P2.7 Treat the gravitational potential energy as a perturbation in the energy operator:
H l'l =mgx
The first-order correction to the ground-state energy, Ei. is [2.34]
E (I)-_ i l11r ( O)* H ( l ) 11r (O) d x-- iL( -2)1/2 sin. (ffX)
- mgx(2)112
- . (1[X
sm - )dx
I 0 'f"1 't"l 0 L L L L
_ 2mg
E1(I) - -L ii .
o
2
x sm ( -;rx) d.x
L
2 2
2 (;rx))I
_ 2mg
E (I) - - - (x xL
---cos ( -Jrx ) sm
. ( -;rx ) ---cos
L - L
I L 4 2;r L L 4Jr 2 L 0
Not surprisingly, this amounts to the energy perturbation evaluated at the midpoint of the box. For
m =m. , E 1(1>1L =4.47 x 10-30 J m- 1•
P2.9 The first-order correction to the ground-state energy, Ei. is (2.34]
where fJ (I ) = axJ + bx4, " ' (O)

't' O
= _l_
( a;rl/2 )
1/2
e- x' 12a'
' a= ( ~: r
4
(2.24]
(a) If the anharmonic perturbation is present for all values of x, then
Use the integrals
i-
o
x 3 e-cx' d.x =1-
2c 2
and
and remember that f~f(x)dx =0 if.f{x) is odd and f~f(x)dx = 2 r /(x)d.x if.f{x) is even.
Thus E1 = ~ (o + 3bas;r112J= I3ba4 I

a;r 4 4
(b) If the anharmonic perturbation is present only during bond expansion, then the perturbation
vanishes for x < 0.
E <IJ = -11-
1 a;r ' 2 o
ei-
- x'ta' ( ax J + bx 4)d.x-
- -1- (aa
--+
an 1'2 2
4 5
8
2
3ba Jrv - -aa
-
3
210 1'2
+3ba
-
8
4
- J-
(c) If the anharmonic perturbation is present only during bond compression, then the perturbation
vanishes for x > 0. Use the fact that
r f (x)dx = - f~! (x)dx if.f{x) is odd and r f (x)dx = [f(x)dx ifj{x) is even.
_ -1-
E1(IJ -
an112
L 3 bx 4)d.x-
e-x'ta' ( ax+ - -11-
a10 12
aa
( ---+
2
4 5 1
3ba n
8
12
_ - -
3
aa- +3ba
2;r1'2
-
8
-
4
J-
P2.11 The normalization integral is

So the normalization constant is
N=[fil
P2.13 The text defines the transmission probability and expresses it as the ratio of I A' 12 /I A 12 , where the
coefficients A and A' are introduced in eqns. 2.12 and 2.15. Eqn. 2.16 lists four equations for the six
unknown coefficients of the full wavefunction. Once we realize that we can set B' to zero, these
equations in five unknowns are
(a) A+B=C+D
(c) ikA-ikB = KC-KD

(d) KCelCL - KDe-KL = ikA' eikl
We need A' in terms of A alone, which means we must eliminate B, C, and D. Notice that B appears
only in eqns. (a) and (c). Solving these equations for B and setting the results equal to each other
yields
KC KD
B=C+D-A=A--+-
ik ik
Solve this equation for C:
C=
2A+D(.K
1k
-1) =2Aik+D(K-ik)
_!_+l K+ik
ik
Now note that the desired A' appears only in (b) and (d). Solve these for A' and set them equal:
- ikL
A'= e-ikl(CelCL +De-ICL) = K:k (Ce/CL -De-ICL)
Solve the resulting equation for C, and set it equal to the previously obtained expression for C:
C= zk(~ -1)ne- 2
1Cl
(K+ik)De-21CL 2Aik+D(K-ik)
K_l K-ik K+ik
ik
Solve this resulting equation for Din terms of A:
(K+ik) 2 e-ZKL -(K-ik) 2 2Aik
---------D = - -
(K-ik)(K+ik) K+ik
D= 2Aik(K-ik)
so
(K+ ik) 2 e-2/CL -(K- ik) 2
Substituting this expression back into an expression for C yields
Substituting for C and D in the expression for A' yields

A' 4ikKe-.-Le-ikl 4ikKe-ikl

so ~--------=---------
A (K+ik)2e-2KL -(K-ik) 2
(K+ik) e-Kl -(K-ik) 2eKL
2
The transmission coefficient is
The denominator is worth expanding separately in several steps. It is
(K+ik) 2(K-ik)2e-2Kl -(K-ik) 4 -(K+ik) 4 +(K-ik) 2(K+ik) 2e2Kl

= (r +k2) 2(e 2.-L +e-2.-l )-(r -2iKk-k2) 2 -(r +2iKk-k2) 2
=(K4 + 2K2k 2+k4 )(e2Kl +e-2KL )-(2K4-12K2k 2 + 2k 2)
If the 12K2k 2 term were -4K2k2 instead, we could collect terms still further (completing the
square), but of course we must also account for the difference between those quantities, making the
denominator
So the coefficient is
We are almost there. To get to eqn. 2.l 7(a), we invert the expression:
(r +k2)2(e.-L -e-.-L)2 +l 6rk2J_, (<r +k2)2(e.-L -e-.-L)2 J-'

T= = +l
( 16k 2r 16k2r
2
. ally, we try to express (r+k2)
Fm k2 r . terms of a ratio
m . of energies,
. E = E IV. Eqns. 2.12 and 2.14
define k and TC The factors involving 2, n, and the mass cancel, leaving Koc (V - £) 112 and k oc £ 112 , so
(r+k2) 2 [E+(V-E)]2 V2 1
= = =---
k 2r E(V-E) E(V-E) e(l-E)
which makes the transmission coefficient
If KL>> 1, then the negative exponential is negligible compared to the positive, and the 1 inside the
parentheses is negligible compared to the exponential:
P2.15 (a) The wavefunctions in each region (see Figure 2.2) are (eqns. 2.12, 2.14, and 2.15)
vr/x) = eik,x + B,e- ik,x

V'2(x) = ~ek,x + B2e-k,x
V'3 (x) = ~e ik3x
With the above choice of A 1 = 1, the transmission probability is simply T = IA 312 • The wavefunction
coefficients are determined by the criteria that both the wavefunctions and their first derivatives
with respect to x be continuous at potential boundaries.
Vi _ __,
0 ,___ _
- x Figure 2.2
0
d If/JO) _ d lf/2(0) . d lf/2(L)

~-~, dx
These criteria establish the algebraic relationships:
1+ B1 - Ai - B2 = 0
(-ik1 -k2 )Ai +(-ik1 +k 2)B2 +2ik1 =0
A2k 2ek,L - B2k 2e -k,L - LJ-'3

; J k3 eik,L = 0
Solving the simultaneous equations for A 3 gives
4k k eik,L
A3 = I 2
(ia+b)ek,L -(ia-b)e-k,L
where a= k; - k1k3 and b = k 1k 2 + k 2 k3 •

Since sinh(z) = (ez -e-z)/2 or ez = 2sinh(z) + e-z, substitute ek'L = 2sinh(k2 L)+e-k,L, giving
ik3 L
A = 2ki k2e
3
(ia + b) sinh(k2L) + be-k,L
2 A A• 4k12 k;
T = I~ 1 = 3 x 3 = (a2 +b2)sinh2(k2L)+b2
2 2
where a 2 +b 2 = (k12 +k;)(k; +k:) and b = ki(k1 +k3 )
(b) In the special case for which v; = V:i = 0, eqns. 2.12 and 2.15 require that k 1 = k3 . Additionally,
2
(!:i_J
k 2
= _E_ = __!!___
V2 -E 1-t:
where t: =EI V2
NANOSYSTEMS 1 : MOTION IN ONE DIMENSION 49
b2 -- 4kI2k22
ki {1+ (t,-
4kl2
fr 4£(1-£)
T= { l+
sinh2(k2 L)}-1 = {l +(ek,L- --e-k'L)2
---
}-1
4£(1-£) 16£(1-£)
This is eqn. 2.17(a). In the high, wide barrier limit, k2L >> 1. This implies both that e-k, L is
negligibly small compared to e*'L and that 1 is negligibly small compared to e2"'2L I {16£(1-£)}.
The previous equation simplifies to eqn. 2.17(b).
T = l 6£(1-£)e-2k,L
.. di . . 1i2 d2\f/ 1 kx2 E

P2.17 Th e Sc hro nger equation is - - - +- \f/= \f/
2m d.x 2 2
We write the trial solution \f/ = e-.n', so : = -2Kxe-Kx'
and
Insert the trial solution into the SchrOdinger equation.
This equation is satisfied if
and 21i 2 K2 =lmk so K= -1 ( mk )1/2

2 , 2 1i2
The corresponding energy is
k )112 ( k )112
E=fn ( m =fnm with m= m
P2.19
( x3 ) oc [ \f/ 2 y3 dy = [fil by symmetry [/ is an odd function of y]

y4Hv = y3 (1Hv+I +vHv-1) = y2 [1(1 H v+2 +(v+ l)Hv)+v(tHv +(v-l)Hv-2)]
= y2 [±Hv+2 +(v+t)Hv +v(v-l)Hv_ 2]

= Y[±(1Hv+) +(v+2)Hv+i) +(v+t)x(1Hv+I +vHv_1)
+v(v- l)x (t H v-I + (v-2)Hv_ 3 )]

2
= Y (iHv+) +i(v+l)Hv+I +fv H v-I +v(v-l)x(v-2)Hv_ 3 )
Only yHv+i and yHv- 1 lead to Hv and contribute to the expectation value (since Hv is orthogonal to all
except Hv) [Table 2.1]; hence
4 2
y Hv =iy{(v+l)Hv+ I +2v H v_ 1}+ ···
= f[ (v+ 1)(1 H v+ 2 + (v+ l)Hv) + 2v (1 H v + (v- l)Hv_ 2 )] + ···

2
2 2
=i{(v+l) H v+v H)+ ···
2
=i(2v +2v+l)Hv + ···
Therefore
so
P2.21 (a) (x) = r(i}' 2
si{ n~x )x(i}' si{ n~x )ctx

2
(x)=(z)f xsin axdx

2
[a=7]
2 2
= (3.)x(£- xsin ax cos 2 ax]/L[Trig functions vanish or cancel at limits.]
L 4 4a 8a 0
=( zJ x (: ] = f [by S}111Illetry also].
( x 2) =L
2 r 2 (2) [x
3
(x
2
1 ) sm2ax--4a2
x sm axdx= L x 6- -4a --8a3
2 • . xcos2axlllo
2) (L L
= (L x 6- 4n 2 2
3 3
Jr
)
=L
2
( 1 2n12Jr 2 )
3-
& = [L (_!_-
2 _ l )- L2 ]
3 2n 2 Jr 2 4
112
=L (_!_- _ l )112
12 2n n 2 2
(P) = 0 [by symmetry]

Ii
>-
2
(b) (x)=a 2 [ v.r 2 ydy[x=ay]=O [bysymmetry,yisanoddfunction].
But (V)=(Ek)= -E =-
2
1(v+-21) nm [2.29b&c],
2
so
and
(p) = 0 [by symmetry, or by noting that the integrand is an odd function of x]
dp= {(v+~)nmmr
2
dpL\x={(v+~)nmmr2 {(v+~)!r2 =GE~~

Both results are consistent with the uncertainty principle, dpL\x ~ !!:_ . Note that for the ground-state
harmonic oscillator (v = 0), the equality holds. 2
P2.23 Call the integral in question J:
f
I= v.rv·XV/vdx=a
2
fv.rv·YV!"v dy [x = ay]
- (1 )
YVl"v - NV 2Hv+l +vHv-l e - / / 2 [Table 2.1]
Forv' = v + 1
r
For v' = v-1
I =va' N ,N ,_, JH :_, e-I dy I

=va' N ,N ,_,,,'" r' (v ~I)! = a(~ I
No other values of v' result in a nonzero value for I; hence, no other transitions are allowed.
P2.25 To address this time-dependent problem, we need a time-dependent wavefunction, made up from
solutions of the time-dependent SchrOdinger equation
H'P(x,t) =iii d'P(x,t) [Table 1.1]

dt
If lfA:x) is an eigenfunction of the energy operator with energy eigenvalue E, then
'P(x,t) = lf/(x)e-iEi t~
is a solution of the time-dependent SchrOdinger equation (provided the energy operator is not itself
time dependent). To verify this, evaluate both sides of the time-dependent SchrOdinger equation. On
the left we have
H'P( x, t) = Hlf/(x)e-iE'th = Elf/(x)e-iE'th = E'P(x,t)
On the right we have
. d'P(x,t) = n1
n1 a -iEtl~ = -1·2 E If/ (x )e-iEI/~ = E\T'(
. If/ ( x ) -e r x ,t
)
dt dt
the same as on the left. Our wavepacket is an arbitrary superposition of time-evolving harmonic
oscillator wavefunctions,
'P(x,t) = L Cvlf/v (x)e-iEJI~

v=O
where lf/.f.._x) are time-independent harmonic-oscillator wavefunctions and
Ev = (v+~}]OJ [2.21]
Hence, the wavepacket is
'P(x,t) = e-iax12Lcvlf/v(x)e-ivl<X
v=O
The angular frequency OJ is related to the period T by T = 2tt I OJ , so we can evaluate the
wavepacket at any whole number of periods after t, that is, at a time t + nT, where n is any integer
(not a quantum number.) Note that
t+nT=t+2:n:nl OJ
so 'P(x,t + nT) = e - i«X / 2e - iwnT / 2 LCvlf/v

(x)e - ivwt e-ivwnT = e - i «X / 2e - i;rn LCvlf/vCx)e-ivl<X e - 2;ri vn
v=O v= O
Noting that the exponential of (2tti x any integer)= 1, we note that the last factor inside the sum is
1 for every state. Also, since e_;,,,,. =(-Ir, we have
'P(x,t+nT) = (-1)"'¥(x ,t)
At any whole number of periods after time t, the wavefunction is either the same as at time tor -1
times its value at time t. In any event, 1'¥1 2 returns to its original value in each period, so the
wavepacket returns to the same spatial distribution in each period.
P2.27 (a) Treat the nelectrons as particles free to move the length of the conjugated system. The energy
levels are given by
h1n2
E = --2
[2.6a]
" 8mL
NANOSYSTEMS 1 : MOTION IN ONE DIMENSION 53
and we are looking for the energy difference between n = 6 and n = 7:

h2(7 2 -62)
M=----
8mL2
Since there are 12 atoms on the conjugated backbone, the length of the box is 11 times the bond length.
L = 11(140xl0- 12 m) = l.54 x l0-9 m
34 2
M= (6.626xl0- Js) (49-36) =J 3 _30 x 10 _19 JJ
so
8(9. l lxl0- kg)(l.54 x l0-9 m) 2
31
(b) The relationship between energy and frequency is
M=hv so v = M = 3.30x10-19 J = 14.98 x 1014 s-1I

h 6.626 x 10-34 Js
The wavelength and frequency are related by c = A.v, so
A=~=2.998 x 10s ms-1 =l6.02x10-1 m=602nml

v 4.98xl0 14 s- 1
(c) Look at the terms in the energy expression that change with the number of conjugated atoms, N.
The energy (and frequency) are inversely proportional to L2 and directly proportional to (n + 1)2 -
n2 = 2n + 1, where n is the quantum number of the highest occupied state. Since n is
proportional to N (equal to N/2) and Lis approximately proportional to N (strictly to N - 1), the
energy and frequency re awroximately proportional to /V 1• So the absor lion s ectrum of a
linear polyene shifts to owe frequency as the number of conjugated atoms increase .
P2.29 In effect, we are looking for the vibrational frequency of an 0 atom bound, with a force constant
equal to that of free CO, to an infinitely massive and immobile protein complex. The angular
frequency is
where m is the mass of the 0 atom

m = (16.0u)(1.66x10-27 kg u- 1) = 2.66x10-26 kg
and k is the same force constant as in Problem 2.3, namely, 1902 N m- 1:
OJ= 1902Nm-
I Jl/2=12.68x1014s-1I
( 2.66xl0-26 kg
P2.31 First, let/= n/N; therefore,/ is the fraction of the totally stretched chain represented by the end-to-
end distance.
F=-kT In(N+nJ=-kT In(N(l+f)J=-kT ln(l+/J

2/ N- n 21 N (1- f) 21 l
1- f l
kT
= -2/[ln(l + f)-ln(l- f)]
When n « N, then f « 1, and the natural log can be expanded: ln( 1+ fJ "" f and In( 1 - fJ "" -f
Therefore
kT jkT nkT kT
F "" - - [ ( -(- f)] = - - =- - = - - x
21 I NI N/2
In the last step, we note that the distance x between ends is equal to nl, son= xii. This is a Hooke's
law force with force constant kT I NP.
The root mean square displacement is (x2) 112 •
In part (b) of P2.21, (x2) for a harmonic oscillator was evaluated and was found to be
x(~J
112
(x = (v + ..!..)2 x(!!!!!___J "" (v + ..!..)

2
)
kforce 2 mkforce
Therefore, putting in the appropriate values for the ground state (v = 0) of this model
2 12 12
(x 2 1 (-
)=-X n X -N/2 J' Iii ( - N )'
=-X
2 m kT 2 mkT
3 Nanosystems 2:
motion in several dimensions
03.1 In quantum mechanics, particles are said to have characteristics of waves. The fact that the particle
exists then requires that the waves representing it not experience destructive interference upon
reflection by a barrier or in its motion around a closed loop. This requirement restricts the
wavelength of a particle on a ring to wavelengths such that a whole number of wavelengths must fit
on the circumference of the ring. That means
nA. = 2Jtr, where n = 0, 1, 2, ...
See Section 3.3(a).
03.3 Fermions are particles with half-integral spin, 1/2, 3/2, 5/2, ..., whereas bosons have integral spin, 0,
1, 2, ... . All fundamental particles that make up matter have spin 1/2 and are fermions, but
composite particles can be either fermions or bosons.
Fermions: electrons, protons, neutrons, 3He, ....
Bosons: photons, deuterons
COMMENT. In the standard model of particle physics , non-composite bosons are carriers of force.
Photons are an example: they are not composite particles, but they are not constituents of matter. In
the standard model, protons and neutrons are composite particles, but they are still fermions by virtue
of their half-integral spin.
03.5 Rotational motion on a ring and on a sphere share features such as the form of the energy (square of
the angular momentum over twice the moment of inertia) and the lack of zero-point energy because
the ground state does not restrict the angular position of the particle. Degeneracy is possible in both
cases. In the case of the ring, the axis of rotation is specified, but it is not in the case of the sphere.
This distinction gives rise to the fact that angular momenta about different perpendicular axes
cannot be simultaneously specified: 1,, iY, and ~ are complementary in the sense described in
Section 1.10.
03. 7 Spin angular momentum and orbital angular momentum have in common the fact that the
magnitude of angular momentum and the z component of angular momentum are both quantized.
Both spin and orbital angular momenta give rise to magnetic effects. The spin angular momentum
is an intrinsic angular momentum rather than one due to rotational motion in the classical sense.
E3.1(a)
34 2
(6.626xl0- Js) = 6.o2 x l0_20 J
8(9.11x10-31 kg)x(l.Ox10-9 m) 2
The conversion factors required are

1 eV = 1.602 x 10- 19 J; 1 cm- 1 = 1.986 x 10- 23 J; 1 eV = 96.485 kJ mor 1
22 22 2
(a) E
22
-E =C + -I2-I2)h =~=6x6.0lx10-20 J
• 1.1 8me L2 8me L2
(b)
E3.2(a) (a) Radiation stimulates a transition if the energy of the photon is equal to the difference between
energy levels. The photon energy is h v, so
v= M = 3.6 x 10-19 J =15 .5 x 1014 s- 11

h 6.626 x 10- 34 J s
The wavelength is the reciprocal of the wavenumber, so
1
A.= =5.S x 10-s cm=ls.sx10-1 ml=lssonml
1.8x10 4 cm- 1
(b) v= M = l.3 x l0-1s J =l2.0 x l01 s s- 11

h 6.626 x 10-34 J s
1
and A.= = 1.5 x 10-s cm= lu x 10- 7 ml= l1so nml
6.7 x l0 4 cm- 1
E3.3(a) (a) The energy is
so the zero-point energy is the ground-state energy:

2 34 2
E =( 1 + I2 J (6.626xl0- Js) =?Sxl0_201
1'1 (1.0 x l0- 9m) 2 (2.0 x l0- 9m) 2 8 x 9.llxl0- 31kg ·
The temperature at which this energy equals the typical thermal energy kT is
20 1
T=~= ? .Sx l0-
23
=l5 .5xl0 3 KI
k 1.38l x l0- JK- 1 • •
(b) The first excited energy level is
E
1·2
= l 12 + 22 J (6.626x10-34 J s)2 = 1 2ox10- 19 J
(l.O x 10-9 m) 2 (2 .0x10- 9 m) 2 8x9.l lxl0- 31 kg ·
so the first excitation energy is
£ 1.2 - E 1.1 =(1 .20 x 10- 19 -1.s x 10-20 ) J = 4.5 x io-20 J

The temperature at which this energy equals the typical thermal energy kT is
T=
5 10 20
4
· x - J = 13 .3 x 103 Kl
1.381 x 10- 23 J K - 1
NANOSYSTEMS 2: MOTION IN SEVERAL DIMENSIONS 57
E3.4(a) The wavefunctions are
"' 2 . (n/CX) . (n21l'Y)

-L- [3.3a, with L 1 = L2]
.,.., ,., =-sin
L -L- sm
The required probability is
where ~ = ~y = 0.02L , and the function is evaluated at x = y = L/2.
(a) Pi.1 =(zJ sin 2 (~}in 2 (~)xo.02Lx0.02L=I0.0016I
(b) Pi.2 =(zJ sin 2 (2;}in 2 (2;)xo.02Lx0.02L=[Q]
E3.5(a) See the comment at the end of the solution to Exercise 2.7(a): Maxima in the probability
distribution, which is equal to v}, correspond to maxima and minima in l/f itself, so we look for
points where al/f = al/f = 0.
dx dy
2
1/12•3 = zsin( ~x }in(3~y) [3.3a, with L = L2] 1
dl/f2.3 = 4Jr cos(27rx)sin(37ry)=o

dx L2 L L
cos B= 0 when Bequals an odd integer times 1l' I 2:
21l'x 2n' + 1 , . L 3L
- - =--Jr for n = 0, 1, 2, ... which corresponds to x = - and -
L 2 4 4
Note: we disregard positions where the sine factor vanishes because they correspond to positions
where the wavefunction vanishes as well.
dl/f2 ,3 = 61l' sin(27rx)cos(37ry) = 0

'dy L2 L L
3Jry 2n" +1 L 3L 5L
L = - - J r for n
2
H
= 0, 1, 2, ... , which corresponds to y = "6, (j, and (j
•
Thus, the positions of maximum probability, expressed as ordered pairs (xiL, ylL) are
k114, 1/6), (1/4, 112), (114, 5/6), (3/4, 116), (3/4, 112), and (3/4, 516~
E3.6(a) Nodes of the wavefunction are sets of points where the wavefunction vanishes.
2
1/12•3 = zsin( ~x }in( 3 ~Y) [3.3a, with L1 = L2]
sin B= 0 when Bequals an integer times 1l".
2Jl'X
- - = n 1l' 1or
I l'
n = 0, 1, 2, ... wh"ich corresponds to [Eilll
I
- = 0, - , 1
L L 2
3
1l'Y = n'1l' for n' = 0, 1, 2, ... which corresponds to E = 0
L L
! 3.
'3'3'
1
Of course, if one factor of the wavefunction vanishes, the whole wavefunction vanishes. Thus, the
wavefunction vanishes not at single points but on the vertical and horizontal lines defined above.
COMMENT. Some of these lines correspond to edges of the square box. The term node is often used to
describe places other than the boundaries where the wavefunction vanishes. These are x = 1/ 2 and
y = 1/ 3, 2/3.
E3.7(a) See Exercise 2.5(a) for the one-dimensional analog to this question. The wavefunction is
The expectation value of the x component of the momentum operator, Px = ~j_ ' is
I dX
(p,) = l V/, ,, * PxV/1 ,1 cixdy = :~ l l sin (~ } in ( trf ):x sin(~ }in ( 7)cixdy
= ~3n rsm ( ~} os( ~ )dx r
sin
2
( 7) dy = [QJ
(The dx integral vanishes.) To find the expectation value of the momentum squared operator,
2 2
2 2 a +a
p• =-n ( - - J weneed
ax2 <Jy2 '
E3.8(a) The zero-point energy is the ground-state energy; that is, with n 1 = n2 = 1,
Set this equal to the rest energy mec2 and solve for L :
2 h2
m e = - -2 so L=-h-
• 4me L 2me c
In absolute units, the length is
L= 6.63x10-34 J s = 1.21x10-12 m = 1.21 pm

2 x (9.ll x l0-31 kg)x(3.00 x l0 8 ms- 1)
In terms of the Compton wavelength of an electron, Ac = ~, L = Ac .

m.c 2
E3.9(a) The energy levels are given by
E =(!S__+!!l__J!!.__ [3.3b] = (!S__+!!l__J_!!___

1 2
" ·"
2
L1 L/ 8m 1 4 8mL2
2 2
2
E 2·2 =( l + 4
2
2
2
J8mL
h 5h
2 = 8mL2
We are looking for another state that has the same energy. By inspection we note that the first term in
parentheses in £ 2,2 works out to be 4 and the second 1; we can arrange for those values to be reversed:
b
So in this box, the state 1= l, n2 = 41 is degenerate to the state n 1 = 2, n2 = 2. The question notes that
degeneracy frequently accompanies symmetry, and it suggests that one might be surprised to find
degeneracy in a box with unequal lengths. Symmetry is a matter of degree, as we will see in
Chapter 7. This box is less symmetric than a square box, but it is more symmetric than boxes whose
sides have a non-integer or irrational ratio. Similarly, there is much more degeneracy associated
with a square box than with this one. Every state of a square box except those with n 1 = n2 is
degenerate (with the state that has n 1 and n2 reversed). Only a few states in this box are degenerate.
A box with incommensurable sides, say, Land i1 12L, would have no degenerate levels.
E3.10(a)
3h 2
E =--
1·1·1 Sm!3'
3E
1,1,1
=..'!!!__
SmL2
Hence, we require the values of ni. n2 and n3 that make
nI2 + n22 + n32 = 9

Therefore, (ni. n2 , n3 ) = (1, 2, 2), (2, 1, 2), and (2, 2, 1) and the degeneracy is []].
E3.11 (a)
K K
M (0 .9L) 2 L2 l
- - K - - = . -l=I0.231, or l23percentl
E 0 81
L2
E3.12(a) Set the particle in a cubic box energy equal to 3kT/2.
( n2+n2+n2)h2
1 2 3
2h2 3
E= 2 [3.5b]=-n-=-kT
8mL 8mL2 2
= (%)xcus1x10-23 JK- 1)x(300K) = 6.214x10-21 J
So n2 = 8mL2 E
h2
If L 3 = 2.00 m 3, then L2 = (2.00m 3) 213 =1.59 m 2,
h2 (6.626xl0-34 Js)2 =6.51x10-43 J
8mL2 1
(S)x( 0.03200kgmol- Jxl.S 9 m2
6.022xl0 23 moi- 1
- 21
6 214
and n2 = · xl0-3 J = 9.55x10 21 · n = l9.77xl0 10 I
6.5lx10-4 J ' · ·
M=E -E = (n+l)2h2 n1h22 =(2n+l)x ( _j!__2J

n+i " 8mL2 8mL 8mL
60 STUDEW SOLUTIONS MANUAL FOR QUANTA, MATIER, AND CHANGE
19.55x1010 h 2
2
h )
!:i.E=E977x1010+1-E9 77x1010 =[(2)x(9.77x10 IO )+l]x ( 8mL2
8mL2
= (19.55x10' 0)x (6.5lx10-43J)=11.27 xl0-31JI
The de Broglie wavelength is obtained from
The velocity is obtained from
2
EK =tmv =fkT=6.214x10- J
21
2 6.214x10-21 J s 2 -2
v= X 10 ms;
2.34 v = 484 m s- 1
(21) x (6.022xl0
so =
0.03200 kg mol-' )
23 moi- 1
A,= 6.626x10-34 J s = 2.58 x lo-" m = 125.8 pml

(5.31x10-26 kg) x (484 ms-')
The conclusion to be drawn from all these calculations is that the translational motion of the
oxygen molecule can be described classically. The energy of the molecule is essentially
continuous,
!:i.E
-<<<1
E
E3.13(a) Orthogonality requires that, if m f- n, then
Performing the integration:
If m -;it. n, then
\21' = N2 (1-1) = 0
f•I// I// d r =
m n
N2 et(n-m)¢
i(n-m)
.
0
i(n-m)
Therefore, they are orthogonal.
E3.14(a) Magnitude of angular momentum={/(/+ 1)} 112 n [3.22a]
Projection on arbitrary axis= m11i [3.22b]

Thus,
Magnitude = (2" 2)x1i = IL49xl0-34 J sl
Possible projections ~ or ± 1i I
E3.15(a) The diagrams are drawn by forming a vector of length U<J + 1)} 112 , with j = s or l as
appropriate, and with a projection m1 on the z-axis (see Figure 3.1). Each vector represents the
edge of a cone around the z-axis (that for m1 = 0 represents the side view of a disk
perpendicular to z).
(a) (b) (c)
1.00~---
2.449
o~--------+
Figure 3.1
Let () be the angle of the vector with the positive z-axis. The cosine of that angle is the ratio of
2
m1 I UU + 1)} "
0.5
(a) cos() =-1-12- = 0.577 so fJ = R.955 radians or 54.7°1
3 12
1
(b) cosfJ= l / i so fJ = lm4 radians or 45°1
2
(c) cosfJ= 0 so fJ = lm2 radians or 90°1
E3.16(a) The rotational energy depends only on the quantum number l (eqn. 3.21), but there are distinct
states for every allowed value of m 1, which can range from -/to l in integer steps. For I= 3, possible
values of m1 = -3, -2, -1 , 0, 1, 2, 3. There are 7 such values, so the degeneracy is QI.
E3.17(a) The energy levels are
2 r,.2
Em, = m;; 1
[3.lOa]
We are looking for the difference between the ground state (m 1 = 0) and the first excited level (m 1 =
±1); that difference is equal to the energy of the photon:
E =M=E -E =!!:.._= (1.0546xlo-34 Js)2 =l2.04x10-2211

photon I O 2/ 2X2.73Xl0-4 7 kg m 2 . .
E =he
photon A
so A=_!!:!:_= 6.626x10-34 Jsx2.998x10s ms- ' =l9.75xl0-4 ml=I0.975mml

£photon 2.04 X 10-22 J
Such a photon would be in the !ffiicrowav~ region.
E3.18(a) We can find the speed of a point on the equator if we know the rotational frequency, ()). the speed is
rm, where r is the radius. Classically, angular momentum is equal to moment of inertia, I, times m.
For a sphere of mass me, the moment of inertia is I= 2mer2/5 [Section 3.4 or any general physics
text]. An electron has spin angular momentum of 0.866 fi (Section 3.5). Putting it all together,
0.8661i = 2mer2 5x0.8661i

{J) so {J) = ----,--
5 2mer2
The speed is
5x0.8661i 34
rm= - - - - 5x0.866xl.0546xl0- J s = ls.s 9 x 1010 m s- i I
2x9.l lxl0-31 kgx2.82xl0- 15 m
COMMENT. This speed is about 300 times the speed of light! Clearly this quasi-classical, non-relativistic
model does not capture this aspect of the electron.
P3.1 The energy of the particle in a cubic box is
( n,2 +n22 +n32) h2

E= [3 .5b]
8mL2
so the difference between the two lowest energy levels is
(12+12 + 22)h2 (12+12 + I2)h2 3h2
M=-----
8mL2 8mL2 8mL2
The mass is m(0 2 ) = (32.00) x (l.6605x10-27 kg)= 5.31xl0-26 kg, so
M=]!!__= 3 x (6.626 x lo-34 Js)2 =l8.86x10-39 11

8mL2 5.31 x 10-26 kg x (5.0 x 10-2 m)2
Set the energy equal to 3kT/2:

2 2
E = 3n h = 3kT
8mL2 2
n=( 4k~~L
2
r 2
In
= 4xl.381 x l0-23 J K- 1 x300 Kx5 .31xl0-26 kgx(5 .0x10-2 m) 2
( (6.626xl0-34 J s) 2 )
= 2.24 x l09
The degenerate energy level immediately below this level has one of the quantum numbers equal to
n - 1 and the other two still equal to n.
3n 2h 2 {2n 2 + (n -1) 2}h 2 (2n-l)h 2
M =E - E = - - - -'----'--"'---'--
n,n,n n,n,n-l SmL2 SmL2 8mL2
9 34 2
(2x2.24xl0 -l)x(6.626x10- J s) =11.llxlO-Jo JI
26 2
8x5.31 x l0- kgx(5.0x10- m) 2
COMMENT. The problem is similar to E3.12(a). The separation in energy levels is much smaller than the
energy of the occupied level. The energy of the molecule is essentially continuous.
P3.3 In C60 , each carbon atom is bound to three others, so each makes three sigma bonds. That
leaves one p orbital and one electron per carbon atom to go into the 7r system. Thus, C60 has 60
7r electrons, which would doubly occupy the lowest 30 particle-in-a-cube "orbitals." The
energy levels are
Levels in which all three quantum numbers are the same are non-degenerate. The degeneracy of
levels that have two quantum numbers in common is three, for the different quantum number can be
in any of three places. The degeneracy of levels that have three different quantum numbers is six,
the number of possible different ordered triplets. The energy levels are shown in Figure 3.2, labeled
by one corresponding set of quantum numbers.
25
2.2,4
2,3.3
-- - - - - 1,2,4
20
1.3.3
1. 1,4
...._J........ 2.2.3
15
;:::
---- 1,2,3
~
..:;: 2,2,2
'-' 1,1.3
...... 10
~ 1,2,2
l ,1 ,2
5
1, 1,1
0 Figure 3.2
Filling the orbitals from the bottom makes the level marked (1,2,4) the highest occupied level. Its
energy is 21h 2/8mL2 • The next level has an energy of 22h 2!8mL 2 (the level marked (2,3,3)). So the
excitation energy is the difference between these levels, namely,
34 2
M = _!!.__ = (6.626x10- J s) = 1. 2 x 10 _,9 J
8m. L2 8 x 9.ll x l0-31 kgx(0.7 x l0-9 m) 2
M=E =he
photon A,
34 8
so A=!!!:_= 6.626xl0- Jsx2.998xl0 ms-' =h .6 xl0-6 ml=ll. 6 ml
M l.2x 10- 19 J µ
P3.5 The excitation energy is the difference between the two lowest energy levels, and that energy
difference is equal to the energy of the photon.
(F'.,,2-F.. 02 )h2 he
M= · Sm a ·2 =Ephoton A,
e
2 2 2 2
2 2 34 9
a= (( F'i,1 - F'i,o ) hA- ]" = ( (1.430 -1 )x 6.626xl0- J sx 1500xl0- m)"
so
8m.e 8x9.l lxl0-31 kgx2 .998xl08 m s- 1
= 16.9xl0- 10 ml= I0.69 nml

P3.7 (a) The normalization integral is
In the last step, we used the fact that the particle-on-a-ring eigenfunctions are themselves
normalized and orthogonal. The overall normalization constant, then, is 1121, and the normalized IN=
wavefunction can be written as a superposition of particle-on-a-ring eigenfunctions:
llF +31/2i11r
l/f='f' -l 'f' +l
2
(b) The particle-on-a-ring wavefunctions are eigenfunctions of the angular momentum, so any
measurement of angular momentum will result in a corresponding eigenvalue (Section 1.8,
Postulate V). The measurements will be m1 n [3.9]. In particular
t.fil,the eigenvalue of lfl- i , with probability 1(112)1 = [!B 2
and ~. the eigenvalue of 1l4 1 , with probability l<3ini/2)1 2 = ~

(c) The particle-on-a-ring wavefunctions are also eigenfunctions of the energy, so any energy
measurement will result in a corresponding eigenvalue. However, both energy eigenstates that make
up the superposition have the same energy eigenvalue, so any measurement will yield that value,
namely,
E
m,
=m,'h'
21
=I 2mpr
h' I [3. 2
!Oa]
(d) Expectation values are weighted averages of eigenvalues; the weights are the squares of the
magnitude of the coefficients in the superposition wavefunction:
(Q) = L lcJ mk [1.17)

k
So the expectation value of angular momentum is

2 2
(!,)=211 l3"2il
x (-n)+-
2
- fh1
Xn=llJ
1
(Note that none of the angular momentum measurements will yield the expectation value.) The
expectation value of the energy can be computed in the same way. We have already noted, though,
that every energy measurement will yield the same value; therefore, the expectation value is also
equal to that value.
2,,, 2 2,,,2
P3.9 E =~[3.lOa]=~2
m, 21 2mr
The ground-state energy is 0, when m1 = 0. The first excited state energy is
E =_!f_= (l.055xl0-34 Js)2 =l.30x10-22 J

' 2mr 2 (2)x(l.008)x(l.6605xl0-27 kg)x(l60xl0- 12 m) 2
This is also the excitation energy (the difference between the first two levels) and the energy of the
photon that can excite rotation. Thus
M =E =he
photon A,
so ,i =~ =6.626x10-34 J s x 2.998x10
22
m 1
s- = li. 53 x 10_3 ml= li. 53 mml
8
M 1.30x10- J
The minimum angular momentum is [ifil.
P3.11 This is an example of rotational motion in two dimensions, so we use results for a particle in a ring.
(a) The expectation value of angular momentum is the weighted average of possible results of
angular momentum measurements.
(/,) =-i- x 3n+ i x(-31i) =l- t nl
(b) The particle-on-a-ring wavefunctions are eigenfunctions of angular momentum and of energy.
The angular momentum eigenvalues are 3 n and -3 n. The corresponding eigenfunctions are !f3 and
lfl--3 , respectively, where
e im,'I'
If/ ( qJ) = - - , /-2 [3 . lOb]
m, (2.n')
The wavefunction of this molecule is a superposition of l//:J and lfl-3 (Section 1.8, Postulate V), so
If/ ( rp) = C11f/3 + C21f/-3
The probabilities of finding the molecule in one of the eigenfunction states is the square of the
magnitude of its coefficient in the superposition:
and
so C1 = 1/2 and
(We can take the coefficients to be real and positive.)
3
lf/(rp) =
3iqi
2c~nf 2 + 2;
( ) 1/ 2
-T
-3iqi
(c) The energy eigenvalues for the eigenfunctions are

2,, 2 2,, 2
E = !!i!!:_ = !!i!!:_
m, 21 2µR 2
Both functions in the superposition have the same energy, and that is why energy measurements
always give the same value, namely,
E = 32(1.0546 x 10-34 Js)2 =l4.004x10-23 JI

m, 2 x 2.000 x 10-26 kg x (250.0 x 10- 12 m) 2
P3.13 The question asks about the most probable angles with respect to an arbitrary axis. We may
take that axis to be the z-axis, in which case we are looking for the most probable values of the
angle B. The most probable values of ()are maxima in the probability, which correspond to
positive maxima and negative minima in the wavefunction. (Note: We can speak as if the
wavefunctions were real because the () dependence of the spherical harmonics is real.) So we
look for ()such that ao = 0 .

ar
For I= 1, there are two forms of dependence on ():
m 1 = 0: Y1,o oc cos B, which has maxima at lo= 0 & .1l"I (i.e. , along the z-axis)
Yi ,±i oc sin B, which has a maximum at lo= .n12I (perpendicular to the z-axis)
For I = 2, there are three forms of dependence on ():
m, = 0: Y2,0 oc (3 cos 2 B- 1), so
ai; o
--
· oc -3 x 2cosBsinB = 0
ao .
The derivative vanishes at lo= 0, 1l" I 2, &1l"I; these are the most probable values of B.
m1 =±l: Y2,±1 oc cos ()sin (), so

OJ; ± I
--·- oc
2
cos {}-sin () = 0
2
()()
The derivative vanishes where cos () =±sin (),namely, at IB= 1lf4 & 31lf~.
2
Y2,±2 oc sin B, so
ai; ±2
--·- oc 2cosBsinB = 0
()()
The derivative vanishes at le= 0, Jr/2, & Jrl.

For I= 3, there are four forms of dependence on e:
m1 = 0: Y3,0 oc (5 cos3 e- 3 cos e), so
(JY:
~ oc -15cos 2 esine+ 3sin e = 0 = -3sin 0(5cos 2 0-1)
ao
The derivative vanishes when sine= 0 and when cos 0= ±(115) 112 . Thus
lo= o, Jr, 63.4°, & 116.6°1

2
Y3 ,±1 oc (5 cos 0- 1), so
01'; ±I
- ·- oc -10 cos 0 sin 0 = 0
ae
The derivative vanishes at lo= 0, Jr/2, & Jrl.
m1 =±2: Y3,±2 oc sin 2
ecos 0, so
(Jy:
---2E. oc 2 sin 0 cos 2 e- sin 3
0 = 0 = sin 0(2 cos 2 0- sin 2 0)
ao
The derivative vanishes when sin 0 = 0 and when 2cos 2 0 = sin 2 0. The latter condition amounts to
tan 2 0= 2. Thus le=
0, Jr, 54.7°, & 125.3°1.
m 1 =±3: Y3,±3 oc sin 3 e, so
ar;±3
- · - oc
2
3 sin Ocos 0 = 0
ao
The derivative vanishes at IO= 0, Jr/2, & Jrl.
P3.15 The wavefunctions in question are solutions of the SchrOdinger equation. The hamiltonian inside
the box is
iI =-.!!._(~+~+~]
2
2m dX 2 2
oy dz
so the equation to be solved is
_.!t._(o----,2--+
1jf(x,y,z) o 1j/(x,y,z) o 1j/(x,y,z)J- E (
2
2 + 2
2
- If/ x,y,z
)
2
2m ~ ~ ~
We look for solutions that factor into functions of one variable. That is, let
lft<x,y,z) =X(x) x Y(y) x Z(z)
and see under what conditions (if any) the differential equation can be solved. In substituting our trial
separated solution into the differential equation, note that each partial derivative acts only on one factor:
2
X~x) +X(x)Z(z) d Y~) +X(x)Y(y) d Z~z)J = EX(x)Y(y)Z(z)
2 2
_.!t._(Y(y)Z(z) d
~ m ~ &
Divide both sides of the equation by the trial wavefunction and by -n 2 I 2m:
1 d 2X(x) 1 d 2Y(y) 1 d 2Z(z) 2mE

-- 2 + - - - - - + - - - -2- = - -2-
X(x) m Y(y) dy2 Z(z) & n
NANOSYSTEMS 2 : MOTION IN SEVERAL DIMENSIONS 67
The right side of the equation is a constant, while the left side is a sum of three terms, each of which
depends only on one of the three independent variables. Because the three terms depend on independent
variables, the only way that they can sum to a constant value is if each is equal to a constant value. Thus,
2 2 2
_1_d X(x) =- 2mEx _l_d Y(y) =- 2mEy and _l_d Z(z) =- 2mE2
X(x) dx 2 li 2 ' Y(y ) dy2 li 2 ' Z(z) dz 2 li 2
where Ex + Er + Ez = E. Each of these equations rearranges to an ordinary differential equation of
the same form as eqn. 2.l(b), the Schrbdinger equation for a one-dimensional particle in a box.
Thus, each factor in the three-dimensional wavefunction has the form given in eqn. 2.6(b):
2 112
X(x)= (~J
12
sin ( n~x J, Y(y)=(l r sin( n~y J. and Z(z)=(:J sin( n~z J

yielding the three-dimensional wavefunction given in eqn. 3.5(a).
P3.17 The Schrbdinger equation is
-li2
-(-d21f/+d2-
1f/ J =Elf/ [3.1]
2m dX 2 (Jy2
To verify that
is actually a solution, we take the required partial derivatives.
dlf/ 2 n/C n Jrx . n Jry

--- 1
12 x - c o s -1 - s m2- -
dX (L I L 2 ) LI LI L2
so
Putting these derivatives into the Schrbdinger equation yields
This expression is a true equation if
With a little rearrangement, we arrive at eqn. 3.3(b) for the energy:
P3.19 (a) By hypothesis, the angular momentum is +Ii, so the corresponding wavefunction is
68 STUDENT SOLUTIONS MANUAL FOR QUANTA, MATTER , AND CHANGE
There is ~o uncertainty in MJ because the wavefunction is an eigenfunction of i, . Therefore, the

uncertainty product !l.l, ti.. sin rp must also be zero. Because the question asks for all pieces in the
uncertainty expression, we evaluate ti.. sin rp :
. .
" e-'qi . .
e+'qi 1 " . 1 -cosrp , ~
(smrp) = r2 - -11-2 smrp--1-12 drp=- r2 smcpdrp=-x--- = 0
.b (2.?r) (2.?r) 2.?r .b 2.?r 2 0
The only way the uncertainty relationship can hold is if the expectation value of sinrp also vanishes:
e-'qi
. e+'qi
. 1 2" 1 sin rp 12"
(cosrp) = r.b --
21r
-
(2.?r) 112
COSqJ---
(2.?r) 112 drp=-
2.?r
r.b Coscpdrp=-X--
2.?r 2 0
=0
so because 0;;::: 0.
(b) A wavefunction proportional to cosrp is a mixture of the two particle-on-a-ring wavefunctions

that have m1 =+1 and m1 = -1 because e-icp + e+icp = 2 cos<fJ.
To compute expectation values, we need the normalization constant:
1 = f2" N e+ii> + e-iqi N e-iqi + e+iqi def>= N 2 f2" (2 + e-2iqi + e+2iqi)d¢

.b (2.?r)l/2 (2.?r)l/2 2.?r .b
N2 e -21qi e +21qi
. . Jl2" =2N2
2rp--+-
=-
2.?r ( 2i 2i 0
So N = 1/2 112 = c_1 = C+i. where the e's are coefficients in the superposition. Because particle-on-a-
ring wavefunctions are eigenfunctions of angular momentum, we can use
(n) =~)ck 12 wk [1.17]

k
So the expectation value of angular momentum is
Both particle-on-a-ring wavefunctions have the same eigenvalue of angular momentum squared,
namely n2, so this is the expectation value of that operator.
Before we look at the expectation values of trigonometric functions, note that the wavefunction can
be written as
1 e+iq> + e-iqi cos rp
lf/(rp) = 2?2 x (2.?r)112 = Jr"2
So (sin rp) =
!
2
"
-cos11-2rp sin rp-
cos -rp drp = -1
112
!
2
" 1 -cos rpl " = 0
cos 2 rpsin tpdrp = -x
3 2
Jr Jr Jr Jr 3 0
2
( sin rp) =
!
2
" cos rp 2 rp--drp
--sin
Jrl / 2
cos rp
Jrl / 2
= -Jr1 1 2
"
cos 2 rpsin 2 tpdrp
= ~ x( i- si~;rp )[" 4
~sinrp=((sin rp)-(sinrp) )
2 2 112
=(
1
-o
)1/2 fll
=11.J
4
(cosrp) =
2
1 "
-cos11-2rp cosrp-
Jr
cosrp
112
1
-drp=-
Jr Jr
f" cos 3 tpdrp
21r
1 sin 3 rp .
=Jr x smrp---
3 ( Jl 0
=0
because tn;::. tfixO = 0.

The uncertainty principle is trivially satisfied in both cases because the minimum uncertainty is
zero. The cases are somewhat different, though, in that there is no uncertainty in the angular
momentum in the first case, and there is uncertainty in the second case.
P3.21 The elliptical ring to which the particle is confined is defined by the set of all points that obey a
certain equation. In Cartesian coordinates, that equation is
x2 y2
-+-=l
a2 b2
as you may remember from analytical geometry. An ellipse is similar to a circle, and an appropriate
change of variable can transform the ellipse of this problem into a circle. That change of variable is
most conveniently described in terms of new Cartesian coordinates (X, Y) where
X=x and Y=aylb
In this new coordinate system, the equation for the ellipse becomes
x2 y2 x2 y2
-+-=l -+-=l x2 + y2 = a2
a2 b2 a2 a2
which we recognize as the equation of a circle of radius a centered at the origin of our (X,Y) system.
The text found the eigenfunctions and eigenvalues for a particle on a circular ring by transforming
from Cartesian coordinates to plane polar coordinates. Consider plane polar coordinates (R,)
related in the usual way to (X,Y):
X=R cos and Y = R sin 
In this coordinate system, we can simply quote the results obtained in the text. The energy levels are
21i2
E = !!!.!._____ [3.lOa]
21
where the moment of inertia is the mass of the particle times the radius of the circular ring
l=ma 2
The eigenfunctions are
eimf
'I' = --,-
/2 [3. lOb]
(27r)
It is customary to express results in terms of the original coordinate system, so express <1> in terms
first of X and Y, and then substitute the original coordinates:
y
- = tan<l> so r_ = tan-1 ay
<1> = tan- 1
x X bx
P3.23 The SchrOdinger equation is
n2 2
- - V lf/=Elf/ [3.18b]
2m
1 (! 2 (rur) 1 2
V 21f/= ___2.,,_+-A 1f/ [Table 3.1]
r C!r r2
since r = constant, the first term is eliminated and the SchrOdinger equation may be rewritten
---
n2 n2 2 If/= Elf/ [I= mr z] or A 111r.,, -- - 2/Elf/
A 2 If/= Elf/ or --A
2
2mr 21
2
n
2 1 a2 1 a . a
where A =----+----smB-
sin2BCJ¢'2 sinBCJB C!B
Now use the specified If/= Y,,m, from Table 3.2, and see if they satisfy this equation.
(a) Because Yo.o is a constant, all derivatives with respect to angles are zero, soA 2Yo 0 =[ill,
implying that E =~and angular momentum=~ [from {/(! + 1) } 112n, eqn. 3.22a].
2 a . C!Y2 -I
(b) A Yi.-i = -2- a-2i;-2·-+----smB--
_I
·- where l'z.-i = N cosBsinB e-'
¢
sin B CJ¢' sinBC!B C!B
·~ (cos 2 B - sin 2 B)
-C!Y2·-- I = Ne_,y
C!B
1 a . - a i;_1 1 a . AT -i¢ c 2 . 2 )
----sm 8 -'-=----sm 81ve cos 8 -sm 8
sinB C!B C!B sinB C!B
= N_e -i¢ (sin B(-4 cos Bsin B) +cos B( cos 2 B - sin 2 B))
smB
cosB) [cos 3 B = cos B(I - sin 2 B)]
= Ne-".1 ( -6cosBsmB+-.-
.
smB
CJ 2}'z _1 - N cos BsinB e- i¢ -N cos B e-i¢

sin 2 B af = sin 2 B = sinB
so A 2Yz._1 = Ne-i¢ (-6cosBsinB) =-6Yz._1 =-2(2+1)Yz.-i [i.e., l = 2]

and hence
2
-6Y2 _ 1 = -2/E . lymg
-2-J-; _1, imp . that ~3n
=-
, TJ . I
and the angular momentum is {2(2+1)}112n=16 112nl.

2
1 a :t;,3 1 a . a :t;,
(c) A 2Y.3 3 = - -2 - - 2
+ - - -- sm 8--3 where Y.3,3 = N sin3 B e3i¢
• sin B C!¢> sin B C!B C!B
C!Y.3 3
· = 3N sin 2 Bcos B e3'¢
.
--
C!B
i a i ar:
- - --sin 8 --22_ = ----3N sin 3 8cos 8 e 3';
a .
sin8 d8 a8 sin8 ()8
3
3i¢
= ~e (3 sin 2 8 cos 2 8- sin 4 8) = 3Ne 3i¢ sin 8(3 cos 2 8- sin 2 8)
Slll 8
= 3Ne3i¢ sin 8(3-4sin 2 8) [cos 3 8 =cos 8(1- sin 2 8)]
a2f 9N . 3 n 3i¢
- - __3_,3 = - sm v e = -9 N sin 8 e3i¢
sin 2 8 <J¢i sin 2 8
A ~. 3 =-12 N sin 8e i¢ =-12~.3 =-3(3+1)~.3 [i.e.,/=3]

2 3 3
so
and hence
21£
-12J".i3 = - -
. 1· h
2 J".i3 , tmp ymg t at
~E
L.IJ
6h2
' T] '
and the angular momentum is {3(3+1)} 112 h = l2.J:3Pzl.
P3.25 rf'J".i:3 J".i.3 sin8d8d¢= ( ;4 )x(~ Jr 6

sin 8sin8d8 f' d(b [Table3 .2]
= ( ; Jx(
4
~ Jx (2n) { 2 3 2 2
(l-cos 8) dcos 8 [sin 8d8 = dcos8, sin 8 = l-cos 8]
=~~{(l-3x 2 +3x 4 -x 6 )dx [x=cos8]
= ~(x - x3 +l5 xs -.Lx7)j'

7 = ~x 32 = '11
32 -I 32 35 L!J
j k
P3.27 i =rxp = x y z [see any book treating the vector product of vectors]
Px Py P,
= i(Jl jJ , - zfJ ) + j(zjJ X- xjJ ,)+k(xjJ y- YP)

Therefore,
We have used px = T:x, etc. The commutator of j x and j Y is [j x'i) = (j J Y- j Yi). Recall that
the operators always imply operation on a function. We form
and i L f=-n 2( zj_-xj_

y OX oz
)(yj_-zj_)f
oz oy
2 2 2 2
=-n2(zy 0 f -z2 0 f -xyo f +xz 0 f +xof )
OXOZ OXOy Oz 2 OzOy oy
Since multiplication and differentiation is each commutative, the results of the operation i)Y and
-- -- of of
l)x differ only in one term. For l)xf, x oy replaces y ox. Hence, the commutator of the
operations (/AAl - lAAl ) is -n 2( y -0 - x- or --1A .

' xy y x ' ox oy i z
0) EEJ
COMMENT. We also would find
P3.29 We are to show that [i 2,i, ] = 0 . Start by expanding the first operator:
A2 A A2 A2 A2 A A2 A A2 A A2 A
[/ ,/,] = [/x +/y +/, , /, ] = [/x ,/,]+[/y ,/,]+[/z , /z]
The three commutators are

A2 A A2A A A2 A3 A3
[/z , /z] = /z /z -/z/z = /z -/z = 0
A2 A A A AA A A A AA A A A A A
[Ix , /z] = /x2f, - /,Ix2 = fx2f, - /), fx + f),/x - f, fx2
= jx(i)z -i)x) + (i)z -i)x )ix =ix[/,' jz]+[ix' jz ]ix
= ix(-in~ )+ (-iniY)iY = -in(i)Y + i)x) [3 .24]
" "" "" "" " " " " " " " " "
= fy(l)z -/)y)+(l)z -/)y)/y = f)/y,l,]+[ly,l,]/y
= i/ini,)+(inix)iy = in(i/x +i)Y) [3 .24]
Therefore, [i 2 , /,] = -in(i)Y +i/x)+in(i)Y +i)x)+O = 0

We may also conclude that [i 2
,ix]= 0 and [i 2
,iy] = 0 because ix, iY, and iz occur symmetrically
A2
in l .
P3.31 P3.30 states that there are 22 electrons in the conjugated systems, so they would doubly occupy the
lowest 11 particle-in-a-square "orbitals." The energy levels are
Levels in which both quantum numbers are the same are non-degenerate; levels whose two quantum
numbers are different are doubly degenerate. The energy levels are shown in Figure 3.3(a), labeled
by one corresponding set of quantum numbers.
20 2,4
3,3
l,4
,,...._ 15
"'~ 2,3
~~ IO
:S 2.2
'"'-l
5 1,2
l,l
0 Figure 3.3(a)
Filling the orbitals from the bottom makes the (3,3) level the highest occupied level. So the
wavefunction to be plotted is
and the corresponding probability density is
4 . 2 (3JZ'
I/I 2 ( x y ) =-sm -- X) sm. 2 (37Z'y)
--
2
3,3 ' L L L
To generalize our plot to any size L , we will neglect the normalization constant and redefine
the coordinates with x = x!L and T] = y/L. The coordinate origin is (X,T]) = (0,0) and the ranges
are 0 $ x $ l and 0 $ ri $ l . The function f(X, TJ) = sin(n/Q')sin(n,7Z'TJ) will represent our
wavefunction . Mathcad™ contour and surface plots are set up by defining a grid of lOlxlOl
coordinate points, assigning values to n 1 and n 2 , and calculating the value of/ at each point:
I
N := 100 i :=0 ... N j:=O ... N '11. :=- Tj := J_
At N J N
Figure 3.3(b)
The Mathcad surface plotting feature easily produces the wavefunction graph of Figure 3.3(b).
Figure 3.3(c) is a surface plot of the HOMO probability density, which is simply f squared. A
portion of the porphine molecule has been sketched onto the Figure 3.3(c) probability density and
the nitrogen atoms of the porphine ring should be viewed as being near the ring's center.
Figure 3.3(c)
Figure 3.3(c) shows a remarkable resemblance between the probability density of the particle-in-a-
square and the conjugated 7r-system of porphine suggested by the structure. It is even possible to
imagine the center spike in the probability density as being representative of the lone pair electrons
on the nitrogen atoms. However useful this model is for conceptualizing the electron density in
porphine, far more accurate computations, to be studied in Chapter 6, are needed to determine the
actual distribution of electron density.
P3.33 (a) In the sphere, the SchrOdinger equation is
2 2
-n- ( -a 2 +--+2A
2 a 1 2) l/f = El/f [Table 3.1]
2m dr r dr r
where A 2 is an operator that contains derivatives with respect to ()and </J only.
Let lfl._r, B, </J)=R(r)Y(B, </J).
Substituting into the SchrOdinger equation gives
Divide both sides by RY:

2
-~(_!_ a R2 +~(JR +-l-A2r)
2
=E
2m R dr Rr dr Yr
The first two terms in parentheses depend only on r, but the last one depends on both r and angles;
however, multiplying both sides of the equation by ? will effect the desired separation:
-~(c a
2
R + 2r aR +_!_A2r) = Er2
2m R dr 2 R dr Y
Put all the terms involving angles on the right side and the terms involving distance on the left:
2
-~(c d R2 + 2r i1R)-Er2 =_!!____A2Y
2m R dr R dr 2mY
Note that the right side depends only on Band </J, while the left side depends on r. The only way
that the two sides can be equal to each other for all r, (), and </J is if they are both equal to a
2
constant. Call that constant - li l(l + l) (with l as yet undefined), and we have, from the right
2m
side of the equation,
_!!___A2Y= /i2/(l+l) so A 2Y = -l(l + l)Y
2mY 2m
From the left side of the equation, we have
-~( C "()2R + 2r <JRJ-Er2 =

2
tz /(/+l)
l
2m R or 2 R or 2rn
After multiplying both sides by RI? and rearranging, we get the desired radial equation:
-~(a2R +3_oRJ+ tz2/(/+l) R=ER

l
2m or 2 r or 2mr 2
Thus, the assumption that the wavefunction can be written as a product of functions is a valid one,
for we can find separate differential equations for the assumed factors. That is what it means for a
partial differential equation to be separable.
(b) The radial equation with l = 0 can be rearranged to read
o 2R 2 <JR 2mER
- - + - - = - -2-
or2 r or tz
Form the following derivatives of the proposed solution:
<JR = ( 2.1l'ar" 2 [cos(nll'rla) ( nll') sin(n!l'r/a)]

or r a r2
~:~ = (2Jrar 112

[ sin(n;r/a) ( n: y 2cos~~Jrrla) ( n:) + 2sin~~Jrr/a) l
Substituting into the left side of the rearranged radial equation yields
( 21l'ar 112 [ sin(n;r/a) ( n: y 2cos~~Jrrla) ( n:) + 2sin~Jrr/a) l

+ (2Jrar 112 [ 2cos~~Jrrla) ( : ) 2sin~.1l'r/a)]
= -( 2Jrar 112 sin(n;r/a) ( n: = -(: R y y

Acting on the proposed solution by taking the prescribed derivatives yields the function back-
multiplied by a constant, so the proposed solution is in fact a solution.
(c) Comparing this result to the right side of the rearranged radial equation gives an equation for
the energy
2rnE
so
tz2
PART 2 Atoms, molecules,
and assemblies
4 Atomic structure and
atomic spectra
04.1 When hydrogen atoms are excited into higher energy levels, they emit energy at a series of discrete
wavenumbers that show up as a series of lines in the spectrum. The lines in the Lyman series, for
which the emission of energy corresponds to the final state n 1 = 1, are in the ultraviolet region of the
electromagnetic spectrum. The Balmer series, for which n 1 = 2, is in the visible region. The Paschen
series, n 1 = 3, is in the infrared. The Brackett series, n 1 = 4, is also in the infrared. The Pfund series,
n 1 = 5, is in the far infrared. The Humphrey series, n 1 = 6, is in the very far infrared.
04.3 (1) The principal quantum number, n, determines the energy of a hydrogenic atomic orbital through
eqn. 4.8.
(2) The azimuthal quantum number, l, determines the magnitude of the angular momentum of a
hydrogenic atomic orbital through the formula {/(/ + l)} 112 h.
(3) The magnetic quantum number, m" determines the z-component of the angular momentum of
a hydrogenic orbital through the formula m1h.
(4) The spin quantum number, s, determines the magnitude of the spin angular momentum through
the formula {s(s + 1)} 112 h. For hydrogenic atomic orbitals, s can only be 1I 2.
(5) The spin quantum number, ms, determines the z-component of the spin angular momentum
through the formula msh. For hydrogenic atomic orbitals, ms can only be ±1 I 2.
04.5 The selection rules are
/),.n =±1, ±2, .. . M=±l /),.ml = 0, ± 1
In a spectroscopic transition the atom emits or absorbs a photon. Photons have a spin angular
momentum of 1. Therefore, as a result of the transition, the angular momentum of the
electromagnetic field has changed by ±In. The principle of the conservation of angular momentum
then requires that the angular momentum of the atom has undergone an equal and opposite change
in angular momentum. Hence, the selection rule on M = ±1. The principal quantum number n can
change by any amount since n does not directly relate to angular momentum. The selection rule
on /),.m 1 is harder to account for on the basis of these simple considerations alone. One has to
evaluate the transition dipole moment between the wavefunctions representing the initial and final
states involved in the transition. See Justification 4.4 for an example of this procedure.
The selection rules are strictly valid (1) only for hydrogenic atoms in which the states can be
described by pure and exact wavefunctions and (2) if there are no other external perturbations
(interactions) that could lead to a mixing of the states.
04. 7 See Fig. 4.8 of the text. The periodic table shows the manner in which the chemical and physical
properties of an element, composed of atoms of one kind only, varies as a function of the atomic number
of the element. This variation is periodic in the atomic numbers of the elements. The configuration of the
electrons in an atom is what determines the chemical and physical properties of the atom (element);
hence the periodicity of the properties is necessarily a result of the electron configurations.
The order of occupation of atomic orbitals, forming the electron configuration of the atom, mirrors
the structure of the periodic table.
The s and p blocks form the main groups of the periodic table. The similar electron configurations for
the elements in a main group are the reason for the similar properties of these elements. Each new
period corresponds to the occupation of a shell with a higher principal quantum number. This
correspondence explains the different lengths of the periods. Period 1 consists of only two elements, H
and He, in which the single ls orbital of the n = 1 shell is being filled with its two electrons. Period 2
consists of the eight elements Li through Ne, in which the one 2s and three 2p orbitals are being filled
with eight more electrons. In Period 3 (Na through Ar), the 3s and 3p orbitals are being occupied by
eight additional electrons. In Period 4, not only are the electrons of the 4s and 4p orbitals being added
but so are the 10 electrons of the 3d orbitals. Hence there are 18 elements in Period 4. Period 5
elements add another 18 electrons as the 5s, 4d, and 5p orbitals are filled. In Period 6, a total of
32 electrons are added, because 14 electrons are also being added to the seven 4f orbitals.
04.9 In the crudest form of the orbital approximation, the many-electron wavefunctions for atoms are
represented as a simple product of one-electron wavefunctions. At a somewhat more sophisticated
level, the many electron wavefunctions are written as linear combinations of such simple product
functions that explicitly satisfy the Pauli exclusion principle. Relatively good one-electron functions
are generated by the Hartree-Fock self-consistent field method described in Section 4.4(f). If we
place no restrictions on the form of the one-electron functions, we reach the Hartree-Fock limit that
gives us the best value of the calculated energy within the orbital approximation. The orbital
approximation is based on the disregard of significant portions of the electron-electron interaction
terms in the many-electron hamiltonian, so we cannot expect that it will be quantitatively accurate.
By abandoning the orbital approximation, we could in principle obtain essentially exact energies;
however, there are significant conceptual advantages to retaining the orbital approximation.
Increased accuracy can be obtained by reintroducing the neglected electron-electron interaction
terms and including their effects on the energies of the atom by a form of perturbation theory
similar to that described in Further Information 2.1. For a more complete discussion consult the
reference in Footnote 3.
04.11 An electron has a magnetic moment and magnetic field due to its orbital angular momentum. It also
has a magnetic moment and magnetic field due to its spin angular momentum. There is an interaction
energy between magnetic moments and magnetic fields. The energy between the spin magnetic
moment and the magnetic field generated by the orbital motion is called spin-orbit coupling. The
energy of interaction is proportional to the scalar product of the two vectors representing the spin and
orbital angular momenta and hence depends upon the orientation of the two vectors. See text Fig. 4.26.
The total angular momentum of an electron in an atom is the vector sum of the orbital and spin angular
momenta as expressed in eqn. 4.36. The spin-orbit coupling results in a splitting of the energy levels
associated with atomic terms as shown on the top of text Fig. 4.28. This splitting shows up in atomic
spectra as a fine structure as illustrated on the bottom of Fig. 4.28.
E4.1 (a) Eqn. 4.1 implies that the shortest wavelength corresponds to n2 =oo, the longest to n2 = 2. Solve
eqn. 4.1 for A.
A= (1 I n~ -11 n~)-
1
RH
Shortest:
Longest:
ATOMIC STRUCTURE AND ATOMIC SPECTRA 81
E4.2(a) For atoms A, eqn. 4.8 may be rewritten in terms of the Rydberg constant Ras
where to within 0.01 % the ratio µAlme is unity. Eqn. 4.1 can then be rewritten as
J.=~v
c
v=-
;.
v = 2.9978x1010 cm s-1 = l9.869x101s s- 1I

3.0376x10- 1 cm
E4.3(a) Identify l and use angular momentum = {/ (l + 1)} 11 2 n.
(a) I= 0, so angular momentum= 0

(b) I= 1, so angular momentum= .Jih
(c) I= 3, so angular momentum = 2.J3h
The total number of nodes is equal to n -1 and the number of angular nodes is equal to I; hence
the number of radial nodes is equal to n - I -1. We can draw up the following table.
2s 3p 5/
n, l 2,0 3,1 5,3
Angular nodes 0 3
Radial nodes
E4.4(a) The ionization energy for one-electron atoms and ions (A) is given by the negative of eqn. 4.8 with n = 1.
This may be rewritten in terms of the Rydberg constant as
IA= Z 2hcRA = Z 2hc µAR= Z2 µA IH

me µH
ftt = 2.1788 aJ. Reduced masses are calculated from eqn. 4.4, the ionization energies from the above
equation.
µH µH/ µHe+fµH ltt/

5.4828 x 10-4 u 5.4850 x 10-4 u 1.00040 8.7188 aJ
E4.5(a) This is essentially the photoelectric effect [eqn. 1.2 of Section 1.2] with the ionization energy of the
ejected electron being the work function <P.
l=hv-_!_m vi =(6.626xl0-34 Jliz-1)x(2.998xl0sms-1)

2 e 58.4xl0-9m
-( t) x (9.109x10-31 kg) x (1.59x106 ms- 1)2 x
= 2.25x10- 18 J, corresponding to 114.0eVI
E4.6(a) The L shell corresponds to n = 2. For n = 2, l = 1 (p subshell) and 0 (s subshell). The degeneracies
of these subshells are 2/ + 1. Hence the total degeneracy of the L shell is m
E4.7(a) The energies are E = - hc~H [4.8 with 4.11], and the orbital degeneracy g of an energy level of
n
principal quantum number n is
(1+2n l)n
g = L
~
(
n- 1
2/ -1) = 1+3 + 5 + · · · + 2n -1 =
2
- =n 2
(a) E = -hcRH implies that n = 1, so lg= 11 [the ls orbital].
(b) E = - hcRH implies that n = 2, so lg= 41 (2s orbital and three 2p orbitals).
4
(c) E = - hcRH implies that n = 4, so lg= 161 (the 4s orbital, the three 4p orbitals, the five 4d
16
orbitals, and the seven 4f" orbitals).
E4.8(a) Rl ,O =Ne - rlao
Thus,
which agrees with Table 4.1.
2
E4.9(a) R oc(2-£)e-p1 4 withp= r [Table4.1]
2,0 2 Go
dR =I_ dR =I_( __!_ _ _!_+!p)e-P14 =0 whenp=8

dr G0 dp G0 2 2 8
Hence, the wavefunction has an extremum at r = l4G0 I· Because 2 - p < 0, If/ < 0 and the
2
d ~ > O at
2
extremum is a minimum (more formally: p = 8) .

dr
The second extremum is at Ir= o.I It is not a minimum and in fact is a physical maximum, though not
one that can be obtained by differentiation. To see that it is maximum, substitute p = 0 into R 2 ,0 •
E4.1 O(a) The 2s radial function is proportional to (2 - p )e- P12 . This factor goes to zero when p = 2.
Since p = (2Zlna)r, r = nap/2Z. If we assume a= a 0 , then
10
r = 4a0 /2 = 2a0 = 2 x 5.292xl0- 11 m = JI.058 x I0- mJ
E4.11 (a) We will solve this exercise by straightforward integration.

2
'1'1,0,0
- R 1,0 Y,0,0
-
-(_£_)1/
-
7rao
e 3
- rlao [Tables 3.2 and 4.1]
The potential energy operator is
v = -~ x (.!_) = -k(.!_)
4nc0 r r
(v) =-k\n[ k = :J
4
=-k f0~ J: J:ff( ,.~~) e- r/a, U 0 2
} - rfa r drsinB dB d¢
= -k x (4n) x( ,.~~) r re-2 '/~dr = -k x( a~ }(~)= -k( :0)

[We have used I: sin BdB = 2, J:ff dB= 27r, and r x"e-ax d.x = a~;I ·]
Hence,
Ze 2
(v) = - - - = !2E1, J
4.m;oao
The kinetic energy operator is _.!t._ V 2
[ 4.4 and Further Information 4.1]; hence
2µ
(EK)=(T)= f!Vi:(-;:)V1/{sdr 2
1
V 2 1/fIs = r
a (r11rn s) +-A
2
1
1f/ 2
[Problem 3 •23]
dr 2 r2 ts
-r/~
2
-( 1 )l/
2
-- 1) (
d r) e
x(- x -
1ta~ r dr 2
[A 2 1/f1s = 0, '!'is contains no angular variables]
Hence, (T) + (V) = -E,, + 2Eis = Ei s.

We determined the ionization energy of the He+ ion in the solution to Exercise 4.4(a) with the result
J(He+) = 8.7188 aJ. Using the relationships demonstrated above, we obtain for the potential and
kinetic energies of the He+ ion
V(He +) = 2)E1s (He+)= -2/(He +) = -2x8.7188 aJ = /-17.4376 aJ/

T(He+) = -E1s(He+) = J(He+) = /8 .7188 aJ!
COMMENT. E 1s may also be written as
Question. Are the three different expressions for E1, given in this exercise all equivalent?
E4.12(a) See Example 4.4. The mean radius is given by (r) = 1=

r 3R; 1dr. After substituting eqn. 4.10 for
Rn.I , and integrating, the general expression for the ~ean ~adius of a hydrogenic orbital with
quantum numbers land n is obtained (see eqn. 10.19 of Atkins and DePaula, Physical Chemistry,
8th edition).
(r
nJ
) =n 2 {1+_!_(1-/(/+l))}~
2 n2 Z
6
For the 2s orbital n = 2 and l = O; hence (r2s) = a0 .
z
See Example 4.5, which illustrates the calculation of the most probable radius. It is obtained by
solving dP(r )/dr = 0 with P(r) = r 2 R(r ) 2 . For the 2s orbital, P(r) oc r 2 ( 2 - J
~ r e-~r. Differ-
entiating this expression with respect to r and solving for those values of r that make the derivative
equal to zero is most readily performed with mathematical software. Here we use MathCad®.
2 r
r - Z· -
r2· 2 - Z·-; ·e •
( )
0
a
2·-
z
2·r{ 2-Z·~J ·exp(-Z·~ ) -2·r { 2-Z· ~}xp(-Z·~}~-r { 2-Z· ~J -~·exp(-Z·~)=Osolve,r ~
2 2
2-(~2 + L.JS)-~
2 z
2-(~-L.JS)-~
2 2 z
The first and second of these roots correspond to minima in the probability. The third and fourth
roots correspond to maxima, with the third being the largest, and hence it is the most probable value
of r. This may be rewritten as / = (3 +JS)!!_ .

z
E4.13(a) The radial distribution function is defined as
~s
3
1
2
=4Jrr ( -
4;r
)x(--)x(_!_)
1
243 a
x(6-6p+p
0
2 2
) e-P
2 2
where p = Zr = Zr. But we want to find the most likely radius, so it would help to simplify the
na0 3a0
function by expressing it in terms of either r or p but not both. To find the most likely radius, we
could set the derivative of P 3s equal to zero; therefore, we can collect all multiplicative constants
together (including the factors of a0 /Z needed to tum the initial r 2 into p 2 ) because they will
eventually be divided into zero.
Pi, = C2p2(6-6p+ p2)2e-p
Note that not all the extrema of P are maxima; some are minima. But all the extrema of (P;jl 2
correspond to maxima of P 3,. So let us find the extrema of CP:is)l/ 2.
d(R )1/ 2 d
Js = 0 =-Cp(6-6p+ p 2)e-P12
dp dp
=C[p(6-6p + p 2 )x(-~) + (6-12p+ 3p]e-Pl2
Numerical solution of this cubic equation yields

p = 0.49, 2. 79, and 8. 72
corresponding to
r = I0.74a0 I Z,4.l9a0 I Z, and 13.08a0 I zl

COMMENT. If numerical methods are to be used to find the roots of the equation that locates the
extrema, then graphical/numerical methods might as well be used to locate the maxima directly. That is,
the student may simply have a spreadsheet compute P3s and examine or manipulate the spreadsheet to
locate the maxima.
E4.14(a) See Fig. 4.14 of the text. The number of angular nodes is the value of the quantum number /, which
for p orbitals is 1. Hence, each of the three p orbitals has one angular node. To locate the angular
nodes look for the value of ethat makes the wavefunction zero.
p, orbital: see eqn. 4. l 7(a) and Fig. 4.14. The nodal plane is the IXJI plan~ and le= 7t/~ is an angular node.
Px orbital: see eqns. 4.18(a) and 4.18(b) and Fig. 4.14. The nodal plane is the~ plane and le= qis
an angular node.
Py orbital: see eqns. 4.18(a) and 4.18(c) and Fig. 4.14. The nodal plane is the~ plane and le= ()j is
an angular node.
E4.15(a) The selection rules for a many-electron atom are given by the set [4.39]. For a single-electron
transition these amount to l:!,.n = any integer; M = ±1. Hence
(a) 3s ~ls; M = o,lforbiddenl
(b) 3p ~ 2s; I:!,./ =-1,lallowedl
(c) 5d ~ 2p; M =-1,lallowedl
E4.16(a) A source approaching an observer appears to be emitting light of frequency
v
vapproaching = - - [4.26b]
1-~
c
Since v oc _!_
A' ,tobs = (1-~),i
C
s = 60 km h- 1 = 16.7 m s- 1 • Hence
Aobs= ( 1-
1
J
16.7ms- _ x(680nm)= I0.999999944x680nm I
2.998xl08 ms 1
For all practical purposes, there is no shift at all at this speed.

1
s:- 5.31cm- ( b] . . h 5.31 ps
E4.17(a) uv "" 4 .28 , imp 1ymg t at r "" _ _1
rips ovlcm
(a)
(b)
E4.18(a) ov"" 5.3lcm-1 (4.28b]

rips
(a) r"" l.Oxl0- 13 s = 0.10 ps, implying that ov ""153cm- 1I

(b) r"" (100) x (1.0x1 o - IJ s) = 10 ps, implying that ov ""I 0.53 cm-I I
E4.19(a)
Isa(!) ls/J(I) 2sa(I) 2s/J(I) 2p 1a(I) 2p 1/J(I) 2p 0 a(I) 2po/J(I) 2p_1a(I) 2p_1/J(I) 3sa(I) 3s/J(l)
lsa(2) ls/1(2) 2sa(2) 2s/J(2) 2p 1a(2) 2p,/J(2) 2p 0 a(2) 2p 0 /J(2) 2p_1a(2) 2p_,/J(2) 3sa(2) 3s/J(2)
lsa(4) ls/J(4) 2sa(4) 2s/J(4) 2p 1a(4) 2p,/J(4) 2p 0 a(4) 2p 0 /J(4) 2p_1a(4) 2p_,/J(4) 3sa(4) 3s/J(4)
I lsa(6) ls/1(6) 2sa(6) 2s/J(6) 2p 1a(6) 2p,/J(6) 2p 0 a(6) 2p 0 /J(6) 2p_1a(6) 2p_,/J(6) 3sa(6) 3s/J(6)
'1'(1,2, .. .,12) = - -
(12!) 1' 2 lsa(7) ls/1(7) 2sa(7) 2s/J(7) 2p 1a(7) 2p,/J(7) 2p 0 a(7) 2p 0 /J(7) 2p_p(7) 2p_,/J(7) 3sa(7) 3s/J(7)
lsa(9) ls/1(9) 2sa(9) 2s/J(9) 2p 1a(9) 2p,/J(9) 2p 0 a(9) 2p 0 /J(9) 2p _1a(9) 2p _,/J(9) 3sa(9) 3s/J(9)
lsa(IO) ls/J(IO) 2sa(IO) 2s/J(IO) 2p 1a(IO) 2p 1/J(IO) 2p 0 a(IO) 2p 0 /J(IO) 2p_1a(IO) 2p_1/J(IO) 3sa(IO) 3s/J(IO)
Isa(! I) ls/J(l I) 2sa(l 1) 2s/J(l 1) 2p 1a(ll) 2p1/J(ll) 2p 0 a(l I) 2p 0 /J(l l) 2p_1a(l I) 2p_1/J(ll) 3sa(l 1) 3s/J(l I)
lsa(l2) ls/1(12) 2sa(l2) 2s/J(l2) 2p 1a(12) 2p1/J(l2) 2p 0 a(l2) 2p 0 /J(l2) 2p_1a(l2) 2p_l/J(l2) 3sa(12) 3s/J(l2)
E4.20(a) The ground state configuration of the carbon atom is ls 22s 22p 2 . The normal valence of carbon is 4
and each of the electrons with principal quantum number 2 can participate in bonding. In the free
carbon atom, the three 2p orbitals are degenerate; hence we have no knowledge about in which two
of the three 2p orbitals the electrons actually reside. We do know that the two 2p electrons are
unpaired and that the total spin is 1, but whether they are both ms = + 112 or both ms = -1/2 is
unknown. The table below summarizes one possible set of quantum numbers.
Electron n m, s ms
1 2 0 0 112 +l/2
2 2 0 0 112 -112
3 2 1 112 +1/2
4 2 0 112 +112
E4.21 (a) Sc: [Ar]4s 23d 1

Ti: [Ar]4s 23d2
V: [Ar]4s 23d 3
Cr: [Ar]4s 23d4 or [Ar]4s 13d5 (most probable)
Mn: [Ar]4s 23d5
Fe: [Ar]4s 23d6
Co: [Ar]4s 23d7

Ni: [Ar]4s 2 3d8
Cu: [Ar]4s 23d9 or [Ar]4s 13d 10 (most probable)
Zn: [Ar]4s 2 3d 10
E4.22(a) (a) Pd 2+: j[Kr]4d 8 j

(b) All subshells except 4d are filled and hence have no net spin. Applying Hund's rule to 4d 8
shows that there are two unpaired spins. The paired spins do not contribute to the net spin;
hence we consider only s1 = t and s 2 = t . The Clebsch-Gordan series [4.35] produces
S = s, +s2 , ••• ,1s1 -s21, hence /s = 1,0/

Ms =-S,-S+l, ... , S
For S = 1, JMs = -1,0, +II
S=O, JMs =01
E4.23(a) We use the Clebsch-Gordan series [4.36] in the form
j=t+s, t+s-1, ... ,lt-sl [lowercase for a single electron]
(a) t = 2, s = .l2 ·, . lI'.lJ

so} =
rTJl
(b) t = 3, so j = Jf,fl
E4.24(a) The Clebsch-Gordan series for It= 3 or 21 and s = t leads to j = f.
The Clebsch-Gordan series for It= 1 or ol and s = t leads to j = f .
E4.25(a) Use the Clebsch-Gordan series in the form
Then, with j 1 = 1 and j 2 = 2,
J =13,2,II
E4.26(a) The letter P indicates that L = 1 , the su erscript 3 is the value of 2S + 1 , so S = 1 and the subscript
2 is the value of J. Hence, L = 1, S = 1, J = 2 .
and
in succession. The multiplicity is 2S + 1 .
(a) S = t+f, t-t = j1,oj with multiplicities 13,ll respectively.
(b) s' = 1,0 ; then s = l·t. tl [from l], Jandtl [from 0], with multiplicities J4,2,2J .
E4.28(a) These electrons are not equivalent (different subshells), hence all the terms that arise from the
vector model and the Clebsch-Gordan series are allowed (Example 4.6).
S = s1 +s 2 ,. • .,ls1 -s21=1,0
The allowed terms are then 3 D and 1D . The possible values of J are given by
3 1
J = L + S,. ..,IL-SI [4.36] = 3, 2, 1 for D and 2 for D
The allowed complete term symbols are then
The 1 3 D set of terms are the lower in energy I [Hund' s rule].
COMMENT. Hund 's rule in the form given in the text does not allow the energies of the triplet terms to
be distinguished. Experimental evidence indicates that 3 0 1 is lowest.
J = L+ S ,L+ S-1,. . ., IL-SI
The number of states ( M 1 values) is 21+1 in each case.
(a) L = O, S = 1; hence IJ = iJ(3s 1) and there are J3 state~.
(b) L = 2, S = 1- ; hence IJ = 5 I 2, 3 I 2 respectively I(2 D 512

,
2
D 312 ) with ~, and 2 states respective!~.
(c) L=l,S=O; hence ll=li('Pi) withJ3state~.
E4.30(a) Closed shells and subshells do not contribute to either L or Sand thus are ignored in what follows.
1
(a) Na: [Ne]3s : S =±, L = O; J =±,so the only term is l s 112
2
i
(b) K:
1
[Ar]3d : S = ±, L = 2; J = %.-i, so the terms are f 2D 512 and 2
D 312 f
E4.31 (a) See eqn. 4.39 for the selection rules.
(a) !anowe~
(b) [orbidde~
(c) Jallowe~
P4.1 All lines in the hydrogen spectrum fit the Rydberg formula
Find n, from the value of A.max, which arises from the transition n, + 1 ~ n,
Since n, = 1, 2, 3, and 4 have already been accounted for, try n, = 5, 6,. .. . With n, = 6 we get
h ~ 61 and the transitions are given by

2 2
n, (n, + l) = 136. Hence, the Humphreys series is
2n1 +1
1
-=(109677cm -I )x ( -1 --
1 J n2 = 7,8, ...
A 36 n; '
and occur at 12372 nm, 7503 nm, 5908 nm, 5129 nm, . .. , 3908 nm (at n2 =15 ), converging to 3282 nm
as n2 ~ 00 , in agreement with the quoted experimental result.
P4.3 A Lyman series corresponds to n, = 1 ; hence,
v = RLi 2• ( 1- : 2 } n = 2, 3,... [v = ±]
Therefore, if the formula is appropriate, we expect to find that v(1---;-)-
n
' is a constant ( R
Lt
2+ ).
We therefore draw up the following table.
n 2 3 4
1
ii/cm- 740747 877924 925933
-
v 1-
( 7 )-11
I
cm
-I
987663 987665 987662
f,Ience, the formula does describe the transitions, and IRLi + = 987663cm-' I· The Balmer transitions
2
he at
ii= R .2+
Lt
(_!_-~)
4 n
n = 3,4, ...
= (987663 cm-' )x(±-: 2

) = l137175cm- ' l.1185187 cm- ' I, ...
The ionization energy of the ground-state ion is given by
ii = R .2•
Lt
(1- ~), n
n ~ oo
and hence corresponds to
ii= 987663 cm-', or 1122.5 evl
P4.5 The 7p configuration has just one electron outside a closed subshell. That electron has I= 1,
s = 1/2, and j = 1/2 or 312, so the atom has L = 1, S = 112, and J = 1/2 or 312. The term
I I,
symbols are 2 P, 12 and 2 P312 of which the former has the lower energy. The 6d configuration also
has just one electron outside a closed subshell; that electron has I= 2, s = 1/2, and j = 312 or 5/2,
so the atom has L = 2, S = 1/2, and J = 312 or 512. The term symbols are 2 D 312 and 2 D 512 of I I,
which the former has the lower energy. According to the simple treatment of spin-orbit coupling,
the energy is given by
E1,s, J = t Ah 2
[j(j + 1)- /(/ + 1)- s(s + 1)]
where ,1 is the spin-orbit coupling constant. So
EC Pl/2 ) = t -1h 2rto 12 +l)-1c1+1)-t o / 2 + l)J = --1h 2

and EC D 31 z) = 1-1h 2[f (3I2+1)- 2(2+1)-1(1 I 2 + l)] = -f-1h 2
This approach would predict the ground state to be 2D 312 I I.
2
COMMENT. The computational study cited finds the P112 level to be lowest, but the authors caution that
the error of similar calculations on Y and Lu is comparable to the computed difference between levels.
P4.7
where R corresponds to an infinitely heavy nucleus, with µ=me .

mm
Since µ = e N [N = p or d]
me +mN
Likewise, R0 = ___!!_, where m is the mass of the proton and md the mass of the deuteron. The
l+ -5.. p
m,
two lines in question lie at
1 1
-A =RH (1-l_)=l.R
4 4 H A = RD (1 - .L)
-
4
= l. R
4 D
H D
and hence
RH= Ao= vH
Ro AH Vo
Then, since
R l+
-=--,
H m,
m,
RD 1 + -5..
m,
we can calculate md from
= 9.10939x10-J1 kg -1 =13.3429x10-21kgl
l + 9. 1039xl0-31 kg) X ( 82259.098cm- 1 )
( l.67262x!0-27 kg 82281.476cm- 1
Since I = Rhc,
1
= R 0 = v0 = 82281.476 cm- = li.ooo 2 nl
/ 0
1
/H RH vH 82259.098cm-
P4.9 (a) The splitting of adjacent energy levels is related to the difference in wavenumber of the spectral
lines as follows :
24 1
so !:iv= JtsB = (9.274x10- J r )(2 T)
hc!lv = M = JtsB,
he (6.626xl0-34 J s)(2.998xl0 10 cm s- 1)
(b) Transitions induced by absorbing visible light have wavenumbers in the tens of thousands of
reciprocal centimeters, so normal Zeeman splitting is lsmalll compared to the difference in energy
of the states involved in the transition. Take a wavenumber from the middle of the visible spectrum
as typical:
9
v=_!_= 1 (10 nmm-')=l.?xl04 cm-'
A. 600 nm 10 2 cm m-'
Or take the Balmer series as an example, as suggested in the problem; the Balmer wavenumbers are
(eqn. 4.1)
v= R (__!__-
22 n3
H
_!__J
The smallest Balmer wavenumber is

v = (109677 cm- 1
) x (1/4-1/9) = 15233 cm-'
and the upper limit is

v = (109677 cm-')x(l/4-0) = 27419 cm- 1
P4.11 (a)
(b) See the solution to Exercise 4.2(a).

For atoms A, eqn. 4.8 may be rewritten in terms of the Rydberg constant R as
where to within 0.01 % the ratio µAlme is unity. Eqn. 4.1 can then be rewritten as
c
V=-
A,
v = 2.9978xl010 cm s-1 = li.234x1016 s-1 /

2.430xl0-6 cm
(c) See the solution to Exercise 4.12(a). The formula for the mean radius is
(r4,I) = [i;]
Hence, since <11.o>= l~a0 I· the mean radius has increased by I~ a 0 I·
P4.13 The ground state wavefunction for a hydrogen-like atom is
_ _ Z 3Jl/2 -z,/a0
Y/1 ,0,0 - R,,0 -fo.o - (- e [Tables 3.2 and 4.1]
:ra03
· may be rewntten
· 3)1/2
This as Yf1"0 0 = R1,0 -fo,0 =(-btr e-br where b = Z!a0 •
(a) For the probability of being in a sphere of radius R centered on the nucleus, allow for the r
dependence of lfl:
P= 1 2
l/f 2 dr=(b 3 /n) f Jr d¢> fJrsinBdB fR r 2 dr(e- 26' )
olume
= (b 3 /n)(2n)(2) r Jo Jo Jo
r 2 e- 2b'dr=l-[1+2br+2(br) 2 ]e- 2 br
For Z = 1, b = (1153 pm), and for R = 53, pm= lib.
P=l-[1+2+2]e-2 =l-5e- 2 =I0.3231
(b) We find the 90% boundary surface by solving
0.90 = 1-[l + 2br + 2(br) 2 ]e-26,.
That is, solve
[l + 2br + 2(br) 2 ]e- 2br = 0.10
Using mathematical software, for example, MathCad®, this solves to bR = 2.66, so R = 1141 pillJ.
P4.15 (a) Consider lfl2 p_ = lf/2, 1,0 , which extends along the z-axis. The most probable point along the
z-axis is where the radial function has its maximum value (for 1f1 2 is also a maximum at that
point). From Table 4.1 we know that
dR -
so - = (1- l. p) e P' 2 = 0 when p = 2.
dp 2
2 0 2 0
Therefore, r* = ; , and the point of maximum probability lies at z = ± ; = 1±106 pm!.
(b) The most probable radius occurs when the radial distribution function is a maximum. At this
point the derivative of the function w/r/t either r or p equals zero.
( ~31 J ~)pe-P' ))
2
~ )e-P12
2
4
= O= (d(( - [Table 4.1] = (4-4p+
p ~ p -
The function is a maximum when the polynomial equals zero. The quadratic equation gives the
roots p = 4 + 2..fi. = 6.89 and p = 4-2..fi. = 1.17 . Since p = (2Zlna0 )r and n = 3, these
7
correspond to r = 10.3xa/ Z and r = l.76xaofZ. However, IR3 iCPi) I= IR31 (1.1 )1=4.90. So we
R3,(p2 ) R31 (10.3)
conclude that the function is a maximum at p = ±1.17, which corresponds to ~~-=-±-1-.7-6-aof~zj. See the
solutions to Exercises 4.12(b) and 4.13(b) for the most probable radii of 2p and 3p electrons. The
results are 4aofZ and 12ao/Z, respectively, both much larger than the points of maximum probability.
COMMENT. Since the radial portion of any 2p or any 3p function is the same, the same result would
have been obtained for all of them. The direction of the most probable point would, however, be
different.
P4.17 (a) We must show that JI 1f13 \2 d'Z'=1 . The integrations are most easily performed in spherical
coordinates (Fig. 3.12). ''
2Jt Jr DO
f\lfl 3 }dT= J J ~lf/3 PJr 2 sin(O)drdOd¢

0 0 0
= f
2......J_tlR
n
31 (p)
{r.i-h-Y.11 }\2 2
r sin(O)drd0d¢ [Table 4.1, eqn 4.18]
where p = 2r I a0 ,r = pa0 I 2,dr = (a0 I 2)dp.
_..!_Zs" ll"f - , Go )3 [( 1 )(_!_)3/2(4-..!_ ) e-p/6]

- 2 tl 2 27(6)1/ 2 a0 3p p
r
0 0
x[ (
8~ 2sin(B)oos(¢) l> sin(B)dpdBd¢
f f -n(4-..!..p)pe-P'
2 2
1 6 2
= sin(O)cos(¢)1 p sin(O)dpd0d¢
46656;r 0 0 ti 3
Jcos (¢)d¢ Jsin (B)d8 K4--p p dp
2
= l 21' 2 " 3 1 ) 4
e-P'
3
46656;r 0 0 0 3
..:..._--~---~
4/3 34992
= 1 Thus, 1f13Px is normalized to 1.
We must also show that flfl3 lfl3ct

Px xy
d't' = 0.
Using Tables 3.2 and 4.1, we find that
3/2
1
1f13
Px
= _!__
54(27r) 112 a0 ( J (4-.!p)pe-P'
3
sin(B)cos(¢) 6
where p = 2rla0 ,r = pa0 !2,dr = (a0 12)dp.
flfl lf/ ct d 'Z' = constantx p 5e - P' 3dp

-J ~
Jcos(¢)sin(2¢)d¢ Jsin (B)dB
" 4
3 P, 3
xy O 0 0
Since the integral equals zero, 1f13 and If! are orthogonal.
Px 3d xy
(lJ) Radja} nodes are determined by finding tke f7 valaes (/1 =2r!a;) for wlrklr dre radial
wavefunction equals zero. These values are the roots of the polynomial portion of the wavefunction.
2
For the 3s orbital, 6-6p+ p = 0, when IPnocte =3+J3 and Pnocte =3-J31.
The 3s orbital has these two spherically symmetrical nodes. There is no node at p = 0 so we
conclude that there is a finite probability of finding a 3s electron at the nucleus.
For the 3Px orbital, (4- p)(p) = 0 when /Pnocte = 0 and Pnocte = 4/. There is a zero probability
of finding a 3p, electron at the nucleus.
For the 3dxy orbital /Pnocte = ol is the only radial node.

52488
( ) = 27a0
r 3s 2
(d) Radial distribution func tions of atomic hydrogen

0.12 ~---------------------
0. 1
0.08 ;
_;
c
M~
4:: 0.06
0.04
0.02
o L:...XL~....L~L___j_~~~J__~~_l_~.:.:.:.:.:::.::..:i~~.,,,-J
0 10 15 20 25 30
rla0 Figure 4.1
The plot, Figure 4.1 , shows that the 3s orbital has larger values of the radial distribution function for r < a0 .
This penetration of inner core electrons of multi-electron atoms means that a 3s electron experiences a
larger effective nuclear charge and, consequently, has a lower energy than either a 3p or 3dX}' electron. This
reasoning also leads us to conclude that a 3px electron has less energy than a 3dxy electron.
E3, < E 3p, < E3dry

(e) Polar plots with B = 90°, Figure 4.2
Thesorbital The p orbital
90
,,:tfl
90 1:?0 60
210 330
240 300
270 330
<P
300
270
Thedorbital
"'
90
l~O 60
240 300
270
Figure 4.2
"'
Boundary surface plots, Figure 4.3

s- orbital boundary surface p-orbital boundary surface
d-orbital boundary surface /-orbital boundary surface
Figure 4.3
l/ 2
P4.19 lfl1 s [ J
= _I_
na0
3 e -rlao[4 . 14)
The probability ofthe electron being within a sphere ofradius r / is
We set this equal to 0.90 and solve for r'. The integral over B and <P gives a factor of 4;r; thus
0.90 = ~ f 'r 2e-2r1a, dr

a~ o
r 2 2 1
r e- "" dr is integrated by parts to yield
r
a0 r 2 e-2rla0 r'
~-2--10 +ao
[
_a~
-2rla0 r' + a0 [
0 r_e_ _
2
1
2
_a~
-2ria0
0 e_ _
2
lr']
0 0
') 2 -2r'la0 2 / 3 3
a0 ( r e a0 r e-2r'ta0 -~e-2r'1 a0 + a0
2 2 4 4
Multiplying by 4 and factoring e-2r'ia,,
ao
It is easiest to solve this numerically. It is seen that Ir'= 2.66a0 I satisfies the above equation.
Mathematical software has powerful features for handling this type of problem. Plots are very
convenient to both make and use. Solve blocks can be used as functions. Both features are
demonstrated below using Mathcad®.
Let z = r18<J. The probability, Prob(z), that a 1s electron is within a sphere of radius z is
Prob(z) := 4 · r x 2 · e- 2 xdx
Variables needed for plot: N := 800
0.8
X-Value 2.6625 Copy X

0 .6
Prob(.,) Y-Value 0.90019 Co~
0.4 V' Track Data Points Close

J
0.2
00
.,
The plot indicates that the probability of finding the electron in a sphere of radius is
sigmoidal. The trace feature of Mathcad is used to find that with z = 2.66 (r = 2.66 Bo) there
is a 90.0% probability of finding the electron in the sphere.
The following Mathcad® document develops a function for calculating the radius for any desired
probability. The probability is presented to the function as an argument
z := 2 Estimate of z needed for computation within following Given/Find solve block for the
function z(Probability).
Given
Probability = 4 · f:X 2
. e-2 xdx
z(Probability) := Find(z)
z(.9) = 2.661
00 27! J[
P4.21 (rm)nl = fr ml\f/l dr= ff fr m+ 1RnY, 2

1 0l
2
sin(B)dBd¢dr
0 0 0
00 2ff /[ 00
= Jrm+ 2
IRl dr JJlr, 1sin(B)dBd¢ = Jr'"+
0
2 2
IRl dr
0 0 0 0
With r = (naof2Z)p and m = -1 the expectation value is
(a) (,-'),_ =u~J H:.rnpo'dp [Table 4.1]
=~ because
(b) [Table 4.1]
2
because fp(2-p) e-Pdp=2
(c) [Table 4.1]
=~(6) because fp 3 e-Pdp = 6

24a0 0
(r-') =8E
2P
The general formula for a hydrogenic orbital is (r- 1)

nl
= +.
n ao
P4.23 Justification 4.4 noted that the transition dipole moment, µfi, had to be non-zero for a transition to
be allowed. The Justification examined conditions that allowed the z component of this quantity to
be non-zero; now examine the x and y components.
As in the Justification, express the relevant Cartesian variables in terms of the spherical harmonics,
Yi,m. Start by expressing them in spherical polar coordinates:
x = rsin0cos¢> and y = rsin0sin¢>
Note that r;,1 and r;,_1 have factors of sin 0. They also contain complex exponentials that can be
related to the sine and cosine of ¢> through the identities
These relations motivate us to try linear combinations r;,1-r;,_ 1and r;,1-r;,_1(from Table 3.2; note
that c here corresponds to the normalization constant in the table):
r; 1+ r; _1=-csin 0( ei¢ + e-i¢) =-2c sin Ocos ¢> = -2cx I r

so x =-Cr;,, + r;,_1)r I 2c
r; 1- r; _1=c sin 0(ei¢ -e-i¢) =2icsin Osin ¢> =2icy I r
so y =er;,, - r;,-1)r/2ic
Now we can express the integrals in terms of radial wavefunctions Rn,1 and spherical harmonics Yi,m,:
The angular integral can be broken into two, one of which contains r;,1and the other r;,_1. A "triple
integral" over spherical harmonics of the form
" 21'
I I r·,,.m,, r;,,Yi,.m,, sinodod¢>
0 0
vanishes unless Ir = I; ± 1 and m1, = m1, ± 1 . The integral that contains r;,_1 introduces no further
constraints; it vanishes unless Ir = I; ± 1 and m1, = m1, ± 1 . Similarly, they component introduces no
further constraints, for it involves the same spherical harmonics as the x component. The whole set
of selection rules, then, is that transitions are allowed only if
IM= ±1 and !:1m =0 or±ll 1
P4.25 (a) The Slater wavefunction [4.32) is
If/a(1 )a(l) If/a(2)a(2) If/a(3)a(3) lf/a(N)a(N)

If/a(1),8(1) If/a(2),8(2) If/a (3) ,8(3) If/a(N),B(N)
lf/(1,2,3, ...,N) =--1
(N!)
-
112
lf/b (1 )a(l) lf/b(2)a(2) lf/b(3)a(3) lf/b(N)a(N)
If/, (1) ,8(1) lf/z(2),8(2) lf/z(3),8(3) If/, (N),B(N)
Interchanging any two columns or rows leaves the function unchanged except for a change in
sign. For example, interchanging the first and second columns of the above determinant gives
If/a(2)a(2) If/a(l)a(l) If/a(3)a(3) If/a(N)a(N)

If/a(2),8(2) If/a(1),8(1) If/a(3),8(3) If/a(N),B(N)
lf/(l, 2, 3, ... , N) =--1
-1-12 lf/b(2)a(2) lf/b(l)a(l) lf/b(3)a(3) lf/b(N)a(N)
(N!)
If/, (2),8(2) lf/z (1),8(1) lf/,(3),8(3) If/, (N),B(N)
= -lj/(2, 1, 3, ... , N)
This demonstrates that a Slater determinant is antisymmetric under particle exchange.
(b) The possibility that two electrons occupy the same orbital with the same spin can be explored by
making any two rows of the Slater determinant identical, thereby providing identical orbital and spin
functions to two rows. Rows 1 and 2 are identical in the Slater wavefunction below. Interchanging these
two rows causes the sign to change without in any way changing the determinant.
If/a(l)a(l) If/a(2)a(2) If/a(3)a(3) If/a(N)a(N)

If/a(l)a(l) If/a(2)a(2) If/a(3)a(3) If/a(N)a(N)
1
lf/(l, 2, 3, ... , N) = - -1-12 lf/b(I)a(l) lf/b (2)a(2) lf/b(3)a(3) lf/b(N)a(N)
(N!) :
lf/z (1),8(1) lf/z (2),8(2) lf/z(3),8(3) If/=(N),B(N)
= -lf/(2, 1,3, ... , N) = -lf/(l, 2,3, ... , N)
Only the null function satisfies a relationship in which it is the negative of itself so we conclude
that, since the null function is inconsistent with existence, the Slater determinant satisfies the
Pauli Exclusion Principle [Section 4.4 b]. No two electrons can occupy the same orbital with the
same spin.
P4.27 The wavenumber of a spectroscopic transition is related to the difference in the relevant energy
levels. For a one-electron atom or ion, the relationship is
Solving for v, using the definition tz = h l 27r and the fact that Z = 2 for He, yields
4
_ J4iee ( 1
v = 2c 2 h 3 c
0
-;;z--;;z1 )
2 l
Note that the wavenumbers are proportional to the reduced mass, which is very close to the mass of
the electron for both isotopes. In order to distinguish between them, we need to carry lots of
significant figures in the calculation.
_
v=~~~~~~~~~~~~~~~~~~~~~~~~~~
µHe(l.60218xl0- 19 C) 4
2(8.85419xlo- 12 r 1c 2m- 1) 2 x(6.62607xl0-34 Js) 3x(2.99792xl0 10 cm s-1)
x(__!__-~)
n~ n
The reduced masses for the 4He and 3He nuclei are
memnuc
µ=-~~
me +mnuc
where mnuc = 4.00260u for 4He and 3.0)603 u for 3He, or, in kg
4He mnuc = (4.00260u)x(l.66054xl0-27 kg u- 1) = 6.64648xl0-27 kg
3He mnuc = (3.01603u)x(l.66054xl0-27 kg u- 1) = 5.00824xl0-27 kg
The reduced masses are

31 27
4He = (9.l0939xl0- kg)x(6.64648xl0- kg) = . x -31k
9 10814 10
µ (9.l0939xl0- 31 +6.64648xl0-27 )kg g
31 27
3He = (9.10939xl0- kg)x(5.00824x10- kg) = .l x -31k
9 0773 10
µ (9.10939xl0-31 +5.00824xl0-27 )kg g
Finally, the wavenumbers for n = 3 ~ n = 2 are
4He v = (4.81870xl035 )x(9.l0814xl0-31 )x(l/4-l/9)cm- 1 =160957.4cm- 1I

3He v = (4.81870xl035 )x(9.10773xl0-31 )x(l/4-l/9)cm-1 = l60954.7cm- 1I
The wavenumbers for n = 2 ~ n = l are
4He v = (4.81870xl035 )x(9.10814xl0-31 )x(l/1-1I4)cm-1 = 1329170cm- 1I

3He v = (4.81870xl035 )x(9.10773xl0-31 )x(l /1-1/ 4)cm- 1 = 1329155cm-1I
P4.29 (a) Compute the ratios v,""lv for all three lines. We are given wavelength data, so we can use
The ratios are
438 392 440 510 44

· run = 0.998884, · run = 0.998889, and 1.5 l O nm = 0.998846
438.882 nm 441.000 nm 442.020 nm
The fre uencies of the stellar lines are all less than those of the stationary lines, so we infer that the
star is receding from earth. The Doppler effect follows:
12
l-s/c) '
vrcceding = vf where f = ( - - ' so
l+s/c
2 ' 2 1- /2
f (l+s/c) =(l-s/c), (f-+l)s/c=l-f, s = -- 2 c
l+ f
Our average value off is 0.998873. (Note: The uncertainty is actually greater than the significant
figures here imply, and a more careful analysis would treat uncertainty explicitly.) So the speed of
recession with respect to the earth is
997747
s=(l-0. )c=l1.128x10-3 cl= l3.38lxl0 5 ms- 1 1
l+0.997747
(b) One could compute the star's radial velocity with respect to the sun if one knew the earth's
speed with respect to the sun along the sun-star vector at the time of the spectral observation.
This could be estimated from quantities available through astronomical observation: the
earth's orbital velocity times the cosine of the angle between that velocity vector and the
earth-star vector at the time of the spectral observation. (The earth-star direction, which is
observable by earth-based astronomers, is practically identical to the sun-star direction,
which is technically the direction needed.) Alternatively, repeat the experiment half a year
later. At that time, the earth's motion with respect to the sun is approximately equal in
magnitude and opposite in direction compared to the original experiment. Averaging/values
over the two experiments would yield f values in which the earth's motion is effectively
averaged out.
P4.31 Electronic configurations of neutral, 4th-period transition atoms in the ground state are summarized
in the following table along with observed positive oxidation states. The most common positive
oxidation states are indicated with white boxing.
Grou 3 4 5 6 7 8 9 10 11 12
Oxidation Sc Ti v Cr Mn Fe Co Ni Cu Zn
State
0 3d 4s- 3d 4s 3d 4s 3d 4s 3d 1 4s
+l Q Q Q Q Q
+2 Q Q Q Q Q
+3 Q Q Q
+4 Q Q Q
+5 G
+6
+7
Toward the middle of the first transition series (Cr, Mn, and Fe), elements exhibit the widest
ranges of oxidation states. This phenomenon is related to the availability of both electrons and
orbitals favorable for bonding. Elements to the left (Sc and Ti) of the series have few electrons,
and a relatively low effective nuclear charge leaves d orbitals at high energies that are
relatively unsuitable for bonding. To the far right (Cu and Zn), effective nuclear charge may be
higher but there are few, if any, orbitals available for bonding. Consequently, it is more
difficult to produce a range of compounds that promote a wide range of oxidation states for
elements at either end of the series. At the middle and right of the series, the +2 oxidation state
is very commonly observed because normal reactions can provide the requisite ionization
energies for the removal of 4s electrons. The readily available +2 and +3 oxidation states of
Mn, Fe, and the +1 and +2 oxidation states of Cu make these cations useful in electron transfer
processes occurring in chains of specialized proteins within biological cells. The special size
and charge of the Zn 2 + cation makes it useful for the function of some enzymes. The tendency
of Fe 2 + and Cu+ to bind oxygen proves very useful in hemoglobin and electron transport
(respiratory) chain, respectively.
5 The chemical bond
05.1 Our comparison of the two theories will focus on the manner of construction of the trial
wavefunctions for the hydrogen molecule in the simplest versions of both theories. In the valence
bond method, the trial function is a linear combination of two simple product wavefunctions, in
which one electron resides totally in an atomic orbital on atom A and the other totally in an orbital
on atom B. See eqns. 5.1 and 5.2, as well as Fig. 5.2 in the main text. There is no contribution to the
wavefunction from products in which both electrons reside on either atom A or B. So the valence
bond approach undervalues any ionic contribution to the trial function by totally neglecting it. It is a
totally covalent function. The molecular orbital function for the hydrogen molecule is a product of
two functions of the form of eqn. 5.7, one for each electron:
l/f = [A(l) ± B(l)][A(2) ± B(2)] = A(l)A(2) + B(l)B(2) + A(l)B(2) + B(l)A(2)
This function gives as much weight to the ionic forms as to the covalent forms. So the molecular
orbital approach greatly overvalues the ionic contributions. At these crude levels of approximation,
the valence bond method gives dissociation energies closer to the experimental values. However,
the molecular orbital approach, albeit in more sophisticated versions, is the method of choice for
obtaining quantitative results on both diatomic and polyatomic molecules. See Sections 5.6--5.9.
05.3 The ion has 24 valence electrons as shown in the Lewis structure. The hybridizations are (from left
to right) sp 2 for the first 0 atom and for the N and sp 3 for the next two 0 atoms. The first bond is a
double bond whose cr component arises from the overlap of sp2 orbitals and whose 7r: component
comes from overlap of unhybridized p orbitals. The next bond is a cr bond involving Nsp 2 and Osp 3
orbitals. The 0-0 bond is a cr bond involving sp3 orbitals.
..·~l~
·t !~ .
..
05.5 Both the Pauling and Mulliken methods for measuring the attracting power of atoms for electrons
seem to make good chemical sense. If we look at eqn. 5.22 (the Pauling scale), we see that if
D(A-B) were equal to 1/ 2 [D(A-A) + D(B-B)], the calculated electronegativity difference would be
zero, as expected for completely non-polar bonds. Hence, any increased strength of the A-B bond
over the average of the A-A and B-B bonds can reasonably be thought of as being due to the
polarity of the A-B bond, which in turn is due to the difference in electronegativity of the atoms
involved. Therefore, this difference in bond strengths can be used as a measure of electronegativity
difference. To obtain numerical values for individual atoms, a reference state (atom) for
electronegativity must be established. The value for fluorine is arbitrarily set at 4.0.
The Mulliken scale may be more intuitive than the Pauling scale because we are used to thinking of
ionization energies and electron affinities as measures of the electron attracting powers of atoms.
The choice of factor 1/ 2, however, is arbitrary, though reasonable, but no more arbitrary than the
specific form of eqn. 5.22 that defines the Pauling scale.
THE CHEMICAL BOND 103
05. 7 The Hiickel method parameterizes rather than calculates the energy integrals that arise in molecular
orbital theory. In the simplest version of the method, the overlap integral is also parameterized. The
energy integrals, aand /3, are always considered to be adjustable parameters; their numerical values
emerge only at the end of the calculation by comparison to experimental energies. The simple form
of the method has three other rather drastic approximations, listed in Section 5.6 of the text, which
eliminate many terms from the secular determinant and make it easier to solve. Ease of solution was
important in the early days of quantum chemistry before the advent of computers. Without the use
of these approximations, calculations on polyatomic molecules would have been difficult to
accomplish.
The simple Hiickel method is usually applied only to the calculation of n-electron energies in
conjugated organic systems. It is based on the assumption of the separability of the a:- and n-
electron systems in the molecule. This is a very crude approximation and works best when the
energy level pattern is determined largely by the symmetry of the molecule. (See Chapter 7.)
05.9 See Impact 15.1 for a more detailed discussion. The ground electronic configurations of the valence
electrons are found in Figs. 5.29, 5.31, and 5.34 of the text.
b=3 2S+ 1=0
b=2 2S+ 1=3
NO 2S+l=2
The following figures show HOMOs of each configuration. Shaded versus unshaded atomic-orbital
(AO) lobes represent opposite signs of the wave funcstions. A relatively large AO represents the
major contribution to the MO.
02 llrg MO, doubly degenerate
NO 2n
Dinitrogen with a bond order of three and paired electrons in relatively low-energy MOs is very
unreactive. Special biological or industrial processes are needed to channel energy for promotion of
2crelectrons into high-energy, reactive states. The high-energy lffg LUMO is not expected to form
stable complexes with electron donors.
Molecular nitrogen is very stable in most biological organisms, and as a result the task of
converting plentiful atmospheric N2 to the fixed forms of nitrogen that can be incorporated into
proteins is a difficult one. The fact that N2 possesses no unpaired electrons is itself an obstacle to
facile reactivity, and the great strength (large dissociation energy) of the N2 bond is another
obstacle. Molecular orbital theory explains both these obstacles by assigning N2 a configuration that
gives rise to a high bond order (triple bond) with all electrons paired. (See Fig. 5 .31 of the text.)
Dioxygen is kinetically stable because of a bond order equal to two and a high effective nuclear
charge that causes the MOs to have relatively low energy. But two electrons are in the high-energy
11tg HOMO level, which is doubly degenerate. These two electrons are unpaired and can contribute
104 STUDENT SOLUTIONS MANUAL FOR QUANTA. MATIER, AND CHANGE
to bonding of dioxygen with other species such as the atomic radicals Fe(II) of hemoglobin and
Cu(II) of the electron transport chain. When sufficient though not excessively large energy is
available, biological processes can channel an electron into this HOMO to produce the reactive
superoxide anion of bond order 11/ 2. As a result, 0 2 is very reactive in biological systems in ways
that promote function (such as respiration) and in ways that disrupt it (damaging cells).
Although the bond order of nitric oxide is 2 1/ 2, the nitrogen nucleus has a smaller effective nuclear
change than an oxygen atom would have. Thus, compared to the HOMO of dioxygen, the one
electron of the 27r HOMO is a high-energy, reactive radical. Additionally, the HOMO, being anti-
bonding and predominantly centered on the nitrogen atom, is expected to bond through the nitrogen.
Oxidation can result from the loss of the radical electron to form the nitrosyl ion, NO+, which has a
bond order equal to 2. Even though it has a rather high bond order, NO is readily converted to the
damagingly reactive peroxynitrite ion (ONOO-) by reaction with 0 2-- without breaking the NO
linkage.
ES.1 (a) The valence bond description of P2 is similar to that of N2, a triple bond. The three bonds are a <J
from the overlap of sp hybrid orbitals and two n: bonds from the overlap of unhybridized 3p
orbitals.
In the tetrahedral P4 molecule there are six single P-P bonds of roughly 200 kJ mor 1 bond enthalpy
each. So the total bonding enthalpy is roughly 1200 kJ mor 1• In the transformation
P4 ~ 2P2
there is a loss of about 800 kJ mor 1 in a-bond enthalpy. This loss is not likely to be made up by the
formation of 4 P-P 7r bonds. Period 3 atoms, such as P, are too large to get close enough to each
other to form strong 7r bonds.
E5.2(a) All of the carbon atoms are sp 2 hybridized. The C-H <J bonds are formed by the overlap of Csp2
orbitals with Hls orbitals. The C-C a bonds are formed by the overlap of Csp 2 orbitals. The C-C 7r
bonds are formed by the overlap of C2p orbitals. This description predicts double bonds between
carbon atoms 1 and 2 and 3 and 4 but (unlike a simple molecular-orbital description of the bonding)
no double-bond character between carbon atoms 2 and 3.
E5.3(a)
We need to evaluate
fh1h2 d-r = J<s + Px +Py + P,)(s-px -py + PJ d-r

We assume that the atomic orbitals are normalized atomic orbitals that are mutually orthogonal. We
expand the integrand, noting that all cross terms integrate to zero. The remaining terms integrate to
one, yielding
E5.4(a) Normalization requires
f If/ * lf/d -r = 1
where Jf/ = Nh = N {s +2 112p). Solve for the nonnaJizarion constant N:
f 2 112
1 = N 2 (s + 2 112 p) * (s + 2" 2 p)dr = N 2 f(Is1 +2 p *s+ i1' s * p+ 21pl )dr=3N
2 2 2
In the last step, we used the fact that the s and p orbitals are normalized to see that the squared terms
integrate to 1 and the fact that they are orthogonal to see that the cross terms integrate to 0. Thus
\N=3- 112
\ and 11f1=3-
112
(s+2 p)I
112
E5.5(a) Refer to Fig. 5.31 of the text. Place two of the valence electrons in each orbital starting with the
lowest-energy orbital, until all valence electrons are used up. Apply Hund's rule to the filling of
degenerate orbitals.
(a) Li 2 (2 electrons) )1o-/,b=1)
(b) Be2 (4 electrons) 2
)lo-/lO-u , b=tj
/lcr/lo-/1JZU , b = ~
4
(c) C 2 (8 electrons)
E5.6(a) Note that CO and CN- are isoelectronic with N2, so refer to Fig. 5.31 of the text for them; note,
however, that the cr and 1t orbitals no longer have u or g symmetry, so they are simply labeled
consecutively. For NO, refer to Fig. 5.34 of the text.
(a) CO (10 electrons) /lcr22dl7t4 3d, b = 3)

(b) NO (11 electrons) )1d2d3d1Jr42Jt, b = 2.5)
(c) c~ (10 electrons) 11d2d11r43d,b=31
E5.7(a) B2 (6 electrons): lcrg2lcru 211tu2 b=l

C2 (8 electrons): 2 2 4
lcrg lcru 17tu b=2
The bond orders of B 2 and C2 are, respectively, 1 and 2, so g
should have the greater bond
dissociation enthalpy. The experimentaJ values are approximately 4eV and 6eV, respectively.
E5.8(a) Decide whether the added electron increases or decreases the bond order. The simplest procedure is
to decide whether the added electron would occupy a bonding or antibonding orbital. We can draw
up the following table, which denotes the relevant orbital. An asterisk (*) in the table denotes an
orbital whose character is primarily antibonding.
N2 NO 02 C2 F2 CN
AB- l 7tg * 2n* l7tg * 2cr8 2cr0 * 3cr
Change in bond order -112 -112 - 112 +1/2 -112 +1/2
Therefore, Ic2 and CN I would be stabilized (have lower energy) by anion formation.
E5.9(a) We can use a version of Fig. 5.29 of the text in which the energy levels of Fare lower than those of
Xe, as in Figure 5 .1.
For XeF we insert 15 valence electrons. The bond order is increased when XeF is formed from
XeF because an electron is removed from an antibonding orbital. Therefore, we predict that XeF
has a shorter bond length than XeF. ·
E5.1 O(a) Form the electron configurations and find the bond order:
NO- (12 electrons) b=2
0/ (11 electrons) b =2.5
Xe XeF F
SP
2.i
Figure 5.1
Based on the electron configurations, we would expect IQJ
to have the stronger and therefore the
shorter bond. Keep in mind, though, that we are comparing molecules with different-albeit not
terribly different-nuclei.
ES.11 (a) ot (11 electrons) 1CJg2 1CJu22CJg21Jl;i41 .?rg I
0 2 (12 electrons) 1CJg2 1CJu22CJg21ll;i41 ni/

0 2- (13 electrons) 1CJ/ 1CJu22CJg21ll;i411rg3
o/- (14 electrons) 1 CJ/ l CJu 22 CJg21ll;i41.?rg4
In each case, the HOMO is an antibonding ~orbital.
E5.12(a) Refer to eqn. 2.24, which defines the harmonic oscillator wavefunctions. The parity of the
wavefunction is the parity of the Hermite polynomial portion; those polynomials are given in
Table 2.1. Examine the inversion through the center of these functions, i.e. , replace x with -x. For
the first four levels,
v = 0, l/f ~ If/, so jg]

v = 1, l/f ~ - If/, so g
v = 2, l/f ~ If/, so jg]
v=3, l/f~-lf/,SOg
If v is even, lf/v is jg]. If v is odd, l/fv is g.
E5.1 3(a) fl/f 2
d !" = N
2
f(l/fA+ Al/fs)2 d!" = N f(l/f~ + A 2 1/f~ + 2-11/fAl/f
2
8) d!" = 1
2 2
= N (1+-1 +2AS) [fl/fAl/f8 d!"=S]
l )112
Hence N- ( 2
- 1+2AS+A-
E5.14(a) Let lfli = N(0.145A + 0.844B) and l/h. = aA + bB.

First, let us normalize 1f1i:
f l/f1 * l/f1d!" = 1 = N
2
f
(0.145A + 0.844B) * (0.145A + 0.844B)d!"
2
0.0210 f1Al d!"+0.712 f1s1 d!"+0.122
2
fs* Ad!"+0.122 f A* Bd!"= ~2
The first two integrals are 1 due to normalization and the latter two are the overlap integral, S =
0.250. So
1
0.210 + 0.712 + 2 x 0.122 x 0.250 = - = 0.795
N2
so W= u~ which makes j\f/, =0.163A+0.947Bj .
Orthogonality of the two molecular orbitals requires
f\f/ *\f/ dr=0 = N f(0.145A +0.844B)*(aA+ bB)dr

1 2
Dividing by N yields
0.145a fl A 1 ctr+ 0.844b f l B 1dr+ 0.844a J B * Adr+ 0.145b J A* Bdr= 0 ,

2 2
0.145a + 0.844b + 0.844a x 0.250 + 0.145b x 0.250 = 0 = 0.356a + 0.880b

Normalization of \f/2 requires
J\f/2 *\f/2 dr=1 = J(aA+bB)*(aA+bB)dr,
2 2 2 2
J
a JI A 1 d r + b J I B 1 d r + ab B * Ad r +ab J A* Bd r = 1
So a 2 + b2 + 2ab x 0.250 = 1 = a 2 + b2 + 0.500ab.

We have two equations in the two unknown coefficients a and b. Solve the first equation for a in
terms of b:
a= -0.880b/0.356 = -2.47 b s
Substitute this result into the second (quadratic) equation:
1 = (-2.47b)2 + b2 + 0.500(-2.47b)b = 5.88b2
So jb=0.412j, ~=-l.02j , and j\f/2 =-l.02A+0.412Bj .
E5.15(a) Energy is conserved, so when the photon is absorbed, its energy is transferred to the electron. Part
of it overcomes the binding energy (ionization energy) and the remainder is manifest as the now
freed electron's kinetic energy.
£photon= f +£kinetic
34 8 1
so E . =E -f=hc_ 1 =(6.626 x l0- Js) x (2.998 x l0 ms- ) 12 _0eV
kmeuc photon A. (lOO x lo-9 m) x (l.602 x 10-t9 J eV-1 )
= 0.40 eV = 6.4x10-20 J
The speed is obtained from the kinetic energy:
2
mv
E kme11c
.. =2- so
E5.16(a) Draw up the following table using data from Table 5.4.
Element Li Be B c N 0 F Ne
XM 1.28 1.99 1.83 2.67 3.08 3.22 4.43 4.60
112
(XM) 1.13 1.41 1.35 1.63 1.75 1.79 2.10 2.14
XP (from table) 0.98 1.57 2.04 2.55 3.04 3.44 3.98
XP (from formula) 0.16 0.53 0.46 0.84 1.00 1.05 1.47 1.53
A plot of the Pauling electronegativities (actual and from the formula) versus the square root of the
Mulliken electronegativities shows that the formula does a poor job (see Figure 5.2). The formula
consistently underestimates the Pauling electronegativity, and it underestimates the rise in
electronegativity across the period.
Electronegativit)': Period 2
4.50
4.00
•
J.50
•
3.00
2.50 • actual
• conversion
2.00 • - l..inear(actua1)
1.5-0 • ••
• ••
1.00
0.50
0.00 •
1.00 1.20 1.40 1.60 1.80 ::!.Do 2.20 2.40
(Mulliken scale) 112 Figure 5.2
E5.17(a) The molecular orbitals of the fragments and the molecular orbitals they form are shown in Figure 5.3.
Figure 5.3
COMMENT. Note that the rt-bonding orbital must be lower in energy than the a-antibonding orbital for n-
bonding to exist in ethene.
Question. Would the ethene molecule exist if the order of the energies of the 7t and a* orbitals were
reversed?
E5.18(a) In setting up the secular determinant we use the Htickel approximations outlined in Section 5.6.
a-E /3 0 a-E /3 /3
(a) fJ a-E fJ =0 (b) /3 a- E /3 = 0
0 /3 a-E /3 /3 a-E
The atomic orbital basis is lsA, ls 8 , l sc in each case; in linear H 3 we ignore A, C overlap because A
and C are not neighboring atoms; in triangular H3 we include it because they are neighboring atoms.
E5.19(a) We use the molecular orbital energy level diagram in Fig. 5.38 of the text. As usual, we fill the orbitals
starting with the lowest-energy orbital, obeying the Pauli principle and Hund's rule. We then write
E" = 2(a+ 2/3) + 4(a+ /3J +(a- /3) = l7a+ 7Pl
(b) C6H/ (5 electrons) : la 2u e 1g

2 3
I
E"=2(a+2/3)+3(a+/3)= 15a+7/3I
E5.20(a) The n-bond formation energy is the difference between the n-electron binding energy and the
Coulomb energies a:
The delocalization energy is the difference between Err and the energy of isolated n bonds:
Ecte1oca1 = Err - N( a+ /JJ

(a) Err=7a+7/3 [ES .19(a)]
so Ebf=7a+7/3-7a= /7/3/
and Ede1oca1 = 7 a+ 7 /3- 7(a+ /JJ = ~
COMMENT. With an odd number of ff electrons, we do not have a whole number of ff bonds in the
formula for delocalization energy. In effect, we compare the 7t-electron binding energy to the energy of
3.5 isolated 7t bonds-whatever that means. The result is that the benzene anion has none of the
"extra" stabilization we associate with aromaticity.
(b) Err =Sa+7/3 [ES.19(a)]

so Ebf =Sa+ 7 /3- Sa= /7 /3/
and E delocal =Sa+ 7/3- S(a+ /JJ = /2/3/
ES.21 (a) The structures are numbered to match the row and column numbers shown in the determinants:
2 4 6
1~7
1~8
13 11 9
anthracene phenanthrene
(a) The secular determinant of anthracene in the Hiickel approximation is
2 3 4 5 6 7 8 9 10 11 12 13 14
a-E fJ 0 0 0 0 0 0 0 0 0 0 0 fJ
2 fJ a-E fJ 0 0 0 0 0 0 0 0 0 0 0
3 0 fJ a-E fJ 0 0 0 0 0 0 0 fJ 0 0
4 0 0 fJ a-E fJ 0 0 0 0 0 0 0 0 0
5 0 0 0 fJ a-E fJ 0 0 0 fJ 0 0 0 0
6 0 0 0 0 fJ a-E fJ 0 0 0 0 0 0 0
7 0 0 0 0 0 fJ a-E fJ 0 0 0 0 0 0
8 0 0 0 0 0 0 fJ a-E fJ 0 0 0 0 0
9 0 0 0 0 0 0 0 fJ a-E fJ 0 0 0 0
10 0 0 0 0 fJ 0 0 0 fJ a-E fJ 0 0 0
11 0 0 0 0 0 0 0 0 0 fJ a-E fJ 0 0
12 0 0 fJ 0 0 0 0 0 0 0 fJ a-E fJ 0
13 0 0 0 0 0 0 0 0 0 0 0 fJ a-E fJ
14 fJ 0 0 0 0 0 0 0 0 0 0 0 fJ a-E
(b) The secular determinant of phenanthrene in the Htickel approximation is

2 3 4 5 6 7 8 9 10 11 12 13 14
a-E /3 0 0 0 0 0 0 0 0 0 0 0 /3
2 /3 a-E /3 0 0 0 0 0 0 0 0 0 0 0
3 0 /3 a-E /3 0 0 0 0 0 0 0 /3 0 0
4 0 0 /3 a-E /3 0 0 0 0 0 0 0 0 0
5 0 0 0 /3 a-E /3 0 0 0 0 0 0 0 0
6 0 0 0 0 /3 a-E /3 0 0 0 /3 0 0 0
7 0 0 0 0 0 /3 a - E /3 0 0 0 0 0 0
8 0 0 0 0 0 0 /3 a-E /3 0 0 0 0 0
9 0 0 0 0 0 0 0 /3 a-E /3 0 0 0 0
10 0 0 0 0 0 0 0 0 /3 a-E /3 0 0 0
11 0 0 0 0 0 /3 0 0 0 /3 a-E /3 0 0
12 0 0 /3 0 0 0 0 0 0 0 /3 a-E /3 0
13 0 0 0 0 0 0 0 0 0 0 0 /3 a-E /3
14 /3 0 0 0 0 0 0 0 0 0 0 0 /3 a-E
E5.22(a) The secular determinants from E5.2l(a) can be diagonalized with the assistance of general-purpose
mathematical software. Alternatively, programs specifically designed for Htickel calculations (such as
the Simple Huckel Molecular Orbital Theory Calculator at the University of Calgary,
http://www.chem.ucalgary.ca/SHMO/ or Htickel software in Explorations of Physical Chemistry, 2nd
Ed., by Julio de Paula, Valerie Walters, and Peter Atkins, http://ebooks.bfwpub.com/explorations.php)
can be used. In both molecules, 14 7t electrons fill seven orbitals.
(a) In anthracene, the energies of the filled orbitals are a+ 2.41421/j, a+ 2/j, a+ 1.41421/j
(doubly degenerate), a+ P (doubly degenerate), and a+ 0.41421/j, so the total Jr-electron
binding energy is l14a+ 19.31368§1.
(b) For phenanthrene, the energies of the filled orbitals are a+ 2.43476/j, a+ 1.95063/j, a+
1.51627 p, a + 1.30580/j, a+ 1.14238/j, a + 0.76905/j, and a + 0.60523/j, so the total Jr-
electron binding energy is l14a+ 19.44824§1.
P5.1 The energy ofrepulsion is given by Coulomb' s law:
E =_ e_2 - = (1.602 x 10-19 C)2 = 3.11x10-1s J

41rc0 R 47rX 8.854x10- 12 r' C2 m- 1x74.l x 10- 12 m
The repulsion energy of a mole of H2 is

E molar =NAE= 6.022 x 1023 mo1- 1 x 3.11 x 10- 18 J =II.87 x 106 J mor 1 = 1.87 MJ mor'I
The gravitational energy is
2 27 2
E = -Grr1im2 = -6.673xl0- 11 m 3 kg-' s- x(l.672x10- kgt = _ . x _54
2 52 10 1
grav R 74.lxl0- 12 m
The gravitational energy is many, many orders of magnitude smaller than the energy of electrostatic
repulsion. This is an illustration of the fact that gravitational effects tend to be negligible on the atomic scale.
THE CHEMICAL BO u lll
PS.3 Draw up the following table.
RI a0 0 2 3 4 5 6 7 8 9 10
s 1.000 0.858 0.586 0.349 0.189 0.097 0.047 0.022 0.010 0.005 0.002
The points are plotted in Figure 5.4. At large separations, the curve is dominated by exponential
decay. At small separations, however, the polynomial factor makes the decay less pronounced than
exponential.
1.0
\
s
0.8 '\
~S(ls, Is)
0.6
.' )
0.4 \
0.2 \
~
...... ._
()
0 2 6 8 10
R!a0 Figure 5.4
PS.5 We require the properly normalized function s

1/ 2
1
If/± = (A± B) [5.7 and Example 5.1)
(
2(1±S) )
We first calculate the overlap integral at R = 106 pm= 2a0 . (The expression for the overlap integral,
S, is given in problem 5.3 .)
2 2
S= (1+2+j(2) )e- =0.586
= (2c1~s)r = (2(1+~. 586)r = 0·561

2 2
Then
N+
112 112
N =( l ) =( l ) = 1.099
- 2(1- S) 2(1-0.586)
11 2 112
We then calculate with A= (~) e-'A 1 °<> ,If/± = N±(~)

Jra 0 Jra 0
{e-'A1a0 ± e-'•100 }, with rA and rB both
measured from nucleus A, that is,
with z measured from A along the axis toward B. We draw up the following table with R = 106 pm
and a0 = 52.9 pm.
z/pm -100 -80 - 60 -40 - 20 0 20 40 60 80 100 120 140 160 180 200
(-1r
I//+
.1l'a~
0.096 0.14 0.20 0.30 0.44 0.64 0.49 0.42 0.42 0.47 0.59 0.49 0.33 0.23 0.16 0.11
(-1r
If/_
0.14 0.21 0.31 0.45 0.65 0.95 0.54 0.20 -0.11 -0.43 -0.81 -0.73 -0.50 -0.23 -0.23 -0.16
.1l'a~
The points are plotted in Figure 5.5.
1.2
0.8
0.4
-IN
~.
~ 0 ........,_..___.._.__..___._..........._..___.._.._....____..........._..,._.......,.______...........__._......_.._..___.__._______...........~
.......
~
- 0.4
-0.8
- 1.2 ~-----------....___----------~
-100 0 100 200
v' pm Figure 5.5
R/2 R/2
P5.7
A z=O B
• • • • z
(a) With spatial dimensions in units (multiples) of a0 , the atomic orbitals of atom A and atom B
may be written in the form
= ( +R / 2)e-[x2 +/+(z+R / 2) 2 ] 112 / 2
Pz,A 4(2Jr)li2 z
= ( -R / 2)e-[x2 +/+(z-R / 2) 2 ] 112 / 2
Pz,B 4(2Jr)li2 z
Following eqn. 5.7 and Example 5.1, we form LCAO-MOs of the form
l//a• = P,A '112 [anti'b on d'mg ]

' +P,e and 11r = Pz,A - P,,e [bonding]
{2(1 + S)} r" {2(1- S)} 1' 2
where S= JJJP,,A Pz,e dx dy dz [5.17).
Computations and plots are readily prepared with mathematical software such as Mathcad (see
Figure 5.6).
Probability densities along internuclear axis (x= y =0) with R =3.

(all distances in units of a0 )
0.02 ......--- - -, . - - - - - - . - - - - - - - , - - - - --...,
0.015
2
11/11 0.DI
0.005
OL-~=.:.:.c.__ _L__ ....

_ _.~c._-""-J...-<'---'-'~"·-"·_·--'----"="'---.J
-IO -5 0 IO
Figure 5.6
(b) With spatial dimensions in units of a0 , the atomic orbitals for the construction of 7t molecular
orbitals are
_ -[ x' +/ +(z+R / 2)'] 1 2 / 2
Px,A - 4(2Jr)lt2 xe
_ 2
e - [x +/+(z- R/ 2)'l
112
/2
Px, B - 4(2Jr)112 X
See Figures 5.7 and 5.8.
R=3
Amplitude of Sigma Anti bonding MO in xz Probability Density of Sigma Anti bonding MO
Amplitude of Sigma Bonding MO inxz Probability Density of Sigma Bonding MO
Amplitude of Sigma Antibonding MO in xz Amplitude of Sigma Bonding MO inxz
Figure 5.7
R=3
2p Pi Bonding Amplitude Surface 2p Pi Bonding Probability Density Surface
2p Pi Antibonding Amplitude Surface 2p Pi Antibonding Probability Density Surface
2p Pi Bonding 2p Pi Antibonding
Figure 5.8
The n MOs are
Px,A +Px,B [b d" J and lj/". =

P x,A -P x,B [
anti"b ond"mg J
If/"= {2(l+S)}u2 on mg {2(1-S)} 112
where S= fff P x,APx,B d.x dy dz.

The plots clearly show the constructive interference that makes a bonding molecular orbital. Nodal
planes created by destructive interference are clearly seen in the antibonding molecular orbitals.
When calculations and plots are produced for the R = 10 case, constructive and destructive
interference is seen to be much weaker because of the weak atomic orbital overlap.
P5.9 EH = E, =-he~ [Section 4.2(a)]

Draw up the following table using the data in the question and using
e2 1 a
so that - - x - = _Q_
4JCE0 R Eh R
R I a0 0 2 3 4 00
--x-
e2 1
00 0.500 0.333 0.250 0
4!lE0 R Eh
(Vi + V2) I Eh 2.000 1.465 0.843 0.529 0.342 0

(E-Ett) I Eh 00 0.212 --0.031 --0.059 --0.038 0
0.5
0.4
0.3
~:i:
r...i
I
0.2
!:::!,
0.1
5
0
-0.l Figure 5.9
The minimum occurs at R = 2.5a0 , so R = 130 pm. At that bond length

E- EH = -0.07 Eh= -l.9leV
Hence, the dissociation energy is predicted to be about II.9 evl and the equilibrium bond length
about 1130 p~.
P5.11 (a) Start from eqn. 5.11 (whose derivation is covered in problem 5.23).
(if) = E H
- J + K + io
l+S R
where we define the Coulomb integral J and the resonance integral K as in eqn. 5.12 and use the
relationship of the normalization constant N to the overlap integral Sas defined in Example 5.1.
We must write the integrals S, J, and K explicitly to evaluate them. Use
e -rA f ao e - re lao
A=--- and B= 3 i12 [5.8]
(:rao3)"2 (:rao )
Define a coordinate system centered on nucleus A so that rA is a coordinate and

r8 = (rA2 + R2 - 2rAR cos B/ 12 [5.9]
The volume element is
di-= r/ sin BdrA dBd¢
Thus, the overlap integral is
Integration over d¢ yields a factor of 2n. Numerical integration over dB and drA can be done by
approximating the differentials by small but finite oBand &A and summing over a series of q and rA,;:
Similar treatment of the other integrals yields
To evaluate the integrals, express the distances in units of a0 . S is dimensionless. J and K have
dimensions of energy; they have units of Jo I a0 = Eh . (See problem 5.9 for Eh.) In the following
table and plots, the numerical values of the integrals were computed using q from 0 to tr in
increments that correspond to 10° and using rA,; from 0 to 5a0 in increments of 0.25a0 .
Rlao Sn um Jnum!Eh KnumfEh San J.n!Eh K./Eh
1.00 0.8524 0.7227 0.7220 0.8584 0.7293 0.7358

1.25 0.7875 0.6460 0.6287 0.7939 0.6522 0.6446
1.50 0.7183 0.5781 0.5408 0.7252 0.5837 0.5578
1.75 0.6480 0.5192 0.4606 0.6553 0.5240 0.4779
2.00 0.5789 0.4684 0.3890 0.5865 0.4725 0.4060
2.25 0.5125 0.4249 0.3262 0.5204 0.4284 0.3425
2.50 0.4501 0.3876 0.2718 0.4583 0.3906 0.2873
2.75 0.3924 0.3555 0.2253 0.4009 0.3581 0.2397
3.00 0.3397 0.3279 0.1858 0.3485 0.3300 0.1991
3.25 0.2922 0.3038 0.1525 0.3013 0.3057 0.1648
3.50 0.2498 0.2829 0.1245 0.2592 0.2845 0.1359
3.75 0.2122 0.2644 0.1012 0.2219 0.2660 0.1117
4.00 0.1791 0.2482 0.0817 0.1893 0.2496 0.0916
A plot of S versus R is shown in Figure 5.lO(a) and a plot of J and K versus R is shown in
Figure 5.lO(b). Note that the numerical results at this level of approximation agree well but not
identically with the analytical ones. The disagreement becomes more noticeable at larger R, which
is not surprising given that all sums were truncated at rA = 5a0 . The disagreement is more
pronounced in K than in Sor J. The numerical results can be made arbitrarily close to the analytical
by using smaller increments and extending the range of r A.
(a) Overlap integral
0.8
0.7
0.6
- numerical
"' 0.5
--+--analytical
0.4 +
0.3
0.2 +-
0. 1
0.5 1.5 2.5 3.5

Ria,
(b) Coulomb and resonance integrals
0.9
0.8
0.7
0.6
-+- numerical J
~ 0.5
---- analytical J
...,s -.- numerical K

[--++--analytical K
0.4
0.3
0.2
0.1
0.5 1.5 2.5 3.5

R/a 0 Figure 5.10
(b) Use eqn. 5.11 to compute the total energy, whether from numerical or analytical values of the
integrals. Results are shown in the table below and in Figure 5 .11.
Rlao Enum / Eh Ean I Eh

1.00 -0.280 -0.288
1.25 -0.413 -0.423
1.50 -0.485 -0.495
1.75 -0.523 -0.534
2.00 -0.543 -0.554
2.25 -0.552 -0.563
2.50 -0.555 -0.565
2.75 -0.554 -0.563
3.00 -0.550 -0.559
3.25 -0.545 -0.554
3.50 -0.540 -0.548
3.75 -0.535 -0.542
4.00 -0.530 -0.537
Total energy
0.25
-0.3
-0.35 \
I.;! -0.4
\
~
· 0.45 \ -+-numcri'';.ll
- :lnaly1ical
~
-0.5
-0.55
~ ~
-0.6
0 0.5 1.5 2.5 3.5 4
Rln 11 Figure 5.11
The minimum in both total energy curves lies at R = ~.5a0 = l.3x10- 10 l 1J . The minimum total
energy is Ernin = t0.555Eh = -15.1 eVJ (numerical) and HJ.565Eh = -15.4 eVJ (analytical). The bond
dissociation energy is
De= EH - Emin = (-0.500 + 0.555)Eh = ~.055Eh = 1.5 eVJ (numerical)

De= (-0.500 + 0.565)Eh = ~.065Eh = 1.8 eVJ (analytical)
COMMENT. Dissociation energies are typically (relatively) small differences between larger quantities
(electron-binding energies). Even small errors in the latter lead to relatively large errors in the former. In
this case, the numerical binding energy differed by about 2% from the analytical value; the difference in
o. was closer to 20%.
P5.13 In the simple Htickel approximation,
a 0 -E 0 0 fJ
0 a 0 -E 0 fJ =0
0 0 a 0 -E fJ
fJ fJ fJ a c -E
Therefore, the factors yield
E- ao = O (twice)
so
Because Coulomb integrals approximate ionization energies in magnitude, Q() is more negative than
Q(:. Therefore, E+ corresponds to the lowest-energy orbital and E_ to the highest-energy orbital; the
degenerate orbitals at E = Q() fall in between.
The 7t energies in the absence of resonance are derived for just one of the three structures, i.e., for a
structure containing a single localized 7t bond.
Expanding the determinant and solving for E gives

2
(E- QO) x (E- oC)-/3 = 0 =E -E(QO + oC)
2
+ aoac-/3 2
There are two 7t electrons in the system, so the delocalization energy is
If 12/3 2 << (QO - 0(:) 2 , we can use (1 + x) 112 "" 1 + x/2, so the delocalization energy is
PS.15 (a) The transitions occur for photons whose energies are equal to the difference in energy between
the highest occupied and lowest unoccupied orbital energies:
If N is the number of carbon atoms in these species, then the number of 7t electrons is also N. These
N electrons occupy the first N/2 orbitals, so orbital number N/2 is the HOMO and orbital number
1 + N/2 is the LUMO. Writing the photon energy in terms of the wavenumber, substituting the
given energy expressions with this identification of the HOMO and LUMO, gives
hcv =(a+ 2/Jcos G-N+ l)JrJ-(a+ 2/Jcos tNJrJ

N+l N+l
= 2 cos (tN+l)Jr -cos--

tNJrJ .
/J( N+l N+l
Solving for /Jyields
/J= hcv
2 ( cos (tN +l);r -cos -
tNn-J
-
N+l N+l
Draw up the following table.
Species N vI cm- 1
Estimated f3/eV
C2!Li 2 61500 -3.813
C4H6 4 46080 -4.623
C6Hs 6 39750 -5 .538
CsH1 0 8 32900 -5.873
(b) The total energy of the 1t electron system is the sum of the energies of occupied orbitals
weighted by the number of electrons that occupy them. In C8H 10 , each of the first four orbitals are
doubly occupied, so
4 4( k 4 k
)=8a+4/3f;cos
E" =2f;Ek =2f; a+2f3cos ; ; =8a+9.518/3
The delocalization energy is the difference between this quantity and that of four isolated double
bonds:
Edeloc = E, -8(a+ /3) = 8a+ 9.518/3-8(a+ /3) = 11.518/31
Using the estimate of /Jfrom part (a) yields Edeloc = 18.913 eV).
(c) Draw up the following table, in which the orbital energy decreases as we go down. For the
purpose of comparison, we express orbital energies as (Ek- a)l/3. Recall that /Jis negative (as is a
for that matter), so the orbital with the greatest value of (Ek- a)l/3 has the lowest energy.
Energy Coefficients
Orbital (Ek-ex)/~ 2 3 4 5 6
6 -1.8019 0.2319 -0.4179 0.5211 -0.5211 0.4179 -0.2319
5 -1.2470 0.4179 -0.5211 0.2319 0.2319 -0.5211 0.4179
4 -0.4450 0.5211 -0.2319 -0.4179 0.4179 0.2319 -0.5211
3 0.4450 0.5211 0.2319 -0.4179 -0.4179 0.2319 0.5211
2 1.2470 0.4179 0.5211 0.2319 -0.2319 -0.5211 -0.4179
1.8019 0.2319 0.4179 0.5211 0.5211 0.4179 0.2319
The orbitals are shown schematically in Figure 5.12, with each vertical pair of lobes
representing a p orbital on one of the carbons in hexatriene. Shaded lobes represent one sign of
the wavefunction (say, positive) and unshaded lobes the other sign. Where adjacent atoms have
atomic orbitals of the same sign, the resulting molecular orbital is bonding with respect to
those atoms; where adjacent atoms have a different sign, there is a node between the atoms and
the resulting molecular orbital is antibonding with respect to them. The lowest-energy orbital is
totally bonding (no nodes between atoms) and the highest-energy orbital is totally antibonding
(nodes between each adjacent pair). Note that the orbitals have increasing antibonding
character as their energy increases. The size of each atomic p orbital is proportional to the
magnitude of the coefficient of that orbital in the molecular orbital. So, for example, in orbitals
1 and 6, the largest lobes are in the center of the molecule, so electrons that occupy those
orbitals are more likely to be found near the center of the molecule than on the ends. In the
ground state of the molecule, there are two electrons in each of orbitals 1, 2, and 3, with the
result that the probability of finding a ;r electron in hexatriene is uniform over the entire
molecule.
Figure 5.12
PS.17 We use the Htickel approximation, neglecting overlap integrals.
The secular determinant of ethene is a-E f3 I

l
/3 a-E
Mathematical software (such as the Simple Ruckel Molecular Orbital Theory Calculator at
Canada's University of Calgary, http://www.chem.ucalgary.ca/SHMO/) diagonalizes the harniltonian
matrix to
and the matrix that achieves the diagonalization is
c = (0.707 0.707 J
0.707 -0.707
a-E /3 0 0
/3 a-E /3 0
The secular determinant of butadiene is
0 /3 a-E /3
0 0 /3 a-E
The hamiltonian matrix is diagonalized to
a+l.618,8 0 0
0 a+0.618,8 0
E=
O O a-0.618,8
[
0 0 0
l
[0372
0.602
0.602
0.372
0.602
0372
-0.372 -0.602
C=
0.602 -0.372 -0.372 0.602
0.372 -0.602 0.602 -0.372
a-E ,8 0 0 0 0
,8 a-E ,8 0 0 0
0 ,8 a-E ,8 0 0
The secular determinant of hexatriene is
0 0 ,8 a-E ,8 0
0 0 0 ,8 a-E ,8
0 0 0 0 ,8 a-E
a+l.802,8 0 0 0 0 0
0 a+l.247,8 0 0 0 0
0 0 a+0.445,8 0 0 0
E=
0 0 0 a-0.445,8 0 0
0 0 0 0 a-1.247,8 0
0 0 0 0 0 a-1.802,8

0.232 0.418 0.521 0.521 0.418 0.232
0.418 0.521 0.232 -0.232 -0.521 -0.418
0.521 0.232 -0.418 -0.418 0.232 0.521
C=
0.521 -0.232 -0.418 0.418 0.232 -0.521
0.418 -0.521 0.232 0.232 -0.521 0.418
0.232 -0.418 0.521 -0.521 0.418 -0.232
The secular determinant of octatetraene is
a-E ,8 0 0 0 0 0 0
,8 a-E ,8 0 0 0 0 0
0 ,8 a-E ,8 0 0 0 0
0 0 ,8 a-E ,8 0 0 0
0 0 0 ,8 a-E ,8 0 0
0 0 0 0 ,8 a-E ,8 0
0 0 0 0 0 ,8 a-E ,8
0 0 0 0 0 0 ,8 a-E
a+l.879fl 0 0 0 0 0 0 0
0 a+ 1.532fl 0 0 0 0 0 0
0 0 a+fl 0 0 0 0 0
0 0 0 a+0.347 fl 0 0 0 0
E=
0 0 0 0 a-0.347 fl 0 0 0
0 0 0 0 0 a-fl 0 0
0 0 0 0 0 0 a-1.532fl 0
0 0 0 0 0 0 0 a-l.879fl

0.161 0.303 0.408 0.464 0.464 0.408 0.303 0.161
0.303 0.464 0.408 0.161 -0.161 -0.408 -0.464 -0.303
0.408 0.408 0 -0.408 -0.408 0 0.408 0.408
0.464 0.161 -0.408 -0.303 0.303 0.408 -0.161 -0.464
C=
0.464 -0.161 -0.408 0.303 0.303 -0.408 -0.161 0.464
0.408 -0.408 0 0.408 -0.408 0 0.408 -0.408
0.303 -0.464 0.408 -0.161 -0.161 0.408 -0.464 0.303
0.161 -0.303 0.408 -0.464 0.464 -0.408 0.303 -0.161
The columns of the C matrices are coefficients of the atomic orbitals in each molecular orbital. The
first column represents the lowest-energy molecular orbital. In each molecule, all the coefficients
are positive, meaning that the lowest-energy MO has no nodes. Note also that the coefficients rise
from one end of the molecule to the middle and then decrease to the other end; thus the lowest-
energy MO extends over all the carbon atoms of the chain. Note that the number of sign changes
within a given column increases as one moves from the lowest-energy MO (leftmost column) to the
highest-energy (rightmost column). Each time the sign of a coefficient changes, there is a node in
the wavefunction. So, for example, the second column in octatetraene has four positive and four
negative coefficients but only one sign change and one node. The eighth column also has four
positive and four negative coefficients, but the sign changes between every atom; there are seven
nodes. The number of nodes increases with the energy of the MO.
P5.19 In butadiene, the HOMO is bonding with respect to the two bonds on the ends (the ones
conventionally depicted as double bonds) and antibonding with respect to the central bond (the one
conventionally depicted as a single bond). The situation is reversed in the LUMO. Thus, a
HOMO ~ LUMO transition weak.ens the terminal C=C bonds and strengthens the central C-C
bond. (See Figure 5.13a.)
LUMO
HOMO
Figure 5.13(a)
In benzene, the situation is more complicated because there are two degenerate LUMOs. (See
Figure 5.13b.) We will analyze these orbitals in terms of the top and bottom halves as shown in
the figure. The HOMO on the left is bonding between the two halves but antibonding within
each half; the HOMO on the right is completely bonding within each half but antibonding
between the halves. The LUMO on the left is also bonding between the halves but completely
antibonding within each half (more antibonding than the HOMO on the left); the LUMO on the
UAL FOR QUANTA, MATTER, AND CHANGE
right is antibonding between the halves and antibonding within each half as well. A transition
from the right-hand HOMO to the right-hand LUMO or left-hand HOMO to left-hand LUMO
would not affect the bonding between the halves, and it would destabilize the bonding within
each half. A transition from the left-hand HOMO to the right-hand LUMO would weaken the
bonding between the halves, leaving the bonding within each half unchanged. A transition
from the right-hand HOMO to the left-hand LUMO would strengthen the bonding between the
halves and destabilize the bonding between each atom within each half.
LUMO
0 0
HOMO
0 0 Figure 5.13(b)
PS.21 What does it mean to say that the antibonding orbital is more antibonding than the bonding orbital
is bonding? It means that the energy level of the antibonding orbital is farther above the energy
level of a free atom (i.e., a non-bonding atom) than the energy level of the bonding orbital is below
the same free-atom level. The free-atom energy level is simply the energy of the ground state of the
hydrogen atom, Ett. In symbols, then, we are asked to show that
which amounts to showing that
Eanti + Ebonct > 2EH
or, equivalently, that the average of the bonding and antibonding orbital energies is greater than the
energy in the free atom:
(Eanti + Ebond)/2 > EH
E +E =E +- e_2 _ _ ~-V2 +E + ~ -~+V2

anu bond H 41l:t:oR 1-S H 41l:t:oR l+S
= E + ~ - {(V 1 - V2 ) x (l+S)+(l-S)x(~ +V2)}

2
H 41l:t:0 R (1-S) x (l+S)
So
The nuclear repulsion term is always positive and always tends to raise the mean energy of the
orbitals above EH , although its effect decreases with increasing internuclear distance. Clearly
the overlap integral decreases with increasing R, and inspection of the analytical expressions
TI~E CHEMICAL 1.:.5
for V1 and V2 (J and K, respectively, in eqn. 5.12) shows that they also go to zero as R
increases. Thus the last term vanishes as R increases, but it is difficult to assess analytically
how it compares to the nuclear repulsion term. So we use numerical values given in problem
5.9, and we can add other points using the analytical expressions given in eqn. 5.12. Draw up
the following table.
Rlao 0.25 0.50 2 3 4 5 6
ez 1
--x- 4.000 2.000 0.500 0.333 0.250 0.200 0.167
4Tr£0 R Eh
sv2 - ~ 1
2
x- --0.188 --0.291 --0.370 --0.357 --0.297 --0.241 --0.198 -0.166
1- S Eh
{(Ebond + Eanti)/2 3.812 1.709 0.630 0.143 0.037 0.009 0.002 0.001
-EH}/Eh
The last term indeed is complicated, appearing to go to zero at both small and large R. At small R, it
appears to be negligible compared to the nuclear repulsion term. At large R, its absolute value
appears to follow closely that of the nuclear repulsion term but to remain smaller. Thus, the
antibonding orbital a ears to be more antibonding than the bonding orbital is bonding at !all valuesl
f the internuclear distanc . (See Figure 5.14.)
Net energy difference

4
3.5
3 ~
~
.: 2.5 +-
I
~
2
~
l
.
+ 1.5
"'c
~ I
0.5 +-
0
0 2 4 5 6
Rla 0 Figure 5.14
PS.23 The hamiltonian is
where we have introduced the abbreviationj0 for the collection of constants e2 I 41ZCQ. Its expectation
value is
1
where 1//± = N±CA ± B) [5.7] and N = [Example 5.1]
± {2(1 + S)} i12
Thus, ;\H-)= f1//± *{ - -2mn V -

2
2
Jo• ( -1+ -
rA r 8
1 --
1 )} l/f±dr
R
Pull out the nuclear repulsion term:
Expand the remaining integral into four integrals, letting fl 8 represent the hamiltonian operator of
a hydrogen atom. Note that
and
So (fl)=N/ fA( flH -:: ) Adr±N/ fA( flH -:: ) sdr
±N/ fs(flH -:: ) Adi-+ N/ Js(flH -:: )sar+ ~
and (fl)= N/ fA(EH - ~: )Adr±N/ fA( EH-:: )sdr
±N/ fs(EH-:: ) Adi-+ N/ fs( EH-:: )sar+ ~

Pull out the terms involving EH:
What multiplies EH
is the normalization integral, which equals 1. Now examine the
remaining four integrals. The first and fourth integrals are equal to each other, as are the
second and third. (This can be demonstrated by interchanging the labels A and B, which are
arbitrary.) Thus
=E -2N 2 (J±K)+ io = E _ J±K + } 0

H ± R H l±S R
This works out to eqns. 5.11and5.14:
and
P5.25 (a) Expanding the determinant yields

This is a quadratic equation in E where a= 1, b = - (a A + a 8), and c = a Aas - /3 2• The solution is

2 2
E = -b±.Jb -4ac = a A +a8 +(a/ +2aAa a +a8 -4aAaa +4/J
2
Y'
2
± 2a 2 - 2
= a A +aB [(a -a ) 2 +4/J 2 ] 1' 2

+-~A-~B _ _ __
2 - 2
(b) By hypothesis, (a A - a 8 ) 2 >> /3 2, so the term in parentheses can be expanded:
··}
and E ""' a A + a a a A - aa
- 2 2
Thus, the energies of these molecular orbitals differ only slightly from the energies of the
component atomic orbitals.
P5.27 The secular determinant for an N-carbon linear polyene (call the determinant PN) has the form
1 2 3 N -1 N
x 1 0 0 0 0 0
1 x 0 0 0 0
0 x 1 0 0 0
0 0 x 1 0 0 =PN
0 0 0 0 0 x
0 0 0 0 0 x
a-E
where x = p .The determinant can be expanded by cofactors; use the elements of the first row:
In this notation, M 1n is the element in the first row, nth column of the determinant and Ctn is the
cofactor of that element. The cofactor c 1n is a determinant whose elements are the elements of the
original determinant with row 1 and column n removed. Note that the elements of the first row after
M 11 and M 12 are zero, so PN = M 11 c 11 - M 12 c 12 , M 11 = x, and c 11 is the secular determinant of an
(N-1 )-carbon polyene; that is, the c 11 cofactor in PN is PN-t .
M 12 = 1, so we are almost there:

We need to examine c12:
* l±l ~ ~ ~ ~ ~
0 0 0 0
*
0 t x 0 0 0
C12 = 0 ~ x 0 0
.:.
0 ~ 0 0 0 x
0 ~ 0 0 0 x
Now c 12 is not itself a secular determinant of a polyene; its first row has ones as its first two
elements and no x elements. Its fust column, though, has only one element, a one. Expanding this
determinant by the elements and cofactors of its first column yields a one-term sum whose cofactor
is illustrated here:
* t ~ ~ ~ ~ ~
[l] * j ff ff y< ff ff
ff t x 0 0 0
c12 = lx ff ~ x 0 o = lxPN_ 2 = PN_ 2
1 -
ff ~ 0 0 0 x
ff ~ 0 0 0 x
That is, the cofactor involved in evaluating c 12 is the secular determinant of an (N-2)-carbon
polyene, i.e., PN-2 . So IPN = xPN-1 - PNJ .
a-E /3 /3
PS.29 (a) /3 a-E /3 =0
/3 /3 a-E
(a- E) 1a-E
/3 /3 1-/31/3
a-E
/3
/3 a-E
I+ /31/3/3 a- El= O
/3
2 2 2
(a- E) x {(a- E) 2 - /3 }- /3{/J(a- E)- /3 } + /3{/3 -(a- E)/3} = 0
(a- E) x {(a- E) 2 - /32 }-2/32 {a- E- /3} = 0
(a- E) x (a- E + /3) x (a- E - /3) - 2/32 (a- E - /3) = 0
(a- E - /3) x {(a- E) x (a- E + /3) - 2/32 } = O
2
(a- E- /3) x {(a- E) x (a- E + 2/3)- /J(a- E)-2/3 } =0
(a- E - /3) x {(a- E) x (a- E + 2/3)- /J(a- E + 2/3)} = 0
(a- E-/3)x(a- E+2/3)x(a-E-/3) = 0

Therefore, the desired roots are E = la-,B, a-,B and a+2,BI. The energy level diagram is shown
in Figure 5.15.
Energy - - - - a -{3
a+ 2{3
Figure 5.15
The binding energies are shown in the following table.
Species Number of e- Binding energy
H/ 2 2(a+ 2/JJ = 2a+ 4/3
2(a+ 2/JJ + (a- jJ) = 3a+ 3/J
2(a+ 2/JJ + 2(a- jJ) = 4a+ 2/J
1
(b) H/ (g) ~ 2H(g) + H+(g) !lH1 = 849 kJ mor
H+(g) + H2(g) ~ H3+(g) !lH2 = ?
!lH3 = [2(217.97)- O] kJ mor'
!lH2 =!lH3 -!lH1 = {2(217.97) - 849} kJ mor

1
!lH2 =RB kJ mo1- I 1
This is only slightly less than the binding energy of H 2 (435.94 kJ mor 1) .
1
(c) 2a+ 4,8= -!lH1 =-849 kJ mo1-
-!lH1 -2a
so ,B = where !lH1 = 849 kJ mol- 1
4
Species Binding energy
2a+4/J = -Affl = l-849kJ mor

1
I
a ) = 3 (~a- ~1 ) =13(a I 2)-212kJ mo1- I

2 1
3a+3/J =3 ( a- Aff1;
4a+2/J=4a- Af{1+2a Af{

-3a--i-= I
3a-425kJmo1- 1 I
2
As ais a negative quantity, all three species are expected to be stable.
PS.31 (a) The orbitals are sketched in Figure 5.16. f//1 is a bonding orbital, showing no nodes
between adjacent atoms, and f//3 is antibonding with respect to all three atoms. f//2 is non-
bonding, with neither constructive nor destructive interaction of the atomic orbitals of
adjacent atoms.
0 C N
ll
ll
Figure 5.16
(b) This arrangement works only if the entire peptide link is coplanar. Let us call the plane defined
by the 0, C, and N atoms the xy plane; therefore, the p orbitals used to make the three MOs
sketched above are p, orbitals. If the p, orbital of N is used in the ;r system, then the a bonds it
makes must be in the xy plane. Hence the H atom and the atom labeled Cai must also be in the
xy plane. Likewise, if the p, orbital of the C atom in the peptide link is used in the 1t system,
then its a bonds must also lie in the xy plane, putting the atom labeled Ca1 in that plane as well.
(c) The relative energies of the orbitals and their occupancy are shown in Figure 5.16. Four
electrons are to be distributed. If we look at the conventional representation of the peptide link
(8 in the text), the two electrons represented by the C=O 1t bond are obviously part of the 1t
system, leaving the two lone pairs on 0, the C-0 a bond, and the two other a bonds of C as
part of the a system. Turning now to the Lewis octet of electrons around the N atom, we must
assign two electrons to each of the a bonds involving N; clearly they cannot be part of the 1t
system. That leaves the lone pair on N, which must occupy the other orbital that N contributes
to the molecule, namely, the p, orbital that is part of the 1t system.
(d) The orbitals are sketched in Figure 5.17. 1/4 is a bonding orbital with respect to C and 0, and lf/6 is
antibonding with respect to C and 0. 1/15 is non-bonding, involving only the N atom. There are four
electrons to be placed in this system, as before, two each in a bonding and a non-bonding orbital.
0 c N
·fil
-CXJ l1
·~ ll
Figure 5.17
(e) This system cannot be planar. As before, the atom labeled Ca1 must be in the xy plane.
Additionally, the atoms bound to N must be in a plane perpendicular to the orbital that N
contributes to this system, which is itself in the xy plane; the bonding partners of N are therefore
forced out of the xy plane.
(f) The bonding MO I/II must have a lower energy than the bonding MO lf/4, for I/II is bonding
(stabilizing) with respect to all three atoms, while lf/4 is bonding with respect to only two of
them. Likewise, the antibonding MO 1//3 must have a higher energy than the antibonding MO
I/fr,, for 1//3 is antibonding (destabilizing) with respect to all three atoms pair-wise, while lf/6 is
antibonding only with respect to two of them. The non-bonding MOs 1/1'2 and I/l's must have
similar energies, not much different than the parameter a, for there is no significant constructive
or destructive interference between adjacent atoms in either one.
(g) Because bonding orbital lf/t has a lower energy than lf/4, the planar arrangement has a lower
energy than the non-planar one. The total energy of the planar arrangement is
Eplanar = 2E1 + 2E2
Compare this to the energy of the non-planar arrangement:
Enon-planar= 2£4 + 2Es > 2Ei + 2E2 = Eplanar
The fact that E 3 > E6 is immaterial, for neither of those orbitals is occupied.
6 Computational chemistry
06.1 The Fock operator,.fi = h1 + V coulomb + V Exchange [6.6], is the sum of three terms. The core hamiltonian
for electron 1, h 1 [6.2], is a one-electron hamiltonian that accounts for the electron kinetic energy and
the potential energy of attraction between the electron and all nuclei. The Coulomb repulsion term,
V coulomb• accounts for the average potential energy due to repulsions between electron 1 and all other
electrons. The exchange potential term provides an average correction to the Coulomb potential for the
phenomenon of electron spin correlation in which electrons of the same spin tend to avoid each
other. Spin correlation reduces the energy description provided by the Coulomb repulsion, and
consequently the exchange potential correction has a negative value.
06.3 The Hartree-Fock equations are
fi 'lfa(1) = Ea'lfa(1) [6.6]
fi 'lfa(1) = Yti'lfa(1) + L {2Jm(1)- K m(1)W a(1) [6.8]
[6.2]
[6.7a]
[6.7b]
The equations are solved iteratively. The first computational step is to select, or guess, the
initial form of all the one-electron wavefunctions 'lfm(l). They are substituted into the right side
of eqns. 6.7a and 6.7b and the integrals are evaluated numerically. The results are used in eqn.
6.8/6.6 to enable the numerical determination of the one-electron wavefunctions and their
energies. The newly found wavefunctions are then used to recalculate the integrals of eqns.
6.7a and 6.7b, and the process is repeated until successive iterations find the wavefunctions and
corresponding energies to be unchanged to within a chosen criterion . Because iteration
continues until self-consistency is achieved, the method is said to provide a self-consistent
field (SCF).
06.5 By writing one-electron wavefunctions as a linear combination of basis functions (the LCAO
method), the extreme difficulty of solving the Hartree-Fock equations by the HF-SCF procedure is
reduced to the somewhat simpler problem of solving the Roothaan equations for LCAO
coefficients. Even so, molecular orbital calculations on even moderately large molecules can
demand more computer memory and more expensive computational time than is available to the
chemist because the very large number of four-center, two-electron integrals (ABICD) that must be
evaluated increases as Nb4 . Consequently, practical molecular orbital calculations require the
judicious selection of a finite basis set.
COMPUTATIONAL CHEMISTRY 133
Commonly used basis sets are listed in Table 6.1. They include
(a) The ST0-3G minimal basis set in which each Slater-type atomic orbital (STO) is expanded in
terms of three Gaussian functions. The linear coefficients have been determined by least-
squares best fit to the STOs. The minimal STO basis set uses one STO to represent each of the
orbitals in an elementary valence theory treatment of the molecule. This is the fewest number of
functions needed to hold all electrons on an atom and maintain spherical symmetry.
(b) The 6-31G basis set in which each core atomic orbital is expanded in terms of six Gaussians.
Valence AOs are split into two basis set functions, called "inner" and "outer" functions. The
inner basis consists of three Gaussians while the outer basis consists of a single Gaussian.
Expansion coefficients have been determined by Hartree-Fock energy minimization on atomic
ground states.
(c) The 6-31G* basis set in which d-type polarization functions have been added to the 6-31G basis
set. The addition of the d-type AO, written as a single Gaussian, removes the restriction of AO
spherical symmetry, thereby accounting for the distortion (or polarization) of AO by adjacent
atoms when bonds form in molecules.
06.7 In ab initio methods an attempt is made to evaluate all integrals that appear in the secular
determinant. Approximations are still employed, but they are mainly associated with the
construction of the wavefunctions involved in the integrals. In semi-empirical methods, many
of the integrals are expressed in terms of spectroscopic data or physical properties. Semi-
empirical methods exist at several levels. At some levels, to simplify the calculations, many of
the integrals are set equal to zero. Density functional theory (DFT) is different from the
Hartree-Fock self-consistent field (HF-SCF) methods and the ab initio methods in that DFT
focuses on the electron density while HF/SCF methods focus on the wavefunction. However,
they both attempt to evaluate integrals from first principles. DFT and ab initio methods are
both iterative self consistent methods in that the calculations are repeated until the energy and
wavefunctions (HF-SCF) or energy and electron density (DFT) are unchanged to within some
acceptable tolerance.
06.9 Density functional theory (DFT) is not a semi-empirical method. In semi-empirical methods, many
of the integrals are expressed in terms of spectroscopic data or physical properties or selectively set
equal to zero to simplify calculations and simultaneously give reasonable agreement with select
experimental data. DFT attempts to evaluate the integrals numerically, using as input only the values
of fundamental constants and atomic numbers of the atoms present in the molecule. In fact, if the
exchange-correlation energy functional [6.22] were known, DFT would be an exact method.
The exchange-correlation energy functional is modeled in DFT methods. One widely used
approximation is the uniform electron gas model for which the exchange-correlation energy is
found to be the sum of an exchange contribution and a correlation contribution. Ignoring the
complicated correlation contribution for simplicity, the uniform gas approximation for the
exchange-correlation energy (see Self-test 6.3 and A brief illustration, Section 6.9) is
Exe [p] = A fp 413 dr with A = -(9/8) (3/1r)1

12
}0
An iteration procedure similar to the HF-SCF methods uses the density functional to calculate an
improved exchange-correlation energy functional which is then used to find an improved density
functional, and so on.
E6.1 (a) ' 1i { V12+V22} -210. {-1+ -

H=--- 1 } +lo. { - 1 }
2me rHel rHe2 fi2
E6.2(a) ' ·{1 1 1 1} ·{ 1 1 1 1} ·{ 1 1

V =-310 - + - + - + - - lo - + - + - + - +lo -+-+-+-+-+- 1 1 1 1}
rLiI rLi2 rw rLi4 rHI rH2 rHJ rH4 1i2 'iJ fi4 r23 r24 r34
E6.3(a) N 0 = 2 for HeH+
2
1i - {V12+V2
' =-
H 2} -210. {-1 + -
1 } -10. { -1 + -
1 } +lo. { - 1 }
2me rHel rHe2 rHI rH2 IJ2
E6.4(a)
E6.5(a) Ne = 2 for HeH+
where
[6.2]
Consequently,
E6.6(a) The complete set of equations for the Ne =2 of HeH+ is

(i) If/a = CHea2'He + CHa2'H and lf/b = CHeb2'He + CHb2'H [6.9]
(ii) fiZHe (1) = '1i2'He (1)+2Ja (1)%He (1)-Ka (l)ZHe (1) [6.8]
J;zH (1) = '1iZH (1)+2Ja (l)zH (1)-Ka (l)zH (1) [6.8]
where
[6.2]
la (l)ZHe (1) = io JzHe (1)_!_ If/a• (2) If/a (2)dr2 [6.7a]

'1 2
Ka (l)ZHe (1) =Jo flf/a (1)_!_ If/a• (2) 2'He (2)dr2 [6.7b]
r12
(iii) Fc=Sce [6.10]and[6.11]
where
f
S = [ XHe(l)XHc (l)d 'Z"1 fXHe(l)XH (l)d 'Z"1
fXH (l)XHe (l)d'Z", fXH (l)XH (l)d 'Z"1
l =( 1
S
~)
Note: JXHe(l)XH (l)d-r, = JXH (l)XHe(l)d -r, = S
E6. 7(a) For the N. = 2 of HeH+,
FAA= JzHe(l)J;XHe(l)d-r, = JzHe (l){~XHe(1)+2Ja (l)XHe(l)-Ka (l)XHe (l)}d-r, [6.1 la] and [6.8]
f f f
= XHe(l)~XHe(l)d'Z", + 2 XHe(l){Ja (l)XHe(l)}d-r, - XHe(l){ Ka (l)XHe (l)}d-r,
= JxHe(l)~XHe (l)d-r, +2 JzHe(l){j 0 JzHe (1)_!_ If/a' (2) If/a (2)d-r2}d-r1

'i2
- fXHe(l){jo flf/a (l)J_ If/a• (2) XHe (2)d-r2} d-r,

'i2
=£He+ 2jo ffXHe(l)XHe(1 )J__{

'i2
CHeaXHe (2) + CHaXH (2)}2 d -r,d 'Z"2
- jO ff XHc(l){ CHeaXHe (1) + CHaXH (1 )}J__ {CHcaXHc (2) + CHaXH (2)} XHe (2 )d-r,di-2
'i2
ff 2 2 2 2
=£He+ 2Jo XHe(1 )XHe(l)J__{ CHca XHe (2) + 2cHeaCHaXHe (2)XH (2) + CHa XH (2)} d -r,di-2
'i2
- Jo ff{ CHeaXHe(l)XHe (1) + CHaXHe{l)XH (1 )}_!.._ {CHeaXHe (2)XHe (2) + CHaXHe (2)XH (2)} d-r,d 'Z"2
'i2
Multiplication of the factors and substituting the symbolism
2 2
FAA = EHe + {2cHea ( HeHel HeHe) + 4cHeacHa ( HeHel HeH) + 2cHa ( HeHel HH)}
2 2
-{ cHea (HeHeiHeHe) + cHeacHa (HeHel HeH) + cHeacHa (HeH/ HeHe) +cHa (HeH/ HeH)}
2 2
IFAA = EHe +cHea (HeHe/HeHe )+ 2cHeacHa (HeHe/HeH)+cHa {2(HeHe/HH)-(HeH/HeH)}I
J J
FAB = XHe(l)J;XH (l)d-r, = XHe (1){ ~XH (1) + 2Ja (l)XH (1)- Ka (1) XH (1)} di-, [6.1 la] and [6.8]
= JxHe(l)~xH(l)d-r, +2 fxHe(l){Ja (l)XH(l)}d-r, - fxH.(l){Ka (l)XH (l)}d-r,
= fXHe(l)~XH(l)d-r, +2 fXH (l){j JzH (1)_!_

0 0
'i2
If/a' (2) If/a (2)ct-r2}d-r1
-fXHe(l){jo fIf/a(l)J_'i2 If/a• (2) XH (2)d-r2}d-r,

= fx1-1eO)l?izH(l)dr1 +2Jo ffxH.(l)XH (l)J_{c-z1-1e (2)+cttaXH (2)}2 <lr1dr2

IJ2
- Joffx1-1eO){ cH..,XHc (1) +cHaxH (l)}J_ {~X1-1e (2) +cHaxH (2)} XH (2)dijdr2
IJ2
f f 2 2 2
= xHc(l)l?izH(l)drl + 2Jo fxHe (l)XH (!)_!_{ cH.,,,2 XHe (2) + 2cHeaCHaXHc(2) XH (2) +cHa XH (2)} dijdr2
IJ2
2
- Jo ff{ cHeazHe (l)zHe (!) +CHaXHe(l)XH (!)}_!_ {CHeaXHc (2)zH (2) +CHaXH (2)} dr1dT2
IJ2
Multiplication of the factors and substituting the symbolism
FAB= JzHe (l)~XH (l)dr1+{2cHe.2 (HeHIHeHe) +4cHcacHa (HeHIHeH) + 2cH} (HeHIHH)}

2 2
- {CHea (HeHeiHeH) + CHeacHa (HeHel HH) + CHeacHa (HeHIHeH) + CHa (HeHI HH)}
Notes:
f
(i) EHe = XHe (l)~XHe (l)dr1 [6.15] is the energy of an electron in orbital XHe, taking into account
its interaction with both the He and H nuclei.
(ii) In the above manipulations we have used the relationship (see E6.8a and E6.8b)
(ABIAA) =(AAIAB)
(iii) We have explicitly shown the integral signs for both the integration over all r 2 values and the
integration over all r 1 values. For example, we have written the four-center, two-electron
integral as
This has the same meaning as the equation that shows a single integral sign only:
.f 1 Xe (2)z (2) dr dr [6.14]

(ABJCD) =Jo XA (l)X8 (1)- 0 1 2
IJ 2
We explicitly show the double integration sign to help with the visual recognition of the
requisite mathematics.
E6.8(a)
This integral is symmetric with the interchange of electron 1 and electron 2. Consequently,
(AAIAB) = (ABIAA). Furthermore, the functions A and B, like all functions, commute, so the
integral may also be written in the forms (AAIBA) and (BAIAA).
(a) Minimal basis set: one basis function for the ls orbital of each of the three hydrogen atoms; one
basis function for each of the ls, 2s, and three 2p orbitals for the carbon atom; one basis
function for each of the ls, 2s, three 2 , 3s, and three 3p orbitals for the chlorine atom. Thus,
the minimal basis set consists of 17 basis function .
(b) Split-valence basis set: two basis functions for the ls orbital of each of the three hydrogen
atoms; one basis function for the ls orbital of carbon and two basis functions for each of the 2s
and three 2p orbitals of the carbon atom; one basis function for the ls, 2s, and three 2p orbitals
of the chlorine atom and two basis functions for each of the 3s and three 3p orbitals of the
chlorine atom. Thus, the split-valence basis set consists of ~8 basis functions!.
(c) Double-zeta basis set: each basis function in the minimal basis is replaced by two functions.
Thus, the double-zeta basis set consists of 134 basis function~.
E6.1 O(a) p-type Gaussian: Ap = Nx; y 1 zk e-ar' where i + j + k = 1 [6.17). Example: Ap, = Nx e-ar'
E6.11 (a) The s-type Gaussian, %, =Ne-a'' [6.17], can be written as the product of these three one-
dimensional Gaussian functions:
N xe -ax , N Ye-ay' , N , e- az
2 2
Proof:
E6.12(a) Analysis of the s-type Gaussian for HeH+ is facilitated by placing the He nucleus at the origin of the
Cartesian coordinate system and placing the H nucleus at the coordinate (x, y, z) = (d, 0, 0). In
general, an s-type Gaussian centered on the point (x, y, z) = (Xe, Ye· ze) has the form
-a{(x-x )2 +(y - y )2 +(z-z )2 }
Ne ' ' ' [6.17]. So with our choice for the coordinate system, the s-type Gaussians
on He and H are
and
Their product is
and it will have the s-type Gaussian form and be in an intermediate position provided that the
2
exponent equals -a{ ( x-e ) + y2 + z 2 } - /3 where a, e, and fJ are constants. If we can find these
constants, which are mdependent of coordinates, we will have demonstrated that the product of two
s-type Gaussians is a Gaussian.
2
aHe {x 2 + y 2 + z 2} + aH {x 2 - 2dx + d 2 + y 2 + z 2} = a {x 2 - 2ex + e 2 + y2 + z } + f3
This last expression can equal zero for any chosen value of the coordinate point (x, y, z) provided
that the coefficients of the polynomial expression each equal zero. Thus, from the quadratic term we
find that a = aHe + aH. The first-order term yields
attd attd
e=--=
a aHe +aH
and the constant term yields
f3=aHd 2-ae2 =aHd2-(aHe+aH) ( aHd J2 =aHd2- (aHd)2

l aHe + aH aHe + aH
Thus,
This demonstrates that the product is a Gaussian centered at (x, y, z) = (e, 0, 0), which is positioned
at a point intermediate between the two nuclei because e = aHd < d.
aHe +aH
E6.13(a) CH3Cl
(a) The 6-31G* basis set consists of the 6-31G basis set plus polarization functions (see Table 6.1).
In the 6-31 G basis set, each core atomic basis function is expanded as a linear combination of
six Gaussian functions. Valence basis functions are split into two basis set functions, called
"inner" and "outer" functions . The inner basis consists of three Gaussians while the outer basis
consists of a single Gaussian. To form the 6-31G* basis set, six d-type polarization functions are
added for each atom other than hydrogen.
6-31G Basis Set for CH3 C!
Core Orbitals Valence Orbitals

Atom Basis Functions Basis Functions
H ls
2
c ls 2s, three 2p
1 4(2) = 8
Cl ls, 2s, three 2p 3s, three 3p
5 4(2) =8
Total number of basis functions (include 3 Hs) = 3(2) + 9 + 13 = 28

Adding 6 polarization functions for both the carbon atom and the chlorine atom gives a 6-31G*
basis set that consists of@O basis functions!.
(b) The 6-31 IG** basis set is a 6-311G basis set plus both a set of five d-type polarization functions
for each atom other than hydrogen and a set of three p-type polarization functions for each
hydrogen atom . In the 6-311G basis set each core atomic basis function is expanded as a linear
combination of six Gaussian functions. Valence basis functions are split into three basis set
functions consisting of three, one, and one Gaussians.
6-31 JG Basis Set fo r CH3 Cl
Core Orbitals Valence Orbitals

H ls
3(1) = 3
c ls 2s, three 2p
1 4(3) = 12
Cl 1s, 2s, three 2p 3s, three 3p
5 4(3) = 12
Total number of basis functions (include 3 Hs) = 3(3) + 13 + 17 = 39

Adding 5 polarization functions for both the carbon atom and the chlorine atom and an addition
3 polarization functions for each hydrogen atom gives a 6-31 lG** basis set that consists of~
~asis function4
(c) The 6-3ll++G basis set is a 6-311G basis set plus both an s-type and three p-type diffuse
functions for each atom other than hydrogen and one s-type diffuse functions for each hydrogen
atom. In the 6-311G basis set each core atomic basis function is expanded as a linear
combination of six Gaussian functions. Valence orbitals are split into three basis set functions
consisting of three, one, and one Gaussians.
Core Orbitals Valence and Diffuse Orbitals

H 1s, one diffuse s

3(1) + 1=4
c ls 2s, three 2p, diffuse s and three p
1 4(3) + 4 = 16
Cl ls, 2s, three 2p 3s, three 3p, diffuse s and three p
5 4(3)+4=16
Total numberof basis functions (include 3 Hs) = 3(4) + 17 + 21 = ~
E6.14(a) Very general equations for setting up the Roothaan equations are used in the first and second A
Brief Illustration of Section 6.2. By replacing the index A with He and the index B with H, we
find that for a linear combination of two basis functions, such as XHe and XH , the coefficients
of the molecular orbitals in lj/0 =cHeaXHe +cHaXH and lf/b =cHebXHe +cttbXH are given by the
equations
and
in conjunction with the normalization condition cHea 2 + cHa 2 + 2cHeacH 0 S = 1.
Applying the Htickel approximation S = 0 and using the symbols aHe =Fttette. aH =FHH• and FHeH =
FHHe=fJ simplifies the equations to
2 2
aHe + aH -({ aHe + aH } -4{ aHeaH - /J2} }1'
£ =~~~~~~~~~~~~~~~~~
a 2
and
in conjunction with the normalization condition cHca 2 + cHa 2 = 1. Thus,
Alternatively, we may use the Htickel approximation much earlier in the derivation and thereby
avoid the general equations of the Brief illustrations. Using this method, we first write the secular
determinant and apply the Htickel approximation before expanding the determinant.
FHeHe -E FHcH-SEl=laHe-E /JI

IFHHe -SE FHH -E /J aH -E = 0
( aHe - E) (aH - E) - /32 = 0
aHe +aH ±({aHe +aH}2 -4{aHeaH -/32})"2

E=----------------
2
2 2)1/2 ( 2 2)1/2
aHe + aH - ({ aHe - aH} + 4 /J aHe + aH + { aHe - aH} + 4 /J
Thus, E = and Eb = - - - - - - - - - - - -
a 2 2
The matrix form of the Roothaan equation can be used to find the wavefunction coefficients.
For example, by equating the matrix 11 elements of the above equation and substituting the
2 2
normalization condition cHea + cHa = 1 , we find the coefficient CHa·
aHeCHea + /JcHa = EaCHea

(aHe -EJcHea = -/JcHa
2 12
(aHe -Ea)(l-cHa Y =-/JcHa
2 2 2 2
(aHe -Ea) (1-cHa ) = /J cHa
1/2
cHa =
E6.15(a) (a) The semi-empirical CNDO (complete neglect of differential overlap) method sets all two-
electron integrals of the type (ABJCD) equal to zero unless XA = xs and Xe = XD· Only integrals
of the type (AAICC) survive.
(b) The semi-empirical INDO (intermediate neglect of differential overlap) method sets all two-
electron integrals of the type (ABICD) equal to zero unless XA = Xs and Xe = Xo except for the
type (ABJAB) when the basis functions XA and xs are both centerd on the same nucleus.
E6.16(a) Twenty basis set functions generate twenty atomic orbitals. The silicon atom has 14 electrons,
which are paired in the 7 lowest AOs to form the ground state. This leaves [!11 virtual orbitals
unoccupied.
E6.17(a)
/2 Il//a ( 1) If/: ( 1) I )l/2 { } ( )1/2{ }

'P=(l / 2)1
I If/: (2)
a 11rbfl (2)[6.5a]wherelfla =(1 ! 2
'I'
Z A+Zs andlflb =l / 2 z A-Zs·
This may be expanded to show that this singly excited determinant is composed of the singlet spin-
112
state wavefunction CY_ {l, 2) = (112 ) { a(l) ,8( 2 )- ,8{1) a( 2)}.
2
'P, = {1 12)" {Illa (l)a(l)lflb(2),8(2)-11'. {l),B{l)lf/b{2)a(2)}
2
= (1 12)" 111. (l)lflb {2){a(l),8{2)-,8{1)a(2)}
= lfla(l)lflb{2)<7_ {1,2)
where the coefficients are determined with the Roothaan equations. The configuration state
functions (CSF) are
'Po= (1 I 2)1'
2
l;n~~ ;Jg~I = (112)"2 \Va(1 )\V. (2 ){ a(l ),8(2)- ,8(1 )a(2)} =\Va (1 )\V. (2 )a_ (1,2)
'P, = (1 I 2)"2 l;fg~ ;fg~1=(1 I 2) 112

\Va(1 )\Vb(2){ a(l ),8(2)- ,8(1 )a(2)} =\Va(1 )\Vb (2)a_(1,2)
Absorbing the normalization constants (1/2) 112 into the coefficients of the configuration interaction
(Cl) linear combination of CSFs gives the CI ground-state wavefunction:
111: (1) 111: u) I 111: (1) 111: u) I

'P=C0 'P0 +C,'P, =C0 ( ) fl ( ) +C, ( ) fl( ) [6.18]
1
111: 2 II'. 2 111: 2 'fib 2
1
The coefficients of the CI ground state wavefunction are determined with the variation principle.
The molecular orbitals are
while the ground and doubly excited configuration state functions are
The first-order perturbation correction [6.20] to the hamiltonian is
H (l)(l)= Jo -2Ja(l)+Ka(l)
'12
The second-order perturbation correction to the energy [6.21] is E~ 2 l = <0l ; 0) • It is our
If'P Ji"<'>ip dif
2
Eo -E2
intent to evaluate the integral in the numerator of the £~ 2 > expression. Since the spin functions
factor from all integrations, they will not be written in the algebraic manipulations.
fJ<'l'f/0 ={Jo -2J {l}+K {l}}{\f/ (1)\f/ (2)}

0 0 0 0
'12 .
= Jo\Va (l )\Va (2 ) 2Ja (1}\f/a (1) \Va (2) +Ka(1)\f/a (1) \Va (2)
'12
2
'12 Yi2
f Yi2
f
- Jo\Va (l) \Va ( ) 2\f/a (2)(Jo llfa(! )__!__ \V: (2) \Va (2) d 1'2 [6.7a]J +\Va (2) (Jo llfa (!)__!__ \V: (2) \Va (2) d1'2 [6. 7b ]J
The last two terms vanish because If/a and I/lb are orthogonal. Thus,
f'¥ fl(l>'¥ d'l" = ff l olf/b(1 )lf/b( 2 )'fa(I )If/a(2 ) d 1" dT =lofflfa(1 )lf/b(1 )_!__If/a(2)1f/b(2)d1" d 1"
2 0 1 2 1 2
'i 2 'i 2
= j o ff__!__( CHeaXHe(l) + CHaXH (1) )( CHebXH, (1) + CHbXH (1) )( CHeaXH, (2) + CHaXH (2) )( CHcbXH, (2) + CHbXH (2) )<l1"1d T2
112
2 2
= j o ff_!__( CHcaCHebXHe(l) + CHeaCHbXHe(l)XH (!) + CHaCHcbXHc(l)XH (!) + CHaCHbXH (1) )
11 2
2 2
X ( CHeaCHebXHc (2) + CHeaCHbXHe (2)XH(2) + CHaCHebXHe (2)XH(2) + CHaCHbXH (2) )dT,d T 2
Multiplying the terms of the integrand and using the definition
(AB ICD) =lo JJXA(1)% (l)J_ Xc (2)% 8 0 (2)dr1dr2 [6.14]

'i 2
yields the result
J'¥ H (')'¥ d
2 0 T=
2
CHea CHeb
2
(HeHelHeHe) +
2 2
2 ( CHea CHeb cHb + CHea cHa cHeb ) ( HeHIHeHe)
+( CHea 2CH b 2 + 2cHea cHa cHebcH b + cHa 2cHeb 2 ) (HeHIHeH) + 2cHea cHa cHeb cHb (HHIHeHe)
+ 2( CHa2 CHeb CHb +cHea cHa CHb2 )(HHIHHe) + CHa 2CHb2 (HHIHH)
where terms have been combined using the relationships (ABICD) = (CDIAB) and (ABICD) =
(ABIDC) = (BAICD). See E6.8(a) and E6.8(b).
E6.20(a) The function j(x) is a mathematical procedure that assigns a number for a specified value of the
independent variable x. The functional G[/] assigns a number for a specified functionj(x) over a
specified range of the variable x. A functional is a function of a function.
Functions: (a)j(x) =d(x 3 )/dx =3x2
(c)j(x) = f x 3dx = x4/4 +constant

Functionals: lili2J G[t) = d(x3)/dxl.r-i = 3 because the number 3 is associated with the function
j(x) = x 3 •
M G[f] =
j(x)=x 3
•
r 3
x dx = 20 because the number 20 is associated with a function
E6.21 (a) Ne= 4 for LiH
p( r) =
N =4
!
t= I
2
llf/; ( r )1 [6.23] = 2{llf/a ( r )1 + llf/b( r
2
)n
N =2
p(r) = I llf/; (r )1 [6.23] = 2llf/1(r1)1

i= I
2 2
{h. +lo. fp ('2) -23(3 I )1/3loP

- - d r2
'i2
. ('i )1/3} lf/1 ('i ) -- E11f/1 ('i ) [6.24]
Jr
where h1 =- --
ti V ~ - ) 0 { -1+ -
1} [6.2]
2me rHe l rHI
E6.23(a) We expect that the basis set having the greatest number of well-chosen basis functions gives a result
that is closer to the Hartree-Fock limit.
The minimal basis set consists of 5 functions for each carbon and oxygen atom and 1 function for
each hydrogen atom. Thus, the minimal basis set of C 2H 50H consists of 21 basis functions.
(a) The double-zeta basis set replaces each function in the minimal basis set with 2 functions. It
consists of 42 basis functions for ethanol.
(b) The split-valence basis set consists of 1 function for each core atomic orbital and each valence
atomic orbital is replaced by 2 basis functions. Consequently, there are 9 basis functions for
each carbon and oxygen atom and 2 functions for each hydrogen. This basis set consists of 39
basis functions for ethanol.
(c) The triple-zeta basis set replaced each function in the minimal basis set with 3 functions, which
means that it consists of 63 basis functions for ethanol.
Of these three basis sets, the ltfiple-zeta basis seG is expected io give a result that is closer to the
Hartree-Fock limit.
P6.1 For H2, the 6-310* basis set is equivalent to the 6-310 basis set because the star indicates that the
basis set adds d-type polarization functions for each atom other than hydrogen. 1 au= 27.2114 eV.
The experimental ground electronic energy of dihydrogen is calculated as De + 21.
Features Calculated with HF-SCF Method

Bond Length (R) in pm and Ground-State Energy (Eo) in eV
H2 (a) 6-31G* (b) 6-311+G** exp

R 73.0 73 .5 74.1
Eo -30.6626 -30.8167 -32.06
F2 (a) 3-31G* (b) 6-311+G** exp

R 134.5 132.9 141.8
Eo -5406.30 -5407.92
' Spartan '06™
Both computational basis sets give satisfactory bond length agreement with the experimental value
for H2• However, the 6-310* basis set is not as accurate as the larger basis set. The smaller set also
yields a higher ground-state energy. Figure 6.1 shows the variation of the dihyrogen ground-state
energy with the internuclear distance.
It is surprising that the 6-311 +O** basis set gives a significantly shorter bond length for F2 • This
might be an indication that the method should be used with caution when fluorine is present in a
molecule.
H2 Ground-State HF-SCF/6-311 +G**

-20
-22
-24
~
..... -26
~
-28
-30
-32 + - - - r - - - - - r - - - r - - - r - - - , - - - - - . , . . - - - , - - - , - - - ,
0 50 I00 150 200 250 300 350 400 450
R/pm Figure 6.1
P6.3 (a) Ethanol
H H
I I
H-C2-C1-0--H
H
I I
H
Ethanol AMI * PM3* exp

R(C1C2)/pm I51.2 I51.8 153.0
R(C10) I42 .0 141.0 I42.5
R(C1H) 112.4 110.8 110
R(C2H) 111.6 109.7 109
R(OH) 96.4 94.7 97 .1
LC 2C10 107.34 107.81 107.8
t'l rH f7 /kJ mol- 1 - 262.I80 - 237 .88I -235 .lO(g)
'Spartan ' 06™
(b) 1,4-dichlorobenzene
Both methods give fair agreement with experiment. However, the PM3 calculation appears to provide
a more reliable standard enthalpy of formation.
I ,4-dichlorobenzene AMI * PM3 * exp

R(C 1C2)/pm I39.9 139.4 138.8
R(C2C3) I39.3 I38.9 138.8
R(CCI) I69.9 I68 .5 I73 .9
LC 6C1C2 I20.58 I21.09
LC 1C2C3 I I9.7 I I I9.45
t'l rHf7 I kJ mor 1 33.363 42.306 24.6(g)
'Spartan '06™
Once again, both methods give fair agreement with experiment. However, this time the AMI
calculation appears to provide a more reliable standard enthalpy of formation . Parts (a) and (b)
together suggest that both methods are in broad agreement with experiment and that neither of them
gives consistently better agreement with experiment.
1
P6.5 (a) The standard enthalpy of formation (11 rHf7 I kJ mol- ) of ethene and the first few linear
polyenes is listed below.
Species Computed* Experimentalt % error
C2H4 69.580 52.46694 32.6

C4H6 129.834 108.8 ± 0.79 19.3
111.9±0.96 16.0
C6Hs 188.523 168. ± 3 ·12.2
CsH10 246.848 295.9t 16.6
0
Semi-empirical, PM3 level, PC Spartan ProTM
1
http://webbook.nist.gov/chemistry/
1
Pedley, Naylor, and Kirby, Thermodynamic Data a/Organic Compounds.
(b) The% error, shown in the table, is defined by
O/
/o error -111rHf7(calc)-11rHf7(expt)l
- x 1000/ /O
11rHf7 (expt)
(c) For all the molecules, the computed enthalpies of formation deviate from the experimental
values by much more than the uncertainty in the experimental value. This observation
serves to illustrate that molecular modeling software is not a substitute for experimentation
when it comes to quantitative measures. It is also worth noting, however, that the
experimental uncertainty can vary a great deal. The NIST database reports !1rHf7 for C 2H 4
to seven significant figures (with no explicit uncertainty). Even if the figure is not accurate
to 1 part in 5000000, it is clearly a very precisely known quantity-as one should expect in
such a familiar and well-studied substance. The database lists two different determinations
for 11rHf7 (C 4 H 6 ), and the experimental values differ by more than the uncertainty claimed
for each; a critical evaluation of the experimental data is called for. The uncertainty
claimed for !1rH~\C 6 H 8 ) is greater still (but still only about 2 %) . Finally, it should go
without saying that not all of the figures reported by the molecular modeling software are
physically significant.
P6.7 (a) The table displays both the experimental and calculated* (HF-SCF/6-3 llG*) 13C chemical
shifts and computed* atomic charges on the carbon atom para to a number of substituents in
substituted benzenes. Three sets of charges are shown, one derived by fitting the
electrostatic potential, another by MuJliken population analysis, and the other by the
method of "natural" charges.
Substituent CH3 H CF3 CN N02
128.4 128.5 128.9 129.1 129.4

Oexp
Ocalc
. 134.4 133.5 132.1 138.8 141.8
Electrostatic charge' I e -0.240 -0.135 -0.138 -0.102 -0.116
Mulliken charge* I e -0.231 -0.217 -0.205 -0.199 -0.182
Natural charge* I e -0.199 -0.183 -0.158 -0.148 -0.135
.Spartan '06TM; HF-SCF/6-3110
.
The idea of atomic charges within molecules is very useful on a conceptual level but this concept is
not a measureable property. Nuclei definitely define the positions of atoms, but the wave character
of electrons causes them to be distributed throughout the molecule in molecular orbitals. Some of
the electrons (e.g.; core electrons) may be largely localized around a particular nucleus while others
are more widely distributed in bonding and antibonding MOs. The case for which a bonding MO is
localized around two adjacent nuclei illustrates the impossibility of defining an absolute scale of
measurable atomic charges as there is no way to define which fraction of the MO should be
assigned to one or the other nucleus. Consequently, there are many ways of defining atomic charges
in a molecule. The most popular three (electrostatic charge, Mulliken charge, and natural charge)
have been computed for this molecular series.
The three methods for calculating atomic charge agree that in going across the substituent series
-CH3 , -H, -CF3 , -CN, -N0 2 the magnitude of the negative charge on the para-carbon decreases.
The electrostatic charge shows the greatest change across the series; the natural charge shows the
least change. The decrease in the magnitude of negative charge across the series is compatible with
the elementary concepts of electronegativity effects at a bond and the effects of substituent releasing
or withdrawing electrons to or from an aromatic benzene ring. The atomic charges show that an
alkyl substituent (e.g., -CH 3) is electron-releasing with respect to -H while -CF3 , -CN, and -N0 2
are progressively stronger electron-withdrawing substituents. See Figure 6.2.
The carbon atom has the greater electronegativity.
0-g~, Alkyl groups release electons to the aromatic ring, thereby

increasing the magnitude of the negative atomic charge on a
carbon atom in the ring.
o-~~, The nitro group withdraws electons from the aromatic ring, thereby
decreasing the magnitude of the negative atomic charge on a
carbon atom in the ring.
Figure 6.2
(b) The very small increase across the series in the experimental chemical shift of the para- 13C strongly
correlates with a decrease in the magnitude of the negative atomic charge across the series.
This effect will be further explored in Chapter 12. Furthermore, it is evident that the uncertainty
in the computed chemical shifts exceeds the actual variation in the chemical shifts across the
series. The calculated shifts do indicate that the cyano and nitro groups are strong electron-
withdrawing groups.
P6.9 We construct a table to determine the Russell-Saunders term symbol for each Slater determinant.
The terms must be consistent with the Pauli Exclusion Principle. L is the total orbital angular
momentum quantum number. S is the total spin angular momentum quantum number. 2S + l is the
spin multiplicity.
Part Slater Determinant L s 2S +I Term Symbol(s)
(a) l'l'1 sa '1'1 / '1'2sal 0 1/2 2 25
(b) l'l'1sa '1'1 / '1'2/ I 0 112 2 25
(c) l'l'1sa '1'1 / '1'2pal 1/2 2 2p
(d) 0
l'l'1 sa 'l'2p 11'2 / I 2,0 1/2 2 2D, 25
(e) 0
l'l'1sa l/'3d 1/13/1 4,2,0 112 2 2G, 2D, 25
(f) 0
l'l'i t 'l'2s '1'3sal 0 3/2 4 4G
The Slater determinants of parts lea), (b), (d), and (e)I have the correct total angular momentum and
spin multiplicity to contribute to the ground state 2S of Li.
P6.11 Non-degenerate, time-independent perturbation theory is mathematically developed in Further

Information 2.1. We outline the results for the ground-state wavefunction, l/fo, corrected to first order.
After expanding the hamiltonian, the ground-state wavefunction, and the ground-state energy in
successive powers of the perturbation parameter Jc, the expansions are substituted into the stationary-state
SchrOdinger equation and powers of Jc are collected. Because Jc is an independent parameter, the
successive powers in the resultant polynomial must equal zero. The first-order term gives
(i)
where H (o), E~ 0 ), and lf/~o) are the unperturbed harniltonian, ground-state energy, and ground-state
wavefunction. H (I), E~'), and lf/~ 1 ) are the first order perturbations to the harniltonian, the ground-
state energy, and the ground-sate wavefunction. The eigenfunctions of the unperturbed harniltonian,
lf/~o) , form a complete orthonormal basis set of functions such that H~ 0 l lf/~o) = E~o) lf/~o).
Let If/~') = :Lan lf/~o). Substitution of the expanded first-order wavefunction correction into equation (i)
gives
L an ( E~ - E~O)) lf/~O) = ( E~') - H (I) ) lf/~O)
Left multiply by lfl'io) with k *- 0 and integrate over all space.
°"a (E 0 - E(o) ) f11r(o) 11r(o) d 1' = E(i) f11r (O) 11r(O) d 1'- f11r (O) H (') 11r(O) d 1'
L,; n n 0 'f' k(o<O) 'f' n 0 'f' k(o<O) 'f'O 'f' k(o<O) 'f'O
~a
L,; n
(En0 - E 0(o) ) (jk(o<O)n = -f11r(o) H (') 11r(O) d 1'
'f' k(o<O) 'f' 0
n ( O (0) ) _
a k(o<o) E k(o<O) - E o - -
f (0)
lf/k(o<O) H
(1) (0)
lf/o d 1'
a
k(o<O)
= f lf/(O) H (') lj/,(O) d1'
k(o<O)
E (o) _ Eo
0
0 k(o<O)
Thus, the ground-state wavefunction corrected to first order in the perturbation is
_ (0) °" f
(I) _
lf/o - lf/o + lf/o - lf/o + L.. {
(0)
n(,.O)
(0) (I) (O) d
lf/n H
E (O)
0 -
lf/o 1'
E o
n
r (0)
n
where the first-order correction to the harniltonian is given by eqn. 6.20.
P6.13 (a) N0 = 2 for HeH+

Very general equations are used in the text Brief illustration for setting up the Roothaan equations
(also see E6.6a and E6.14a). By replacing the index A with He and the index B with H we find that
for a linear combination of two basis functions, such as XHe andzH , the coefficients of the
molecular orbitals in
If/a = CHea.lHe + CHa.lH and lf/b =CHeb.lHe + CHbXH

are given by the equations
£
FHeHe + FHH - S(FHeH-FHHe)-({ FHeHe + FHH -S(FHeH-FHHe)} -4{J-S
=~~~~~~~~~~~~~~~~-=---~--,--~~~~~~~~~~~~~~~
2 2
}{ FHeHeFHH -FHeHFHHe} f 2
a 2{1-s 2 }
and
and
in conjunction with the normalization condition cHea 2+ cHa 2+ 2cHeacHaS = 1.

Also,
s (F~leH -
2
s (FHeH- FHHe )} - 4{ 1- S 2 HFHeHeFHH - FHeHFHHe})"
2
FHeHe + F; ,H - FHHe) + ({FHeHe + FHH-
E = - - - - - - - - - - - - - - - - - -2 - - - - - - - - - - - - - - - -
b 2{1-s }
and
in conjunction with the normalization condition cHeb 2 + cHb2 +2cHebcHbS=1.

(b) N. = 2 for LiH2+
Very general equations are used in the text brief illustration for setting up the Roothaan equations
(also see E6.6b and E6.14b). By replacing the index A with Li and the index B with H we find that
for a linear combination of two basis functions, such as xLi and XH , the coefficients of the
molecular orbitals
are given by the equations
FLiLi + FHH - r H f
s (FLiH - FHLi )-({FLiLi + FHH - s (FLiH- FHLi)
c =-----------------------------------
-4{ l -S
2
FLiLiFHH - FLiHFHLi} 2
a 2{1-s 2
}
and
Cua =-
FLiH-Sca
CHa and
f
S = XLiXHd'Z"
F u Li - ca
2 2
in conjunction with the normalization condition cLia + cHa + 2cua cHaS = 1.
Also,
2
2
FULi +FHH -S(FLiH-FHLJ+({FLiLi +FHH -S(FLiH-FHLJf-4{1-S }{FLiLi FHH -FLiHFHLJ)"
c = - - - - - - - - - - - - - - - - - - 2- - - - - - - - - - - - - - - - -
b 2{1-s }
and
Cub =
FLiH-Scb
cHb an
d f
S = XLiXHdr
FLiLi -Eb
in conjunction with the normalization condition Cub 2 + cHb2 + 2cLibcHbS = 1.
P6.15 (a) Applying the Hi.ickel approximation S = 0 and using the symbols aHe = FtteHe, aH = FHH, and
FHeH = FHHe = /3 simplifies the secular determinant [6.12] for HeH+ and rapidly produces an
approximation for E:a and E:b.
FHeHc -£ FHeH-Scl=laH. -£ fJ I
IFHHe -Sc Fi1H -£ fJ aH -£ =0
( a He - c) (aH - c) - /3 2 = 0
aHe +aH ±({aHe +aH}2-4{aH, a H-/32})"2

c =----------------
2
2 2 )1 / 2 ( 2 2 )1 / 2
aHc + aH - ( {aHe - aH } + 4 /3 aHe + <Xii + {aH. - a,i} + 4 /3
Thus, c = and £ = - - - - - - - - - - - - ' - - - - 1
a 2 b 2
(b) Applying the Hilckel approximation S = 0 and using the symbols au= FuLi• aH = FHH, and FuH =
FHLi = fJ simplifies the secular determinant [6.12] for LiH2+.
FLiLi-£ FLiH-Sel=laLi-£ /3 l=O

IFHLi -Se FHH -£ /3
2
aH -£
( aLi - e) ( aH - e) - /3 = O
£2 - ( aLi + aH ) e +au aH - /32 = 0
au +aH ±({au +aH}2 -4{aLpH -/32}f2
e =----------------
2
2 2)1/2 ( 2 2)1/2
aLi +aH - ({au -aH} +4/3 aLi +aH + {au -aH} +4/3
Thus, £0 = and eh = - - - - - - - - - - - -
'---------2=o_____ __J 2
P6.17 We begin by choosing a coordinate system centered on the N atom of ammonia, which is shown in
Figure 6.3 and is compatible with the one used in E6.12(a). dis the bond length. is the bond angle, e
and the xz plane bisects the H 3NH 2 bond angle.
z
(x2,y2,z 2) =(dcos9,dsin(9/2),d(cos9 -x,' + y,' l'n)
,.,,,,,.11111111u1111H2
H=----+--- y
9
x Figure 6.3
The s-type Gaussians on the nitrogen atom and the hydrogen atoms of ammonia are
= N e -aN lrl' = N e -aHlr-rH, I' = N e -aH lr-r"' '' = N e - aH lr-rH, I'

XN N ' XH, H, ' XH, H, ' XH, H,
where rH, , rH, , and rH, are position vectors of the atoms as shown in the figure.
In E6. l 2(a) it is shown that
-v v =
ANAH 1
(NNNHe-p, )xe-a,jr-r,I'
1
Thus, the two-center XiXi s-type Gaussian can be replaced with a one-center Gaussian at the position
rNH, =(ePO,O) between N and H 1 atoms. This result also allows us to conclude that the product
XH,XH, can be replaced with a one-center Gaussian that is halfway between H2 and H 3 because the
hydrogen atoms have identical a values.
-v -v = (N 2e-P" ) x e -alr-r,I'
AH 2 AH 3 H
dHH 2 2 ( )
wherea=2aH, /3 =--=2y
2
2 ,andrc = x 2 ,0,z2 •
These products can be substituted in the four-center, two-electron integral (NHIHH).
(NH1IH2H3) =lo fxN(l)XH, (l)~XH, (2)XH, (2)d1' =iofxN(l)XH, (l)~XH, (2)xH, (2)d1'1d1'2
12 12
This shows that the four-center, two-electron integral reduces to an integral over two different
centers at r 1 and re. The demonstration may also proceed using any arbitrarily placed coordinate
system using the results of E6.12(b) where it is shown that
-v -v = Ne -alr-r,I' where N = N N e-a-•a,a.lr, -r·I' a= a +a and r = (a r +a r. ) I a

AA Ae A e ' A e c AA e e
P6.19 Ne = 2 for H 2 and from E6.17(a) and E6.17(b),
2 2 112
lfla = (1 12}1' {XA +Xe} and I/lb = (112)1' {XA - Xe}, a_(1,2) = (1 12) {a(l),8(2)-,B(l)a(2)}
'P0 = l/f" (l)lfla(2)a_(1,2), 'P1 = l/f" (1)1/fb(2)a_(1,2), 'P2 =I/lb (l)lflb (2)a_(1,2)
H 22 = f'P2( '1-i +~+lo b2dr

'12J
f
= l/fb(1) \f/b( 2) ( h, + h2 + l 0
'12
}b (I) \f/b( 2) d r (The spin states are normalized.)
Evaluating the first two integrals to the right, we find
f\f/b(1)1/fb(2)'1-i\f/b(1)1/fb(2)dr = f\f/b(l)hi\f/b (l)dr, f\f/b(2)\f/b(2)dr2 = f\f/b (1)'1-i\f/b (l)dr, (ii)
f f
Similarly, \f/b(1)\f/b(2)h 21/fb(1)1/fb(2)dr = \f/b(2)h 21/fb(2)dr2 , which is identical to integral (ii).
Evaluation of the third integral to the right of equation (i) proceeds as follows.
2 2 2
= f{xA(1) -2xA(l)Xe (1)+ Xe (1) } l o {xA(2) -2xA(2)Xe (2)+ Xe (2)2}<lr
'1 2
= ( AAI AA) - 2 ( AAI AB)+ ( AAI BB) - 2 ( ABI AA)+ 4 ( ABI AB) - 2 ( ABI BB)
+ (BB/ AA)- 2 ( BBi AB)+ ( BBi BB)
= 2(AAIAA )-8( AAIAB )+ 2(AAIBB )+4(ABIAB) (iii)
where we have used (BBIBB) = (AAIAA), (ABIAA) = (AAIAB) = (ABIBB) = (BBIAB), and
(BB/AA)= (AA/BB) .
With (i), (ii), and (iii) we find that
Likewise,
IH00 =2EH +1{(AAIAA)+4(AAIAB)+(AAIBB)+2(ABIAB)}I
where EH= f\f/a(l)h1\f/a(l)dr1 .

= JV. (I )\lf (2 )(h, +hi+ Jo (,,b(I)\lfb(2 )dr

0
(The spin states are normalized.)
'i2f'
= fv. (I)\lf. (2)h,\Vb(I)\lfb(2)dr+ fv. (l)\lf. (2)h \lfb(l)\lfb(2)dr+ fv. (I)\lf (2)~b
2
'i2
(1)\lfb(2)dr 0 (iv)
f\f/. (1)\f/. (2)'1i\f/b(1)\f/b (2)dr = f\f/. (I)'1i\f/b(l)dr f\f/. (2)\f/b(2)dr = 01 2 (v)

because \f/ and \f/b are orthogonal.
0
f
Likewise, \f/. (l)\f/. (2)FLi\f/b(1)\f/b(2)dr = 0. (vi)
4 f\f/ (l)\f/ (2)~b (1)\f/b(2)dr = 4 f\f/ (1)\f/b(1) Jo \f/ (2)\f/b(2)dr

0 0
'i 2
0
'i 2
0
= f{xA (1)+ Xs (l)}{xA (1)- Xs (1)} io{xA (2)+ Xs (2)}{xA (2)- %8 (2)}<lr
'i 2
= f{xA (1) 2
-
2
Xs (1) } io {xA(2/- %8 (2) }dr
2
'i2
=fAA~AA )-fAA~BB)-fBB(AA) r(BB(BB)

= 2(AAjAA)-2(AAjBB) (vii)
where we have used {BB} BB) = {AA} AA) and {BB} AA) = {AA} BB)
With (iv)-(vii) we find that
(ffo 2 =-f{(AA(AAj-(AA(BBjj =h';0 f (by symmetry)
P6.21 This solution is based on the solution to problem 9.17 in P. W. Atkins and R. S. Friedman, Solutions
Manual for Molecular Quantum Mechanics, 3rd ed., Oxford University Press, 1997.
We are to show that
where '!'0 is the HF ground-state wavefunction and 'f':

is a singly excited determinant in which
the virtual spinorbital l/fp replaces the occupied spinorbital I/fa of the ground-state.
The hamiltonian is
tz2
H = z>;
N,
;
+1
N,
i ,J
.
L h__rij [6.la] where h; = -2m- V7- L ____!h__
r
0
N,
1
Z ·
1;
i"¢j
The spinorbitals are orthonormal eigenfunctions of the Fock operator Ji [6.6], so
(i)
We begin by showing that

f\V. (t )J;\V, (t) dr, = f\V. (t) { ~\V, (t) +"'""'1"""'""' {J. (t)- K , (t) ]\V, (I)}dr, [6.8]
= f\f/a (l)h1\f/p (l)dTI + ~ f\f/a (1){ f\f/p (1) :: \l/m (2)\f/m(2)dT2}dt"I

- ~ f\f/a (1){ f\l/m(1) :: \l/m(2)\f/p (2)dT2}dt"1
= f\f/a (1) '2i\f/p (1) dTl +L {(\l/a\f/pI\l/m\l/m)-( \l/a\l/m I\l/m\l/p)}
m
We also need to see that

N,
L f'Pohmlf': di- =Nef'Po'2ilf': di- (iii)
The reason is that h 111 is a one-electron operator and electrons in the determinant wavefunction are
indistinguishable, so f'PA'P: di- = f 'P0h21f': dt" = f 'P0 ~1f':di- = ··· = f'P0hN, lf': di-.
Thus,
N,
L f'P0hmlf': di-= f'PA If': d T + f'PA'P: d T + f'P0 ~1f': di- + ···+ f'P0hN, If': d T = N f lf' '2i lf':d T
m
0 0
To find a simplifying relationship for flf' '2i If': d we must find the number of possible orbital
0 T,
permutations given by the Slater determinants. With I/fa occupied by electron 1 in lf' and 0 l/fp
occupied by electron 1 in If': , there are (Ne - 1)! ways of permuting electrons 2, 3, ... ,Ne among
the other Ne - 1 spinorbitals in each of the determinants lf' and If': . Each of the (Ne - 1)!
0
permutations in lf' makes a nonzero contribution to the determinant expansion if it matches
0
identically one of the (Ne - l)! permutations in If':. Thus, there are a total of (Ne - l)! terms that
contribute to the summation and since the spinorbitals are normalized, each of the (Ne - l)! terms
f
gives an equal contribution of \f/0 (1)'2i\f/P (l)d-r.
\{/, (1)
(iv)
One additional relationship must be demonstrated before these equations can be used to prove the
Brillouin theorem. It is
(v)
To demonstrate the relationship, first expand the sum.

N .
L. f•Tf
2I ""' T0- ITfaPd T -_ 2I Jo· f•Tf
Jor T 0 {'i2- I + r21- I + fj 3- I + '3 1-I . . .} T
ITfapd T
i,j riJ
i'l:j
Since fj 2 = r21, fj 3 = r31, and so on,

N .
2I""' f•Tf Jo1upd - . f•TF { - I - I -I -I
L, T 0 - r a T - Jo T 0 'i 2 + lj 3 . . . + r23 + r 24 + ... + ~ N, - l )N,
-l}tTF
T aPd T
i,J riJ
i:l:j
The electrons in the determinants are indistinguishable, so each term in the summation gives an
+
identical result. There are N. ( N. -1) equal terms so the previous equation simplifies to
The operator r 12- 1 within the above integral is a two electron operator leaving N e - 2 electrons that
can be permutated in (Ne - 2)! ways in the determinant wavefunctions with each term in the
resultant sum being equal.
...
~ I'. (I) lf/b(I)
... " · (1) ~ _, lf/p(2)
lf/p(I) lf/b(I) If/, (!)
I~ flffo ~o'ff:dr = f N, ~;-1) Jo If/a~2)
lf/b(2)
: 12
lf/b(2)
ctr
, IJ e
;; j ( )
If/a N, lf/b(N, ) If/, (N, ) lf/p(N, ) lf/b( N, ) If/, ( N.)
The above minus signs appear because permutations in 'P: differ by a sign if two electrons are
interchanged. Because electrons 1 and 2 are indistinguishable, the first and third terms in the sum
are equal as are the second and fourth terms. Furthermore, the restriction that m ~ a, p can be
removed because, if included in the sum, the subtractions will cause their elimination.
=
, -1 )( N, - 2) ! . ~{I
2 ( t ) N, ( N N
1
() ( )
-1 ( ) ( ) \~ - 1 ( ) ( ) }
loL,, lf'a I lf'm 2 fj 2 l/Fp I lf'm 2 dr- lf'a 1 lf'm 2y 12 !fFp 2 lf'm 1 dr
I () (
e • m
N,
= J0 L;{Jv (l)lf'm (2)'i2-11/Fp (I)lf'm (2)dr- Jva(l)lfFm (2)'i 2 - 11/Fp (2)1f'm (l)<lr}
0
m
= t {(lf'a!fFpIVmlf'm)-( lfF 1fFmIVmlf'p)}.

m
0 which completes the demonstration of (v).
Equations (i)-(v) are used to show that f'P0 H'P:dr = 0.
f'PoH'P:dr = f'Po t
{th;++ ~: }'P:dr t f'PA'P:dr++
''*l
= t
'*J
f'Po [ ~; )'P:dr
N,
= N, f'Po~'P:dr+ L{(lfFalfFpllfFmlf'm)-(lfF 1Jimllfimlfip)} 0 by (iii) and (v)

m
N,
= flfia(1) ~IJip (1) dr + :L{(lfialfipIlfimlfim )-( lfialfim Ilfimlfip)} by Civ)

m
by (ii) and (i)
This proves the Brillouin theorem: f'P0 H'P: d r = 0.

P6.23
When the density changes form p[r] to p[r] + i5 p[r] at each point, the functional changes form
ExdP] to Exc[p+i5p] :
f
Exe [p + i5p] = C(p + i5p ) 513 dr
The integrand can be expanded in a Taylor series:
Discarding terms of order i5P2 and higher we obtain
Therefore, the differential t5Exc of the functional (the difference Exc[p+i5p] - ExdP] that depends
linearly on i5p) is ·
i5Exc [P] = HCp 213'5pdr
f
Comparison with i5Exc [p] = Vxc ( r )i5pdr [6.25] yields
3
IVxc (r) = t C p (r )2' I
P6.25 (a) The hydrocarbons in questions form a homologous series. They are straight-chain alkanes of the
formula C"H 2 ,,+ 2 , or R-H where R = C,,H 2,,+i · Draw up the following table.
n 2 3 4 5
7t 0.5 1.0 1.5 2.0 2.5
The relationship here is evident by inspection: Jr= n/ 2, so we predict for the seven-carbon
hydrocarbon in question
Jr= 7/2=13.51.
(b) The plot, shown in Figure 6.4, is consistent with a linear relationship, for R2 = 0.997 is close to
unity. The best linear fit is
log K = - l.95 - l.49n
so lslope=-1.491 and lintercept=-l.951 .
-1.5
-2.0
- 2.5
-3 .0
-3 .5
- 4. 0 L-..J'--1---'---'--'--'--'---'---'---'--'---''--'--'
- 0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 Figure 6.4
(c) If we know 7C for the substituent R = H, then we can use the linear SAR just derived. Our best
estimate of 7C can be obtained by considering the zero-carbon "alkane" H 2 , whose radical H ought to
have a hydrophobicity constant 7C =0/2 = 0. This value yields
logK =-1.95-1.49(0) =-1.95 so
Note: The assumption that R = H is part of the homologous series of straight-chain alkanes is a
reasonable but questionable one.
7 Molecular symmetry
07 .1 The point group to which a molecule belongs is determined by the symmetry elements it possesses.
Therefore the first step is to examine a model (which can be a mental picture) of the molecule for
all its symmetry elements. All possible symmetry elements are described in Section 7.1. We list all
that apply to the molecule of interest and then follow the assignment procedure summarized by the
flow diagram in Fig. 7. 7 of the text.
07.3 Within the context of quantum theory and molecular symmetry a group is a collection of
transformations (R, R', and so on) that satisfy these criteria:
(1) One of the transformations is the identity, E.
(2) For every transformation R, the inverse transformation K 1 is included in the collection so that
the combination RR- 1 is equivalent to the identity: RR- 1 = E.
(3) The combination RR' is equivalent to a single member of the collection of transformations.
(4) The combination R(R'R'') = (RR')R".
07.5 A molecule may be chiral and therefore optically active only if it does not posses an axis of
improper rotation , Sn. An improper rotation is a rotation followed by a reflection and this
combination of operations always converts a right-handed object into a left-handed object and vice versa;
hence an Sn axis guarantees that a molecule cannot exist in chiral forms. When discussing optical
activity, it is helpful to remember that
(a) the presence of both a Cn and a ah is equivalent to an Sn.
(b) i=S2 .
(c) a= S 1• Thus, a molecule cannot be optically active if it possesses a center of symmetry or a
mirror plane.
07.7 See Sections 7.4(a) and 7.4(b).
07 .9 The letters and subscripts of a symmetry species provide information about the symmetry behavior of
the species. An A or a B is used to denote a one-dimensional representation; A is used if the character
under the principal rotation is +1 (symmetric behavior), and B is used if the character is -1
(antisymmetric behavior). Subscripts are used to distinguish the irreducible representations if there is
more than one of the same type: A 1 is reserved for the representation with the character 1 under all
operations; E denotes a two-dimensional irreducible representation; T indicates a three-dimensional
irreducible representation. These labels are called Mulliken symbols. For groups with an inversion
center, a subscript g (gerade) indicates symmetric behavior under the inversion operation; a subscript u
(ungerade) indicates antisymmetric behavior. A horizontal mirror is assigned 'or" superscripts if the
behavior is symmetric or antisymmetric, respectively, under the ah operation.
E7.1 (a) Chloromethane belongs to the point group C3v. The elements other than the Iidentity are a El
I I I I·
C3 axis and three vertical mirror planes a v The symmetry axis passes through the C-Cl nuclei.
MOLECULAR SYMMETRY 157
The mirror planes are defined by the three CICH planes. The C3 principal axis and one of the av
mirror planes are shown in Figure 7.1.
'
''
''
''
Figure 7.1
E7.2(a) Naphthalene belongs to the point group D 2h and it has the symmetry elements shown in Figure 7.2.
There are 3C2 axes, a center of inversion, and 3ah mirror planes.
r----------------------------------------------~
' '
f:c2
Figure 7.2
E7.3(a) List the symmetry elements of the objects (the principal ones, not necessarily all the implied ones);
then use the remarks in Section 7.2, and Figure 7.3 below. Also refer to Figs. 7.7 and 7.8 of the text.
(a) (b)
c.
Figure 7.3
(a) Sphere: an infinite number of symmetry axes; therefore ~

(b) Isosceles triangles: E, C2 , rJv, and <1'~; therefore~
(c) Equilateral triangle: E, C3 , C2 , a h
D3
ID3hI
(d) Cylinder: E, c~, C2, O'h; therefore ID~h I
E7.4(a)
E7.5(a) (a) cis-CHCl=CHCI; E , C a v, a~; ICvI

2, 2
(b) trans-CHCl=CHCl; E, c 2, O'h, i ; 1c 2hI
E7.6(a) Only molecules belonging to the groups Cm Cnv• and Cs may be polar [Section 7.3a] ; hence, of the
molecules listed, only !Ca) pyridine Iand ICb) nitroethanel are polar.
E7.7(a) The parent of the dichloronaphthalene isomers is shown to the right.

Care must be taken when determining possible isomers because
naphthalene is a flat molecule that belongs to the point group D 2h
(see E7.2a). It has an inversion center, mirror planes, and rotational
axes that cause superficially distinct visual images to actually be the
same molecule viewed from different angles. For example, the
structures in Figure 7.4 are all 1,3-dichloronaphthalene. By drawing figures that avoid the redundancy
caused by the symmetry elements, you will find a total of ten dichloronaphthalene isomers.
Cl
Cl
Cl
Cl
Cl Figure 7.4
The names and point groups of the ten isomers are summarized in the following table.
Isomers and Point Groups of m ,n-Dichloronaphthalene
m,n 1,2 1,3 1,4 1,5 1,6 1,7 1,8 2,3 2,6 2,7
Point group C, C, C2v C2h c. C, C2v C2v C2h C2v

E7.8(a) Since the p, orbitals are perpendicular to the molecular plane, we recognize that the set of p, orbitals
on each atom of BF3 experiences the ah change.
-1 0 0
0 -1 0
D(<J'h) = 0 0 -1
[
0
0
0
l
Consequently, we find by inspection that
0 0 0 -1
E7.9(a) The matrix representations of the operations uh and C3 are deduced in E7.8(a) and E7.8(b). Accoriling
to the precepts of group theory, the successive application of these operations yields another
member of the D 3h group to which BF3 belongs, and, in fact, by definition the operation uhC3 should
yield the S3 symmetry operation. The matrix representation of S3 can be found by matrix
multiplication of the component operations.
The result may be checked by matrix operation on the Pz orbital vector where the effort should yield
ff i i n
(pB ,pFI •PF2 ,pF3)D(S3) = (-pB ,-pF3•-pFI '-pF2)
(p, ,p,,,pn ,pn) = (-p,, -p 8 , -p.,, -pn) , which is the expected '°'"''
E7.10(a) Consider the equilateral triangle P 1P2P 3, which belongs to the D 3 h point group (text Fig. 7.8). The
three C2 axes and the three O'v mirror planes of this triangle are shown in Figure 7.5.
P1
tJ p/~~P,
' :'
'' '
'
C2"':
.. J
'
Figure 7.5
The C2 and c; axes belong to the same class if there is a member S of the group such that c; =
S 1C2S [7.5] where S 1 is the inverse of S. We will work with S = (}';,an operator for which S 1
= (}';.
By comparison of the action of S 1C2S on the vector (Pi.P2,P3) with the action of c; on the same
vector, we can determine whether or not the equality of eqn. 7.5 holds. If it does, C2 and axes c;
belong to the same class.
1
s - c 2s (PPP2,P3) = (}':c2(}': (Pi'P2,P3)
= O':C2(P2,P1 ,P3)
= O': (P2,P3,P1)
= (P3,P2,P1) (i)
c ; (P" P2,P3 ) = (P3,P2,P1) (ii)
Eqns. (i) and (ii) indicate that c; =s - 1c 2S where S = O':, and we conclude that C2and c; belong
to the same class.
By either using the same argument or seeing the necessities of symmetry, we find that C2 and c;
also belong to the same class. Consequently, C2 , c; and c; all belong to the same class.
E7 .11 (a) The Px orbital spans B 1 of the C2v point group while z and p, span A 1• Following the first A Brief
Illustration of Section 7 .5(a), we write a table of the characters of each function and multiply the rows.
I
C 2v E C2 CTv (}'v
Px 1 -1 1 -1
z 1 1 1 1
Pz 1 1 1 1
PxZPz 1 -1 1 -1
The characters of the product PxZPz are those of B 1 alone, so the integrand does not span A 1• It
follows that the ~ntegral must be zer~.
E7.12(a) For a C3v molecule, x and y span E while z spans A 1. Thus, the x and y components of the dipole
moment [7.10] have transition integrands that span A2 x E x A 1 for the A 1-+A2 transition. By
inspection of the C3v character table, we find the decomposition of the direct product to be A2 x E x
A 1 = E. The integrand spans E alone. Since it does not span Ai. the x and y components of the
transition integral must be zero. The transition integrand for the z component spans A2 x A 1 x A 1 =
A2 for the A 1-+A2 transition. Consequently, the z com onent of the transition integral must also
equal zero, and we conclude that the transition is forbidde .
Should these considerations prove confusing, write a table with columns headed by the three
components of the electric dipole moment operator,µ.
Component ofµ x y z
A1 l 1 1 l
f(µ) 2 - l 0 2 -10
A1 1 1 -1 1 1 -1 1 -1
A 1 r(µ) A 2 2 -1 0 2 - 1 0 1 -1
E E A2
Since A 1 is not present in any product, the transition dipole moment must be zero.
E7.13(a) We first determine how x and y individually transform under the operations of the C4 v group. Using
these results we determine how the product xy transforms. The transform of xy is the product of the
transforms of x and y.
Under each operation the functions transform as follows.
E C2 C4 Uv Uct
x x -x y x -y
y y -y -x -y -x
.xy .xy xy - xy - .xy Xy
x -1 -1 l
From the C4 v character table, we see that this set of characters belongs to B2 •
E7.14(a) In each molecule we must look for an improper rotation axis, perhaps in a disguised form
(S, =a, S2 = i) (Section 7.3b). If present, the molecule cannot be chiral. D 2h contains IT], and C3h
contains~ ; therefore, molecules belonging to these point groups cannot be chiral and cannot be
optically active.
E7.15(a) Because the largest character is 3 in the column headed E in the Oh character table, we know that
the maximum orbital degeneracy is~· (See Section 7.4c).
E7.16(a) Benzene belongs to the D 6h point group. Because the largest character is 2 in the column headed E
in the D 6h character table, we know that the maximum orbital degeneracy is~. (See Section 7.4c).
E7.17(a) Recall that p x oc x, p y oc y, p z oc z, dxy oc xy, dxz oc xz, d _,_~ oc yz, d z, oc z 2 , dx, -y , oc x 2 - y 2 (Section
4.2g). Additionally, when the functions Ji and h of an overlap integral are bases for irreducible
representations of a group, the integral must vanish if they are different symmetry species; if they are
the same symmetry species, then the integral may be nonzero (Section 7.5a). Since the combination
px(A) - p,(B) of the two 0 atoms (with x perpendicular to the plane) spans A2 , the orbital on N must
span A2 for a non-zero overlap. Now refer to the C2v character table. The s orbital spans A 1 and the p
orbitals of the central N atom span A, (p, ), B, (p, ), and B 2 (p Y) . Therefore, Ino orbitals Ispan A2, and
hence p, (A)- p, (B) is a non-bonding combination. If d orbitals are available, as they are in S of the
I·
S02 molecule, we could form a molecular orbital with ldxy which is a basis for A2.
E7.18(a) The electric dipole moment operator transforms as x(B, ), y(B 2 ), and z(A,) (C2v character table).
Transitions are allowed if / lj/;µlf/; d-r is non-zero (Example 7.6) and hence are forbidden unless
rr xr(µ)xr; contains A,. Since r; =A,, rr xr(µ) =A,. Since B, xB, =A" B 2 xB 2 =A" and
A, xA, =A,, x-polarized light may cause a transition to a B 1 term, y-polarized light to a B2 term,
and z-polarized light to an A 1 term.
E7.19(a)
C4 v. h = 8 E C2 2C4 2uv 2uct
A, 1 l 1 1 l
A2 l 1 l -1 -1
B, l l -1 1 -1
B2 l l -1 -1 l
E 2 -2 0 0 0
n (r) = _!_ L2,(r) (R) x( R) [7.7] where x(R) = ( 5, 1, 1, 3, 1)

h R
n(A 1 ) = Ys {l(l x 5)+1(1x1)+2(1x1)+2(1x3)+2(1xl)} = 2

n( A 2 ) = Ys {l(l x 5) + l(lxl) + 2(1xl) + 2(-lx3) + 2(-lxl)} = 0
n(B 1 ) = Ys {l(l x 5) + l(lxl) + 2(-lxl) + 2(1x3) + 2(-lxl )} = 1
n(B 2 ) =Ys {l(l x 5) + 1(lxl)+2(-lxl) + 2(-lx3) + 2(1xl)} = 0

n(E) = Ys {1(2 x 5) + 1(-2xl) + 2(0xl) + 2(0x3) + 2(0xl)} =1
Thus, this set of basis functions spans l2A 1 + B 1 + ij.
E7.20(a) (a) The point group of benzene is D 6h. In D 6h, µspans E 1u(x, y) and A 2u(z), and the ground term is
A1g· Then , using A2u x A1g = A2u• E1u x A1g = E,u, A2u x A2u = A1g, and E1u x E1u = A1g + A2g +
E2g, we conclude that the upper term is Ieither E 1uor A 2u I·
(b) Naphthalene belongs to D 2h· In D 2h itself, the components span B 3u(x), B 2u(y), and B1u(z), and
the ground term is A . Hence, since A 2 x r = r in this group, the upper terms
arelB 3u(x-polarized)I, B 2u(y-polarized), andl B1u(z-polarized)I.
E7 .21 (a) We consider the integral
I= [fifid8= [sin8cos8d8
and hence draw up the following table for the effect of operations in the group C, (see Figure 7.6).
fi = sine sine - sine

12 =cos e cos e cos e
,.- --- -- ----------------- ...
/)e ./·/
/;h /
--- Figure 7.6
In terms of characters,
E ah Symmetry Species
;; -1 A"
h A'
fih -1 A"
Since the product does not span the totally symmetric species A', the integral is necessarily zero.
P7 .1 (a) Staggered CH3CH3: E , c 3' c2, i, 30'd ' s6;ID3dI [see Fig. 7.6b of the text]
(b) Chair C 6 H 12 :E, C3, C 2 , i, 3ad , s6 ;ID3dl
Boat C 6 H 12 : E, C 2 , O'v, O'~; IC2 v I

3
Only boat C6 H 12 may be polar since all the others are D point groups. Only [Co(en)J + belongs to
a group without an improper rotation axis (S 1 =a) and hence is chiral.
P7.3 The operations are illustrated in Figure 7.7. Note that R2 = E for all the operations of the. groups,
1
1
that ER = RE = R always, and that RR = R R for this group. Since Cph = i, CJhi = C2 , and
iC2 = CJh, we can draw up the following group multiplication table.
E C2 (jh
E E C2 (jh
C2 C2 E oh
(jh (jh E C2
I (jh C2 E
Figure 7.7
The ltrans-CHCl=CHCll molecule belongs to the group C2h.
COMMENT. Note that the multiplication table for C2h can be put into a one-to-one correspondence with
the multiplication table of 0 2 obtained in Exercise 7 .13(b). We say that they both belong to the same
abstract group and are isomorphous.
Question. Can you find another abstract group of order 4 and obtain its multiplication table? There
is only one other.
P7.5 Refer to Fig.7.3 of the text. Place orbitals h 1 and h2 on the H atoms ands, Pn pY, and p, on the 0
atom. The z-axis is the C2 axis; x lies perpendicular to CJ~ and y lies perpendicular to av. Then draw
up the following table of the effect of the operations on the basis.
I
E C2 (JV (JV
h, h, hz hz h,
hz hz h, h, h1
s s s
Px Px - Px Px - Px
Py Py - py - py Pr
Pz Pz Pz Pz Pz
Express the columns headed by each operation R in the form
(new) = D(R)(original)
where D(R) is the 6 x 6 representative of the operation R. We use the methods set out in Section 7.4(a).
(i) E: (hi. hz, s, P:v p>,, p,) f- (h1> h2, s, P:v py, p,) is reproduced by the 6 x 6 unit matrix.
0 1 0 0 0 0
1 0 0 0 0 0
0 0 1 0 0 0
D(C )-
2 - 0 0 0 -1 0 0
0 0 0 0 -1 0
0 0 0 0 0 1
0 1 0 0 0 0
1 0 0 0 0 0
0 0 1 0 0 0
D(aJ =
0 0 0 1 0 0
0 0 0 0 -1 0
0 0 0 0 0 1
(iv) a:: (~ , hz , s,-p,, Py' pJ f-(~, hz , s, p,, Py' pJ is reproduced by
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
D(a: ) =
0 0 0-1 0 0
0 0 0 0 1 0
000001
(a) To confirm the correct representation of C2 a v =a:, we write

0 10 0 00 0100 00
10 0 0 00 1000 00
0 0 1 0 00 0 0 10 00
D(C2 )D(av) =
0 0 0-1 00 0 0 0 1 00
000 0-10 0000-10
000 0 01 0000 01
100000
010000
0 0 1 0 0 0
0 0 0 -1 0 0 = D( a:)
000010
000001
(b) Similarly, to confirm the correct representation of av a~ = C2 , we write
0100 00 1 0 0 000
1000 00 0 1 0 000
0 0 1 0 00 0 0 1 000
D( a.)D( a~) =
0001 00 000-100
0000-10 000 0 1 0
0000 01 000 0 0 1
0 1 0 0 00
100 0 00
0 0 1 0 00
= D(C2 )
000 -1 00
000 0-10
000 0 0 1
(a) The characters of the representatives are the sums of their diagonal elements:
E
6 0 2 4
(b) The characters are not those of any one irreducible representation, so the representation is
reducible.
(c) The sum of the characters of the specified sum is
E C2 (}"v (}"~
3A1 3 3 3 3
B1 -1 -1
2B2 2 -2 -2 2
3A1+B1+2B2 6 0 2 4
which is the same as the original. Therefore the representation is 3A 1 + B 1 + 2B 2 .
P7.7 The basis set consists of four ls hydrogen orbitals, which is written as f = (A, B, C, D) when
positioned as shown in Figure 7.8. When reflected in the mirror plane O"ctAB of the figure, the basis
vector becomes (B,A,C,D). The order of the Tct group is 24, so there are 24 matrices to find. In
addition to E there are 8C3 operations; clockwise and counterclockwise C3 axes along the C-HA
bond, shown in the figure, are labeled c;A and c;A. Likewise, the clockwise and counterclockwise
C3 axes along the C-Hs bond, shown in the figure, are labeled c;B and c;B. There are 3C2
operations; the one that bisects the HA-C-H 8 angle is labeled C2AB· There are 6S4 • The clockwise
and counterclockwise S4axes that bisect the HA-C-H 8 angle are labeled s;AB and s;AB . Finally,
there are 6uct mirror planes; the one, shown in the figure, that bisects the HA-C-H 8 angle is
labeled O"ctAB·
~]=
0 0
1 0
Ef = ( A,B,C,D) = f [ fa(E);z=4
0
0 0
/[~ ~]=JD(
0 0
0 0
c;J =(A,C,D,B) = 1 0 c;, ); z =I
0 1
0 0
0 1
c;,J =(A,D,B,C) =/[ 0 0
] =JD( c;, ); Z =I
1 0
~ ~] =JD(c;,);
0 1
1 0
c;,J =(D,B,A,C) = J [ 0 0 z=I
0 0
~]=JD(
0 0
1 0
c;,J =(C,B,D,A) = /[ 0 0 c;,); z= 1
0 1
~ ~]=
0 0
0 0
c;J =(B,D,C,A) =f [ 0 1 JD(c;, );z= 1
1 0
/[~
1 0
0 0
c;J =(D,A,C,B) = 0 1
]= JD(c;, );z= 1
0 0
s+
4AB$s-4AB
Figure 7.8
c;,J = (C,A,B,D) = f [~
~]=JD( c;, ); x
0 1
0 0
c;,J =(B,C,A,D) = / [ 1 0 =1
0 0
c,"1=(B,A,o,c)=1[I
C,,cf = (D,C,B,A) = f [ ~
1
[o o0 0
C,,cf = (C,D,A,B) = J r 0 0
;] =JD( c,,,); x = o
1 0
~]
1
[o o0 0
s;"J = (D,C,A,B) = J ~ 1 0 = JD(s;"); x= o
0 0
s;"J =(C,D,B,A)=/[~ ~ ~J=JD(s;.,);x=o

I
s;,c1=(B,D,A,C)=1[ ~~ ] = JD(s:oc);x=O
s;ocf = (C,A,D,B) = J[ ~ ~ ;] =JD( s;oc); x = O
o 0 0
+ 1 0 0
S.,cf = (B,C,D,A) = f :
1 0
[
0 1
~ JD(S;~);
0
0
s;,J =(D,A,B,C) = f [ 0 0 rJ = X =0
0 0
o-~f =(B,A,C,D) =/[i ~J

0
0 0
0 =JD( "•AA); X = 2
0 0
~J
0
1 0
o-" cf =(C,B,A,D) =/[r 0 0 =JD( o-,., ); x =2
0 0
o-~f =(D,B,C,A) =/[~ ~J= JD(o-~);

0 0
0
0 1 x=2
0 0
/[~ ~J= JD(o-~);x= 2

0 0
0 1
o-.,cf =(A,C,B,D) = 1 0
0 0
~J =
0 0
o-.,, f =(A,D,C,B) = /[l 0 0

0 1 JD(o-.,,);x= 2
0
/[~
0 0
o-_,, f =(A,B,D,C) = 0 0
0
rJ =JD(o-.,,); x =2
0
Exercise: Find the representations for the ls orbital basis at the comers of a regular trigonal
bi pyramid.
P7.9 Representation 1
D(C3 )D(CJ = lxl = 1 = D(C6 )

and from the C6 v character table, this is either A 1 or A2 • Hence, either D(aJ = D(ad) =I+ 1 or -11,
respectively.
Representation 2
D(CJD(C2 ) = l x (-1) =-1 = D(C6 )
and from the C6 v character table this is either B 1 or B 2 • Hence, either D(aJ = -D(ad) = [!]
or D(av) = -D(ad) = t], respectively.
P7 .11 A quick rule for determining the character without first having to set up the matrix representation is to
count 1 each time a basis function is left unchanged by the operation because only these functions
give a non-zero entry on the diagonal of the matrix representative. In some cases there is a sign
change, (... -f .. .) f - ( .. .f .. .) ; then -1 occurs on the diagonal, so count -1. The character of the
identity is always equal to the dimension of the basis since each function contributes 1 to the trace.
£: All four orbitals are left unchanged; hence x = 4

C3 : One orbital is left unchanged; hence x = 1
C2 : No orbitals are left unchanged; hence x = 0
O"ct: Two orbitals are left unchanged; hence x = 2
S4 : No orbitals are left unchanged; hence x = 0
The character set 4, 1, 0, 2, 0 spans IA, + T2I. Inspection of the character table of the group Tct
shows that an s orbital spans A 1 and that the three p orbitals on the C atom span T 2 • Hence, the
Is and pl orbitals of the C atom may form molecular orbitals with the four Hls orbitals. In Tct, the d
orbitals of the central atom span E + T 2 (character table, final column), so only the T 2 set
l<d.ty ,dyz ,d::-r)I may contribute to molecular orbital formation with the H orbitals.
P7.13 The most distinctive symmetry operation is the @J

axis through the central atom and aromatic
nitrogens on both ligands. That axis is also a !SJ
axis. The group is @J.
P7.15 (a) C2v. The functions x 2 , y2, and z2 are invariant under all operations of the group, so 2(5z2 - 3r2)
transforms as 2(A 1), y(5/- 3r2) as y(B 2), x(5x2 - 3r2) as x(B 1), and likewise for 2(x2 - / ) , y(x2 -
z2), and x(z2 - /). The function xy2 transforms as B 1 x B2 x Ai = A2. Therefore, in group
c2v, f ~ l2A, +A 2 +2B, +2B 2I.
(b) C3v- In C3v, 2 transforms as A 1, and hence so does 23 • From the C3v character table, (x2 -y2,xy) is
2
a basis for E, so (xy2, 2(x - / )) is a basis for A 1 x E = E. The linear combinations
y( 5y 2 - 3r 2) + 5y(x 2 - 22) ex y and x( 5x 2 - 3r 2) + 5x( 22 - y 2) ex x are a basis for E. Likewise,
the two linear combinations orthogonal to these are another basis for E. Hence, in the group
c3v• f ~ IA,+3EI.
(c) Tct. Make the inspired guess that the/ orbitals are a basis of dimension 3 + 3 + 1, suggesting the
decomposition T + T + A. Is the A representation Ai or A2? We see from the character table
that the effect of S4 discriminates between Ai and A2 • Under S4 , x ~ y, y ~ -x, 2 ~ -2 , so
xy2 ~ xy2 . The character is x = 1, so xy2 spans A 1. Likewise, (x , y3, 2 ) ~ (y3, -x , -z ) and
3 3 3 3
x = 0 + 0-1 =-1 . Hence, this trio spans T2 . Finally,

{x(2 2 - y2 ), y(2 2 -x 2), 2(x 2 - y2)} ~ {y(z 2 - x 2), -x(2 2 - y2 ), -2(/ - x 2)}
resulting in x = 1, indicating T 1• Therefore, in ~, f ~ IA 1 + T1 + T21.
(d) oh. Anticipate an A + T + T decomposition as in the other cubic group. Since X, y, and 2 all
have odd parity, all the irreducible representatives will be u. Under S4 , xy2 ~ xy2 (as in (c)),
and so the representation is x = 1 (see the character table). Under S4 ,
(x , / , z3) ~ (/, -x , -z3), as before, and x = -1, indicating Tiu· In the same way, the
3 3
remaining three functions span T2u· Hence, in oh' f ~ IA2u + T:i..i'J.

(The shapes of the orbitals are shown in D. F. Shriver and P. W. Atkins, Inorganic Chemistry, 3rd
Ed., Oxford University Press and W. H. Freeman and Company, 1999.)
The f orbitals will cluster into sets according to their irreducible representations.
Thus, (a) f ~ A 1 + T1 + T2 in Tct symmetry, and there is one non-degenerate orbital and two sets of
triply degenerate orbitals. (b) f ~ A 2" +I;" + T2", and the pattern of splitting (but not the order of
energies) is the same.
P7.17 We begin by drawing up the following table for the C2v group.
N2s N2px N2py N2pz 02px 02py 02pz 0'2px 0'2py 0'2pz x
E N2s N2px N2py N2pz 02px 02py 02pz 0'2px 0'2py 0'2pz 10
C2 N2s -N2px -N2py N2pz -0'2px -0'2py 0'2pz -02px -02py 02pz 0
av N2s N2px -N2py N2pz 0'2px -0'2py 0'2pz 02px -02py 02pz 2
av' N2s -N2px N2py N2p, -02px 02py 02p, -0'2px 0'2py 0'2p, 4
The character set (10, 0, 2, 4) decomposes into l4A 1+2B 1+3B 2 +A 2 I. We then form symmetry-
adapted linear combinations as described in Section 7.5(e).
lf/(A 1 ) = N2s (column 1) lf/(B 1) = 02px +Q'2px (column 5)
lf/(A 1 ) = N2p, (column 4) lf/(B 2 ) = N2py (column 3)
lf/(A 1) = 02pz + 0'2pz (column 7) lf/(B 2 ) = 02py +0'2py (column 6)
lf/(A 1) = -02p y + 0'2p y (column 9) lf/(B 2 ) =02p, -0'2pz (column 7)
lf/(B 1) = N2p x (column 2) lf/(Az) = 02px -Q'2px (column 5)
(The other columns yield the same combinations.)
P7.19 Consider phenanthrene with carbon atoms as labeled in the structure below.
a a'
d'
e f f' e'
(a) The 2p orbitals involved in the n system are the basis we are interested in. To find the
irreducible representations spanned by this basis, consider how each basis is transformed under the
symmetry operations of the C2v group. To find the character of an operation in this basis, sum the
coefficients of the basis terms that are unchanged by the operation.
a a' b b' c C' d d' e e' f f g g' x

E a a' b b' c C' d d' e e' f f g g' 14
C2 -a' -a -b' -b -c' -c -d' -d -e' -e -f -f -g' -g 0
(jv a' a B' b c' c d' d e' e f f g' g 0
<74 -a -a' -b -b' -c -c' -d -d' -e -e' -f -f -g - g' -14
To find the irreducible representations that these orbitals span, multiply the characters in the
representation of the orbitals by the characters of the irreducible representations, sum those
products, and divide the sum by the order h of the group (as in Section 7.5a). The table below
illustrates the procedure, beginning at left with the C2v character table.
I
E C2 (jv (jv ' Product E C2 (jv (jv Sum/h
A1 1 14 0 0 -14 0
A1 1 -1 -1 14 0 0 14 7
B1 -1 1 -1 14 0 0 14 7
B2 -1 -1 1 14 0 0 -14 0
The orbitals span 17 A 2 + 7B 1 I·

To find symmetry-adapted linear combinations (SALCs), follow the procedure described in Section
7.5(c). Refer to the table above that displays the transformations of the original basis orbitals. To
find SALCs of a given symmetry species, take a column of the table, multiply each entry by the
character of the species' irreducible representation, sum the terms in the column, and divide by the
order of the group. For example, the characters of species A 1 are 1, 1, 1, 1, so the columns to be
summed are identical to the columns in the table above. Each column sums to zero, so we conclude
that there are no SALCs of A 1 symmetry. (No surprise here: the orbitals span only A2 and Bi-) An
A2 SALC is obtained by multiplying the characters 1, 1, -1 , -1 by the first column:
'c , , ) 21c
- a-a -a +a = - a-a
4
')
The A2 combination from the second column is the same. There are seven distinct A2 combinations
in all: l~(a-a'), ~(b-b'),. .., ~ (g-g')I.
The B 1 combination from the first column is ±(a +a'+ a'+ a) = ~ (a +a').
The B 1 combination from the second column is the same. There are seven distinct B 1 combinations
in all: ~ (a+ a'), ~ (b + b'), ... , ~ (g + g') . There are no B2 combinations, as the columns sum to zero.
(b) The structure is labeled to match the row and column numbers shown in the determinant. The
Htickel secular determinant of phenanthrene is
I I I I
a b c d e f g g f' e d' c b' a
a a-E fJ 0 0 0 0 0 0 0 0 0 0 0 fJ
b fJ a-E fJ 0 0 0 fJ 0 0 0 0 0 0 0
c 0 fJ a-E fJ 0 0 0 0 0 0 0 0 0 0
d 0 0 fJ a- E fJ 0 0 0 0 0 0 0 0 0
e 0 0 0 fJ a- E fJ 0 0 0 0 0 0 0 0
f 0 0 0 0 fJ a-E fJ 0 0 0 0 0 0 0
g 0 fJ 0 0 0 fJ a-E fJ 0 0 0 0 0 0
I
g 0 0 0 0 0 0 fJ a- E fJ 0 0 0 fJ 0
f' 0 0 0 0 0 0 0 fJ a-E fJ 0 0 0 0
I
e 0 0 0 0 0 0 0 0 fJ a-E fJ 0 0 0
d' 0 0 0 0 0 0 0 0 0 fJ a-E fJ 0 0
I
c 0 0 0 0 0 0 0 0 0 0 fJ a- E fJ 0
b' 0 0 0 0 0 0 0 fJ 0 0 0 fJ a-E fJ
I
a fJ 0 0 0 0 0 0 0 0 0 0 0 fJ a-E
This determinant has the same eigenvalues as in exercise 5.22a(b).
(c) The ground state of the molecule has A 1 symmetry because its wavefunction is the product
of doubly occupied orbitals, and the product of any two orbitals of the same symmetry has A 1
character. If a transition is to be allowed, the transition dipole must be non-zero, which in turn
can happen only if the representation of the product ip;µ«Jf, includes the totally symmetric
species A 1 • Consider first transitions to another A 1 wavefunction, in which case we need the
product A,µA ,. Now A 1A 1 = A 1, and the only character that returns A 1 when multiplied by A 1
is A 1 itself. The z component of the dipole operator belongs to species A 1, so z-polarized A 1 <---
A 1 transitions are allowed. (Note: Transitions from the A 1 ground state to an A 1 excited state are
transitions from an orbital occupied in the ground state to an excited-state orbital of the same symmetry.)
The other possibility is a transition from an orbital of one symmetry (A 2 or B 1) to the other; in that case,
the excited-state wavefunction will have symmetry of A2B 1 = B 2 from the two singly occupied orbitals in
the excited state. The symmetry of the transition dipole, then, is A 1µB 2 = µB 2 , and the only species that
yields A 1 when multiplied by B2 is B2 itself. They component of the dipole operator belongs to species
B2 , so these transitions are also allowed (y-polarized).
P7.21 The p, orbitals of the fluorine atoms in XeF4 are shown in Figure 7.9. (The orbital has a
positive wavefunction sign in shaded lobes and a negative wavefunction sign in unshaded
lobes.) These orbitals may form n molecular orbitals with .the xenon atom provided that a non-
zero overlap integral exists.
Figure 7.9
To find the symmetry species spanned by the fluorine p, orbitals, we use a quick rule for
determining the character of the basis set under each symmetry operation of the group: count 1 each
time a basis function is left unchanged by the operation because only these functions give a non-
zero entry on the diagonal of the matrix representative. In some cases there is a sign change,
(... -f ...) f- ( .. .f ...) ; then -1 occurs on the diagonal, so count -1. The character of the identity is
always equal to the dimension of the basis since each function contributes 1 to the trace. Although
XeF4 belongs to the D 4h group, we will use the D 4 subgroup for convenience. Here is a summary of
the characters exhibited by the fluorine orbital under each symmetry operation.
D4 E C2 2C4 2c; 2c;

Fluorine p, orbitals 4 0 0 -2 0
Inspection of the D4 character table shows that the fluorine p, orbitals span A2 + B2 + E. Further
inspection of the D 4 character table reveals that p, belongs to A2 , dxy belongs to B 2 , and both the (px,py) set
and the (dmdyz) set belong to E. Consequently, only these orbitals of the central atom may possibly have
non-zero overlap with the fluorine Pz orbitals. We must now use the procedure of Section 7.5(c) to find
the four symmetry-adapted linear combinations (SALC) of the fluorine p, orbitals. Using clockwise
labeling of the Fp, orbitals, we write a table that summarizes the effect of each operation on each orbital.
(The symbol A is used to represent the orbital p,(A) at fluorine atom A, and so on.)
D4 A B c D
E A B c D
C2 c D A B
c 4+ D A B c
c-4 B c D A
C~(A-C) -A -D -C -B
C~(B-D) -C -B -A -D
c;(A-Xe-B) -B -A -D -C
c;(B-Xe-C) -D -C -B -A
To generate the B2 combination, we take the characters for B2 (1,1,-1, -1, -1, -1,1,1) and multiply
column 3 and sum the terms. Then we divide by the order of the group (8):
p,(B2) = /s{C +A- B - D + C +A- D - B} = 1/4{p,(A)- Pz(B) + Pz(C)- Pz(D)}

1
To generate the A 2 combination, we take the characters for A2 and multiply column 1:
To generate the two E combinations, we take the characters for E and multiply column 1 for one of
them and multiply column 2 for the other:
p3(E) = 1/4{pz(A)-pz(C)}
p4(E) = 1/4{p,(B)-pz(D)}
Other column multiplications yield these same combinations or zero.
Figure 7.lO(a) shows that the Pz(A 2) orbital of the central atom does have nonzero overlap with p2.
Figure 7.lO(b) shows that dxzCE) has a non-zero overlap with p 3. However, Figure 7.lO(c) shows
that, because of the balance between constructive and destructive interference, there is zero overla
between dxy(B 2) and p 1• Thus, there is no orbital of the central atom that forms a non-zero overlap
with the p 1 combination, so p 1 is nonbonding.
(b)
Figure 7.10
P7.23 (a) Following the flow chart in Fig. 12.7 of the text, note that the molecule is not linear (at least not
in the mathematical sense); there is only one C" axis (a C2 ), and there is a crh. The point group,
then, is 1c2 h 1.
b d f h k' i' g' e' c' a'

..-?j
..-? ..-? ..-? ..-? ~ ~ ~ ~ ,0
?"
a c e g k j' h' f' d' b'
(b) The 2pz orbitals are transformed under the symmetry operations of the C2h group as follows .
, .,
a a' b b' c c J k k' x
, .,
E a a b b' c c' J k k' 22
, , .,
C2 a a b b c c J k' k 0
, , ., .,
-a -a - b' -b -c -c -J -J -k' -k 0
, .,
(jh -a -a -b - b' -c -c ' -j -J -k -k' -22
To find the irreproducible representations that these orbitals span, we multiply the characters of
orbitals by the characters of the irreproducible representations, sum those products, and divide
the sum by the order h of the group (as in Section 12.5a). The table below illustrates the
procedure, beginning at left with the C2h character table.
E C2 crh product E C2 crh sum/l!
Ag 22 0 0 - 22 0
Au -1 -1 22· 0 0 22 11
Bg -1 1 -1 22 0 0 22 11
Bu -1 -1 22 0 0 -22 0
The orbitals span 11 lAu + l lBg I·

To find symmetry-adapted linear combinations (SALCs), follow the procedure described in
Section 12.5(c). Refer to the table above that displays the transformations of the original basis
orbitals. To find SALCs of a given symmetry species, take a column of the table, multiply each
entry by the character of the species' irreducible representation, sum the terms in the column, and
divide by the order of the group. For example, the characters of species Au are 1, 1, 1, 1, so the
columns to be summed are identical to the columns in the table above. Each column sums to zero,
so we conclude that there are no SALCs of Ag symmetry. (No surprise: the orbitals span only Au
and Bg)· An Au SALC is obtained by multiplying the characters 1, 1, -1, -1 by the first column:
I ( a+a I +a +a =
I ) I ( a+a ')
4 2
The Au combination from the second column is the same. There are 11 distinct Au combinations
in all: ~(a+ a'), ~(b + b'), .. . ~(k + k') .
The Bgcombination from the first column is: ~ (a - a' - a'+ a) = ~ (a - a').
The Bg combination from the second column is the same. There are 11 distinct Bgcombinations in
all: l~(a -a'), ~(b- b'), .. .~(k-k')I. There are no Bu combinations, as the columns sum to zero.
(c) The structure is labeled to match the row and column numbers shown in the determinant. The
Hiickel secular determinant is
·I •I I I
a b c j k k' J I c b' a
a a-E /3 0 0 0 0 0 0 0 0 0 0
b /3 a-E /3 0 0 0 0 0 0 0 0 0
c 0 /3 a-E 0 0 0 0 0 0 0 0 0
0 0 0 a-E /3 0 0 0 0 0 0 0
j 0 0 0 /3 a-E /3 0 0 0 0 0 0
k 0 0 0 0 /3 a-E /3 0 0 0 0 0
k' 0 0 0 0 0 /3 a-E /3 0 0 0 0
J
•I
0 0 0 0 0 0 /3 a-E /3 0 0 0
I
•I
0 0 0 0 0 0 0 /3 a-E 0 0 0
c
I
0 0 0 0 0 0 0 0 0 a-E /3 0
b' 0 0 0 0 0 0 0 0 0 /3 a-E /3
/3 a-E
I
a 0 0 0 0 0 0 0 0 0 0
The energies of the filled orbitals are a.+ 1.98137,8, a.+ 1.92583,8, a.+ 1.83442,8, a.+ 1.70884,8,
a.+ 1.55142,8, a.+ 1.36511,8, a.+ 1.15336,8, a. +0.92013,8, a. +0.66976,8, a. +0.40691,8, and a.+
0.13648,8. Then energy is 27.30729,8.
(d) The ground state of the molecule has Ag symmetry because its wavefunction is the product of
doubly occupied orbitals, and the product of any two orbitals of the same symmetry has Ag
character. If a transition is to be allowed, the transition dipole must be non-zero, which in turn
can happen only if the representation of the product 'F; µ 'P; includes the totally symmetric
species Ag. Consider first transitions to another Ag wavefunction, in which case we need the
product AgflAg. Now AgAg =Ag, and the only character that returns Ag when multiplied by Ag is
Ag itself. No component of the dipole operator belongs to species Ag, so no Ag <---- Ag transitions
are allowed. (Note: Such transitions are transitions from an orbital occupied in the ground state
to an excited-state orbital of the same symmetry.) The other possibility is a transition from an
orbital of one symmetry (Au or Bg) to the other; in that case, the excited-state wavefunction will
have symmetry of AuBg = Bu from the two singly occupied orbitals in the excited state. The
symmetry of the transition dipole, then, is Agf1Bu = µBu, and the only species that yields Ag
when multiplied by Bu is Bu itself. The x and y components of the dipole operator belong to
species Bu, so these transitions are allowed.
Molecular assemblies
08.1 Molecules with a permanent separation of electric charge have a permanent dipole moment. In
molecules containing atoms of differing electronegativity, the bonding electrons may be displaced
in such a way as to produce a net separation of charge in the molecule. Separation of charge may
also arise from a difference in atomic radii of the bonded atoms. The separation of charges in the
bonds is usually, though not always, in the direction of the more electronegative atom but depends
on the precise bonding situation in the molecule as described in Section 8.2. A heteronuclear
diatomic molecule necessarily has a dipole moment if there is a difference in electronegativity
between the atoms, but the situation in polyatomic molecules is more complex. A polyatomic
molecule has a permanent dipole moment only if it fulfills certain symmetry requirements as
discussed in Section 7.3(a) of the text.
An external electric field can distort the electron density in both polar and nonpolar molecules,
which results in an induced dipole moment that is proportional to the field. The constant of
proportionality is called the polarizability.
08.3 See Fig. 8.4 of the text for typical charge arrays corresponding to electric multipoles.
The interaction potential between a point charge q2 (monopole, n = 1) and any of the multipoles (m = 2
1
or 3 or ... ) is given by eqn. 8.5 as V oc - - where r is the separation distance between q2 and the
rm
multipole. This is a steeper potential energy decrease with r than that observed for the interaction
between two point charges: V oc .!.. [8.la]. The steeper decline originates in the case for which
r
r >> I, where I is the separation of charge within the multipole because, as r becomes relatively large,
the array of charges in the multipole appears to blend together into neutrality causing lower order
interaction terms to cancel. For example, the dipole terms within the monopole-quadrupole (m = 3)
interaction potential cancel leaving only a l/? term. We use the linear quadrupole charge arrangement
shown in Figure 8.1 to show this cancellation of lower order terms. Since we are interested in the case
x =!Ir<< 1, the following Taylor series expansions are useful substitutions:
(1 +xr' = l-x+x -x
2 3
+··· and (1-xt' = 1+x+x 2 +x3 +· ··
r
Figure 8.1
MOLECULAR ASSEMBLIES 177
Begin by adding the terms for the Coulomb potential interaction [8.la] between the charge array of
the quadrupole and the monopole q 2 , substitute x = !Jr, and perform Taylor series expansions on the
functions of x.
41rEoV = q,q2 - 2q,q2 + q,q2

r+l r r-l
= q,q2 {-1--2+-l-}
r l+x 1-x
- - {I 7x
=q,q2 L +x 2 -x3 +x4 A ,,,{ .L +x 2 +x3 +x4 ··· }
+···7..:._;1"17..t
r
2x 2 q q
= 1 2 {l+x2 +x4 + · ·-}
r
The higher order terms within the polynomial are negligibly small compared to 1 in the case for
which x = !Ir<< 1, thereby leaving the simple expression
V = 2x2q,q2 z2q,q2 1
or Voc-
4Jr£0 r 2Jr£0 r 3 r3
08.5 A hydrogen bond ( · · ·) is an attractive interaction between two species that arises from a link of the
form A- H . .. B, where A and B are highly electronegative elements (usually nitrogen, oxygen, or
fluorine) and B possesses a lone pair of electrons. It is a contact-like attraction that requires AH to
touch B. Experimental evidences supports a linear or near-linear structural arrangement and a bond
strength of about 20 kJ mol- 1• The hydrogen bond strength is considerably weaker than a covalent
bond but it is larger than and dominates other intermolecular attractions such as dipole-dipole
attractions. Its formation can be understood in terms of either the (a) electrostatic interaction model
or (b) molecular orbital calculations (Chapter 6).
(a) A and B, being highly electronegative, are viewed as having partial negative charges (en in the
electrostatic interaction model of the hydrogen bond. Hydrogen, being less electronegative than
A, is viewed as having a partial positive (8+). The linear structure maximizes the electrostatic
attraction between Hand B:
1r 5+ 5-
A--H· ···· ······----- :s
This model is conceptually very useful. However, it is impossible to exactly calculate the
interaction strength with this model because the partial atomic charges cannot be precisely
defined. There is no way to define which fraction of the electrons of the AB covalent bond
should be assigned to one or the other nucleus. (See numerical problem 6.7.)
(b) Ab initio quantum calculations are needed in order to explore questions about the linear
structure, the role of the lone pair, the shape of the potential energy surface, and the extent to
which the hydrogen bond has covalent sigma bond character. Yes, the hydrogen bond appears
to have some sigma bond character. This was initially suggested by Linus Pauling in the 1930s,
and more recent experiments with Compton scattering of X-rays and NMR techniques indicate
that the covalent character may provide as much as 20% of the hydrogen bond strength. A
three-center molecular orbital model provides a degree of insight. A linear combination of an
appropriate sigma orbital on A, the ls hydrogen orbital, and an appropriate orbital for the lone
pair on B yields a total of three molecular orbitals. One of the MOs is bonding, one is almost
nonbonding, and the third is antibonding. Both bonding MO and the almost nonbonding orbital
are occupied by two electrons (the sigma-bonding electrons of A-Hand the lone pair of B). The
antibonding MO is empty. Thus, depending on the precise location of the almost nonbonding
orbital, the nonbonding orbital may lower the total energy and account for the hydrogen bond.
08. 7 The formation of micelles is favored by the interaction between hydrocarbon tails and is opposed by
charge repulsion of the polar groups that are placed close together at the micelle surface. As salt
concentration is increased, the ·repulsion of head groups is reduced because their charges are partly
shielded by the ions of the salt. This favors micelle formation causing the micelles to be larger and
the critical micelle concentration to be smaller.
08.9 The van der Waals equation of state (eqn. 8.24) provides an accounting of both the repulsive and
attractive interactions between molecules by employing the van der Waals constants a and b to
account for the attractive and repulsive interaction, respectively. These interactions are negligibly
small in the limit of zero pressure because the average intermolecular distance is very large
compared to the size of a molecule in this limit. Consequently, the perfect gas law accurately
describes p, Vm , T behavior in the limit of zero pressure.
p= vmRT-b _...!!.___
v m2
[8.24b]
The van der Waals constants a and b do not exactly reflect the fact that interaction potential
energy is a function of distance from a molecule. The potential is a periodic function in solids, in
liquids, and in gases at small molar volumes because molecular closeness causes the potential to
depend on many nearest-neighbor molecules (covalent compound), ions (ionic compound), and
atoms (element). The potential is not a constant. However, the van der Waals constants do
represent an average value of the repulsive and attractive interactions, which is an improvement
over the perfect gas equation at higher pressures and lower temperatures. The van der Waals
constant b treats the repulsive interaction as if molecules were hard spheres for which the
repulsion is zero until there is contact between two colliding spheres with an ensuing infinite
repulsion potential.
Fig. 8.30 of the text illustrates the physically implausible van der Waals loops that are produced
by the van der Waals equation in regions of gas-liquid equilibrium. This error is resolved by
using a Maxwell construction to replace the loops with horizontal straight lines so that the loops
have equal areas above and below the lines. One end of the isotherm line provides a molar
volume estimate for the gas phase; the other end gives an estimate for the molar volume of the
liquid phase.
08.11 The radial distribution function, g(r) , is defined so that g(r)r2dr is the probability that a
molecule will be found in the range dr at a distance r from the molecule. Figure 8.2(a) illustrates
a sketch of a radial distribution function for a solid. g(r) spikes at intervals that depend on the
crystal structure and the identifiable spikes continue to the edge of the crystal because of the
long-range order of the perfect atomic array. Figure 8.2(b) illustrates a radial distribution function
for a liquid. The distribution shows several broad peaks, which indicate some short-range local
order around each molecule, but there is considerable variance in the positions of even nearest-
neighbor molecules. This happens because molecules are no longer at fixed lattice sites. They
have more freedom to move and slip past one another. All r values beyond the closest contact
distance become possible, causing g(r) to exhibit broadened short-range peaks and to never
decline to zero. Molecular mobility also destroys Jong-range order so that no spike in seen after
several molecular diameters.
(a)
(b)
g(r)
r r Figure 8.2
08.13 Kevlar is a polyaromatic amide. Phenyl groups provide aromaticity and a planar, rigid
structure. The amide group is expected to be like the peptide bond that connects amino acid
residues within protein molecules. This group is also planar because resonance produces
partial double-bond character between the carbon and nitrogen atoms. There is a substantial
energy barrier preventing free rotation about the CN bond. The two bulky phenyl groups on
the ends of an amide group are trans because steric hindrance makes the cis conformation
unfavorable.
....';/\ ....';/\ e
\.=!__ ~o \.=!__ A / o
H
/tr~ 'Q
N-C
V_ ....
------.
Resonance
l /
H nm
N=C
'Q
V_
+Energy
H 0
"N-C ~
..0 'O . cis
The flatness of the Kevlar polymeric molecule makes it possible to process the material so that
many molecules with parallel alignment form highly ordered, untangled crystal bundles. The
alignment makes possible both considerable van der Waals attractions between adjacent molecules
and strong hydrogen bonding between the polar amide groups on adjacent molecules. These
bonding forces create the high thermal stability and mechanical strength observed in Kevlar.
··n
. . 'Q "-, .
\.=!__
Hydrogen bond
""' /Hd'"
N-
/ ci-
C 'Q
~o
f ~
v~ / \
0/ ci- - ...
-
'O
~
Hydrogen bond N- C ~ct+ ----..._
....'Jr\ ~/jct+\
ci- Polar, covalent bonds
\.=!__ ~o ci-
if
N- c
'Q
~
Polar, covalent bonds
Kevlar is able to absorb great quantities of energy, such as the kinetic energy of a speeding bullet,
through hydrogen bond breakage and the transition to the cis conformation.
E8.1 (a) A molecule with a center of symmetry may not be polar, but molecules belonging to the groups Cn
and Cnv may be polar (Section 7.3). The C atom of CIF3 is approximately sp 3 hybridized, which
causes the molecule to belong to the C3v point group. The highly electronegative F atoms cause the
C-F bonds to be very polar and the av~agl dipole of the three very polar C-F bonds is unbalanced
by the less polar C- 1 bond. Therefore, IF3 is polar.
Ozone is a bent molecule that belongs to the C2v point group. Lewis resonance structures for the
molecule show a central atom with a double bond to an end oxygen atom and a single bond to
oxygen at the other end. The central oxygen has a formal charge of+ 1 while the double-bonded end
oxygen has a formal charge of zero. The single-bonded end oxygen has a - 1 formal charge. The
average position of the -1 formal charge of the two resonance structures predicts a small negative
charge that lies halfway between the extremities and a fraction of a bond length away from the
central oxygen, which is expected to have a small positive charge. Consequently, ~ is polar.
Hydrogen peroxide belongs to the C2 point group with each carbon atom approximately sp 3
hybridized. The H-0- 0 bond angles are 96.87°. The H-0-0 plane of one hydrogen atom is at a
93.85° angle with the 0 - 0-H plane of the other h~torn atom. Consequently, the dipole moments
of the two polar 0-H bonds do not cancel and the 20 molecule is polar.
E8.2(a) µ = (µ 12 + µ~ + 2µ 1µ 2 cose)1' 2 [8.2a]
= [(1.5) 2 + (0.80) 2 + (2) x (1.5) x (0.80) x (cos 109.5°)] 112 D = li.4 DJ
E8.3(a) The dipole moment is the vector sum (see Figure 8.3).
y - 2e
Lx]:~~~;~~~~~~~~:.~~~~~~~~~~~~====:-:-::::::-
'z -e Figure 8.3
µ = L q;r; = 3e(O)- er 2 - 2er3
r2 = ix2, 13=ix3 +j 3
x2 = +0.32nm
-
x3 = r3 cos20° = (+0.23nm) x (0.940) = 0.216nm
3 = r3 sin 20° = (+0.23 nm) x (0.342) = 0.0787 nm
The components of the vector sum are the sums of the components. That is (with all distances in nm),
-
µ , = -ex2 -2ex3 = -(e) x {(0.32) + (2) x (0.216)} = -(e) x (0.752nm)
-
µ = - 2e 3
=-(e) x (2) x (0.0787)=-(e)x(0.1574nm)
µ = (µ; + µ 2 ) 112 = (e) x (0.76Snm) = (1.602x10- 19 C) x (0.76S x 10-9 m)
= 1.23 x 10-28 Cm= j37 Dj
The angle thatµ makes with the x-axis is given by
cose) µ ,I = o.752
µ 0.768,
E8.4(a) The 0-H bond length of a water molecule is 95.85 pm and the Li+ cation is 100 pm from the dipole
center. Because these lengths are comparable, a calculation based on the assumption that the water
dipole acts like a point dipole with a dipole length much shorter than the dipole-ion distance is
unlikely to provide an accurate value of the dipole-ion interaction energy. However, such a
calculation does provide an "order-of-magnitude" estimate. The minimum value of the dipole-ion
interaction occurs with the dipole pointing toward the cation.
µH,O qL~· [8.4] =- µH ,oe

min
4n-.s-0 r 47L&0 r 2
(1.85 D) x (3 .336 x l0-3° C mD- 1 ) x (1.602 x l0- 19 c)

(1.113 x l0- 10 r 1
C2 m- 1 )x(10ox10- 12 mf
- -8.88 x 10- 19 J
The interaction potential becomes a maximum upon flipping the dipole. This effectively changes
the sign of the dipole in the previous calculation:
max - 8.88 X10-l9 J
The work w required to flip the dipole is the difference Vmax - Vmin·
w-Vmax -Vmin =l.78 x 10-1s J
E8.5(a) The two linear quadrupoles are shown with a collinear configuration in Figure 8.4.
1~
q, q,
r
I· ·I Figure 8.4
The total potential energy of the interaction between the quadrupoles is
4JrE:
0
v - 9..L_222 2 2 2 4 2 2 2 2 2 2 2
_ _!fJ_ +_qi__ _!!J_ + _!!J_ _ _!fJ_ +_qi_ - _!fJ_ + 9..L
- r r+l r + 2/ r- l r r+l r - 2/ r- l r
41l"E:orV = 6--4___ 4_+_1_+_1_ where x =-

2
q1 1+ x 1- x 1+ 2x 1- 2x r
With the point quadrupole condition that x << 1, the last four terms in the above expression can be
expanded with the Taylor series:
(1 + zr 1 = 1-z + z 2 - z 3 + z 4 - ••• and 1

(l-zr =l+z+z 2 +z 3 +z + · ··
4
where z is either 2x or x.
4JrE:0 r V
qi 2 = 6 - 4 { 1- x + x 2 - x 3 + x 4 - ... + 1+ x + x 2 + x 3 + x 4 + .. .}
2
+{ 1-(2x) + (2x) -(2x) 3 + (2x) 4 - • • ·} +{ 1 + (2x) + (2x) 2 + (2x) 3 + (2x) 4 + · · ·}
= -8x 2 - 8x 4 + 8x 2 + 32x 4 + · · ·
= 24x 4 + higher order terms
In the limit of small x values, the higher order terms are negligibly small, thereby leaving
4 2 6/4 2
v--6-
x qi- -
- -qi-5
1l"E:or 1l"E:or
Thus, V oc ~ for the quadrupole-quadrupole interaction is in agreement with eqn. 8.5.

r
E8.6(a) The induced dipole moment is
µ •tt,o = a:E [8 .10] = 4JrE:0 a~ 20 E [8.11]
= (41l")X(8.854xl0- 12 r 1C 2 m- 1)x(l.48 x l0-30 m 3 )x(l.O x l0 5 V m- 1)
= 1.6xl0- 35 Cm [l J = 1 CV]
which corresponds to 14.9 µDI

3( I I )2 3( I )2I He
E8.7(a) aHe He [8.J4] = aHe
VLondon - 6
2 (1 He +IHe ) r 4r
3x( 0.20xl0-30 m3 )2 x( 2372.3 kJ mol- 1)
4x(1.0x!0-9 m)6
= lo.0111 mor 1I
E8.8(a) Using the partial charge presented in Table 8.2, we estimate the partial charge on each hydrogen
atom of a water molecule to be qH = lie where 8 = 0.42. The electroneutrality of an H20 molecule
implies that the estimated partial charge on the oxygen atom is q0 = - 2be. With a hydrogen bond
length of 170 pm, the point charge model of the hydrogen bond in a vacuum estimates the potential
of interaction to be
2(J )2
V = qHqo =---e- [8.la]
4Jrt"0 r 41rt'0 r
---------
2(0.42xl.60xl0- 19 cf
- - - - - - = - 4 . 8 x 1 0- 19 J
4Jr(8.85xl0- 12 r 1 C2 m- 1)x(170xl0- 12 m)
The molar energy required to break these bonds is
Em =-NAV=-(6.022xl0 23 mo1- 1)x(-4.8xl0- 19 J)=l289 kJmor 1I
E8.9(a) nN =3.15g x ( I mo! N 2 ) =0.112molN 2

2
28.01 g
3
2 05
v;" = !:.__ = · dm = 0.0183 m3 mol- 1 = 1.83x10 4 cm 3 mol- 1
nN, 0.112 mo! N 2
Assuming that the dinitrogen virial equation of state has C!Vm 2 << B!Vm,
RT ( B)
.. = - 1+- [8.22b] =
(8.3145 J mol- 1 K- 1)(273 K) ( 1- JO 5
· cm
3
mo
1- 1 )
[Table 8.5]
P vmai Vm Vm 0.0183 m3 mol- 1 1.83x10 4 cm 3 mor 1
=l.24xl0 5 Pa=l1.24barl
According to the perfect (ideal) gas equation of state,
Pperfcct = vRT = (8.3145Jmor1

m
K-1)(273K) =l.24xl0s Pa = l1.24barl
0.0183 m mol 3 I
The fact that P viriaJ = Pperfect for nitrogen under these conditions results from the low pressure, high
temperature conditions for which the molar volume is large enough to cause B!Vm << 1. The second
coefficient of the virial equation of state is negligibly small under these conditions and the perfect
gas equation of state provides accuracy.
E8.1 O(a) The second virial coefficient equals zero at the Boyle temperature, so the perfect gas law will
accurately describe the pressure.
1 mol C0 2 )
nco 2 = 4.56 g x
( 43.99 g
= 0.104 mo! co2
=~-
3
vm
2.25 dm
nco, - 0.104 mol CO = 0.0216 mJ mol-1
2
RT (8.3145 J mol- 1 K- 1)(714.8 K)

Ppenee• = - 0
= _ [Table 8.6] = 2.75x10 5 Pa= 12.75 barl
vm 0.0216 ill 3 mol 1
3
E8.11 (a) (a) The amount of xenon is n = l lg 1 = l.OOmol.
131gmol-
Vm = V = 1.0 dm3 = 1.0 dm3 mor1

n 1.00 mol
1
1
=RT= (8.3145 JK- mol- )x(298.15K) =
25 x 105 Pa=1 25 barl
Pperfee• Vm 1.0xl0-3 m 3 mol- 1
(b) For xenon, Table 8.7 gives a= 4.137 dm 6 atm mol-2 and b = 5.16xl0-2 dm 3 mol- 1.
RT a
P vandcrWaals = V -b - V 2
m m
1 1
(8.3145 JK - mol- )x(298.15K) 4.137xl0-6 atm m 6 m~r2 (l.013xl0 5 Pa)
3 3 1
(1.0-0.0516)x10- m moi- (1.0xl0-3 m3 mo1-1) 1 atm
= 22xl0 5 Pa= 122 barl
E8.12(a) The conversions needed are as follows:
1 atm = 1.013 x 105 Pa 1 Pa= 1 kg m- 1 s-2 1 dm 6 = 10--0 m6 1 dm 3 = 10- 3 m3

Therefore,
6 2
a= 0.751 atm dm mol- becomes, after substitution of the conversions,
a= 17.61 x 10-2 kg m5 s-2 mo1- 2 I, and

b = 0.0226 dm 3 mol- 1 becomes
b=l2.26 x10-5 m 3 mo1- 1 I.

E8.13(a) The definition of Z is Z = pVm = Vm0 [8.20 and 8.21].
RT V
Vm is the actual molar volume, v; ~s the perfect gas molar volume. v; = RT
p
. Since Vm is 8 percent
smaller than that of a perfect gas, vm = 0.92 v;, and

(a) z = 0·92vo v; = lo.921
m
1
(b) Vm -
_ ZRT _ (0.92)x(8.206xlo- dm 3 atmK- mol- )x(250K)
-
2 1 -I d _1
- L6 m3 mol 1.
p 12 atm
Since Vm < v; ~ttractiv~ forces dominate.

E8.14(a) The amount of gas is first determined from its mass. Then, the van der Waals equation is used to
determine its pressure at the working temperature. The initial conditions of 300K and lOOatm are
in a sense superfluous information.
92 .4kg
n= =330
• x 103mo l
28.02x10-3 kg mol- 1
3
V = 1.000 m = 1.000x10 dm
3 3
3 1 1
= nRT _ an 2 [ . a] = (3.30 x l0 mol)x(0.08206 dm 3 atm K - mol - )x(500 K)
8 24 1
p V-nb V2 (1.000 x l0 3dm 3)-(3.30 x l0 3mol) x (0.0391 dm 3 mol - )
(1.39 dm 6 atm mol -2) x (3.30x10 3 mol) 2
(1.000 x l0 3 dm 3) 2
= (155-15) atm = 1140 atm l
E8.15(a) The Boyle temperature, TB , is the temperature at which B = 0 . To express TB in terms of a and b,
the van der Waals equation must be recast in the form of the virial equation.
RT a ]
P =---- [8.24b
2
v -b v
m m RT { 1 a }
Factoring out ~~ yields P = Vm 1- b / Vm - RTVm .
So long as bl ~n < 1 , the first term inside the brackets can be expanded using (1- xr 1 =
1+ x + x 2 + ··., which gives
p=;~ {1+ ( b- RaT )x( : m) + ··}

We can now identify the second virial coefficient as B = b-_!!_.
RT
Since at the Boyle temperature B = 0, TB = _!!_.

bR
2 1
From Table 8.7, a= 6.260dm atm moi- , b = 5.42xl0-2 dm 3 mol - . Therefore,
6
6 2
T. = 6.260dm atmmol- = li. 4 lxl03 Kl
B 2 3 - I 2 3 - I I
(5.42xl0- dm mol ) x (8.206 x l0- dm atmK mor)
E8.16(a) Figure 8.5 shows how the collision of two hard-sphere molecules establishes an excluded volume.
4
The closest distance between two molecules of radius r and volume Vmolecule = / 3;r? is 2r, so the
4 3
volume excluded is / 3;r(2r) , or 8 Vmolecule- The volume excluded per molecule, a quantity that
provides an estimate of the van der Waals coefficient b, is one-half this volume, or 4Vmolecule-
Excluded volume
Figure 8.5
1
t where hc1, = 5.42 x 10-5 m 3 moi- [Table 8.7]
3
b = 4 vmolcculcN A = 4 ( Jrr ) NA
1/3
3b 113 3(5.42 x l0-5 m3 morl)
115
r=(i6JrNJ = [ 16n(6.022x10 23 moi- 1) ] =l Pml
E8.17(a) The van der Waals equation [8.24b] is solved for b, which yields
RT
b=Vm
(p+ ~ )
Substituting the data,

1
-4 3 _1 (8.3145JK- mol- 1)x(273K)
b = 5 .00 x 10 m mo 1 -~---'---------'---'-----'---
6 2
(3.0xl06 Pa)+( 0.50m Pamol- )}
{ (5 .00 x l0-4 m 3 mor 1) 2
= r-10_.4_6_x_l_0_-4_m_3 _m_o_r~1I
6
E8.18(a) z = pVm 3
[8.21 ] = (3.0xl0 Pa)x(5.00x10-4 m ) = I0.
661
RT (8.3145JK-I mol- 1)x(273K)
COMMENT. The definition of Z involves the actual pressure, volume, and temperature and does not
depend on the equation of state used to relate these variables.
P8.1 The positive end of the dipole, which bisects the hydrogen atom positions, will lie closer to the
(negative) anion. The electric field generated by a dipole is
T =(
4
:C }(~) [8.7]
0
(2)x(l.85)x(3.34xl0-3° Cm) l.l l x l0- 19 vm- 1 l.1 lxl0 8 vm- 1

(4n')x(8.854x10- 12 r 1 C 2 m- 1)x r 3 (r I m)3 (r I nm) 3
(a) T = ll.lxl08 vm- 1 I when r = l.Onm
(b) T=l.llx~~;3 vm-i =14xl0 9 Vm- 1 I forr=0 .3nm
(c) T=l.llx~~: vm-i =14kvm- 1 I forr=30nm.
P8.3 The point charge model can be used to estimate the magnitude of the electric dipole moment of
hydrogen peroxide as a function of rp (defined in Figure 8.6(b) as a view down the z-axis of the 0-0
o;
bond). Each hydrogen atom has a partial charge of each oxygen atom has a partial charge of -o.
The dipole moment magnitude is
µ = ( µ · µ ) 1/2 = ( µ x2 + µY2 + µ, 2 )1 / 2 where µx = """'

L,,qJxJ =OX { xH, -x0, -x02 + xH, } [8.3a], etc.
J
We will use the Cartesian coordinate system defined in Figure 8.6(a). The bond lengths are loH = 97 pm and
/ 00 = 149 pm. We also use the ratio /ratio = /00 I loH = 1.54 and calculateµ in units of <5/oH so that it is
unnecessary to estimate the magnitude of <5 (though an estimate is found in Table 8.2). The 0-0-H bond
angle may be estimated as 90°, but we will use the experimental value of 100°. The computations of µx, µ>"
andµz require the coordinates of each atom; those ofH 1 and the oxygen atoms are shown in Figure 8.6(a).
(/0 , cos(0- 9()'),0,-/00 sin(0 - 90")) x

H, H,
, , , '• 1scr-e
I .. z
y
(a) (b) Figure 8.6
The coordinates of H 2 can be determined by analogy to the relationships between Cartesian

coordinates and spherical polar coordinates. They are
x = l0 H sin(180° -B)cos¢
Y = /0Hsin (180° -B)sin(<?
Z = /00 +/OH COS ( 180° - 0)

Substitution of variables into eqn. 8.3(a) yields
(µ / 8/0H) 2 = (µ x / 8/0H) 2 + ( µy / 8/0H) 2 + (µ 1 / 8/0H) 2

2
= { cos(l0°) +sin (80°)cos(<?} + {sin (80°)sin (<? r +{-sin (10°)- /,.,io +/ratio + cos(80°)}
2
={cos(10°) +sin (80°)cos¢f +{sin (80°) sin ¢}2 +{-sin (10°) + cos(80°) f
We now draw a table to calculate (µ I 8!0 H )2 in rp increments of 15° and subsequently calculate
µ I 8!0 H values at each rp. Figure 8.7 is a plot of the variation. As expected, there the dipole is a
maximum of almost twice the single 0-H bond dipole when the hydrogen atoms are eclipsed, and it
is zero when they have a gauche conformation.
¢ I deg ¢ I radians sq(µ I 81 ) µ I 81
0 0 3.879385 1.969616
15 0.261799 3.813292 1.952765
30 0.523599 3.619516 1.902502
45 0.785398 3.311262 1.819687
60 1.047198 2.909539 1.705737
Dipole Moment of Hydrogen Peroxide

2
1.5
-
§;
-
'e 1
::t.
0. 5
0
0 60 120 180 240 300 360
ip /deg Figure 8.7
P8.5 The energy of the dipole is -µ 1'E in the electric field 'E. To flip it over requires a change in energy
of 2µ 1 'E. This will occur when the energy of interaction of the dipole with the induced dipole of the
Ar atom equals 2µ 1'E. The magnitude of the dipole-induced dipole interaction is
2 I
v = µ, a 2
6
[8.13] =2µ,'E [after flipping over]
4JrE0 r
(6.17xl0- °Cm)x(l.66xl0- m )
3 30 3
r 6 = µ,a; = . x - s3 m6
4 6 10
8Jr£0 'E (8Jr)x(8.854xl0- 12 r' C 2 m-')x(l.Oxl0 3 Vm-')
r = l.9xl0-9 m = li.9 nml
COMMENT. This distance is about 11 times the radius of the Ar atom.

P8.7 The induced dipole momentµ * is given by
Consequently, the dipole-proton distance needed to induce a particular dipole is
m
= (1.48x l0-30 m3) x (1.602 x l0-19 c) =1196 ml
[ (1.85D) x (3.336 x l0-3° Cmn- 1) ) p
P8.9 Let the partial charge on the carbon atom equal Je and the N-to-C distance equal /. Then
µ = i5el [8.3a] or
(1.77 D) x (3 .3356 x 10-3° Cm ff 1) r;:;-;--;:;-;;i

.5= =&:..!n.1
(1.602 x l0- 19 c) x (299 x 10- 12 m)
P8.11 By the law of cosines, r~·· H = r~-H + r~-o - 2r0 _H r0 _0 cos () . Therefore,
2 2 )1/2
r0 •• H = f (B) = ( r0 _H + r 0 _ 0 -2r0 _Hr 0 _ 0 cos B
{.5o.5H + .5o.5H + .5~-o} = NAe {o. 0. .5~-o}

2 2
V = NAe ( -1-+-'-) +
m 4nco ro- H r O·· H ro - o 4nco o H ro- H f(B) ro- o
{o. 0. ( .5~_ 0 }
2
_ NA e I I )
- 4nc0 x (10- 12 m) 0
H r0 _H / pm+ f( B) / pm + r0 _ 0 / pm
2
= 139 MJ mol- 1 x J0JH I + 1 ) + 0.0- o }
( ) { ( r _H I pm f (B) I pm
0
r0 _ 0 I pm
With J 0 = -0.83, btt = 0.45, r0-H= 95 .7 pm, and r o-0 = 200 pm, we draw up a tabular computation
of j{()) and Vm(B) over the range 0 ::; () ::; 2rr and plot Vm(B) in Figure 8.8. As expected, the
potential is a minimum when() =0 because at that angle the hydrogen lies directly between the two
oxygen atoms, which repel.
- - 200
I deg I radian /( ) V l kJ/mol
0 0 104.30 - 561
15 0.261799 110.38 - 534 - 300
30 0.523599 126.52 - 474 I_
0
45 0.785398 148.63 - 413 E
60 1.047198 173.26 - 363 ~ -400
75 1.308997 198.12 - 326 E
90 1.570796 221.72 - 298 :::..
105 1.832596 243.04 - 277 - 500
120 2.094395 261.34 - 262
135 2.356194 276.09 - 252
150 2.617994 286.90 - 245 - 600
0 90 180 270 360
165 2.879793 293.49 - 241
180 3.141593 295.70 - 239 B /deg
Figure 8.8
nRT 3 1 1
(10.0mol)x(0.08206 dm atm K- moi- )x(300K) = lso. atml
PB.13 (a) p=----v 4.860dm 3
7
2
(b) nRT (n) [8.24a]
p = V-nb -a V
3 1 1
(10.0mol)x(0.08206 dm atmK- mol- )x(300K)
1
(S.4 89 dm6atmmor2)x( IO.Omo! J2
(4.860dm3)-(10.0mol) x (0.06380dm 3mol- ) 4.860dm 3

=135.l atml
The compression factor is calculated from its definition [8.20 and 8.21] after inserting Vm = V.
n
To complete the calculation of Z, a value for the pressure, p, is required. The implication in the
definition (8.21] is that p is the actual pressure as determined experimentally. This pressure is
neither the perfect gas pressure nor the van der Waals pressure. However, on the assumption that
the van der Waals equation provides a value for the pressure close to the experimental value, we can
calculate the compression factor as follows:
(35.latm)x(4.860~~ )
3
Z = pV = = lo. 693 1
nRT (10.0mol)x(0.08206dm 3atmK mol- 1)X(300K)
COMMENT. If the perfect gas pressure had been used, Z would have been 1, the perfect gas value.
PB.15 From the definition of Z [8.21] and the virial equation [8.22b], Z may be expressed in virial form as
Z = l+B(:J+c(:mJ + ...
Since Vm =RT [assumption of perfect gas], _VI = _p_; hence, on substitution and dropping terms
p m RT
beyond the second power of ( Jm ),

2
Z=l+B(:T )+c(:T )
IOOatm )
Z = l+(-21.7xl0-3 dm3 mol-1)x ( (0.082ldm3 atmK lmol 1)x(273K)
2
IOOatm
+ (l.200xl0-3 dm6 mor2)x( (0.082ldm3 atmK 1mol l)x(273K) )
z = 1-co.0968) + co.0239) = I0.9271

Vm = (0.927)x( R:) = (0.927)x( (0.082ldm3 at~O~::or1)x(273K)) = /0.208 dm3/
Question. What is the value of Z obtained from the next approximation using the value of Vm just
calculated? Which value of Z is likely to be more accurate?
PB.17 The virial equation is
pV
m
=RT(I+~+_£_+
vm v~ .. ·)
or
pVm
RT
B C
- = l + - + - + ...
Vm V~
. pV
(a) If we assume that the senes may be truncated after the B term, then a plot of RT versus V1
m
will be linear with slope Band a y-intercept equal to 1. Transforming the data gives
p /MPa Vm I (dm3 mor- 1) p VmlRT Vm-t I (mo! dm- 3)

0.4000 6.2208 0.9976 0.1608
0.5000 4.9736 0.9970 0.2011
0.6000 4.1423 0.9964 0.2414
0.8000 3. 1031 0.9952 0.3223
1.000 2.4795 0.9941 0.4033
1.500 1.6483 0.991 2 0.6067
2.000 1.2328 0.9885 0.8112
2.500 0.98357 0.9858 1.017
3.000 0.81746 0.9832 1.223
4.000 0.60998 0.9782 1.639
A plot of the data in the third column against the data in the fourth column is shown in Figure 8.9.
The data fit a straight line reasonably well, and the y-intercept is very close to I. The regression
yields B=l - l.32 x l0-2 dm 3 mor 1 I.
(b) A quadratic function fits the data somewhat better (Figure 8.10) with a slightly better correlation
coefficient and a y-intercept closer to I . This fit implies that truncation of the virial series after
the term with C is more accurate than after just the B term. The regression then yields
B = 1-1.51 x 10-2 dm 3 moi- 1 I and C = 11.07x10-3 dm 6 mo1-2 I
LOO . . . - - - - - -y-=-0.-9-99_4_9___ 1_.3_2_4_5_x_J_o-"""'2-x""'

. R2 = 0.999 .
······:·············· ·····:···················:····················
0.99 ........... ......... ~ ................. ;................... ; .... ............ ... .
.. ..
0.98 ................... , ....... ............ , ................. ; ................ ....
0.97 ~------~---~--~
0 2
Figure 8.9
LOO . . - - - - - - - - , - - - - - , - - - - - - - - - - .
· ··· ·t ·············· · · · ··~ · ····· ·· ·· · ·· · ·····~···· ·· ·· · ········ · ··
0.99 ................... +....... ......... j................... ~ ....................

~ ~ ~
···················t···················r·· ··············:····················
0.98 ···················t···················t················· i···················
.•.•• ... .•..•..•. ..•; .•.... •.. ..•• .•..•. j •... . ..•.....•..... j ...... ..... . ..... .
y = 0.99947 - 1.5051 x 10- 2 x 1.0741 x I 3 x 2 + o-
0.97 l = 1.000 ~ ~
0 2
( 1/Vm)/(dm 3mol- 1J
Figure 8.10
(
P8.19 (a) The classical perturbation energy for interaction between the vector dipole 71
\
and an applied
vector electric field i is given by the dot (scalar) product expression
H perturbation = -!l•i =-{µ/ Ex+µ/£ )' +µ,'£ ;}

The dipole moment components of a one-dimensional (x ) oscillator are (µ,,O, 0). For a
perpendicular field the components are something like (0, ~" 0). The dot product of these
vectors is clearly zero, meaning that a perpendicular field cannot perturb the one-dimensional
oscillator. Eqn. 8.10, µ· = ai , addresses the question as to whether or not the applied field can
induce a dipole. The induced response is in the direction of the applied field and the response is
the same irrespective of the direction of the field. The constant of proportionality can be called
the isotropic polarizability. In this problem, however, we ask whether '.EYcan elicit the
responseµ; . An affirmative answer requires an anisotropic material and polarizability; label it
axy' for which µ ; = aX)' '.EY. For a one-dimensional harmonic oscillator, ~xv must equal zerq
because there is no possible coupling of electron motion in the perpendicular directions.
(b) Eqn.8.12 is used to calculate the polarizability when the applied field is parallel to the one-
dimensional oscillator, which is chosen to be the x direction in part (a).
2
lµx.o,,!1 _ lµx,01 l
a= 2 L E,,(oJ - E (oJ
11#0 0
2 E (o)
1
- E (o)
0
2
2 Pt 1/ 2
2e 2 e2
- Pt.w { e( J 2mw }
[2.21]=--2 = (
2mw m kIm
) [2.21]
-[t]
The mass independence of the polarizability arises from the fact that the static (zero-frequency)
polarizability is a response to the stationary electric field and does not depend on the inertial
properties of the oscillator (the rate at which it responds to a changing force).
P8.21 Consider a single molecule surrounded by N - 1( ""N) others in a container of volume V. The number
of molecules in a spherical shell of thickness dR is 47rR 2 x N dR . Molecules cannot approach more

v
closely than the molecular diameter d so R ~ d, and therefore the pair interaction energy is
u=[ 47rR2x ( N Jx( -C66 J dR= -41CNC6 rdR=4

( 47rNC6 Jx(- l3 _ _!___)
d V R V d R 3V 00 d3
-4JCNC6
3Vd 3
The mutual pairwise interaction energy of all N molecules is U = 1Nu (the 1 appears because
each pair must be counted only once, i.e., A with B but not A with Band B with A). Therefore,
U = /-21CN<c 6 /
3Vd 3
For a van der Waals gas, n2~ = ( au ) = 2JCN2C6

v av r 3v 2 d' '
2JCN 2C6
and therefore a= I ~ I [N = nNAl·
3d
RT a
P8.23 p = - - - - 2 [8.24b]
vm -b vm
Factoring out ~T yields p = RT {
1
- _a_}
m Vm 1-b/Vm RTVm
z = p vm = 1 __ a_
RT (1-b / Vm) RTVm
1
~ )- = 1+ ~ + ( ~)
2
which upon the Taylor series expansion ( 1- + ... yields
We note that all terms beyond the second are necessarily positive, so only if
can Z be less than one. If we ignore terms beyond ( , the conditions are simply stated as
m
Z <1 when~>b Z>l when~ 1 when size effects (short-range
repulsions) predominate.
P8.25 For a real gas we may use the virial expansion in terms ofp [8.22a]:
p =nRT (1 + B'p+. ··) =p RT (1 + Bp+···)

V M
. p RT RTB'
which rearranges to - = - + - - p + ·· ·
p M M
Therefore, if terms that are second order and higher in p are negligibly small, P = RT + RTB' p . This
p M M
has the linear form p =intercept + slopex p where the intercept equals RT and the slope equals RTB'.
p M M
Thus, the slope is proportional to B'.
P8.27 Refer to Figure 8.11.
Figure 8.11
The scattering angle is B =7r - 2a if specular reflection occurs in the collision (angle of impact equal
to angle of departure from the surface). For b ~ R1 + R2 , sin a= __b_ _
R, +R2
() =
1Z" _ 2 arcsin ( R
1
!RJ b ~ R, +R2
0 b>R, +R2
The function is plotted in the Figure 8.12.
180°
--- --.......__ -....._
e -........._
---...._
90'
I'---.
'-..,
' I"\
\
0
0 0.2 0.4 0.6 0.8 1.0 1.2
bl(R ,+R2) Figure 8.12
P8.29 The number of molecules in a volume element dT is N: r = Ndr. The energy of interaction of
these molecules with one at a distance R is V(R)N dr. The total interaction energy, taking into
account the entire sample volume, is therefore
u = J V(R)N dr =NJV(R)dr [V(R)is the interaction energy,not the volume]
The total interaction energy of a sample of N molecules is Yi.Nu (the Y2 is included to avoid double
counting), so the cohesive energy density is
U -~Nu 1 1 2
U=--v=-v-=-2Nu=-2N V(R)dr
f
For V(R) =
c
--f and dr = 4JZ"R 2 dR ,
R
v = 2JZ"N 2 C6
- U r d
dR _ 2JZ"
R4 - N C6
- X --
3 d3
2
However, N = N ;,f, where Mis the molar mass; therefore

2
U=i(2f)x(¥ ) x(§tJ
P8.31 The interaction is a dipole-induced-dipole interaction. The energy is given by eqn. 8.13:
= _[(2 .7D)(3.336xl0-3°CmD- )]2(1.04x10-29 m 3 )

1
V =-µ/a/
6
4JZCor 4tr(8.854xl0- 12 r 1 C 2 m- 1 )(4.0xlo-9 m) 6
V=J-1.8xl0-27 J=-1.lxl0-3 Jmor 1 J.
COMMENT. This value seems exceedingly small. The distance suggested in the problem may be too
large compared to typical values. A distance of 0.40 nm, yields V = -1.1 kJ mol_, .
P8.33 (a) The left side molecule in Figure 8.13 is methyladenine. Please note that we have taken the
liberty of placing the methyl group in the position that would be occupied by a sugar in RNA
and DNA. The wavefunction, structure, and atomic electrostatic charges (shown in the figure)
calculation was performed with Spartan '06™ using a Hartree-Fock procedure with a 6-31G*
basis set. The atomic electrostatic charge (ESP) numerical method generates charges that
reproduce the electrostatic field from the entire wavefunction. The right side molecule in Figure
8.13 is methylthymine.
(b) The two molecules will hydrogen bond into a stable dimer in an orientation for which hydrogen
bonding is linear, maximized, and steric hindrance is avoided. We expect hydrogen bonds of
the type N-H · · · · · 0 and N-H · · · · · N with the N and 0 atoms having large negative
electrostatic charges and the H atoms having large positive charges. These atoms are evident in
the figure.
(c) Figure 8.13 shows one of three arrangements of hydrogen bonding between the two molecules.
Another can be drawn by rotating methylthymine over the top of methyladenine and a third
involves rotation to the bottom. The dashed lines show the alignments of two strong hydrogen
bonds between the molecules.
(d) The A-to-T base pairing shown in Figure 8.13 has the largest charges in the most favorable
positions for strong hydrogen bonding. Also the N-to-0 distance of one hydrogen bond equals
the N-to-N distance of the other, a favorable feature in RNA and DNA polymers where this
pairing and alignment is observed naturally.
0.2 1 0.20
0.43
-0.99
r
0.82
Figure 8.13
(e) The favorable orientation for hydrogen bonding between methylguanine (left side molecule)
and methylcytosine (right side molecule) is shown in Figure 8.14. Large counter charges align
within distances that result in three strong hydrogen bonds.
0.42
- 1.03 ~I
0.43 0.18
,,.,.,,.~
0.20
.,..
-0.49
,, ,,;*'
0.42
0.18
0.41
--0.97
0.22 Figure 8.14
P8.35 Molecular mechanics computations with the AMBER force field using the HyperChem package are
reported below. The value of the total potential energy will vary between different force fields , as
will the shape of the potential energy surface. The local energy minimum at r/J= -179.6° and If/=
-4.1 ° is found to have a potential energy equal to 28.64 kJ mor 1 when R = H. This value is used as
a reference to calculate energy differences (11£) on the potential energy surface. till values give the
relative stability of different conformations with higher values indicating energetically unstable
conformations. Similarly, till values were calculated with respect to the local energy minimum at
r/J= -152.3° and If/= 163.2° when R = CH 3•
Initial Optimized
¢1 0 I/fl 0 ¢1 0 If/I 0 El(kJ mor 1) t:.El(kJ mor 1)
(a) R= H 75 -65 - 176.0 8.3 28.765 0.126
180 180 180 180 32.154 3.515
65 35 - 179.6 -4.1 28.639 0.000
(b) R=CH3 75 -65 54.5 19.7 46.338 7.531
180 180 -152.3 163.2 38.807 0.000
65 35 52.9 24.1 46.250 7.443
The computations were set up by using the software's "model build" command- that is, initially
setting default values for bond lengths and angles except for the specified initial values of r/J and If/.
Care must be taken to build the proper chirality at the central carbon when R = CH 3 • Then the
constraints were removed, and the entire structure was allowed to relax to a minimum energy. Not
all the initial conformations relaxed to the same final conformation. The different final
conformations appear to represent local energy minima. It ought not to be surprising that there are
several such minima in even a short peptide chain that contains several nearly free internal
rotations. It is instructive to compare the all-trans ( r/J = If/= 180°) initial conformations in the R = H
and R = CH 3 cases. In the former, neither angle changes, but the resulting structure is not the lowest
energy structure. In the latter, the methyl group appears to push the planes of the peptide link away
from each other (albeit not far) due to steric effects; however, the resulting energy is lower than that
of the other conformations examined.
Two of the initial conformations of each molecule converge to the same energy minimum. These
energy wells are rather broad, and the exact angle at which the computation stops within the
minimum depends on details of convergence criteria used in the iterative methodology of the
software as well as details of the force field. Both sets of computations also found a second local
energy minimum.
An alternative method for studying the energy dependence on ¢>and \{/involves a method like that
specified above but with the AMBER computation performed at fixed values of both angles.
Figure 8.15 summarizes a set of computations with -180° < ¢> < 180° and \f/= 90°. To characterize
the energy surface, one would carry out similar calculations for several values of \f/.
!....0
E 50 ->--~-+---~--+-~--+~-----l~~+--~-+--~--+-~-1
?
"'
40+-~-+-~-t--~------r~----,r--~~~-+-~-+-~-!
- 180 - 135 - 90 - 45 0 45 90 135 180

.pr Figure 8.15
9 Solids
09.1 A space lattice is the three-dimensional structural pattern formed by lattice points representing the
locations of motifs that may be atoms, molecules, or groups of atoms, molecules, or ions within a
crystal. All points of the space lattice have identical environments and they define the crystal
structure. The unit cell is an imaginary parallelepiped from which the entire crystal structure can be
generated, without leaving gaps, using translations of the unit cell alone. Each unit cell is defined in
terms of lattice points. The smallest possible unit cell is called the primitive unit cell. Non-
primitive unit cells may exhibit lattice points within the cell, at the cell center, on cell faces, or on
cell edges.
09.3 We can use the Debye-Scherrer powder diffraction method, follow the procedure in Section
9.3(b)-(d), and in particular look for systematic absences in the diffraction patterns. We can
proceed through the following sequence:
(1) Measure distances of the lines in the diffraction pattern from the center.
(2) From the known radius of the camera, convert the distances to angles.
(3) Calculate sin 2 e.
(4) Find the common factor A=A. 2 /4a 2 in sin 2 B=(A. 2 /4a 2 )(h 2 +k2+/ 2 ).
(5) Index the lines using sin 2 BI A = h 2 + k2 + / 2 •
(6) Look for the systematic absences in (hkl). See Fig. 9.22 of the text. Body-centered cubic
diffraction lines corresponding to h + k +I that are odd will be absent. For face-centered cubic,
only lines for which h, k, and l are either all even or all odd will be present; others will be
absent.
(7) Solve A = A. 2 I 4a 2 for a.
09.5 There are two large-angle meridional reflection spots in the x-ray diffraction pattern obtained from
parallel fibres of B-DNA (Fig. 9.26 of the text). They are reflections off the relatively close planes
(340 pm) of nucleotide bases that run perpendicular to the axis of the molecule (see Fig. 9.28 of the
text). Between these meridional spots is an X-shaped distribution of reflection spots that originates
from planes of longer periodicity (3400 pm; see Fig. 9.27 of the text). The pitch p of the helix, the
distance d between parallel, reflective planes, and the angle a from the meridional of the spots of
the X-pattern are shown in Figure 9.1. The x-rays approach the helix on a path almost perpendicular
to the molecular axis. Regions of high electron density act like reflective planes with each coil of
the helix providing one plane that reflects at a clockwise angle and another that reflects at a
counterclockwise angle. A set of parallel planes that reflect the x-rays at the angle a is shown in
Figure 9.1; one of the set of parallel planes that reflect the x-rays at the angle -a. is also shown.
Reflections from each set of parallel planes constructively interfere to produce one of the legs of the
crossed spot patterns seen at the center of text Fig. 9.26. Constructive interference requires that d =
p cos a. The sequence of spots outward along a leg corresponds to the first-, second-, ... order
diffraction (n = 1, 2, ... where b Bra o-'s law, nil = 2 d sin B [9.2a]). Examination of Figure 9.1
reveals that~~~~~~~~~~~~
SOLIDS 197
a·
~Meridional line
Figure 9.1
09.7 The structure factor Fhkt is the sum over all) atoms of terms each of which has a scattering
factorjj:
The importance of the structure factor to the x-ray crystallographic method of structure
determination is its relationship to the electron density distribution, p(r), within the crystal:
p ( r) = _!_ L F,,k,e - 2m(hx+ky+lz ) [9.5]

v hkl
Eqn. 9.5 reveals that if the structure factors for the lattice planes can be measured, then the electron
density distribution can be calculated by performing the indicated sum. Therein lies the phase
problem. Measurement detectors yield only the intensity of scattered radiation, which is proportional
to 1Fhkil 2, and give no direct information about Fhkl· To see this, consider the structure factor form
I
F,,k, = JFhkl eia,,, where ahkt is the phase of the hkl reflection plane. Then
and we see that all information about the phase is lost in an intensity measurement. It seems
impossible to perform the sum of eqn. 9.5 since we do not have the important factoreia,., .
Crystallographers have developed numerous methods to resolve the phase problem. In the Patterson
synthesis, x-ray diffraction spot intensities are used to acquire separation and relative orientations of
atom pairs. Another method uses the dominance of heavy atom scattering to deduce phase. Heavy
atom replacement may be necessary for this type of application. Direct methods dominate modem
x-ray diffraction analysis. These methods use statistical techniques and the considerable computational
capacity of the modem computer to compute the probabilities that the phases have a particular value.
09.9 In a face-centered cubic close-packed lattice, there is an octahedral hole in the centre. The rock-salt
structure can be thought of as being derived from an fee structure of c1- ions in which Na+ ions
have filled the octahedral holes.
The cesium chloride structure can be considered to be derived from the ccp structure by having er ions
occupy all the primitive lattice points and octahedral sites, with all tetrahedral sites occupied by Cs+ ions.
This is exceedingly difficult to visualize and describe without carefully constructed figures or models.
Refer to S.-M. Ho and B. E. Douglas, J Chem. Educ. 46, 208 (1969) for the appropriate diagrams.
09.11 The Davydov splitting in the exciton bands of a crystal can be understood by considering the
allowed transitions of interacting dipoles of neighboring molecules. As shown in Fig. 9.58 of
the text, the parallel alignment of transition dipoles is energetically unfavorable, and the
exciton absorption is shifted to higher energy (blue-shifted) than in the isolated molecules.
However, a head-to-tail alignment is energetically favorable, and the transition occurs at a
lower frequency (red-shifted) than in the isolated molecules. Transition dipoles are rarely in a
single parallel or head-to-tail alignment. As shown in Fig. 9.59 of the text, transition moments
may often be either energetically favored or energetically unfavorable . These crystals exhibit
both the blue-shifted and the red-shifted band and the separation of the bands is the Davydov
or exciton splitting.
E9.1 (a) The kenter of each edg~ of the body-centered cubic unit cell is equivalent to the point (O,Y2,0).
E9.2(a) The monoclinic P unit cell is defined by the small spheres of Figure 9.2. The separation between
(100) planes is d =a cos(/J- 90°).
b
>
f3
c
a,"13 40°
• > d Figure 9.2
V =bed= be{ acos(/J-90°)}

= abe{ cos(fJ) cos ( 90°) +sin (/J) sin ( 90°)} (standard trigonometric addition formula)
= abe{ cos (fJ)x 0 +sin (/J) x 1}
Iv= abcsin /JI

E9.3(a) When the axis intersections are (3a, 2b, c) and (2a,oob,ooc), the Miller indices of the planes are
{236} and {100}. Simply take the inverse of the intersection multiple and clear fractions to find
these planes.
E9.4(a) For the cubic unit cell, d hkl = a 11 , [9 .1 b].

( h2 + k 2 +/2)
d a - 562 pm -1229 ml
112 (12 +12 +22f 2 - (6)" 2 - p
dllO-
- , _ a \ 1/ 2
= 562, 1~~ = 1397 pml
/ -
a
d 224 = ' - - ' 1/2
SOLIDS 199
E9.5(a) Refer to Fig. 9.22 of the text. Systematic absences correspond to h+k+l=odd . Hence the first
three lines are from planes (110) , (200) , and (211).
sin Bhkt = ~ [9 .2b]

a
d hkt = 2 2 2 1/2 [9.lb], then
2dhkl (h + k + l )
2~)
2 2 2
sin B hkt = (h + k2 + / ) 1/ x(
In a bee unit cell, the body diagonal of the cube is 4R where R is the atomic radius. The relationship
of the side of the unit cell to R is therefore (using the Pythagorean theorem twice)
2 2 2 2 4R
(4R) = a + 2a = 3a or a= 3i/2
This can be seen from Figure 9.3 .
Figure 9.3
4 x l26 pm
a=
3112 =29lpm
,1, 72
pm = 0.124
2a (2) x (291 pm)
sinB110 =.Ji x(0.124) = 0.175
sinB200 =(2) x (0.124)=0.248
sinB211 =.J6x(0.124)=0.304
B = arcsin ~
E9.6(a)
2 [9.2b, arcsin = sin - 1]
flB = arcsin ~ - arcsin {d = arcsin ( ( 2~5:(~~~l;1m) ) -arcsin ( ( 2~5:(~~ ~8P;m) )

=l1.07°l=0.0187 rad
E9.7(a) Justification 9 .1 demonstrates that the scattering factor in the forward direction equals the number
of electrons in the atom or simple ion. Consequently, Ifs,- = 361 .
mass of unit cell m
E9.8(a) p= =-
volume of unit cell V
m = nM = !!_ M [N is the number of formula units per unit cell]

NA
NM
Then, p = -
VNA
and N == pVNA
M
== (3.9xl0 6 gm-3)x(634)x(784)x(516xl0-36 m 3)x(6.022 x l0 23 mol- 1) == _
39
154.77gmol- 1
Therefore, IN== 41 and the true calculated density (in the absence of defects) is
1
p (4)x(154.77gmol - ) ==/4.0lgcm 3/
E9.9(a) dw =[(~H~HHJ'" [9.k]
3 2 2 2 1 2] -1/2
d321 == - + - + - m == 220 m
[ C12) c47) (637) p , p 1
E9.10(a) Ow =»c,;n :w[92b]=a<e,;n{~[(~)' +(H+(~J']"}lc]

2
0,00 =filC,;Il{ 1 ~4 x[( 5~,)' +( 9~? )'+(~Jr}= 1816°1
e,,. ="'°';" {1~4 x[(s~il' +(9: +(~Jr} = l•s2ol 7 r

0,,, = filC,in {~ x[(S~,)' +( 9:? )' +(~Jr}= 111 75°1
1 4
E9.11 (a) From the discussion of systematic absences (Section 9.3 and Fig. 9.22 of the text) we can conclude
that the unit cell is [ace-centered cubig.
E9.12(a) F hkl == L~e 2 "i (h<, +'9·1 +'z, ) (9.4] with f j == t f (each atom is shared by eight cells).
Therefore, F;,k, == t f {l + e21rih + e21rik + e21ri1+ e21ri(h+kJ + e21ri(1i+1) + e21ri(k+i) + e21ri(h+k+1) }.
However all the exponential terms equal 1 since h, k, and I are all integers and
ei9 ==cos B + i sin B [ B == 2;rrh, 2;rrk, ...] == cos B == 1
Therefore, F hkl == [Z].

E9.13(a) The structure factor is given by
F.hkr == "L..J JI";ei¢· where </J; == 2;rr( hx; + ky; + lz;) [9 .4]
All eight of the vertices of the cube are shared by eight cubes, so each vertex has a scattering factor
ofj!8 and their total contribution to the structure factor equals/(see E9.12a). The two side-centered
(C) ions of the unit cell are shared by two cells, and in this problem each has a scattering factor of
2f Their coordinates are (Via, Yia, 0) and (1120, Yw, a). Thus, the contribution of the face-centered
ions to the structure factor is
L f/ ¢; == H2f)e 21ri(h12+k12) +H 2f)e 21ri{h12+k12+1) == fe"i(h+k) {1+e2Jl"il}
i(face-centered)
SOLIDS 201
But, according to Euler's identity (e;9 = cosB + i sinB),
elri(h+k) =cos( n{ h + k}) + isin (n{ h + k}) = cos(n{ h + k}) = (-Itk

and
e2m1 = cos(2nl)+isin(2nl) = cos(2n/) = 1
Thus, L f/ ;' =/(-l)h+k{l+l}=2(-l)h+k f

i(face-centcred)
and the structure factor becomes
F;,*1 = "~ J;e'·i;,· + "~ J;e'.,,' =/+2(-1) h+k f=f { 1+2(-1) h+k}
i(vertices) i(face-centered)
F hkl = 13f for h + k even and - f for h + k odd I
E9.14(a) The electron density is given by
p ( r) = _.!._ L F hkl e -2,,.i(hx+ky+lz) [9.5]

v hkl
The component along the x direction is
( )
px--~r he
- 1" 17 -2lrihx
h v
Using the data of this problem, we sum from h = -9 to +9 and use the relationship Fh = Flhl· The
following Mathcad computation of p(0.5) uses unit volume. Figure 9.4 shows high electron density
at the center of a unit cell edge.
10
-10
8
-8
6
F:=
-6
4
9
-4 p(x ) := L (flh 1
• cos(2 · Jr · h · x))
h=-9
2
p(.5) = 110
-2
120 · . - - - - , - - - - . - - - . - - - - - , - - - - - - ,
100
80
60
p(x)
40
20
- 200·'-----:o"='.
2- --coc"c.4---o::"-.6,.-----:-'o.8, . - - - -
x
Figure 9.4
E9.15(a) Using the information of E9.14(a), the Mathcad computation of P(l.O) is performed with eqn. 9.6.
10
-10
8
-8
6
F:=
-6
4
9
-4 P(x) := L [(Fjhl)2. e - 2 ;rh x J
h=-9
2
P(l.O) = 780
-2
The Patterson synthesis P(x) of Figure 9.5 shows that atoms represented by this data are separated
by 1 a unit along the x-axis.
1000
800
600
P( x) 400
200
-200
-1 -o.5 0 0.5
x Figure 9.5
E9.16(a) Draw points corresponding to the vectors joining each pair of atoms. Heavier atoms give more intense
contribution than light atoms. Remember that there are two vectors joining any pair of atoms
~ f--
( AB and AB ) ; don't forget the AA zero vectors for the center point of the diagram. See Figure 9.6.
BF3
0
0 o~o~
0 ~" '}
0000
0 Figure 9.6
SOLIDS 203
E9.17(a) J. =!!_ =_!:__

p mv
Hence,
E9.18(a) Combine E = t kT and E = t mv 2 = ~ to obtain

2mJ.
J.- h - 6.626x10_34 J s -1233 ml

- (mkTY 12 - [(1.675xl0-27 kg)x(l.38lxl0-23 J K-')x(350K)]"2 - p
E9.19(a) The hatched area in Figure 9.7 is hx2R=3 112 Rx2R=2J3R 2 where h=2Rcos30° . The net
number of cylinders in a hatched area is 1, and the area of the cylinder's base is ;rR 2 • The volume
of the prism (of which the hatched area is the base) is 2J3R 2 L, and the volume occupied by the
cylinders is 7rR 2 L . Hence, the packing fraction is
Figure 9.7
E9.20(a) f =NV. where N is the number of atoms in each unit cell, v. their individual volumes, and Ve the
v
volumecof the unit cell itself. Refer to Figure 9.8 for a view of the primitive unit cell, the bee unit
cell, and the fee unit cell.
Figure 9.8
4 3 3
(a) For a primitive unit cell, N = 1, V. = -JrR , and fl.:= (2R) .
3
4 R3)
1=
(3
7r
(2R) 3
=~=lo.s236I
6
(b) For the bee unit cell, N = 2, v. = ~JZ'R 3 , and fl.: = ( ~ J [body diagonal of a unit cube is 4R].
4
2x - nR 3 r;;
1= 3 =~=lo.6802\
(~J 8
(c) For the fee unit cell, N = 4, V. = .±nR3 , and V,, = (2JiR) 3 •
3
4
4x - 7rR 3
f ~ = 1(~ = lo.74051
(2v L.R) 3 3v2
E9.21 (a) (a) For sixfold coordination, see Figure 9.9.
Figure 9.9
We assume that the larger spheres of radius R touch each other and that they also touch the smaller
interior sphere. Hence, by the Pythagorean theorem,
2
(R+r) =2(R)
2
or (1+ ~ J =2
Thus, ~ = 0.414 and r = 0.414R = (0.414)x(181 pm) =174.9 pmj .
(b) For eightfold coordination, see Figure 9.10.
:,
,' Qv:J
I ~<
1' )I.<,.
..,.,.
Figure 9.10
The body diagonal of a cube is aJ3 . Hence,
aJ3 =2R+2r or J3R=R+r [a=2R]
~=0.732 and r=0.732R=(0.732)x(18lpm)=jl32pmj

R
E9.22(a) The volume change is a result of two partially counteracting factors: (1) different packing fraction
(j) and (2) different radii.
V(bcc) /(hep) v(bcc)

- -=--X--
V(hcp) /(bee) v(hcp)
/(hep)= 0.7405, /(bee)= 0.6802 [Justification 9.3 and E9.20a]
3
V(bcc) = 0.7405x(l42.5) =l.Ol 6
V(hcp) 0.6802 (145 .8) 3
Hence, there is an jexpansionl of 1.6%.

SOLIDS 205
E9.23(a) The lattice enthalpy is the difference in enthalpy between an ionic solid and the corresponding
isolated ions. In this exercise, it is the enthalpy corresponding to the process
The standard lattice enthalpy can be computed from the standard enthalpies given in the exercise by
considering the formation of CaO(s) from its elements as occurring through the following steps:
sublimation of Ca(s), removal of two electrons from Ca(g), atomization of 0 2(g), two-electron
attachment to O(g), and formation of CaO(s) lattice from gaseous ions. The formation reaction of
CaO(s) is
Ca(s) + Y2 0 2(g) - CaO(s)
!:.rHB (CaO,s) = !J.subHB (Ca,s) + !:.; HB (Ca,g)

00
+tt:.bonctctissHB (0 2,g) + !:. 08 HB (0,g) + !:. 08 HB (0- ,g)-!J.LHB (CaO,s)
So the lattice enthalpy is
!J.LHB (CaO,s) = !J.,0 bHB (Ca,s) + !:.;0 0 H B (Ca ,g)

+tt:.bondfasHB (02,g) + !J. 08 HB (0,g) + !:. 0 gHB (0- ,g)-!J.rHB (CaO,s)
!J. LH B (CaO ,s) = [178+ 1735+1( 497)-141+844+635] kJ moi- 1 = 13500. kJ mo1- 1 I
normal stress _ -2
E9.24(a) Young's modulus: E= . [9.13a]=l.2GPa=l.2xlO9 kgm 1 s
normal stram
We solve this relation for the normal strain after calculating the normal stress from the data
provided.
normal stress= force per unit area= F l A
normal strain= relative elongation= M IL
M IL= F IA= mg/A= mg= mg

2
E E AE 7r(d12) E
1.5 kgx9.81 m s- 2
=~~~~~~~~~~~~~~
7r(2.0xl0-3 m!2)2x1.2xl0 9 kgm- 1 s- 2
= lo .0039/ or about 0.4% elongation
. , .
E9.25(a) P OlSSOn s ratio: v = transverse strain [ ]
9 .15 = 0 .45
P normal strain
We note that the transverse strain is usually a contraction and that it is usually evenly distributed in
both transverse directions. That is, if (M IL) , is the normal strain, then the transverse strains,
(M IL) x and (M IL)Y , are equal. In this case of a 2.0% uniaxial stress,
(~ l = +0.020 ( ~ l = - 0.0090 = ( ~) y
New volume= (1-0.0090) 2 x(l + 0.020)xl.O cm 3

3
= 1.0017 cm
3
The change in volume is li.7xl0- cm 3 1.
E9.26(a) Answer: n-type; the dopant, arsenic, belongs to Group 15, whereas germanium belongs to Group 14.
E9.27(a)
_
34 8
_he _(6.626xl0- Js)(2.998xl0 ms-')(
E -hv . - - -
leV
- 3.54 eV
)-1 I
g mm A-max 350.xl0-9 m 1.602xl0-' 9 J
E9.28(a) m = ge {S(S + 1)} 112 µ 8 [9.27, with Sin place of s]
Therefore, because m = 3. 81 µ 8 and ge "" 2,
S(S + 1) = (t)x(3 .81) 2 = 3.63, implying that S = 1.47
Because S "" f , there must be ~hree unpaired spin~.
E9.29(a) Xm = zVm[9.23] = zM I p= (-7.2x 10-1 )x(78.l lg mol- 1) /(0.879 g cm-3)
= l-6.4xl0-5 cm 3mo1-'I = l-6.4xl0- 11 m 3 moi- I

1
E9.30(a) The molar susceptibility is given by
_ NAg;µoµ~ S(S+l) [9.28] 3kTXm

Xm - 3kT so
S(S + 1) = NA g;µoµ~
3
S S+l = 3(1.38lxl0-23 JK-')x(294.53K)x(0.1463xl0-6 m moi-')
( ) (6.022 x 10 23 mor') x (2.0023) 2 x (4n x 10-1 T 2 r' m 3) x (9.27 x 10-24 Jr' ) 2
=6.84
so
-l+Jl+4(6.841)
S 2 +S-6.841=0 and S= =2.163
2
corresponding to 14.3261 effective unpaired spins. The theoretical number is m,corresponding to
the 3d 5 electronic configuration of Mn2+.
COMMENT. The discrepancy between the two values is accounted for by an antiferromagnetic
interaction between the spins, which alters Xm from the form of eqn 9.28.
E9.31 (a) Xm = (6.300lxl0-6 ) x (S(S + l) m 3mo1- 1) [See A BriefIllustration in Section 9.1l(b).]

T!K
Since Cu(II) is a d 9 species, it has one unpaired spin, so S = s = t . Therefore,
(6.300lx10-6 )x(1 )x( f ) m3mol-'=l+l.6xl0 8 m 3 mol ' I

Xm = 298
E9.32(a) The relationship between critical temperature and critical magnetic field is given by
HcCT) = H«o{ 1- ~:) [9.29]
Solving for T gives the critical temperature for a given magnetic field.
1/2 ( 2 I )1/2
T=T l-HcCT) =(7.19K)x 1- 0kAm- =16.0KI
c ( HcCO) ) 63.9 kA m-'
SOLIDS 207
2
P9.1 A.=2d sine = asinehkl [9.2band9.lb] =2asin6.0°=0.209a
hkl hkl (h2+k2+12y12
In a NaCl unit cell (Figure 9.11) the number of formula units is 4 (each corner ion is shared by 8
cells, each edge ion by 4, and each face ion by 2).
Figure 9.11
Therefore,
1/3
implying that a= ( 4 M [Exercise 9.8a]

pNA )
a=( (4)x(58.44gmol-1) J113=563S m

(2.17xl0 6 gm-3)x(6.022xl0 23 mol- 1) · p
and hence A,= (0.209)x(563.5 pm)= jl 18pmj.
P9.3 For the three given reflections
sin19.076° = 0.32682 sin 22.171° = 0.37737 sin32.256° = 0.53370
A.(h2 +k2 +12t2

For cubic lattices sin ehkl = [9 .2b with 9 .1 b]
2a
First, consider the possibility of simple cubic; the first three reflections are (100), (110), and (200).
(See Fig. 9.22 of the text.)
sin e 100 _ 1 0.32682
-- - - -:/:- [not simple cubic]
sine1w J2 0.37737
Consider next the possibility of body-centered cubic; the first three reflections are (110), (200), and (211).
sin el 10 = J2 = _l_ -:/:- 0.32682 (not bee)

e
sin 100 J4 J2 0.37737
Consider finally face-centered cubic; the first three reflections are (111), (200), and (220).
sin el 11 = .J3 = 0.86603

sine200 J4
0 32682
which compares very favorably to · = 0.86605. Therefore, the lattice is !face-centered cubic I.
0.37737
This conclusion may easily be confirmed in the same manner using the second and third reflection.
a= A, (h2+k2+12y12=( 154.18pm )x.J3 = j408.55pmj

2 Sin el I I (2) X (0.32682)
1
NM [E . ] (4)x(l07.87gmol- )
= - - xerc1se 9 .8a
p NAV (6.022lxl0 23 mol- 1 )x(4.0855xl0-8 cm) 3
= 110.507 gcm-31
This compares favorably to the value listed in the Data Section.
P9.5 8111 (lOOK) = 22.0403°, 8111 (300K) = 21.9664°
sin 8111 (lOOK) = 0.37526, sin 8111 (300K) = 0.37406
sinB(300K) = 0.99681 a(lOOK) [see Problem 9.4]

sinB(lOOK) a(300K)
a(300K) = A,Jj (154.0562pm)xJi = 356.67pm

2sin8111 (2)x(0.37406)
a(lOOK) = (0.9968l)x(356.67 pm)= 355.53pm
8a = 356.67-355.53 = . x _3
3 206 10
a 355.53
3 3
8V = 356.67 -355 .53 = 9 .650 x 10_3
v 355.53 3
3
_ _!_ 8V = 9.560 x io- = 14 .8x10-5 K 'I
a vo1ume - V or 200 K
3
=l_8a =3.206x10- =ll.6x10-5 K-'I
a,inear a 8T 200 K
P9.7 V = abcsin/3
and the information given tells us that a= l.377b, c = l.436b, and /3=122°49'; hence
V = (l.377)x(l.436b 3)sinl22°49' = l.662b

3
. NM_ 2M we find that

Smee p = VNA - l.662b3 NA,
1/3
b- 2M
(
l.662pNA )
= (2)x(l28.18g mol- I ) )m = 605 .8 m

( (1.662)x(l.152xl0 6 g m-3)x(6.022xl0 23 mol- 1) p
Therefore, a= 1834pml, b = 1606pml , c = 1870pml.
P9.9 As shown in E9.2(a), the volume of a primitive monoclinic unit cell is
V = abc sin/3 = (1.0427 nm)x(0.8876nm)x(l.3777 nm)xsin(93.254°)

= 1.2730 nm 3
The mass per unit cell is

m = pV = (2.024 g cm -3) x (1.2730 nm 3) x (10 -1 cm nm-
1)3 = 2.577x10-21 g
SOLIDS 209
1
M = [63.546+7(12.011)+13(1.008) + 5(14.007) + 8(15 .999) + 32.066] g mol -
= 390.82 g mol- 1
The number of monomer units, then, is the mass of the unit cell divided by the mass of the
monomer.
21
N = mNA = (2.577 x l0- g) x (6.022~10 mol - ) = .
23 1
3 97
or @]
M 390.82g mo! -
P9.11 The problem asks for an estimate of L'1 rH B(CaCl,s). A Born-Haber cycle would env1s10n
formation of CaCl(s) from its elements as sublimation of Ca(s), ionization of Ca(g), atomization of
Cl 2(g), electron gain of Cl(g), and formation of CaCl(s) from gaseous ions. Therefore,
Before we can estimate the lattice enthalpy of CaCI, we select a lattice with the aid of the radius-
ratio rule. The ionic radius for c1- is 181 pm (Table 9.3); use the ionic radius of K + (138) for Ca+
r= 138pm = 0.762
181pm
suggesting the CsCl structure (A = 1.763, Table 9.4). We can interpret the Born- Mayer equation
(eqn. 9.12) as giving the negative of the lattice enthalpy.
'-'ALH B _ Al z,z2 INAe2(1-d*) w here d*.is tak en to b e 345

. pm (common ch.
01ce )
4trE0 d d
The distanced is d = (138+18l)pm=319pm.

23 19 2
L'1 H B "" (1.763) x I (1)(-1) Ix (6.022 x l0 mol -')x(l.602 x l0- C) ( l 34.5 pm)
L 4JT(8.854Xl0- 12 r'C 2 m- 1 )X(319X10-l2 m) 319pm
"" 6.85 x 10 5 J mor' = 685 kJ mol- 1
The enthalpy of formation , then, is
L'1rHB (CaCl, s) ""[176+589.7+121.7 -348.7 -685] kJ mol-' = 1-146 kJ mo1- 1 I
Although formation of CaCl(s) from its elements is exothermic, formation of CaC1 2(s) is still more
favored energetically. Consider the disproportionation reaction 2 CaCl(s) ---+ Ca(s) + CaCL 2 (s) for
which
L'1HB = L'1 rH B (Ca,s) + L'1 rH B (CaC1 2, s)-2L'1rHB (CaCl,s)

"" [0- 795.8-2(-146)]kJ mor '
"" -504 kJ mol- 1
and the thermodynamic instability of CaCL(s) toward disproportionation to Ca(s) and CaClz(s)
becomes apparent.
Note: Using the tabulated ionic radius of Ca (i.e., that of Ca 2+) would be less valid than using the
atomic radius of a neighboring monovalent ion, for the problem asks about a hypothetical
compound of monovalent calcium. Predictions with the smaller Ca2+ radius (100 pm) differ from
those listed above, but the conclusion remains the same: the expected structure changes to rock salt,
the lattice enthalpy to 758 kJ mor 1, L'1 rH B (CaCl,s) to -219 kJ mo!-' , and the disproportionation
enthalpy to -358 kJ mor' .
P9.13 The molar magnetic susceptibility is given by
Xm NAg:µoµ~S(S + l) = (6.300lxl0--6)x S(S + 1) m 3moJ- 1[A brief illustration in Section 9.1 l(b)]
~T T!K
For S =2,zm (6.300lxl0--6) x (2) x (2 + 1) m3m01 -1=lo.127x10--6 m 3 mol 1 I.

298
6
_ (6.300lxl0- ) x (3) x (3+1) m3m 01 -1 = lo.254 xl0-6 m 3 mo! 1
For S = 3, Xm - 298
I.
_ (6.300lxl0--6) x (4) x (4 + 1) m3m01 -1 = lo.423 xl0-6 m 3 mo! 1

For S = 4, Xm - 298
I.
Instead of a single value of S we use an average weighted by the Boltzmann factor.
3 1
ex ( - 50xl0 Jmoi- J=l.?xl0_9
P (8.3145Jmor 1K- 1)x(298K)
Thus the S = 2 and S = 4 forms are present in negligible quantities compared to the S = 3 form. The
compound's susceptibility, then, is that of the S = 3 form, namely, ~.254 cm3 mo1- I.
1
P9.15 Consider for simplicity the two-dimensional lattice and planes shown in Figure 9.12.
d
a
b
blk Figure 9.12
The (hk) planes cut the a and b axes at a/h and blk, and we have
sina= d hd cosa= d kd
(a/h) =-;;, (blk) = b
Then, since sin 2 a+ cos 2 a= 1 , we can write
(h:Y +(~Y =l
and therefore
~ 2 =(~Y +(~Y
The same argument extends by analogy (or further trigonometry) to three dimensions, to give
2 2 2
di=
I ( -;;
h) f)
k ) + ( -;;
+ ( -;; I [9.lcJ
SOLIDS 211
P9.17 The scattering factor is given by
f = 41l oof p(r)--r

sinkr 2
dr [9.3] h
were 41l . ()
k =-sm
0 kr -1
and the integral may be divided into segments such as
f Rf Sin kr
= 41l p(r)--r dr+41l p(r)--r dr
2 f
00
Sin kr 2
0 kr R kr
In the case for which p = 3Z/47rR3 when 0 ::; r ::; R and p = 0 when r > R, the second integral
vanishes, leaving
f = 3Z3 Rf sin kr r2dr = 3Z

3
R
fsin (kr) rdr
R 0 kr R k 0
_ 3Z [sin kr r cos kr ]r=R

- R 3k ~---k- r=O
= _E__3 {sin kR - cos kR}

(kR) kR
This shows that the scattering factor is proportional to the atomic number Z, which is illustrated in a
plot of/against sin(8)/.A in Figure 9.13 . As expected,/= Zin the forward direction.
15 R = 75 pm
Z = 20
10
-5 ~~~~~~---'-~~~~~~~~-
o 0.004 0.008 0.012 0.016 O.D2
Figure 9.13
Figure 9 .14 is a plot of the scattering factor for several R values at constant Z. As R increases, the
scattering factor shifts to the forward direction.
Z = JO
-2~~~-"-~~~'--~~---'-~~~~~~
0 0.004 0 008 0.012 0.016 002

sin8 I (A. pm-' ) Figure 9.14
P9.19 Replacing an exponentially decreasing ls wavefunction with a Gaussian function effectively

replaces the cusp of the exponential decay near r = 0 with a broader, flatter function while
simultaneously decreasing the long tail of the exponential. Physically, this is analogous to
contraction of the orbital by an increase in the nuclear charge Z. In Problem 9.18 an increase in Z
was found to cause a shift of the scattering factor away from the forward direction. To confirm this
hypothesis, we first fit the ls(Z = 1) exponential exp(p/2) with the exp(-br2) Gaussian by choosing
the constant b so as to minimize the sum of the squared errors (SSE) in the range 0 ~ r ~ 2a.
Doing this in a Mathcad worksheet yields the following b value.
J. rmax
N = 40 j := 0 ... N rmax:= 2 ·a ri:=~
-p(r;, I) ]2
SSE(b) := I ' [ -2 -< - b( r/
Estimate of b: b := 1 · pm-2
Given SSE(b) =0 b:= Minerr(b)

b = 0.00035 pm- 2
" "\
0.8 \
\
\
- p(rj' 1)0.6
\
2
\
e \
-b( r)2 \
e J 0.4 ~
\
\
0.2
\
o~~~~~~~~~~~~~~~~~~~~~~~
"' " ........
-
0 20 40 60 80 100 120
__2__
pm
The absence of both cusp and long tail in the Gaussian is clearly apparent in the worksheet plot.
For the one-electron hydrogen-like atom, 411'p(r) = R15(r) 2 [4.15b] or 411'p(r) = g(r)2, and the
scattering factor is given by
~J sin ( 4Jrxr) 2 sin8

f (r,Z) = 4;r p(r,Z) r dr [9.3] where x=--
0
4Jrxr A,
The next section of the worksheet normalizes the Gaussian g(r) and defines the Gaussian scattering
factorfg .
N := [ ( "
·pm
e-•<d.~-•M' ·r' dr r N = 0.00649 pm 2
2
=1
g(r) = N · e - b(r)' j g(x) := rlOO a g(r) ·Sin(4·7l:·X·r)·r

Ji .pm 4 ·n·x dr
SOLIDS 213
The worksheet setup for the ls radial wavefunction (Table 4.1) and its scattering factor /follows.
pm := 10- 12 · m a:= 52.91772108 pm
z)+
2.Z ·r
( ·e
- p(r , Z)
p(r,Z):=-- R, , (r,Z):=2 · -;; 2
a
ooa R 1 (r Z) 2 ·sin(4 ·.7r ·x ·r)·r

J (x, Z) := 1 pm
' '
4·.lr ·X
dr
The subsequent plots of .f(x,l) and fg(x) confirm the hypothesis that replacement of the ls
wavefunction by a Gaussian function causes the scattering factor to shift away from the forward
direction.
X ·=I· Xmax
N := 200 i:=O ... N xmax := 0.0 l ·pm- I ;· N
0.8
0.4
0.2
0.002 0.004 0.006 0.008

Xj
- I
pm
P9.21 Close-packed rods of length L and elliptical cross-section with semi-major axis a and semi-minor
axis b have a rod volume of 7rabL. The parallelepiped unit cell is shown in Figure 9.15(a) in a cross-
section of the packed rods. Examination of the figure reveals that each unit cell contains one rod.
Thus, the packing fraction/is given by
__ JrabL = Jrab where~
f is the cross-section area of the unit cell
LAP AP
Figure 9.15(b) defines the parameters needed for the determination of Ap· Examination of the center
positions of a pair of stacked ellipses reveals that they have the relative coordinates (0, 0) and
(0, 2b ). The adjacent ellipse column is centered b higher, and consequently the vertical contact
point between the adjacent ellipses is necessarily at b/2. The horizontal component of the contact
point, x, is calculated with the formula for an ellipse using y = b/2.
(~Y +(fY=l
(~Y +(b~2y =l or x = 1-J?,a
2
The parallelepiped area has a base of 2b and its height h is
h = 2x = .J3a
Thus,
~ = 2bh = 2.J3ab
and
f = 1Z"ab _ 1Z"
2.J3ab -
2
.J3 =lo.9011
The above formula for the packing fraction shows that it is independent of the ellipse eccentricity.
(0,2b)
....
h
~
.
2a
2b t
(x, b/2)
(0,0)
(a) (b) Figure 9.15
P9.23 Fhkl ='"" r e 11ri(1u,+1<y,+1z,> [ 4 ]

L,.J ; . 9
For each A atom use t / A (each A atom shared by eight cells), but use / 6 for the central atom
(since it contributes solely to the cell).
F
hkl
= .!. f,
8 A
{l + e 11rih + e21rik + e 11ri1 + e21ri(h+kl + e 11ri(h+1> + e21ri(k+1) + e11ri(h+k+1)}
+f s e "i(h+k+I)
= JA + (-1 ) (h+k+I) / 6
[ h, k,l are all integers, e i1r = -1]
(a) J A =f , / 6 = O; F hkl = f lno systematic absences I

(b) ' = .l2 f,A'· Fhkl = f,A
J B
[1+ .!. (- 2
l) <h+k+i>]
Therefore, when h + k +I is odd, F hkl = JA ( 1-t) = t / A, and when h + k +I is even, F hkl = f / A.
That is, there is an Ialternation of intensity I(I oc I

F 2) according to whether h+ k +I is odd or even I.
(c) /A =/6 =/; F hkl =f{l+(-lt+k+l }=O ifh+k+lisodd
I
Thus, all h + k +I odd lines are missing I·
P9.25 The distance between adjacent ions on the two diagonal lines is d, and consequently the distance
between adjacent ions on the horizontal and vertical lines is c = dcos(45 °) = d/2 112 • These four lines
with their constant, close distance between adjacent ions determine the Madelung constant when
there are very large numbers of ions in a line. The textbook figure shows that distances between
ions on different lines quickly grow to a large value, and consequently the total interaction between
ions on different lines contributes very negligibly to the lattice energy per mole of ions. Thus, the
Madelung constant of this ion arrangement is twice the Madelung constant for a line of alternating
SOLIDS 215
+e cations and -e anions separated by d plus twice the Madelung constant for a line of alternating
+e cations and -e anions separated by c (see the one-dimensional model discussion in Section 9.6b
of the textbook).
2 2
Er=2x(-21n2)x
[ Ne_ A _ )
4:rr&0 d
+2x(-21n2)x [N
_ Ae_ )
41ZC0 c
) +2x(-21n2)x 2 [i12N 2)
= 2x(-2ln2)x ~
N Ae
[ 41ZC0 d 41ZC0 d
2
=-2x(2ln2) x (l +2 112 )x[ NAe )
41ZC0d
Comparing the above equation with eqn. 9.10 yields the Madelung constant.
12
A= 2x(21n2) x (1+i )=16.6941
P9.27 In Justification 9.4 it is shown that the bulk modulus at equilibrium volume is
V (aU)
K = 9a2r4 ar2
2
where r = re is the interatomic separation, a is a constant such that V = ar3, the internal energy U at
T = 0 is the potential multiplied by N, and -lt:I is the minimum value of the potential.
(a) General Mie potential: Vpotenllal = C11

- Cm where n>m
rn rm
aVpo1emia1 nC mC"'
---=---+-- 11
ar r n+I rm+l
0 vpotential
2
n ( n + l) ell m ( m + 1) cm
ar2 rn+2 r m+2
The Mie potential is very general, so we will simplify the discussion of K by examining the special
case for which n = 2m. In this case, it can be shown that
Furthermore, r0 is the separation at which the potential equals zero. Substitution of the special case
values into the K equation gives
2
K= VNlclr "' {2m(2m+l) 2mr~:~l)}
9a2r4 r2m+2
_ 2m
2
VNlcl
9a 2 r 6
Finally, we recognize that ar3 = Vand obtain
K = 2m2N lcl = 2m2 lcl or 2m2NA lcl for n = 2m special case

9V 9 V.nolccule
1
(b) Exp-6potential: Vpotemiai =-Alcl{e-' '0 -(r0 / r) 6 }
where V(0.7525 r )=V(l.2269 r0)=0, V(re)=-14 V(r0 )=0.6321Alcl, A=7.0121, and re =l.6305 r0.
0
avpotential. = --{-e_,1,
Al&I 0 + 6(ro I r)1}
or ro
o Vpo~nt1al. = -Ale!- {e-r/r
2
0 _
42 (ro/ r)8}
r r02
K -_ VN
2 4
{-~{e-rlro -42(r / r) 8}}
2 0
9a r ro
It follows that the bulk modulus at the separation r =re = 1.6305r0 , or r0 = 0.6133r, is
K _ VN {-Ale! {e-1.6Jos _ 42 }}
8
- 9a 2 (1.6305r0 }4 r0 2 1.6305
0.07110l&IVN l.3359l&IVN
= =
2
a r0 6 a2r6
Finally, we recognize that ar3 = V, and obtain
K = l.3359Nlcl = 11.33591£1 or l.3359NAj&I

v vmolecule vm
COMMENT. The exp-6 potential used above has the disadvantage that it is non-zero at r =r0 . The exp-6
potential that is developed in problem 8.22 , VpotentiaJ = -Alel{ e1-' 1' 0 -(r0 /r) 6 }. does equal zero at r = r0 . Its
properties are V(r0 ) = 0 , V(r. ) = -1£1, A= 1.8531 , and r. = 1.3598 r0 . This form of the potential yields
K = 1.1022Nlel = 1.10221£1 or 1.1022NA lel

v vmolecule vm
P9.29 Permitted states at the low-energy edge of the band must have a relatively long characteristic
wavelength while the permitted states at the high-energy edge of the band must have a relatively
short characteristic wavelength. There are few wavefunctions that have these characteristics, so the
density of states is lowest at the edges. This is analogous to the MO picture that shows a few
bonding MOs that lack nodes and a few antibonding MOs that have the maximum number of nodes.
Another insightful view is provided by consideration of the spatially periodic potential that the
electron experiences within a crystal. The periodicity demands that the electron wavefunction be a
periodic function of the position vector r. We can approximate it with a Bloch wave: IJI oc e;;;.,
where k = k x i + ky } + k z k is called the wave number vector. This is a bold "free" electron
approximation and, in the spirit of searching for a conceptual explanation, not an accurate solution.
Suppose that the wavefunction satisfies a Hamiltonian in which the potential can be neglected:
if= -( n2 I 2m) V 2 • The eigenvalues of the Bloch wave are E = n2 I k 12 /2m. The Bloch wave is
periodic when the components of the wave number vector are multiples of a basic repeating unit.
Writing the repeating unit as 27r/L where L is a length that depends on the structure of the unit cell,
we find kx = 2nx 7r/L where nx = 0, ±1, ±2,. ... Similar equations can be written for ky and k,, and with
substitution the eigenvalues become E = (1 I 2m) ( 2:rrn I L ) ( n; + n~ + n: ) . This equation suggests
2
that the density of states for energy level E can be visually evaluated by looking at a plot of
permitted nx, ny, n, values as shown in the graph of Figure 9.16. The number of nx, ny, n, values
within a thin, spherical shell around the origin equals the density of states which have energy E.
Three shells, labeled 1, 2, and 3, are shown in the graph. All have the same width but their energies
increase with their distance from the origin. It is obvious that the low-energy shell 1 has a much
lower density of states than the intermediate-energy shell 2. The sphere of shell 3 has been cut into
the shape determined by the periodic potential pattern of the crystal, and because of this
SOLIDS 217
phenomenon, it also has a lower density of states than the intermediate-energy shell 2. The general
concept is that the low-energy and high-energy edges of a band have lower density of states than
that of the band center.
Figure 9.16
1
P9.31 P(E) = e (E-µ) t kr + [9.20] where Eis measured from in minimum value of Emin = 0.
1
In the case for which E < µ,
lim(E-µ) I kT = lim(-IE-µ1 1kT) = -oo

T~O T~O
Thus,
1
limP(E) = _ I- = - - = 1
T ->0 e- + J 0+ J
I
Conclusion: ii.To P( E) = 1 when E < µI
In the case for which E > 1-1,
lim(E-µ) I kT
T->0
= T->0
lim(IE-µI / kT) = + 00
Thus,
.
hmP(E) = - - = - - =
1 1 0
T ->0 e t<o + 1 oo +}
Conclusion: IV.ToP(E) = 0 when E >µI
~ µ ~
f f
Since Ne= p(E)P(E)dE = p(E)P(E)dE+ p(E)P(E)dE, we findµ at T= 0 by substitution f
0 0 µ
of P = 1 in the first integral and P = 0 in the second integral.

µ(O) ~ µ(0)
N0 = f p(E)xl dE + f p(E)xO dE = f p(E) dE

0 µ(O) 0
t
µ(0) µ(0)
= f p( E)dE = C f E 112
dE where C = 4n-V ( 2m I h
0
2 2
= 2CE312 1£=µ(0J 2Cµ(0) 312

3 E=O
3
Solving for µ(0) yields

213
µ(0)= ( 3N~ )
2
3 2
=1(3Af / 8nf (h /2m.)I where At =N. I V
Because a sodium atom contributes a single valence electron and sodium has a density of about
0.97 g cm-3,
At = N. Iv = NA I vm = NA x mass density I molar mass

= ( 6.022xl0 23 moi- 1)x(0.97 g cm-3) I ( 23 g mol- 1) = 2.5xl0 28 m-3
and
2/3 ( -34 J ) 2
3(2.5xl028 m-3 ) 6.63xl0 s =5.0xl0-1 9 J=l3.l evl
µ(O) =[ 8Jl' ] 2(9.llxl0-31 kg)
P9.33 If a substance responds non-linearly to an electric field E, then it induces a dipole moment:
µ=aE+/JE 2
If the electric field is oscillating at two frequencies, we can write the electric field as
E = E, cos OJil + E2 cos OJ2t
and the non-linear response as
/JE 2 = /J(E1 cos OJil + E2 cos 0Jif) 2
/JE 2 = /J( £ 12 cos 2 OJil + E; cos 2 @it+ 2E1E2 cos aJilcosaJil)
Application of trigonometric identities allows a product of cosines to be rewritten as a sum:

cos A cos B = t cos( A - B) + t cos( A + B)
Using this result (a special case of which applies to the cos 2 terms), yields
/JE 2 = t /J[ E,2 (1+cos20Ji!) + E 2 (1+cos20J2t) + 2E,E2(cos(0Ji + wi)t + COS(OJi - OJ2)t J

This expression includes responses at twice the original frequencies as well as at the sum and
difference frequencies .
P9.35 (a) Hl//+or- = v+ or-1//+or- and ( fJ -v+or- )!//+or- = o
(
vmon-v+or- /J
-Vmon - v+or-
-
)ur'f'+or- =0 where /J =
2
µmon 3 (1- 3 cos 2 B)
/J 41lE hcr
0
(x+;- / +or- )lfl'+or- = 0 where x+or- = ( vmon -v+or_ )! /J
\x+;r- X 1
+or-
I=x2
+or- -1=0
x+or- =(vmon -v+or- )! /J=±l and v+or- =vmon ±/J

v+ = vmon - /J and v_ = vmon + /J
v+ and v_ are plotted in Figure 9.17 as a function of Busing µmon = 4.00 D, vmon = 25000 cm- 1, and
r=0.5 nm.
SOLIDS 219
2.6
V+
2.55
V+or-
2.5
104 cm- 1
2.45
v_
2.4
2.35
0 0.2 0.4 0.6 0.8
Figure 9.17
(J/(rr/2)
The ratio ofµ/ !µ_2 (and the relative intensities of the dimer transitions) doesn't depend on fJ or B
because 14 = 0. To see this, we use the coefficients of the normalized wavefunctions for If/+ and If/-
and the overlap integral S = ( lf/1 11.f/2 ) .
l
x+or -
J(C+or-,1
c+or- ,2
J
=O where x +or- = ±1
(i)
The coefficients must also satisfy the normalization condition.
(If/+or- IIf/+or-) = ( c+or-.1 1.f/1 + c+or- ,21.f/2 Ic+or-.1 1.f/1 + c+or-.2 1.f/2)
2 2
= c+or- ,1 + c+or- ,2 + 2c+or-,l c+or-,2 s
2 2 2
= c+or-, 1 + c+or- ,1 - 2x+or-c+or-,1 S =l (ii)
Thus,
and
l
c =----.,..,..,..
2 c - .2 = c-,1
- ,l {2(l+S)}11
2
c + 1-c+1
[see Problem 9.34] = · · ) =0
[
c - ,1 +c_,1
(b) The secular determinant for N monomers has the dimension NxN.
vmon - vdimer v 0
v Vmon -Vdimer v
=0
0 v iJmon - Vdimer
vdimer = vmon + 2V cos(_!!!_) k = 1, 2, 3, ... , N [9.18]

N+l
2 2
V = /J(O) = µmon (1-3cos 2 o) = -µmon
4trE0 hcr 3 2trE0 hcr 3
The plot in Figure 9.18 shows the dimer transitions for = 0 and N = 15. The shape of the e
transition distribution changes slightly with N and transition energies are symmetrically distributed
around the monomer transition. The lowest energy transition changes only slightly with N giving a
value that goes to
25000 cm- 1 + 2V = 25000 cm- 1 + 2 x (-1289 cm- 1) = 22422 cm- 1 as N ~ oo
Since the model considers only nearest-neighbor interactions, the transition dipole moment of the
lowest energy transition doesn't depend on the size of the chain.
2.8
2.7
2.6
vdimer 2.5
104 cm- I
2.4
2.3
2.2
2 4 6 8 10 12 14
k Figure 9.18
P9.37 N 2 0 4 (g)~2 N0 2 (g)
(l-a)n 2an amounts
1-a
l+a
2a
l+a
mole fractions
(1-a) (
-- p
l+a
-2a
-) p
l+a
. pressures [p = plp<Ct here]
partial
2
(2a/l+a) p 4a 2
K= =--p
2
(1-a/l+a) l-a
Now solve for a.

2
az =K
-
4p+K' a=( 4P:Kr
The degree of dimerization is d = 1- a = 1-( 4 p ~ K) 1/2 = Il - ( 4(p / k) + 1)1/2
The susceptibilit varies in proportion to a= I - d. As pressure increases, a decreases and the
susceptibility decreases .
SOLIDS 221
To determine the effect of temperature we need l:!.,H "" l:!. ,H & for the reaction above.
1 1
l:!. ,H & =2x(33.18 kJmol - )-9.16 kJmol - =+57.2 kJmol -'
A positive l:!.,H& indicates that N0 2(g) is favored as the temperature increases; hence, the
susceptibility lincreasesl with temperature.
Solutions for applications
P9.39 The density of a face-centered cubic crystal is 4m/ V where mis the mass of the unit hung on each
lattice point and Vis the volume of the unit cell. (The 4 comes from the fact that each of the cell's 8
vertices is shared by 8 cells, and each of the cell ' s 6 faces is shared by 2 cells.)
4m 4M 1 3
So p=-=--andM= - pN a
a3 N a3 4 A
A
M = "i- (1.287 g cm-3 ) x (6.022 x l0 23 mor' ) x (l2.3 x l0- 7 cm) 3

5
= 13.6l x l0 gmor' I
P9.41 Tans and coworkers (S. J. Tans et al. , Nature , 393, 49 (1998)) have draped a semiconducting carbon
nanotube (CNT) over metal (gold in Figure 9.19) electrodes that are 400 nm apart atop a silicon
surface coated with silicon dioxide. A bias voltage between the electrodes provides the source and
drain of the molecular field-effect transistor (FET). The silicon serves as a gate electrode and the
thin silicon oxide layer (at least 100 nm thick) insulates the gate from the CNT circuit. By adjusting
the magnitude of an electric field applied to the gate, current flow across the CNT may be turned on
and off.
Figure 9.19
Wind and coworkers (S. J. Wind et al., Applied Physics Letters, 80, 20 (May 20), 3817 (2002)) have
designed a CNT-FET of improved current carrying capability (Figure 9.20). The gate electrode is
above the conduction channel and separated from the channel by a thin oxide dielectric. In this
manner the CNT-to-air contact is eliminated, an arrangement that prevents the circuit from acting
like a p-type transistor. This arrangement also reduces the gate oxide thickness to about 15 nm,
allowing for much smaller gate voltages and a steeper subthreshold slope, which is a measure of
how well a transistor turns on or off.
mil .·' Nanotube
Silicon Wafer
Gate Oxide Figure 9.20
A single-electron transistor (SET) has been prepared by Cees Dekker and coworkers (Science, 293,
76 (2001)) with a CNT. The SET is prepared by putting two bends in a CNT with the tip of an AFM
(Figure 9.21). Bending causes two buckles that, at a distance of 20 nm, serves as a conductance
barrier. When an appropriate voltage is applied to the gate below the barrier, electrons tunnel one at
a time across the barrier.
Figure 9.21
Weitz et al. (Phys. Stat. Sol. (b), 243, 13, 3394 (2006)) report on the construction of a single-wall CNT
using a silane-based organic self-assembled monolayer (SAM) as a gate dielectric on top of a highly
doped silicon wafer (Figure 9.22). The organic SAM is made of 18-phenoxyoctadecyltrichiorosilane.
This ultrathin layer ensures strong gate coupling and therefore low operation voltages. Single-electron
transistors (SETs) were obtained from individual metallic SWCNTs. Field-effect transistors made
from individual semiconducting SWCNTs operate with gate-source voltages of -2 V, and they show
good saturation, small hysteresis (200 mV), and a low subthreshold swing (290 mV/dec).
Source Drain
SWCNT
,,,,,,,..sAM2nm
I Heavily doped Si 1- Si0 2 (4 nm)
Figure 9.22
SOLIDS 223
John Rodgers and researchers at the University of Illinois have reported a technique for producing
near-perfect alignment of CNT transistors (Figure 9.23). The array is prepared by patterning thin
strips of an iron catalyst on quartz crystals and then growing nanometer-wide CNTs along the strips
using conventional carbon vapor deposition. The quartz crystal aligns the nanotubes. Transistor
development then includes depositing source, drain, and gate electrodes using conventional
photolithography. Transistors made with about 2,000 nanotubes can carry currents of 1 ampere,
which is several orders of magnitude larger than the current possible with single nanotubes. The
research group also developed a technique for transferring the nanotube arrays onto any substrate,
including silicon, plastic, and glass. See Coskun Kocabas, Seang Jun Kang, Taner Ozel, Moonsub
Shim, and John A. Rogers, J. Phys. Chem. C, 2007, 111, 17879, Improved Synthesis of Aligned
Arrays of Single-Walled Carbon Nanotubes and Their Implementation in Thin Film Type
Transistors.
99.97% aligned tubes

-20µm
Figure 9.23
PART 3 Molecular spectroscopy
10 Rotational and
vibrational spectra
010.1 Symmetric rotor: the energy depends on J and K2 [eqn. 10.10], hence each level except the K = 0
level is doubly degenerate. In addition, states of a given J have a component of their angular
momentum along an external, laboratory-fixed axis, characterized by the quantum number M1 , that
can take on 2f + 1 values. The quantum number M1 does not affect the energy; consequently all
2f + 1 orientations of the molecule have the same energy. It follows that a symmetric rotor level is
2(2! + 1)-fold degenerate for K""' 0 and 2f + 1 degenerate for K = 0.
Linear rotor: A linear rotor has K fixed at 0, but there are still 2f + 1 values of M;, so the
degeneracy is 2f + 1.
Spherical rotor: A spherical rotor can be regarded as a version of a symmetric rotor in which A = B,
and consequently, the energy is independent of the 2f + 1 values that K can assume. Hence there is
simultaneous degeneracy of 2f + 1 in both Kand M1 , resulting in a total degeneracy of (2! + lf
Asymmetric rotor: In an asymmetric rotor there is no longer a preferred direction in the molecule
that carries out a simple rotation about J. Thus for each value of J, there is only a degeneracy of
2f + 1, as in a linear rotor.
If a decrease in rigidity affects the symmetry of the molecule, the rotational degeneracy could be
affected also. For example, if a wobble resulted in a spherical rotor being transformed into an
asymmetric rotor, the rotational degeneracy of the molecule would change.
010.3 In addition to the quantum numbers J and K, the rotational states of molecules are characterized by
a quantum number ~, which can take on 2f + 1 values 0, ± 1, ±2, ... , ±J. In the absence of
external fields, the energy of the molecule does not depend on M1 , and for linear rotors, for
example, there is a degeneracy of 2f + l associated with the quantum number M1 in the state J This
degeneracy is partly removed when an electric field is applied to a polar molecule, such as HCl.
This splitting of the energies of the M1 states is called the Stark effect and is proportional to the
permanent dipole moment of the molecule. The observation of the Stark effect can therefore be used
to measure molecular dipole moments in microwave spectroscopy. The Stark effect is also of
importance in the technology of microwave spectrometers because an oscillating electric field will
modulate the position of spectral lines and therefore the intensity of absorption or emission at a
particular frequency. Spectrometers using detectors that make use of this oscillation of the intensity
are called Stark modulation spectrometers.
010.5 (1) Rotational Raman spectroscopy. The gross selection rule is that the molecule must be
anisotropically polarizable, which is to say that its polarizability, a, depends on the direction of
the electric field relative to the molecule. Non-spherical rotors satisfy this condition. Therefore,
linear and symmetric rotors are rotationally Raman active.
(2) Vibrational Raman spectroscopy. The gross selection rule is that the polarizability of the
molecule must change as the molecule vibrates. All diatomic molecules satisfy this condition as
the molecules swell and contract during a vibration, the control of the nuclei over the electrons
varies, and the molecular polarizability changes. Hence both homonuclear and heteronuclear
diatomics are vibrationally Raman active. In polyatomic molecules it is usually quite difficult to
judge by inspection whether or not the molecule is anisotropically polarizable; hence group
theoretical methods are relied on for judging the Raman activity of the various normal modes of
vibration. The procedure is discussed in Section 10.lS(b) and demonstrated in A BriefIllustration.
010.7 1
=
H 12 C 12 C 1H is a linear molecule. It has hydrogen nuclei with half integral spin and carbon nuclei
with zero spin. Rotation by 180 degrees produces an equivalent form. This rotation is equivalent to the
interchange of identical hydrogen nuclei. Since hydrogen is a fermion, the overall rotational wave
function must be antisymmetric with respect to exchange of identical particles. The overall statistics
are Fermi statistics. This leads to the result that symmetric hydrogen nuclear spin functions must be
paired with antisymmetrical spatial wave functions for rotation and vice versa. Consequently
1
=
H 12 C 12 C 1H will exhibit ortho and para forms just as for H2 • The (odd ])/(even J) statistical weight
ratio is 3/1.
2
=
H 12 C 12 C 2 H is a linear molecule. It has deuterium nuclei with integral spin and carbon nuclei
with zero spin. Rotation by 180 degrees produces an equivalent form. This rotation is equivalent to
the interchange of identical deuterium nuclei. Since deuterium is a boson, the overall rotational
wave function must be symmetric with respect to exchange of identical particles. The overall
statistics are Bose statistics. This leads to the result that symmetric deuterium nuclear spin functions
must be paired with symmetrical spatial wave functions for rotation and also leads to the result that
antisymmetric deuterium nuclear spin functions must be paired with antisymmetrical spatial wave
functions for rotation. Consequently 2 H 12 C = 12 C 2 H will exhibit ortho and para forms. The
(odd ])/(even J) statistical weight ratio is 3/6.
From the point of view of the effect of nuclear statistics on the occupation of rotational energy levels,
the situation in 1H 13 C = 13 C 1H is similar to the case of 2 H 12 C = 12 C 2 H. 1H 13 C = 13 C 1H will exhibit
ortho and para forms. The (odd ])/(even J) statistical weight ratio is 6/10.
010.9 The rotational constants in vibrationally excited states are smaller than the constants in the
vibrational ground state and continue to get smaller as the vibrational level increases. Any
anharmonicity in the vibration causes a slight extension of the bond length in the excited state.
This results in an increase in the moment of inertia and a consequent decrease in the rotational
constant. Problem 10.13 gives the equation that describes how the rotational constant changes
~ith increasing vibrational level. That equation is Bv=Be -a(v+!), where Be is a constant and
Bv is the rotational constant in level v.
010.11 The exclusion rule applies to the benzene molecule because it has a center of symmetry.
Consequently, none of the normal modes of vibration of benzene can be both infrared and Raman
active. If we wish to characterize all the normal modes, we must obtain both kinds of spectra. See
the solutions to Exercises 10.25(a) and 10.25(b) for specific illustrations of which modes are IR
active and which are Raman active.
E10.1 (a) Ozone is an asymmetric rotor similar to H20; hence we follow the method of Example 10.1 and use
I= Lmixi [10.l] to calculate the moment of inertia, fc, about the C2 axis.
I= m0 (x6 +O+x6) = 2m0 x6 = 2m0 (Rsin¢) 2

where the bond angle is denoted 2¢ and the bond length is denoted R. Substitution of the data gives
I= 2xl5 .9949uxl .66054x10-27 kg/ux(l.28x10- 10 mxsin58.5°) 2
6 2
= j6.33 x 10-4 kg m j
ROTATIONAL AND VIBRATIONAL SPECTRA 229
The corresponding rotational constant is
A=-tz-= l.05447xl0-34 Js =44.21m-1 =I0.4421cm-'I

4trclc 4nx2.998xl0 8 m s- 1x6.33xl0-4 6 kg m 2
E10.2(a) In order to conform to the symbols used in the first symmetric rotor figure of Table 10.1, we will use
the molecular formula B~. / 11 is along a bond and I J.. is perpendicular to both / 11 and a molecular
face that does not contain / 11 (see the spherical rotor of text Figure 10.4). For our molecule, R '= R,
me= mA, and the equations of Table 10.1 simplify to
/
11
I mAR 2 =2(1-cosB)
IJ.. I mAR 2 = 1-cosB+ ( mA + m6 ) x (l + 2cosB) I m
2
+{ (3mA + m6 ) + 6mA[.X (1+2cosB)]'1 } I m where m = 4mA + m6
The / 11 I mAR 2 moment of inertia ratio does not depend on specific atomic masses, so the plot of this
ratio against e, shown in Figure 10.1 , describes the angular dependence of all molecules having the
formula BA4. However, the IJ.. I mAR 2 moment of inertia ratio does have a specific atomic mass
dependency, so we will plot its angular dependence for CH4, an important fuel and powerful
greenhouse gas. The computational equation is
IJ.. I mAR2 = 1-cosB+ 13(1+2cosB) I 16+{ 15 + 6[,X' (1+2cosB)]1'2} I 16

and its plot is also found in Figure 10.1. As e increases, atoms move away from the axis of / 11 ,
which causes the moment of inertia around this axis to increase. Atoms move toward the axis of
IJ.. as eincreases, thereby decreasing the moment of inertia around this axis.
COMMENT. Figure 10.1 suggests that /11 (0161,8 ) = /J.. (0101,8 ) for all tetrahedral molecules where 0161,8 is the
tetrahedral angle (approximately 109.471 °). Can you provide an analytic proof that this is true? Hint: The
1
exact value of e101ra is 1C I 2 + sin- (1 I 3) in radians where sin- () is the arcsin() function .
1
2.8
2.6
2.4
2.2 /
11
all BA 4 molecules
2 ~~~~~~~~~~~~~~~~~
90 95 100 105 110 Figure 10.1

0
BI
E10.3(a) (a) asymmetric (b) oblate symmetric (c) spherical (d) prolate symmetric
E10.4(a) NO is a linear rotor, and we assume that there is little centrifugal distortion; hence
F(J) = BJ(J + 1) [10.12]
with
- tz
B=-- l=m tr R [TablelO.l],and
2
4trcl' e
m0 ff = ~mo [nuclide masses from the Data Section]

mN+mo
= ( (14.003 u)x (15.995 u) Jx (1.6605 xl0-27 kgu-t) = l.240x 1o-26 kg

(14.003 u) + (15.995 u)
Then I= (1.240xl0-26 kg)x(l.15x10-' 0 m) 2 = l.640xl0-46kg m 2
and
B= l.0546x10-34 Js _ 1
(4n)x(2.998xl0 8 m s 1 )x(l.640 xl0-46kg m2) = 170.7m-' = l.707cm-
The wavenumber of the J = 3 f-- 2 transition is
v = 2B(J + 1)[10.l 7a] = 6B[J = 2] = (6)x(l.707cm-')=10.24cm- 1
The frequency is
102
v = vc = (10.24 cm- 1 )x( m~' Jx(2.998xl0 ms- 8 1
) = l3 .07xl0 11 Hzl
1 cm
When centrifugal distortion is taken into account, the frequency decreases, as can be seen by
considering eqn. 10.17(b).
Question. What is the percentage change in these calculated values if centrifugal distortion is
included?
E10.5(a) The wavenumber of the transition is related to the rotational constant by
hcv =till= hcB[J(J + 1)-(J - l)J] = 2hcBJ [10.6, 10.8]
where J refer to the upper state (J = 3) . The rotational constant is related to molecular structure by
s = _n_
4ncl
[10.5]
where I is moment of inertia. Putting these expressions together yields

34
v = 2sJ = __!!!___ so !=__!!!___= (1.0546xl0- Js)x(3)
2ncl 2ncv 2n(2.998xl0' 0 cm s-')x(63.56cm-')
= 2.642xl0-47kg m 2
The moment of inertia is related to the bond length by
l=m.rrR 2 soR= - -
m.rr
f,E
m-l =m-l +m-l = (1.0078 ur' +(34.9688 ur' = 6 . 1477 Xl026 k - I
eff H Cl l.66054Xl0-27kgu-l g
and R = ~(6.1477xl0 26 kg-')x(2. 642xl0-4 7 kg m 2) = l.274x10-' 0 m = 1127.4 pml
E10.6(a) If the spacing of lines is constant, the effects of centrifugal distortion are negligible. Hence we can
use for the wavenumbers of the transitions
F(J)-F(J-1)=2BJ [10.8]
Since J = 1, 2, 3, ... , the spacing of the lines is 2 B.
12.604 cm- 1 = 2B
B = 6.302 cm- 1 = 6.302xl0 2m- 1

I= 4ncB
1i
= m.rrR2
1i l.0546x 10-34 Js
4nc (4n)x( 2.9979xl0sm8 -1) = 2.7993x10-44kg m
1 =2.7993xl0-« kgm=1 4 .442 x 10-47k m2I

6.302 x l0 2m- 1 g
= ( (26 .98)x (1.008)) u x (1.6605x10-21k u -1) = 1.6136x10-21 k

(26.98) + (1 .008) g g
1 112 ( 4 42 -47 2 J"2

R= - - = .4 xl0 kg 27 m = l.659xl0- 10 m=ll65.9 pml
( meff ) l.6136xl0- kg
E10. 7(a) The determination of two unknowns requires data from two independent experiments and the
equation that relates the unknowns to the experimental data. In this exercise, two independently
determined values of B for two isotopically different HCN molecules are used to obtain the
moments of inertia of the molecules, and from these, by use of the equation for the moment of
inertia of linear triatomic rotors (Table 10.1), the interatomic distances RHc and RcNare calculated.
Rotational constants that are usually expressed in wavenumber (cm- 1) are sometimes expressed in
frequency units (Hz) . The conversion between the two is
B ! Hz=c x B / cm-' [cincms- 1]
Thus, B(in Hz)=_!!__ and I=-;,,-

4Jr1 4TrB
2
Let 'H = H, H = D, RHc =Roe = R, RcN = R'. Then
34
J(HCN) = l.0 5457 xl0- J s = l.8937xl0-46kg m 2
(4Tr) x ( 4.4316 x 10 10 s- 1)
J(DCN)= l.05457xl0-J4 Js =2.3178xl0-46 kgm2

( 4Tr)x (3.6208xl0' 0s-')
and from Table 10. l with isotope masses from the Data Section,
2
2 2 (1.0078R-14.0031R') ]]
J(HCN) = ( 1.0078R ) + (14.0031R' )- u
[ ( 1.0078+12.0000+ 14.0031
Multiplying through by m I u = (mH +me + mN) I u = 27.0109,

2
27.0109xJ(HCN) = {27.0109x(l.0078R 2 +14.0031R'2)-(1.0078R-14.0031R') }u
27 0109 18 2
or · Jx(1.8937xl0-4 6k m 2) = 3.0804xl0- m
( l.66054xl0-27 kg g
= {27.0109 x (l .0078R 2 +14.0031R' 2)-(l .0078R-14.0031R')2} (a)
In a similar manner we find for DCN
28 0172
· ) x(2.3178xl0-46k m 2)=3.9107xl0- ' 8m 2
( l.66054xl0- 27 kg g
= {28.0l 72x( 2.0141R 2 +14.0031R'2 )-(2.0141R-14.0031R') 2} (b)

Thus there are two simultaneous quadratic equations (a) and (b) to solve for R and R'. These
equations are most easily solved by readily available computer programs or by successive
approximations. The results are
R = l.065xl0- 10 m = 1106.5 pml and R' = l.156xl0- 10 m = 1115.6 pml
These values are easily verified by direct substitution into the equations and agree well with the
accepted values RHc = 1.064 x 10- 10 m and RcN = 1.156 x 10- 10 m.
E10.8(a) The Stokes lines appear at
v(J + 2 f- J) = V;-2B(2J + 3)[10.20a] with J = 0, v = v ;-6B
Since B= 1.9987 cm- 1

(Table 10.2), the Stokes line appears at
v = (20487)-(6)x(l.9987 cm- 1) =120475cm-1I

E10.9(a) The separation of lines is 4B [10.20a and 10.20b] , so B= 0.2438cm- 1
• Then we use
l/2
R- n
(47tmerrcB J
5
with merr = 1m(3 Cl) = (1)x(34.9688u)=17.4844 u
Therefore
2
R=( 1.05457x10- J s
34
Jl/
(47t)x(l 7.4844)x(l .6605xl0-27 kg)x(2.9979xl0 10 cm s- 1)x(0.2438cm- 1)
= l.989x10- 10 m = ll98.9pml
E10.1 O(a) Polar molecules show a pure rotational absorption spectrum. Therefore, select the polar molecules based
on their well-known structures. Alternatively, determine the point groups of the molecules and use the
rule that only molecules belonging to c ., c .v, and C, may be polar, and in the case of c . and c .v, the
dipole must lie along the rotation axis. Hence the polar molecules are
(b) HCI (d) CH 3 Cl (e) CH 2 Cl 2
Their point group symmetries are
(b) Cv (d) c 3v (e)C2h (trans) ,C2)cis)
COMMENT. Note that the cis form of CH 2 Cl 2 is polar, but the trans form is not.
E10.11 (a) We select the molecules with an anisotropic polarizabili . A ractical rule to apply is that spherical
rotors do not have anisotropic polarizabilities. Therefore (c) C~ is inactiv . All others are active.
E10.12(a) For diatomic molecules, we can use eqn. 10.21 to determine the statistical ratio of weights of
populations. For chlorine-35 I= 3/2, and hence
Ratio of (odd J/even J) weights of populations is

1 1
+ =
I
fil
llJ
k )112
E10.13(a) w = 2.nv = ( m
k = 4Tt2v 2m = 47t2x(2.os- 1) 2 x(O.lOOkg)=16kgs-2 = l16N m- 1 I

1/2
E10.14(a) w= (_ls_ ) [10.32]
m.rr
The fractional difference is
of-wJif-(tf JtJ'-(tf
w (-l (_5__J1/2 J1/2 m;rr
112
=(m·rrJ _1
m.rr m.rr
5 7 l/ 2
3 3
= m{2 Na)m(3 Cl){m(2 Na)+m(3 Cl)} _1
(
{m(23 Na)+m(3 5 Cl)}m{23 Na)m(3 7 Cl) J
J1/2
~
5 3 7
= m(3 Cl) x m(2 Na)+ m(3 Cl) _1
( m(3 7 Cl) m{23 Na)+m(3 5 Cl)
= 34.9688 x 22.9898 + 36.9651 -1=-0.01077
( 36.9651 22.9898 + 34.9688 )
Hence, the difference is 1.077 percent I I·
1/2
E10.1 S(a) W= ( :.ff ) (10.32]; W= 2JW = 2Jr(1) = 2JrcV
= (4Jr 2 )x(3 4 ·~688 )x(l.66054xl0- 27 10 1

kg)x[(2.997924xl0 cms- )x(564.9cm-
1
)]2
= 1328.7 N m- 1 I
1/2
E10.16(a) W= -
k 2
[10.32], so k = m.rrw = 4Jr m.rrc v
2 2-2
(
meff )
m (H19F) = (1.0078)x(18.9984) u=0.9570u

eff (1.0078)+(18.9984)
m (H 35 Cl) = (1.0078) x (34.9688) u = 0. 9796 u

eff (1.0078) + (34.9688)
m {H 81 Br)= (1.0078)x(80.9163) u =0. 9954 u

elf (1.0078) + (80.9163)
m (H 127 I) = (1.0078)x(l26.9045) u=0. 9999 u

eff (1.0078) + (126.9045)
We draw up the following table.
HF HCI HBr HI
1 4141.3 2988.9 2649.7
ii/cm- 2309.5
m,rr /u 0.9570 0.9697 0.9954 0.9999
k I (Nm-') filg ~ fill] filTil
Note the order of stiffness HF > HCI > HBr > HI.
Question. Which ratio, B(Ak_ B) or B(:- B) , where B(A- B) are the bond energies, is the
more nearly constant across the series of hydrogen halides? Why?
E10.17(a) Data on three transitions are provided. Only two are necessary to obtain the value of v and xe. The
third datum can then be used to check the accuracy of the calculated values.
~G(v = 1 +--- o) = v-2vx0 = 1556.22cm- 1[10.38J

~G( v = 2 +--- 0) = 2V - 6v x 0 = 3088.28 cm- ' [10.39]
Multiply the first equation by 3, then subtract the second
ii= (3) x (1556.22 cm- ' )-(3088.28 cm- ') =11580.38 cm-' I
Then from the first equation
v-1556.22cm -' (1580.38-1556.22)cm-i = /7.644xl0 3/

xe = 2v (2)x(1580.38cm ')
xedata are usually reported as xev, which is
xev = 12.08cm- '
~G(v = 3 +--- 0) = 3v-12Vxe

= (3) x (1580.38 cm- 1) - (12) x (12.08 cm- 1) = 4596.18cm- 1
which is very close to the experimental value.
E10.18(a) The R branch obeys the relation
vR (J) = v+ 2B(J + 1) [l 0.42c]

Hence, vR (2) = v+ 6B = (2648.98 cm- ')+ (6)x(8.465 cm- ') [Table 10.2] = 12699.77 cm- ' I.
E10.19(a) See A Brief Illustration. Select the molecules in which a vibration gives rise to a change in dipole
moment. It is helpful to write down the structural formulas of the compounds. The infrared active
compounds are
(b) HCl (c) co 2 (d) H 20
COMMENT. A more powerful method for determining infrared activity based on symmetry considerations
is described in Section 10.15. Also see Exercises 10.23-10.24.
E10.20(a) The number of normal modes of vibration is given by (Section 10.15)
3N - 5 for linear molecules }

N .b = {
VI 3N - 6 for nonlinear molecules
where N is the number of atoms in the molecule. Hence, since none of these molecules are linear,
(a) 3 (b) 6 (c) 12
COMMENT. Even for moderately sized molecules, the number of normal modes of vibration is large and
they are usually difficult to visualize.
E10.21 (a) This molecule is linear; hence the number of vibrational modes is 3N - 5. N = 44 in this case;
therefore, the number of vibrational modes is 11211.
1/2
1
E10.22(a) vq = -- !s_ [l0.46J
2nc [ mq )
The lowest energy term is Ji2 , corresponding to the normal mode for bending. For this mode the
oxygen atom may be considered to remain stationary and the effective mass is approximately
2
m = mttmo . For the other modes, the effective mass expression is more complicated and is
q 2mH +m0
beyond the scope of this text. However we know that in the ground vibrational state all normal
modes have v = 0. Thus, since H 20 has the three normal modes shown in text Fig. 10.41, the ground
vibrational term is the sum of eqn. 10.46 normal mode terms: Gground = G1(0) + G2 (0) + G3 (0) =
IYi(v1 +v2 +v3)I.
E10.23(a) See Figs. 10.4l(H20, bent) and 10.40(C02 , linear) of the text as well as A Brief Illustration. Decide
which modes correspond to (i) a changing electric dipole moment and (ii) a changing polarizability,
and take note of the exclusion rule (Sections 10.13a-10.15).
(a) Nonlinear: All modes are both infrared and Raman active.
(b) Linear: The symmetric stretch is infrared inactive but Raman active.
The antisymmetric stretch is infrared active and (by the exclusion rule) Raman inactive. The two
bending modes are infrared active and therefore Raman inactive.
E10.24(a) The uniform expansion is depicted in Figure 10.2.
Figure 10.2
Benzene is centrosymmetric, so the exclusion rule applies (Section 10.14). The mode is infrared
inactive (symmetric breathing leaves the molecular dipole moment unchanged at zero), and
therefore the mode may be (and is) IRaman active!. In group theoretical terms, the breathing mode
has symmetry A 18 in D 6h , which is the point group for benzene, and quadratic forms x 2 + y 2 and z 2
have this symmetry (see the character table for C6h, a subgroup of D 6h ). Hence, the mode is Raman
active.
E10.25(a) Use the character table for the group C2v (and see Example 10.3). The rotations span A 2 + B1+ B 2 .
The translations span A 1 + B1 + B2 • Hence the normal modes of vibration span the difference,
l4A 1+ A 2+ 2B 1+ 2B 21.
COMMENT. A 1, 8 1 and 8 2 are infrared active; all modes are Raman active.
E10.26(a) See the comment in the solution to Exercise 10.25(a). AP B1 and B 2 are infrared active; all modes
are Raman active.
E10.27(a) The ratio of coefficients A/B is
A 8nhv 3 •
- =- -3 - [Eqn. l 0.55, Further Informatzon l 0.1]
B c
The frequency is
c A 8trh
V=- SO -=-
/!. B 11.3
34
(a) A_ 8tr(6.626xl0- Js) = lo.0469Jm 3 sl
B - (70.8xl0 12 m) 3
34
(b) A_ 8trh = 8tr(6.626xl0- ;s) =l1.33xl0- 13 Jm 3 sl
B - 11.3 (500xl0-9 m)
(c) A= S~h = 8trhv 3 = 8tr{6.626xl0-34 J sx[3000cm- 1 x (l0 2 m- 1 /lcm- 1)]3 }

B A,
= 14.50xl0- 16 J m-3 sl
COMMENT. Comparison of these ratios shows that the relative importance of spontaneous transitions
decreases as the frequency decreases. The quotient ~ has units. A unitless quotient is ~ with p
B Bp
given by eqn. 10.51.
Question. What are the ratios _i_ for the radiation of (a) through (c) and what additional
Bp
conclusions can you draw from these results?
P10.1 Rotational line separations are 2B in wavenumber units, 2Bc in frequency units, and ( 2B r 1 in
wavelength units. Hence the transitions are separated by ~96GHzj, 119.9 cm- 11, and R.503 ~-
Ammonia is a symmetric rotor (Section 10.1), and we know that
s=-"-[10.111
4trcll.
and from Table 10.1,
2 2
fl. =mAR (1-cosB)+ ( m:nms ) R (1+2cosB)
mA = 1.6735 x 10-21 kg,m8 = 2.3252 x 10-26 kg, andm = 2.8273 x 10- 26 kg with R = 101.4 pm and B =
106°47', which gives
27 12
fl. = ( l .6735xl 0- kg )x( 1Ol .4 x l o- m )2x(1-cos106°47')
27 26 2
+ ( ( 1.6735x10- ) x ( 2.3252xl0- kg )]
26
2.8273xl0- kg
2
x (101.4xl0- 12 m ) x(l + 2cos 106°47')
= 2.815Sxl0-47 kg m 2
Therefore,
B= l.05457xlo-34 Js 994.1 m-1 =J9.941 cm-1J

(4n)x(2.9979xl0 8 m s- 1)x(2.8158x10-47kg m 2)
which is in accord with the data.
P10.3 Rotation about any axis perpendicular to the C6 axis may be represented in its essentials by rotation
of the pseudolinear molecule in Figure 10.3 about the x-axis in the figure.
l.._Rc---. .,____ RH(D) ---+I

0 0 02mc
0
x Figure 10.3
The data allow for a determination of Re, and

which may be decomposed into Rec and
RHCDJ• RcHCDJ.
7
JH = 4mHR~ + 4mc R~ = 147.59xl0-4 kg m
2
ID =4mDR~ +4mc~ = 178.45xl0-47kgm 2
Subtracting I H from ID (assume that RH = RD) yields

4( % -mH )R~ = 30.86Xl0-47kg m 2
4(2.01410 u-1.0078 u)x( l.66054x 10-21 kg u- 1)x( R~) = 30.86xl0-47kg m 2
Rl:, = Rl:, = (147.59xlQ-47kgm 2

)-(4~R~)
4mc
= (147.59xl0-4 7 kgm 2) -(4)x(l.0078u)x(l.66054xl0-27 kgu- 1)x(4.6169x10-20 m 2)
(4)x(l2.0l l u)x(l.66054xlo-21 kgu- 1)
= 1.4626 x 10-20 m2
Re,= l.209xl0- 10 m
Figure 10.4 shows the relation between RH, Re,, Rec, and Rew
Figure 10.4
10
Re _ l.209 x 10- m=l.396 x l0- 10 m=ll39.6 pm l
Rec = cos30o - 0.8660
- RH -Re 0.940 x 10-10 -l.08S x l0-10=1108.5 pml

Rm - cos30o 0.8660
RCD = RcH
COMMENT. These values are very close to the interatomic distances quoted by Herzberg in Electronic
Spectra and Electronic Structure of Polyatomic Molecules, p. 666, which are 139. 7 and 108.4 pm
respectively.
P10.5
-
v=2B(J+l) [10.17a]=2B
-
Hence, B('HCI) = 10.4392cm- 1, B(2 HCI) = 5.3920cm- 1
s= _-n_[10.5J
4Jrc!
I= merr R 2 [Table l 0.1]
R2 = n Ii
- = 2.79927 x l0-44 kgm
4Jrcmeff' B 47rc
-( (1 .007825u) x (34.96885u) )x (l .66054 x l0-27 kgu - 1)

merr (HCI) - (1 .007825 u) + (34.96885 u)
= 1.62665 x 10-21 kg
m (DC!)= ( (2.0140u) x (34.96885u) )x (l. 66054 x 10_2 7 k u-1)

eff (2.0140u)+(34.96885u) g
= 3.1622 x 10-27 kg
R2(HCI) = 2.79927xl0-44 kgm = l.64848 x l0-20 m2

(l.62665 x lo- 21 kg) x (l.04392 x l0 3 m- 1)
R(HCI) = l.28393xl0-'0 m=1128 .393 pml
R 2(2 HCI) = 2.79927 x l0-44 kgm = 1_6417 x l0_20 m 2

(3.1622 x l0-27 kg) x (5.3920 x l0 2 m- 1)
R(2 HCI) = l.2813 x 10- 10 m = lt28 .13pml
COMMENT. Since the effects of centrifugal distortion have not been taken into account , the number of
significant figures in the calculated values of R above should be no greater than 4, despite the fact that
the data are precise to 6 figures.
P10.7 From the equation for a linear rotor in Table 10.1 , it is possible to show that J x m =
2 2 2
m. mcCR+R') +m. mbR +mbmcR' •
Thus, I(' 60' 2C32S) = ( m('6O)m(32S) ) x (R + R')2 + ( m(' 2C) {m('6O)R 2 + m(32 S)R'2})
m('60 '2 c 32s m('60' 2c 32S)
1('60 '2 C34S) = ( m(' 60)m(34 S) )x(R + R')2 + ( m(' 2C) {m('6 O)R 2 + m(34 S)R'2})
m('60 '2c 34S m('60' 2C34S)
m(' 6 0) = 15.9949 u, m(' 2C) = 12.0000u, m(3 2S) = 31.9721 u, and m(3 4S) = 33 .9679u .
Hence,
1(' 6 0 12 C32 S)/u = (8.5279)x (R + R') 2 + (0.2001 l)x (15.9949R 2 + 3 l.9721R' 2 )
J(' 6 0 12 C34 S)/u = (8.7684)x(R + R') 2 + (0.19366)x(15.9949R 2 + 33.9679R'2 )
The spectral data provide the experimental values of the moments of inertia based on the relation
- - n
v = 2cB(J + 1) [10.l 7a] with B = - - [10.5]. These values are set equal to the above equations,
41rcl
which are then solved for R and R' . The mean values of I obtained from the data are
Therefore, after conversion of the atomic mass units to kilograms, the equations we must solve are
l.37998xl0-4 5 m 2 = (l.416lxl0-26 )x(R + R') 2 + (5.3150xl0-27 R 2 )

+ (1.0624xl0-26 R'2 )
l.41460xl0-4 5 m 2 = (1.4560xl0-26 )x(R+R') 2 +(5.1437xl0-27 R 2 )

+ (l.0923x10-26 R' 2 )
These two equations may be solved for R and R' . They are tedious but straightforward to solve by
hand. Exercise 10.7(b) illustrates the details of the solution. Readily available mathematical
software can be used to quickly give the result. The outcome is R = 1116.28 pml and
R'= jl55.97 pml. These values may be checked by direct substitution into the equations.
COMMENT. The starting point of this problem is the actual experimental data on spectral line positions.
Exercise 10.7(b) is similar to this problem; it starts, however, from given values of the rotational
constants B , which were themselves obtained from the spectral line positions. So the results for R and
R' are expected to be and are essentially identical.
Question. What are the rotational constants calculated from the data on the positions of the
absorption lines?
P10.9 Examination of the wavenumbers of the transitions allows identifications to be made as shown in
the table below. The J value in the table is the J value of the rotational states in the
v = 0 vibrational level. The notation (R) or (P) after the J values refers to the R and P branches of
the vibration-rotation spectrum.
2998.05 2981.05 2963.35 2944.99 2925.92 2906.25 2865.14 2843.63 2821.59 2799.00
J 5(R) 4(R) 3(R) 2(R) l(R) O(R) l(P) 2(P) 3(P) 4(P)
The values of Bo and B1 are determined from the equations for the combination differences, eqns.
10.44(a) and (b).
A0 = vR (J -1)-vP(J +l) = 4Bo(J + Y:!), and

A, = vR (J)-vp(J) = 4B, (J + Y:!)
Substituting values for VR and VP from the above table for J = 1, 2, 3, and 4, we obtain the
following values for Ao and A1•
J 1 2 3 4
J+ Y2 3/2 5/2 7/2 912
~cm- 1 62.62 104.33 145.99
'1i/cm- 1 60.78 101.36 141.76 182.05
i30 !cm- 1
10.437 10.433 10.428
B1/cm- 1 10.130 10.136 10.126 10.113
An average of these values gives IBo = 10.433 cm- 11and IB1 = 10.126 cm- 11. Values for Bo and B1
can als2 be obtaj_ned by plotting the combination differences, L1o and .1 1, against J + ~; the slopes
give 4 Bo and 4 B1, respectively.
P10.11 Plot frequency against Jas in Figure 10.5.
260000
... . y = 8300.2 + 8603.2x ........... .
R 2 = 1.000
250000 ..... .... ... . .... ·· · ·-:·· ·· ·· . ... .. ........... . .. . , ... .. . ..... .
N
... .. .. .. .... .... ····1······ ........ . .. .. ... ............ . ·· ··1· ·····
~ 240000 ..... .. .. ... . ··-:·· · .. .. .. .. .. . ....... . ...... .... · ···-:· · · · · ·
--
1?
.,=
....... ..... . .... .. ·-:··· ·· · ... . .. ................... .... · · · ·-:· · ··· ·
& 230000 ................. ····-:· · .. ... .. ... .. ................... ·· · · -:······
J: .. ... .... .... .... ·· 1·.. .. . ..... .... . ..... ..... .... . ..... ... -~· .....
220000 .... ····:······ ... . .. .. .... . ............... ··· ·-:·· · ···
. .
.... ... . · · ·· -:· · ··· · ..... ····· ........ ........... ..... . ~
210000 ~~~~~-~------~-~-
23 24 25 26 27 28 29 30
J Figure 10.5
The rotational constant is related to the wavenumbers of observed transitions by
- v -
v = 2B(J + 1) = - so v = 2Bc(J + 1)
c
A plot of v versus J, then, has a slope of2Bc . From Figure 10.5, the slope is 8603 MHZ, so
6
_ 8603 x 10 s-i = 114.35 m 1 I
B = 2(2.988x10sm s i)
The most highly populated energy level is roughly
J
max
=( kT- )112
2
2hcB
\ 1/ 2
_ ( (1.381 x 10- J K - ) X (298 ~\ )1
23 1
so _ _!_ = [l§} at 298 K
J max -l(6.626 x l0-34 Js) x (8603 x l0 s ) 2
\ 1/ 2
_ ( (1.38l x l0- JK- )x(l00~) ) 1
23 1
and 1
max - l (6.626 x l0-34 J s)x(8603x10 s ) 1 _ _!_=fil}atlOOK
2
P10.13 For IF, the rotational constant Be = 0.27971 cm- 1 and a= 0.187 m- 1 = 0.00187 cm- 1• Values
for Boand B1 are calculated from Bv =Be -a(v+t) .
Bo=Be- fa =0.27971 cm - -f (0.00187 cm- = /0.278775 cm- 1 1

)
1
/
B1 =Be-i a= 0.27971 cm- 1 - i (0.00187 cm- 1) = /0.276905 cm- 1 I

The wavenumbers of the J' ~ 3 transitions of the P and R branches of the spectrum are given by
eqn. 10.43.
When anharmonicities are present v in the formulas above is replaced by
AG(v)=v-2(v+l)x.v [10.38]
For v =0,
AG(v) = v-2x.v = 610.258 cm- 1 -2 x 3.141 cm-' = 603.976 cm- 1
For the P branch J' =J = 4, and for the R branch J' =J = 2. Substituting all these values into eqn.
10.43, we obtain
vR (J) = AG(v) +(B1+Bo)(J+1) + (B 1-Bo)(J+1) 2 =1605.626 cm- 1 I
The dissociation energy of the IF molecule may be obtained from De = - - - [l 0.36] and the
- v2
4x. v
relation D0 =De - ~ v+ ~ xe v [10.36] if a Morse potential energy is assumed.
Substituting the values given for v and vxe, we obtain
De 1
= 29641 cm- and jD 0 = 29337 cm- j
1
P10.15 See Figure 10.6 for a plot of AG(v) = v- 2(v + l)x. v [10.38] against v + 1.
2160
.00
2140
2120 2.00
,-._
-.=.,
c..J 2100
<j 3.00
2080
4.00
2060
2040 5.00
2020
1.00 1.50 2.00 2 .50 3.00 3.50 4.00 4.50 5.00
v+l Figure 10.6
The intercept gives Iv= 2170.8 cm- 11and the slope gives 2xev = 27.4 cm- 1; thus, jxev = 13.7 cm- ' I·
P10.17 D o = D e -ii' with ii'= t ii' -,\-x.v' [Section 10.9]
(a) ' HCl: V = {(1494.9)-(-i') x (52.05)} ,cm- 1 =1481.8cm- 1, or 0.184eV
Hence, Do=5.33-0.18=/5.15 eV/.

2
2 1
(b) 2HCI meff{))Xe = a 2[10.36]' so iixe oc - - as a is a constant. We also have D e = " - ; so
h mill 4~ v
v2 oc - 1-, implying v oc
meff meff
-h-. Reduced masses were calculated in Exercises 10.16(a) and (b), and we
can write
v(2 HCI) = meff (2HCI)

I Jl/2xv(' HCI) = (0.7172) x (2989.7 cm- 1
= 2144.2cm-'
(
meff ( HCl)
)
(~
xev(2HCI) = ( meff HCI) )xxev(' HCI) = (0.5144)x(52.05cm- 1) = 26.77 cm-'
meff ( HCI)
ii'(2HCI) = (t)X(2144.2)-(~)x(26. 77cm- 1)=1065.4cm- 1, 0.132eV
Hence, D o(2HC1) = (5.33-0.132)eV = 15.20 evl.
P10.19 (a) In the harmonic approximation,
D e =Do +fii so ii=2(De -Do)
ii = 2(1.51x10-23 J - 2x10-26 J) = (I52m - 1 (

(6.626xl0-34 J s)x(2.998 x l0 8 m s- 1)
The force constant is related to the vibrational frequency by
1/2
{)) = _!___ ) = 2Jtv = 2Jtcii so k = (2ncii) 2meff
( meff
The effective mass is
meff = f m = t(4.003 u)x(l.66 x l0-27 kg u- 1) = 3.32 x l0-27 kg
k = [ 2n(2.998xl0 8 ms-' ) x (152m- 1) J2 x (3.32x10-21 kg)
= l2.72x10-4kg s-2I
The moment of inertia is
I= meff R; = (3 .32x10-27 kg) x (297xl0- 12m) 2 =12.93x10-46kg m 2I

The rotational constant is
(b) In the Morse potential,

v
x =---=-
0
and
4De
This rearranges to a quadratic equation in ii:
ii2 1- - - f - (1-)2 - 4(D, _::DoJ

ii = - - -~-1 6-0-
'-
2
---=- - -v +De - Do = 0 SO
l 6De 2 2(16De r'
- -( [Kl
v=4De 1-~De
= 4(1.5lxl0-
23
J) (l- 2xl0-
26
J]
(6.626 x l0- 34 J s) x (2.998xl0 8 m s- 1 ) l.5lxl0-23 J
34 8 1
x = (293 m-')x(6.626xl0- J s)x(2.998xl0 m s- ) = )o. 1
and 96
e 4(1.51X10-23 J)
P10.21 (a) Vibrational wavenumbers (wcm- 1 ) computed by PC Spartan Pro™ at several levels of theory
are tabulated below, along with experimental values.
A, A, B2
Semi-empirical PM3 412 801 896
SCF 6-316G** 592 1359 1569
Density functional 502 1152 1359
Experimental 525 1151 1336
The vibrational modes are shown graphically in Figure 10.7.
Figure 10.7
(b) The wavenumbers computed by density functional theory agree quite well with experiment.
Agreement of the semi-empirical and SCF values with experiment is not as good. In this molecule,
experimental wavenumbers can be correlated rather easily to computed vibrational modes even
where the experimental and computed wavenumbers disagree substantially. Often, as in this case,
computational methods that do a poor job of computing absolute transition wavenumbers still put
transitions in proper order by wavenumber. That is, the modeling software systematically
overestimates (as in this SCF computation) or underestimates (as in this semi-empirical
computation) the wavenumbers, thus keeping them in the correct order. Group theory is another
aid in the assignment of transitions: it can classify modes as forbidden, allowed only in particular
polarizations, and so on. Also, visual examination of the modes of motion can help to classify
many modes as predominantly bond-stretching, bond-bending, or with an internal rotation; these
different modes of vibration can be correlated to quite different ranges of wavenumbers (stretches
highest, especially stretches involving hydrogen atoms, and internal rotations lowest).
P10.23 Summarize the six observed vibrations according to their wavenumbers (v I cm- 1) .
IR 870 1370 2869 3417

Raman 877 1408 1435 3407
(a) If H 2 0 2 were linear, it would have 3N - 5 = llJ vibrational modes.
(b) Follow the flow chart in Fig. 7.7. Structure 6 is not linear, there is only one enaxis (a e 1 ), and there is
a O"h; the point group is Ie 2h 1. Structure 7 is not linear, and there is only one C,, axis (a c 2 ), no O"h ,
but two O"v ; the point group is Ic 2v I · Structure 8 is not linear, and there is only one en axis
(a e 2 ) , no O"h, and no O"v; the point group is [SJ .

(c) The exclusion rule applies to structure 6 because it has a center of inversion: no vibrational
modes can be both IR and Raman active. So structure 6 is inconsistent with the observations.
The vibrational modes of structure 7 span 3A 1 + A 2 + 2B 2 • (The full basis of 12 cartesian
coordinates spans 4A 1 + 2A 2 + 2B 1 + 4B 2 ; remove translations and rotations.) The e2 v
character table says that five of these modes are IR active (3A 1 + 2B 2 ) and all are Raman
active. All the modes of structure 8 are both IR and Raman active. (A look at the character
table shows that both symmetry species are IR and Raman active, so determining the
symmetry species of the normal modes does not help here.) Both structures 7 and 8 have
more active modes than were observed. This is consistent with the observations. After all ,
group theory can tell us only whether the transition moment must be zero by symmetry; it
does not tell us whether the transition moment is sufficiently strong to be observed under
experimental conditions.
P10.25
Figure 10.8
Let us assume that atom C is the most massive. Then the center of mass, CM, will be located at a
distance, D , from atom B. In the notation of Table 10.1, we must have the relation
mA(R + D) + m 8 D = me (R' - D) , which may be rearranged into
D(mA +m 8 +me )= meR' -mAR

. meR' -mAR E d'

Solving for D, we obtam D = , where m = mA + m8 +me . xpan mg,
m
After substituting the above formula for D and using m = mA + m8 +me, we obtain
QED.
P10.27 If we apply the selection rules !:J.J = ±1and11K=0 to the formula for the rotational terms given in
the problem, we obtain for the frequencies of the allowed transitions the expression
3 2
V1 +i ,K.-J,K = F(J + 1, K)- F(J, K) = 2B(J + 1)- 4D1 (J+1) - 2D1K (J + l)K
In terms of wavenumbers, the following expression is similar:
- - - - - 3 - 2
V1 +i ,K.-J.K = F(J +1,K)-F(J,K) = 2B(J + l)-4D1 (J+1) -2D1x (J + I)K
To work with the latter expression one must convert the data given in frequency units to
wavenumbers. Here we solve the problem in frequency units using the former expression. We note
that A and Dx drop out of the expression for the transition frequencies; hence these constants cannot
be determined from the data given. Examination of the data suggests that the identification of the
transitions as shown in the table below can be made.
Transition 1 2 3 4 5
Transition
frequency, 51.0718 102.1426 102.1408 153.2103 153.2076
v/GHz
Transition K=O K=O K=I K=O K=I

quantum
J=O~I J=I~2 J=I~2 J=2~3 J=2~3
numbers
Transition
frequency 2B-4D1 4B-32D1 4B- 32D1 -4D1K 6B-I08D1 6B -108D1 - 6D1K
expression
Examination of these expressions reveals that the difference in trans1t10n frequencies between
transitions 3 and 2 and between transitions 5 and 4 yields the value of D 1K directly.
IDJK = 4.5 x 10
2
kH~
Band D1 can be found from simultaneous solution of the equations for transitions 1 and 2 and also
from transitions 2 and 4. The average value of D1 obtained in this way is 1 = 56 kH~. The value of !0
B obtained from transition 1 is then jB = 25.5360 GH~. If desired, these results in frequency units,
Hz, can be converted to units of wavenumber, cm- 1, by division by c, the velocity of light,
expressed in units of cm s- 1•
P10.29 Noc ge-Ef kT [Boltzmann distribution, Chapter 13)
N J oc g J e - E,/kT oc (21 + l)e - hcBJ(J+ l )/kT [g1 =2J + 1 for a diatomic rotor]
The maximum population occurs when
~NJ oc {2-(2J+J) 2 x( ~J J}e-hcBJ(J+tJ/kT =O
and, since the exponential can never be zero at a finite temperature, then
(2J+l)2x( hcB J - 2
kT -
1/ 2
or when J rrrax =i(~ ) 2
For ICI, with kT = 207.22 cm- 1 (inside front cover)

he
207.22 cm- I Jl/2 __1 = [lQJ

}max = ( 0.2284 Cm I 2
For a spherical rotor, N1 oc (21+1) 2 e -hciiJ(J+ IJ/ kT [gJ = (21+1) 2 ] , and the greatest population
occurs when
dN
1
-- oc
( 81+4 hcB(2J + 1)
3
Je - 0
-hcii1t1+1)/kT _
dJ kT
which occurs when
4(2J + l) = hcB(2J + !)3

kT
or at j max =I( kl'_ )1/

hcB
2
207.22 cm- I Jl/2__1 = [§]

For CH4' J rrrax = ( 5.24 cm-1 2
P10.31 The energy levels of a Morse oscillator, expressed as wavenumbers, are given by
G(v) =(v+i)v-( v+i)\v =(v+i)v-(v+if v2 I 4De

States are bound only if the energy is less than the well depth, De, also expressed as a wavenumber:
G(v)<De or (v+1)v-(v+1)\;; 2 /4De<De
Solve for the maximum value of v by making the inequality into an equality.
(v+ifv! 4De-( v+i)v+De =0

Multiplying through by 4De results in an expression that can be factored by inspection into
[(v+1)v-2i5eJ2 =o so v+1=2Del v and v=l2De/ v-11·
Of course, v is an integer, so its maximum value is really the greatest integer less than this quantity.
P10.33 We work with eqn. 10.45, which gives the transition energies for the S and 0 branches of the
vibrational Raman spectra. Transitions having Vs (J - 2) and v0 (J + 2) have a common upper state;
hence, the corresponding combination difference, !l0, is a function of B 0 only. Likewise, transitions
vs (J) and v 0 ( J) have a common lower state and the combination difference, L'l 1, is a function of B 1
only. Using eqn. 10.45 we obtain
v0 (J + 2) and vs (J - 2), we obtain for the combination difference

Taking the difference between
Jll =v0 (J+2)-vs(J-2)=8Bo(J+t)J . In a similar manner we can obtain Jll =v0 (J)-J
0 1
Jvs(J) =8B1(J +t)J.
P10.35 No solution. This is a report left for the student.
P10.37 The question of whether to use CN or CH within the interstellar cloud of constellation Ophiuchus
for the determination of the temperature of the cosmic background radiation depends on which one
has a rotational spectrum that best spans blackbody radiation of 2.726 K. Given
1
Bo(CH) = 14.19 cm- , the rotational constant that is needed for the comparative analysis may be
calculated from the 226.9 GHz spectral line of the Orion Nebula. Assuming that the line is for the
12 14
C N isotopic species and J + 1f-J=1, which gives a reasonable estimate of the CN bond
length ( 117.4 pm), the CN rotational constant is calculated as follows.
v v
Bo =B l c = - - - (1)
2c(J + 1) 4c
= 1.892 cm- 1 (2)
Blackbody radiation at 2.726 K can be plotted against radiation wavenumber with suitable
transformation of the Planck distribution law.
_ 8tthcv 3
p(v) = ehcii l kT _ 1
12
Spectral absorption lines of C 14 N and 12
C 1H are calculated with eqn. 10.17(a).
v(J +l f-J) = 2s(J +1) J=0,1,2, 3.... ...
The cosmic background radiation and molecular absorption lines are shown in Figure 10.9. It is
evident that only CN spans the background radiation.
p(v) at 2.726 K 3
10- 11kg s-2
CH
4 5 J=(} I
0 0 p 0
J ~
II I
0 JO 20 30 40 50 60
Figure 10.9
VJcm- 1
P10.39 (a) The H; molecule is held together by a two-electron, three-center bond, and hence its structure
is expected to be an equilateral triangle. Looking at Figure 10.10 and using the law of cosines:
R 2 = 2R~ -2R; cos(180° -2B)
= 2~ (1-cos(120°)) = 3R~
Therefore
Re = R l.J3
l e = 3mR~ = 3m(Rl.J3) 2 = mR 2
18 = 3mR8 = 2m(R /2) 2 = mR 2 /2
Therefore
f e = 2/B
c
m=mH () = 30°
',
B Figure 10.10
(b) B- _11__ 211 = ti (10 llJ

- 4trcl8 - 4trcmR 2 2trcmR 2 •
1/2 [ )1/2
R= n = nNA
( 2trcmB) 2trcMH B
(1.0546 X l0-3 4Js) x (6.0221 x l023mol-i)x ( :mm

10
2 ) ]1/2
[
2tr(2.998 x 108 ms- 1) x (0.001008kgmol- 1) x (43.55cm- 1)
= 8.764xl0- 11 m = l87.64pml
Alternatively the rotational constant C can be used to calculate R .
- 1i 1i
C=--= (10.11)
4trclc 4trcmR 2
1/2 [
R= 1i = nNA )1/2
- [
( 4trcmC) 4ncMH C
(1.0546xl0- Js)x(6.022lxl0 mol- )x(~)

34 23 1
4n(2.998xl08 ms- 1)x(0.001008kgmol- 1)x(20.7lcm- 1)

l
= 8.986x10- 11 m = ls9.86pml
The values of R calculated with either the rotational constant C or the rotational constant B differ
slightly. We approximate the bond length as the average of these two.
(R) == (87.64+~9.86)pm =ISS.?pml
_ 1i (l.0546xl0-34 J s)x(6.022lxl0 23 mo1- 1)x( 10::m)

(c) B=---
2trcmR2 2n(2.998xl08 ms- 1)x(0.001008kgmol-1)x(87.32xl0- 12 m) 2
= 143.87 cm- 1I
1
C=tB=l2i.93 cm- 1
3
(d) -=- or m.rr =im
m
Since m0 = 2mH , m.rr.o = 2mH I 3,

l/ 2
m.rr(H 3)
Vi
- (D+) =
3 ( (D )
m.rr 3 J
- (H ) (10.31)
V2 3
l/ 2
= mH I 3 _ (H ) = v2(H2)
(
2mH I 3
J vi 3 i '2
- - 1
Since B and C oc - , where m = mass of H or D,
m
B(D; ) = B(H; )x MH = 43.55cm- 1 x ( l.OOS ) = l21.80cm- 1 I

MD 2.014
C(D; ) = C(H; )x MH = 20.71cm- 1 x( l.OOS ) = 110.37 cm- 1 I

MD 2.014
11 Electronic spectroscopy
011.1 The ground electronic configuration of dioxygen, lo/ lo/2og2 11!" u4 11!" g2 , is discussed in Section
5.4(d), and the determination of the term symbol 3 L; is described in Section l 1.3(a). The term
symbol L represents a total orbital angular momentum about the internuclear axis of zero. This
happens because for every 1l" orbital electron with It= +l, there is a 1l" orbital electron with It= -
1. For example, the two l 1l"g electrons are, according to Hund's rules, in separate degenerate
orbitals for which one orbital has It = + 1 and the other has It = -1 . Except for the two l 7r g
electrons, electrons have paired a. and fJ spins, which results in zero contribution to the total
spin angular momentum. According to Hund's rules, the two 17rg electrons (i.e., l7rg 1 17rg 1) have
parallel spins in the ground state. They provide a total spin angular momentum of S = V2 + V2 =
1 and a spin multiplicity of 2S + 1 = 3, which appears as the left superscript 3. The term
symbol . indicates a gerade total symmetry because electrons are paired in the ungerade
molecular orbitals and u x u = g, and the resultant symmetry of electrons in different molecular
orbitals must therefore be given by g x g = g. The 7r orbitals change sign upon reflection in the
plane that contains the internuclear axis. Consequently, the term symbol has the superscript -
to indicate that the molecular wavefunction for 0 2 changes sign upon reflection in the plane
containing the nuclei.
011.3 A band head is the convergence of the frequencies of electronic trans1t1ons with increasing
rotational quantum number J. They result from the rotational structure superimposed on the
vibrational structure of the electronic energy levels of the diatomic molecule. (See Figs. 11 .10 and
11.13 in the textbook.) To understand how a band head arises, one must examine the equations
describing the transition frequencies (eqn. 11.9). As seen from the analysis in Section l l.3(e),
convergence can arise only when terms in both (B' - B) and (B' + B) occur in the equation. Because
only a term in (B' - B) occurs for the Q branch, no band head can arise for that branch.
011.5 (a) The transition intensity is proportional to the square of the transition dipole moment. We
initially suspect that the transition dipole moment should increase as the length L of the
alternating carbon-to-carbon double/single/double/single ... bond sequence of the polyene is
increased, and consequently, the transition intensity should also increase as L increases. To test
this hypothesis, consider that the polyene has N pi electrons that fill the first n = N/2 quantum
states of the particle in a one-dimensional box of length L = Nd = 2nd where d is the average
carbon-to-carbon bond length. (The length choice L = Nd adds half a bond length at each end to
the distance between the two end-carbon nuclei.) The transition dipole moment of this model is
µx = f Vn, xvn, dx
We quickly find a selection rule for transitions with the substitution x =j(x) + L/2 where j(x) =x - L/2
is a function of ungerade symmetry w/r/t inversion through the center of symmetry at x = L/2, and we
note that the wavefunctions have alternating gerade and ungerade symmetry as n increases. Then
The last integral vanishes because the wavefunctions of different energy levels are orthogonal,
which leaves
µx = r \l'n,/(x)\lfn;dx
Because the integrand factor fix) has ungerade symmetry, the product \l'n, \l'n, of an allowed transition
must also have ungerade symmetry so that the total symmetry of the integrand has u x u = g symmetry
and the integral can be non-zero. Thus, the lowest energy transition is n + 1 <--- n where n = ni. It is
now convenient to return to the original transition dipole moment integral and substitute the
wavefunctions for the final and initial states:
2 1fL sin ((n+l)trx

µ x =L L
) xsin ( L
ntrx ) dx [2.6b]
We need not evaluate the integral exactly because the development of a method to improve the
intensity of a dye requires only a knowledge of the approximate relationship between ux and either n
or L (proportional properties for a polyene), so we recognize that n + 1-n for a large polyene and
we make the estimate
µ x oc ±r xsin 2 ( n~x )ctx (The integral is found in standard mathematical tables.)
oc L
The model confirms the hypothesis that as the trans1t1on dipole moment is increased, so the
transition [ntensity is increased by increasing the length of the pol yen~.
2hi (2n + l)h2 hi

(b) Since E" = ~ [2.6a], M = 2
[l1n = +l] ~ ~for large n.
8meL 8meL 4meL
But L =2nd is the length of the chain where dis the average carbon-carbon interatomic distance.
Hence
Moc_!_
L
Therefore, the !transition moves toward the red as L is increased!. When white light is used to
illuminate the dyed object, the color absorbed is the complementary color to the reflected,
observed color. Newton's color wheel , shown in Figure 11.1 , usefully displays complementary and
observed colors. For example, draw a line from complementary violet through the circle centre to
find the observed color of green-yellow. As the polyene length is increased, the complementary
color progresses from violet to indigo to blue to green and so on, while the observed color
progresses from green-yellow to yellow-orange to orange-red to red-violet to violet-indigo. We say
that the !apparent color of the dye shifts toward blu~.
Observed Complementary
color
Orange
• color
Blue
Yellow
Green
Figure 11.1
011.7 Several characteristics of fluorescence are consistent with the accepted mechanism: (1) Fluorescence
ceases as soon as the source of illumination is removed; (2) the time scale of fluorescence, -10-9 s, is
typical of a process in which the rate-determining step is a spontaneous radiative transition between
states of the same multiplicity-slower than a stimulated transition but faster than phosphorescence;
(3) fluorescence occurs at longer wavelength (lower frequency) than the inducing radiation; (4) its
ELECTRONIC SPECTROSCOPY 253
vibrational structure is characteristic of that of a transition from the ground vibrational level of the
excited electronic state to the vibrational levels of the ground electronic state; (5) the fluorescence
spectrum is observed to shift and in some cases be quenched by interactions with the solvent.
011.9 See the table below for a summary of the characteristics of laser radiation that result in its many
advantages for chemical and biochemical investigations. Two important applications of lasers in
chemistry have been to Raman spectroscopy and to the development of time-resolved spectroscopy.
Characteristics of Laser Radiation and Their Chemical Applications
Characteristic Advantage Application

High power Multiphoton processes Nonlinear spectroscopy
Saturation spectroscopy
Low detector noise Improved sensitivity
High scattering intensity Raman spectroscopy
Monochromatic High resolution Spectroscopy
State selection Isotope separation
Photochemically precise
State-to-state reaction dynamics
Collimated beam Long path lengths Sensitivity
Forward scattering observable Nonlinear Raman spectroscopy
Coherent Interference between separate Coherent anti-Stokes Raman spectroscopy
beams (CARS) (Section 10.14c)
Pulsed Precise timing of excitation Fast reactions
Relaxation
Energy transfer
Modem Raman spectroscopy (Section 10.4) utilizes an intense excitation beam of a laser to increase
the intensity of scattered radiation and thereby to increase measurement sensitivity. The
rnonochromaticity of laser radiation is also a great advantage, for it makes possible the observation of
scattered light that differs by only fractions of reciprocal centimetres from the incident radiation.
Such high resolution is particularly useful for observing the rotational structure of Raman lines
because rotational transitions are of the order of a few reciprocal centimeters. Monochromaticity also
allows observations to be made very close to absorption frequencies, giving rise to the techniques of
Fourier-transform Raman spectroscopy and resonance Raman spectroscopy (Section 10.14b).
Time-resolved laser spectroscopy can be used to study the dynamics of chemical reactions. Laser pulses
are used to obtain the absorption, emission, and Raman spectrum of reactants, intermediates, products,
and even transition states of reactions. When we want to study the rates at which energy is transferred
from one mode to another in a molecule, we need femotosecond and picosecond pulses. These time
scales are available from mode-locked lasers, and their development has opened up the possibility of
examining the details of chemical reactions at a level that would have been unimaginable before.
E11.1 (a) The reduction in intensity obeys the Beer-Lambert law introduced in Section 11.2.
I I
log - = - log_..2._=-E[J]/ [11.3and11.4]
10 I
= (-723 dm 3 mor' cm- 1 )x(4.25x10-3 mo! dm-3 )x(0.250 cm)
= -0.768
Hence,!_= 10-0·168 = 0.171, and the reduction in intensity is j82.9 percent j.

lo
I I
E11.2(a) log-=-log_Q_=-e[J]/ [11.3, 11.4)
I0 I
1 I
Hence, e =--log-=
log(0.181)
-4
I
=5.34xl0 3 dm 3 mo1- 1 cm- 1
I
•
[J]/ I0 (l.39xl0 mo! elm-3 )x(l.00 cm)
E11.3(a) logT =-A= -E[J]l [11.1, 11.3, 11.4)
[J] =-_!__logT = -log(l-0.385)

£1 (386 dm 3 moi- 1 cm- 1)x(0.500 cm)
3
= li.09 mmol dm- 1
E11.4(a) A= f e(v)dv [11.5)= _("e(v)dv

1
band
Since ii=A.- 1 and v / cm- 1 =10 7 /(A. / nm),

ii; I cm- 1 =10 7 I (300) = 3.3xl0 4
Vpeak / cm- 1 =10 7 / (270)=3.7xl0 4
Vr I cm- 1 =10 7 I (220) = 4.5xl0 4
The pos1t1ons of the wavenumber end points and peak (max) of the band are schematically
presented in Figure 11.2. It is apparent that, because of the relative position of the peak, the molar
absorption coefficient is not symmetrically distributed around the peak wavenumber. The
distribution is skewed toward higher wavenumbers. However, a reasonable estimate of the area
under the curve may be approximated by adding the areas of triangle 1 and triangle 2 shown as
dashed lines in the figure.
A= 1,'e(v) dv = area 1+area2

= ll(_Vpeak -V;- )epeak + ll(_Vr -Vpeak
- )epeak = ll(_Vr -Vi-) epeak
=_!_x(l.2xl0 4 cm- 1 )x2.2lxl0 4 dm 3 mol- 1 cm- 1

2
=IL3xl08 dm 3 mol- 1 cm-2 1
8 ma'<
0 -L-4-----------'l;:-.-
vi vmax vf
v Figure 11.2
E11.5(a) £=-[J~/log~ [11 .3,11.4] with/=0.20cm
We use this formula to draw up the following table.
[Br2] I mo1 dm-3 0.0010 0.0050 0.0100 0.0500
I llo 0.814 0.356 0.127 3.0 x 10-5

449 448 452 Mean: 449
Hence, the molar absorption coefficient is E: = ~50 dm 3 moi- 1 cm-~.

1
E11.6(a) £=---log__{_ [11.3, 11.4]= -\ log(0.48)=ll59dm 3 mol-' cm-' I
[J]/ I0 (0.010 mol dm- ) x (0.20 cm)
T = __{_ = 1o - PJei [ 11.l, 11.2]

lo
' - ' ' ')x(0.40
= 10(--0.0 10mol dm- )x(159 dm mor cm - cm) - I
= 10--0.636 = 0.23, or 23 percent I
E11. ?(a) The Beer-Lambert law [11.3, 11.4] is
I l I
log- =-£[1]1 so I= - - l o g -
10 c[J] 10
1.00 kg/dm 3 d _3
For water, [H 2 OJ "" 1
= 55 .5 mo1 m
18.02 g mo!-
1
and £ [J] = (55.5 mol dm -3) x (6.2 x l0-5 dm 3 mor' cm - 1) = 3.4 x l0-3 cm -', so - = 2.9 m.
c{J]
./
Hence, l l m=-2.9xlog-.
~
(a) __{_=0.50, /=-2.9m x log(0.50)=I0.87ml

Io
(b) __{_=0.1, /=-2.9m x log(0.10)= 12.9ml

Io
E11.8(a) The left superscript of the dihydrogen excited state 3Tiu is the value of 2S + 1 = 3, so S = 1, which
means that the two electrons of H2 are parallel (S = s 1 + s 2 = Y2 + Y2 = 1) in this excited state. The
symbol TI indicates that the total orbital angular momentum around the molecular axis is !Al = 1.
Since A is the sum of the individual electron orbital angular momentum quantum numbers around
the molecular axis, we see that one of tlie unpaired electrons must 6e in a (J' orbital (A. = 0) and the
other electron must be in a n orbital (A. = 1). The excited state has ungerade overall parity. Since a (J'
bonding orbital has gerade symmetry while a n bonding orbital has ungerade symmetry and g x u = u,
we deduce that one possible electron configuration is !1(J'~ !Jr~ I (see Fig. 5.29 of text) .
E11.9(a) The 1(J': l(J'~ lJr~ lJr~ valence configuration has two unpaired electrons so S = s 1 + s 2 = Y2 + Y2 = l and
the spin multiplicity is given by 2S + l = 2(1) + 1 = ~. Because u x u = g and g x g = g, the net
parity of two electrons paired in an orbital is always gerade. Consequently, the overall parity is
found by multiplying the parity of unpaired electrons. For this configuration, u x g =l!!J.
E11.1 O(a) The electronic spectrum selection rules concerned with changes in angular momentum are (Section
ll.3b)
M = 0, ±1 L\S = 0 Li.[= 0 M2 = 0, ±1 where .Q =A + I
A gives the total orbital angular momentum about the internuclear axis, and I gives the total spin
angular momentum about the internuclear axis. The ± superscript selection rule for reflection in the
plane along the internuclear axis is ++-++ or -+-+- (i.e. , ++-+- is forbidden) . The Laporte selection
rule states that for a centrosymmetric molecule (a molecule with a center of inversion), the only
allowed transitions are transitions that are accompanied by a change of parity: u+-+g.
(a) The changes in the transition 2I1 H 2I1 are M = 0, M = 0, dI: = 0, and ~Q = 0, so the
transition is ~Bowe~.
(b) The changes in the transition 1I H 1I are M = 0, M = 0, dI: = 0, and ~Q = 0, so the
transition is ~Bowe&
(c) The changes in the transition I H ~ are M = 2, so the transition is [orbidde~.
(d) The transition I + HI- is [orbidde~ because++-+--.
(e) The transition I + Hr is laBowe~ because M = 0 and++-++.
E11.11 (a) We begin by evaluating the normalization constants N0 and N.-
N 01 -_ [
1 (2)" (standard integral); No = (~r4
e-2ax' dx = :
2
Likewise, N
v2 =
(
1 - (2b )1/2; N, ~ (-;;;)
, -"hl' dx - -;;;
2b 1/4
Furthermore, we can easily check that

b 1
- - x02
ax 2 +b ( x -x0 )2 = z 2 +ab
I/ 2
where z = ( a+b ) x- 11 2 x0 and dx= 2 dz
a+b (a+b) (a+b}11
Then the vibration overlap integral between the vibrational wavefunction in the upper and lower
electronic states is
S(v, 0) =(vi o) = NONv [ e-ax' e-b(x-xol' dx = NONv [ e ~ax' +b(x-x,J')dx
=
N oN v [e-z+a+bx,
{ 2 ab '} dz= N oN v e-a+b....,
ab 2 [e -" dz=NN ( ___!!_ )1/2 e-a+bx,
ab 2
(a+b)1 12 o v a+b
114 114 112 112
= -
(2a) 7r
(2b) - (
7! a+b
a+b =(4ab) ( -1
e -~x~
-7!- )
114
- ) e -~~
a+b
a+b
For the case b =a/2, this simplifies to
2 -ax5 13
S(v, 0) = (3J2.f2 e
The Franck-Condon factor is
!S(v, 0)1 2 =12"2.

-e_2axo, /3
3
112
E11.12(a) Z) 7) ~ ~
l//o = ( sin ( for 0 x L and 0 elsewhere
(L2) zx-4L)} "4 ~ x~ 4

112
l//v = sin { ( for L SL and 0 elsewhere
S(v, O) = (v I0) =z J:i 7}in {~ ( x -~)}dx

4sin (
The above integral is recognized as the standard integral (see math handbook):
x sin ( 2ax + b)
Jsin (ax) sin (ax+ b) dx = 2- cos(b) - - -4a- -
with the transformations a= 7r/L and b = -7r/4. Thus,
sin(2trx ! L-tr ! 4)]x=L _2[x (Jr ) sin(2trx ! L-tr ! 4)]x=L

s ( v 0 )-- -2[x-cos (Jr
--
)
- - -cos - - - - - - - - -
' L 2 4 4tr I L x=L/4 L 2 4 4tr I L x=L/4
I~:
= [ x cos ( : ) sin(2tr;Jr-;r I 4)
14
= cos ( ;r ) - sin ( 2tr- Jr I 4) [.!.cos ( !!_) - sin (tr I 2 -tr I 4 )]
4 2tr 4 4 2tr
=~cos (!!_) - sin(7tr / 4) + sin(tr / 4) =~cos ( ;r ) + sin(tr / 4) + sin(tr / 4)

4 4 2tr 2tr 4 4 2tr 2tr
The Franck- Condon factor is

2
2
ls(v,O)I :.: 1 ( 3+;
4)
32
E11.13(a) Pbranch (A!=-1) : vp(l)=v-(B'+B)l+(B'-.8)J2 [ll.9a]
When the bond is shorter in the excited state than in the ground state, B' > B and B' - B are
positive. In this case, the lines of the P branch appear at successively decreasing energies as J
increases, begin to converge, go through a head at l head• begin to increase with increasing J, and
become greater than v when J > (B' + B) I ( B' - B) (see Section l 1.3e; the quadratic shape of the
vP against J curve is called the Fortrat parabola). This means that vP ( J) is a minimum when J =
lhead· It is reasonable to deduce that lhead is the closest integer to lri (B' + B) I ( B' - B) I because it
takes twice as many J values to reach the minimum line of the P branch and to return to v. We can
also find lhead by finding the minimum of the Fortrat parabola: dvP I dJ = 0 when J =]head .
~ = ~ {v- (jj' + jj) J + ( jj' - jj) J 2 } = -( jj' + jj) + 2 ( jj' - jj) J
-( jj' + B) + 2( B' -B)Jhead = 0

(B' + fi)
Jhead = 2 ( jj' -B)
E11.14(a) Since B' < B and B' - B is negative, the R branch shows a head at the closest integer to the value
of )ri (B' + .B) I)( B' -fi)/-1} (see E11.13b).
(.B' +.B) l= (0.3101+0.3540) 1=6.6

2 l(s' -s)I 210.3101-0.35401
] head = [ZJ
I(
E11.15(a) When the R branch has a head, l head is the cl~sest integer to Yi (B' + B) I B' - B)1-1 (see El 1.13b).
Thus, if we are given only that l head = 1 and B = 60.80 cm- 1 , we know only that
o.5< Yi( .8'+ .B) (.8-.B')-1<1.5

because the fractional value of a .Yi(iJ' +B) ! (B'-iJ)-l calculation must be rounded-off to give
the integer value Jhead· Algebraic manipulation of the inequality yields
{1+2(0.5)}iJ -, {1+2(1.5)}iJ
---<B<---
{3+2(0.5)} {3+2(1.5)}
iJ
-<
B-, 2B
<-
2 3
130.4 cm-'< B' < 40.5 cm-' I
When B' < B, the bond length in the electronically excited state is l!iieate~ than that in the ground state.
Here's an alternative solution that gives the same answer with insight into the band head concept:
At the head of an R band, v,..,., > v,,_,_, where v,....,_, is the transition J heact f- J = J heact -1 . Substitution
of eqn. 11.9(c) into this inequality yields the relation B' > J headjj I (Jhead + 1) . Similarly, v, > v, +I
""'' ""'
where v,"',,+i is the transition Jheact + 2f-J=Jheact+1. Substitution of eqn. l 1.9(c) into this inequality
yields the relation B' < (Jhead + l)B I (Jhead + 2). Consequently,
J headB/ (Jhead + 1) < jj' < (Jhead + l)B / (Jhead + 2)
1
E11.16(a) The transition wavenumber is v=..!_= =14 x 10 3 cm- 1.
A. 700 nm
Water molecules are weak ligand field splitters, so we expect the d 5 electrons of Fe3+ to have the
t;ge~ high-spin ground-state configuration in the octahedral [Fe(H 20) 6] 3+ complex. The d-orbital
electron spins are expected to be parallel with S = 512 and 2S + 1 = 6 by Hund' s maximum
multiplicity rule. We also expect that P > Llo where P is the energy of repulsion for pairing two
electrons in an orbital. A d-d transition to the t;g e~ octahedral excited state is expected to be both
spin and parity forbidden and therefore to have a very small molar absorption coefficient. This
transition releases the energy .!l0 and requires the energy P needed to pair two electrons within a t2g
orbital. Thus, v = P- Ll 0 and l.!l 0 = P-vl. Using the typical value P - 28 x 103 cm- 1 yields the
estimate .!l0 -114 x 103 cm-'I. See F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 4th
ed. (New York: Wiley-lnterscience, 1980), p. 646, for electron-pairing energies.
E11.17(a) The normalized wavefunctions are
'l'i -- ( -1 )"2 for 0 $ x $ a and 0 elsewhere

a
2
lflr = ( - -
1-
b- ,Yi a
J" for Yi a $ x $ b and 0 elsewhere
flflrX lfli dx =(± r r~a =(±r

2
( b-lYz a
2
xdx
2
( b-
1
.Yia]
112
x; [~a
I(
=( ±)112 ( b-1.Yi a Jl/2 ( 3;2J = ~~3 JI/2
E11.18(a) The normalized wavefunctions are
1 Jl/2
'l'i = ( a.JJi e-" 12a' for -oo $ x $ oo and width a
I/2
_ 1 - (x-a / 2) 2 12a 2
lflr - ( J
a.JJi e for - oo $ x $ oo
•
and width a
I
\f/rX \f/i
-(
dx-
1 ) ~I
r= xe
-x' 2a 2 -(x-a / 2)' 2a'
e
-
dx -
(
r= ~I xe -{x +(x-al 2) }12a
1 )
2 2 2
dx
G'\/lr _ G'\/lr _
2 2
a a a a
. 2
Smcex +(x-a / 2)
2
=( 2112x-3i2 +-, letz=2
1'2 - 112
x-3i2 andx=2 z+-.
) 2 8 2 4
Then dx = r 112 dz, and substitution gives
I
-1116 ){ 2-112 ~ ze -z'12a' dz+ ~ ~ e -z'12a' dz }
= _e__
( a.fi1i
I
- -
The factors within the first integral have ungerade and gerade symmetry. Because u x g = u, the
integrand has ungerade symmetry and the first integral is necessarily zero (the integral of an
ungerade function over a symmetric interval equals zero).
f\f/rX\f/i dx =(~ ){ ~ l e -z'l2a' dz}= ( :~ }2a Jrf 2 2
= l,v.;e-1116al
E11.19(a) The weak absorption at 30,000 cm- 1 (330 nm) is typical of a carbonyl chromophore of an enol. The
assignment is 11"*+-n where a non-bonding electron comes from one of the two lone pairs of the
oxygen valence. The two lone pairs of oxygen are in sp 2 hybrid orbitals, which define the xy plane
that contains the 6 bond of the carbonyl. The 7r* molecular orbital is perpendicular to this plane.
There is little overlap between the n and 7r* orbitals, thereby producing a low value for the dipole
transition integral and a low molar absorption coefficient.
The strong absorption at 46,950 cm- 1 (213 nm) has the 7r*+-7r assignment. The conjugation of the 7r
bonds of the ethenic chromophore and the carbonyl chromophore causes this transition to be shifted to
lower energies w/r/t both the 7r*+-7r transition of ethene (165 nm) and the 7r*+-7r transition of
propanone (190 nm). This shift can be understood in terms of the simple Htickel theory of 7r molecular
orbitals using the butadiene 7r energy model shown in text Figure 5.36 and Figure 11.3 below. The
figure demonstrates a broad principle (see Section 9.9a): the difference between neighboring energy
levels becomes smaller as the number of adjacent, overlapping orbitals becomes larger.
----- --.
- - - - 165 nm
p,(C) p,(C)'·..
---------r :
1~
=- - - - - - - - -
213 nmt H
330 nm
'•, • '----'--< - - - - - - - - - - - - - • • sp 2(0) sp 2(0)
LJl _H
·····- ..... ~-----------~~~:::::....:....:.:...~--
I /
- - - - - - - _-_-_-_-_-_-_·::: =;-.,....-__··-- -
11r
190 nm·.·,__
PzC9-
', ,'--, - --- p,(O)
C=C C=C-C=O C=O Figure 11.3
E11.20(a) The propanone weak absorption at 1280 nm has the Jr* f - n assignment I where a non-bonding
electron comes from one of the two lone pairs of the oxygen valence. See El l.19(a) for the explanation
of the weakness of this absorption band. The strong absorption at /189 nm has the 7r*+-7r assignmeng.
Both bands are associated with the carbonyl chromophore, and they can be identified in Figure 11.3.
E11.21 (a) Because the molecular response is proportional to the square of the electric field, a field of angular
frequency w elicits the response cos 2 wt = _!_{ 1 +cos ( 2wt)} (standard formula for a power of a
2
trigonometric function; see math handbook) and we conclude that the effect is equivalent to an
incident field of 2w.
E11.22(a) (a) Vibrational energy spacings of the llowerl state are determined by the spacing of the peaks of
fluorescence spectrum A of benzophenone. = 1800 cm- 1j Iv
(b) The peaks of A give no information about the spacing of the upper vibrational levels (without a
detailed analysis of the intensities of the lines).
E11.23{a) When the steeply repulsive section of the 0 2 potential energy curve for the excited state lies
slightly toward the short side of the equilibrium bond length of the ground state and the
minimum of the excited state lies to the longer side (as shown in text Fig. 11.31 ), a great many
excited vibrational states overlap with the lowest energy vibration of the ground state. The
Franck-Condon factor is appreciable for many vertical transitions (see text Fig. 11.10) and
the absorption band is broad. Furthermore, predissociation to the unbound 5Ilu state shortens
the lifetime of excited vibrational states. This causes the high resolution lines of the
corresponding vibrational-rotational transitions to be broad through the Heisenberg uncertainty
principle Mb..t ~ 1i I 2.
E11.24(a) Only an integral number of half-wavelengths fit into the cavity. These are the resonant modes.
A. = 2L I n [I I . I I] where n is an integer and L is the length of the cavity.
The resonant frequencies are iven b v = c I A,= nc I 2L . The lowest energy resonant modes (n = 1)
in a 30-cm cavity are = 60 cm (v = 500 MHz).
E11.25(a) Referring to Example 11.3 of the text, we have

p peak= Epuls./lpulse and P average= Etotai!t = Epulse x Vrepetition
where Vrepetition is the pulse repetition rate.
=E I P = O.lOmJ =~
/pulse pulse peak 5.0 MW ~
7.0kW
vrepetition = P.verage I Epu1se = = 170 MHz I
0.10 mJ
E11.26{a) This Mathcad worksheet simulates the output of a mode-locked laser. The radiation intensity is
shown in text Justification 11.5 to be proportional to the functionj(t, N) of the worksheet. The plots
demonstrate that the superposition of a great many modes creates very narrow spikes separated by
t = 2L/c.
L :=30·cm c := 299792458m-s- 1 ns := 10-9 ·s
tmax := 5·2-L·c-l tmax = l.00I x l0-8 s
i·t
1max := 1000 i := l...imax t; .=~
I max
f(t, N) := ( si~(N·7tC·tT1 r1 )J2

sm(nc·t·T1 -L-1)
2 4 6 8 10
ns
ELECTR lC s~ECl?OSCO 161
f(t , 10)
-- 2
OL.L..L...L.L.L..L..L...L..J....1....1..L..L.L..L.JL..L..l...L..L.L..L..L..L..l'-L.L..L..L..L..LIL.L..L...L.L.L..L..LJ....1....1....1..L..L.L..L.Ju...J
0 2 4 6 8 10
ns
f(t , 1000)
2~
o'-~~~-'-~~~---'-~~~~-'-~~~-'-~~~--'
0 2 4 6 8 10
ns
E11.27(a) The Nd-Y AG laser transition at 1064 nm is very efficient and capable of substantial power
output. Frequency doubling of the infrared band yields green light at 532 nm, and frequency
quadrupling gives 266 nm ultraviolet radiation. The latter radiation can initiate the fast chemical
reaction.
P11.1 Solutions that have identical transmittance must have identical values of the absorbance [11.3] and
identical values of G[J]/ [ 11.4]. Consequently,
[Jtell 2 = [Jte111 /cell I / t11 2

= 25 µg dm- 3 x(l.55 cm) I (1.18cm)=133 µg dm-3 1
P11.3 For a photon to induce a spectroscopic transition, the transition moment (µ) must be non-zero, a
requirement that leads to electronic spectrum selection rules concerned with changes in angular
momentum. The rules for a homo nuclear diatomic are (Section 11.3b)
M = 0, ± 1 LlS = 0 ill' = 0 ~Q = 0, ± 1 where Q = A + I
A gives the total orbital angular momentum about the internuclear axis and L gives the total spin
angular momentum about the internuclear axis. The ± superscript selection rule for reflection in the
plane along the internuclear axis is +~+ or -~- (+~- is forbidden). The Laporte selection rule
states that for a centrosymmetric molecule (those with a center of inversion), the only allowed
transitions are transitions that are accompanied by a change of parity: u~g.
The electric-dipole transition 2 ~ 2 L; L:
is allowed because none of the above rules negates the
possibility of this event. You may a so w1s to reac this conclusion by direct examination of the
f
dipole transition moment integral, lf/;µlf/;dt', where the dipole moment operator has components
proportional to the Cartesian coordinates. The integral vanishes unless the integrand or at least some
part of the integrand belongs to the totally symmetric representation (A 1g; see Chapter 7). To find the
symmetry species of the integrand, we multiply the characters of its factors. Homonuclear diatomic
molecules and ions belong to the D oo h point group and the Dooh character table tell us the symmetry
species of each integrand factor.
I/ff : A1 8 ( ~ )
µ, : A1u (L;:)
'Yi : A1 u(L::)
Symmetry product: A18 x A1u xA1u = A18 xA18 = A18
Since the integrand spans A 1g, the transition 2 1:; f- 1:: is allowed.
2
An electric-dipole transition from a L;:

2
ground state to a Il 0 excited state is forbidden by the
Laporte selection rule.
Finally, we check the possibility of a transition from a 2L;: ground state to a 2Ilg excited state by
finding whether or not the integrand of the transition integral spans the totally symmetric
representation. The symmetry product for the µx component is !; 8 xA1" xA1u = !; 8 xA18 = E18.
Since the integrand does not span A 1g, the transition is forbidden for z-polarized light. The
symmetry product for both the µx and µy components is J; 8 x Eiu x A1u = E1g x E1g • Since the species
product Bigx E1g has an angular dependence and therefore does not contain the totally symmetric
representation, the transition is forbidden for x- and y-polarized light. You may also wish to show
this by application of the orthogonality theorem to find the coefficient of A 1g in the integrand.
Daoh E ooc; 2C; i OO(Jv 2S;
L: (A 1. ) 1 -1 1 -1 1 -1
µx or µ y(E1u) 2 0 2 cos¢ -2 0 2 cos¢
Ilg(E1 g) 2 0 2 cos¢ 2 0 -2 cos¢
Integrand 4 0 4 cos 2 ¢ 4 0 4 cos2 ¢
The orthogonality theorem gives the coefficient of A1g in the integrand as

2
cA =(1/h)L g(C)z(C)=[4+0+2(4cos' ¢)+4+0+2(4cos ¢)] / h
lg c
Since the group order h, which equals infinity, does not cancel with a numerator factor, cA = 0.
lg
P11.5 The ionization is HBr ---+ HBr+ + e- with the accompanying electronic energy change given by the
2
equation I; + M v'+-v=O = hv- Yi meV • This modified form of eqn. 5.19(b) accounts for the possibility of
an excitation change in the vibrational energy in going from the ground electronic vibrational state v = 0,
in which a majority of molecules start, to the ionized electronic vibrational state v' = 0, 1, 2 ... The
vibrational transition v' = 0 +- v = 0 is called an adiabatic transition. Figure 11.4 shows the potential
energy relationships between the ground electronic state and two possible ionized electronic states.
ff + Br
~
OJ
c
OJ
t;j
·;::: I.
c
~0. I"
~
:;
u
OJ
~
HBr
Internuclear separation Figure 11.4

(a) The photoelectron spectrum band between 15.2 eV and 16.2 eV is the ejection of a bonding
a electron. Loss of this electron reduces the bond order from 1 to V2, reduces the magnitude
of the bond force constant, and lengthens the equilibrium bond length of the ionized
molecule. The electronic transition is labeled as 10 in Figure 11.4. The longer bond length of the
ionized state cause the Franck-Condon factor for the adiabatic transition (v' = 0 +- v = 0) to be
small. This is the lowest energy transition of the band at about 15.3 eV. The increasing
spectral intensity for the v' = 1 +- v = 0 and v' = 2 +- v = 0 transitions indicates that these
vertical transitions have successively larger Franck-Condon factors (see text Fig. 11.10).
The separation of lines (-0.162 e V) corresponds to an ionized vibrational wavenumber of
about 1300 cm- 1, which is considerably lower than the 2648 .98 cm- 1 of the neutral ground
state. The presence of one unpaired electron in the bonding a orbital means that the ionized
molecule is in a 2 I:+ state.
(b) The lines between 11.6 eV and 12.3 eV involve transitions of a non-bonding electron of the
chlorine p valence subshell to two very closely spaced electronic states of the ionized
molecule. The ionization energy of these states is labeled as In in Figure 11.4. The unpaired
electron of the ionized state makes it a doublet with spin-orbit coupling producing j = ll +
sl, ... ,ll - sl = Jl + V2I, ll - V2I = 3/ 2, 1/ 2 • Consequently, the term symbols of these states are
2
TI 112 and 2 0 312 , and Hund' s rule predicts that 2 0 312 is lowest in energy because the subshell
is more than half-filled. Excitation of a non-bonding electron does not affect the molecular
bond, nor does it affect the bonding force constant or the equilibrium bond length. Only the
vertical, adiabatic transition (v' = 0 +- v = 0) has an appreciable Franck-Condon factor. The
transition v' = 1 +- v = 0 of the 2 0 312 transition has a very small vertical, vibrational overlap
integral; it cannot be seen in the spectrum because it lies below the 2 TI 112 adiabatic transition
at 12.0 ev. The transition v' = 1 +- v = 0 of the 2 TI 112 transition has a very small vertical,
vibrational overlap integral located at 12.3 eV. The 0.3 eV line separation corresponds to an
ionized vibrational wavenumber of about 2400 cm- 1• This is consistent with the vibrational
wavenumber of the ground state (2648.98 cm- 1) and confirms the expectation that excitation
of a non-bonding electron does not affect the cr bond.
P11.7 The spectrum gives the peak and half-height points:
£peak = 250 dm 3 mol- 1 cm- 1 , A.peak = 284 nm ( v = 35200 cm- 1 )
£112 = 125 dm 3 mol- 1 cm- 1 , Ain = 305 nm ( v = 32800 cm- 1 )

Ai 12 = 265 nm (v = 37700 cm- 1 )
We estimate that the wavenumber band has a normal Gaussian shape.
£ = £max e-(v-v,...)' ta' where a is a constant related to the half-width Llv112 =

(37700-32800) cm- 1 =4900 cm- 1
A= f t:(v) dv [11.5]=£max [ e -(v-v,... )'ta' dv

band
= £max aJJi (standard integral)
The relationship between the half-width and a is found by evaluation of the line shape at c:( v112 ) =
emaxf2.
ln(l/ 2) = -( v112 -vpeak

2
r I a2
a 2 = ( v112 - vpeak ) _ ( Liv112 I 2 )2

ln(2) ln(2)
Livi 2
a=2-J1;2
Thus,
A= !Yi ~ii 112 cmax ~Jr /ln(2) I= 1.0645 ~V112 cmax

A =Yi (4900 cm-') x ( 250 dm 3 mor' cm- 1 ) ~Jr /ln(2) =Ii .30x10 6 dm 3 mol- 1 cm-2 I
Since the dipole moment components transform as A 1(z), B,(x), and B 2 (y) , excitations from A,
to A, , B, , and B2 terms are allowed.
P11.9 The anthracene vapour fluorescence spectrum gives the vibrational splitting of the lower state. The
wavelengths stated correspond to the wavenumbers 22 730, 24 390, 25 640, 27 030 cm- 1, indicating
spacings of 1660, 1250, and 1390 cm- 1• The absorption spectrum spacing gives the separation of the
vibrational levels of the upper state. The wavenumbers of the absorption peaks are 27 800, 29 000,
30 300, and 32 800 cm- 1• The vibrational spacings are therefore 1200, 1300, and 2500 cm- 1• The
data are compatible with the deactivation of the excited-state vibrational modes before spontaneous
emission returns the molecule to the ground electronic state. This produces a fluorescence band of
lower energy than the energy of the absorption band. Furthermore, while the absorption band has a
vibrational progression that depends on vibrational modes of the excited state, the fluorescence
band has a vibrational progression that depends on vibrational modes of the ground state. The
absorption and fluorescence spectra are not mirror images.
P11.11 (a) The molar concentration corresponding to 1 molecule per cubic µmis
3
1 10 6 m-' ) _
3
!!_=
23 1
x ( µm 3
=ll.7 x l0-9 moldm 1
V 6.022xl0 mol (1.0 µm 3 )(10 dm m- 1 )
i.e. , nanomolar concentrations.

(b) An impurity of a compound of molar mass 100 g mor 1 present at 1.0 x 10-7 kg per 1.00 kg
water can be expected to be present at a level of N molecules per cubic µm where N is
7 23
N = l.O x l0- kg impurity x 6.022xl0 mor' x (l .0 x 10 3 k g water m - 3 ) x (l0-6 m )
3
3
1.00 kg water 100 x l0- kg impurity mor'
N = /6.0 x 10 2 /.
Pure as it seems, the solvent is much too contaminated for single-molecule spectroscopy.
P11.13 The light-scattering equation
10 10 2 b = 16n2R1
=a+b x( sin (B / 2)J where a= (KcMMr' and
5..1.2
le le
has a linear form when ! 0 /Ie is plotted against ~sin 2 (B / 2) . The intercept a and slope bare
le
determined with a linear regression fit of this plot. Knowing a and b, the above equations can be
used to calculate Mand R. We begin by drawing up the requisite data table, preparing a plot (shown
in Figure 11 .5), and calculating the linear regression fit.
8I 0
15.0 45.0 70.0 85.0 90.0
100 x Joffe 4.20 4.37 4.63 4.83 4.90

100 x IcJio x sin2(812) 0.0716 0.640 1.52 2.20 2.45
5
4 ·8 y = 0.2944x + 4.1804
......,""
4.6
=
6
0
4.4 -,
.....
4.2 -<
4 .,.-
0 0.5 1.5 2 2.5 3
100 I 0 sin( 0/2) I I 8
Figure 11.5
Thus, a= 0.0418 and b = 0.294.
M = (KcMa r1 = {( 2.40x10- 2
mo! m 3 kg-2 ) x ( 2.0 kg m-3 ) x (0.0418)} -
1
= j498 kg mo1- 1 j
R=(5b( -1 / (4n)=(5 x 0.294}'12x (532 nm) / (4n)
=151.3 nml
P11.15 The derivation is similar to that of the Beer- Lambert law in Justification 11.1 , but let dx be the
infinitesimal thickness of the layer containing the absorbing species J. Then
dI = -K[l]ldx
dJ = -K[J]dx
I
J:, ~ =-Kf[J]dx=-K[1]0 e-xudx f

Jn(f)J/=I = ci[J] e-xi.1 1x=I
1=10 0 x=O
-In~ =-cl[J] 0 (1-e-

11
" )
10
(in 10) log = cl[J] 0 (1-e- 11 " )
I
10
LetA=log [11.3] andc'=cl / (in!O) .
I
Then
IA= c'[J] 0
( 1-e-'' ,i )I
In the case for which /IA>> 1, e-//J. = 0 and A = s'[J]o.
In the case for which /IA<< 1, e-//J. - 1 +(-!IA) + (-llA)2/2 (Taylor series truncated after 2nd order).
Thus,
A=c'[J](l-e-"A )
A=c'[J](l-l+l / ..1-(l ! A,/ 12)

c'l[J]
A=-(1-l ! 2A)
..1
)f
jA = cl[J]x(l-l I 2..1 when l/ ,1 « 1
P11.17 Suppose that non-absorbing species B (pyridine in this problem) is progressively added to a solution
of light-absorbing species A (12 in this problem). Furthermore, suppose that A and B form a
complex of light-absorbing species AB. Suppose that all absorbance measurements are made at the
equilibrium A+ B ~AB. By the conservation of mass, the sum of the equilibrium concentrations
of the absorbing species, [A]e + [AB]e, is a constant for all additions of B. That is, the sum of
concentrations of all species that contain A must equal the concentration of A present before any B
is added, [A] 0 . The absorbance at any wavelength is
AA= cA,Al[A]e +cAB)[AB]e

= cA)([A] 0 -[AB]e) + cAB,A/[AB]e
= cA)[A]o + ( cAB,A -cA,A )/[AB]e
The first term to the right in the above equation is a constant for all additions of B; the second term
is generally not constant, and consequently, A_. generally varies with the addition of B. However, at
any wavelength for which cAB,.< = cA,;,, the second term vanishes, making AA a constant at all
additions of B. The wavelength at which this happens is called the isosbestic point. It is
characterized by the equilibrium between absorbing species and cAB,.< = c A,A.
P11.19 We need to establish whether the transition dipole moments
f
µfi = ¥;µ¥1"i cir [10.56]
connecting the states 1 and 2 and the states 1 and 3 are zero or non-zero. The particle-in-a-box
112
wavefunctions are Vl"n =(2 1 L) sin(n.7rxl L) [2.6b].
Thus µ 2,1 oc sin( f 2

oc :x
~x )xsin( :X )c1x fx[ cos( )-cos(3~x) Jc1x
and Ji-J,1 oc
f . (3Jrx)
Sill L dx fx [cos (2Jrx)
L x , (Jrx)Sill L - cos (4Jrx)]
oc L dx
having used sin a sin ,8 = t cos( a- ,8)-t cos( a+ ,8). Both of these integrals can be evaluated using
the standard form
fx(cosax)dx = --;..cosax+~sin
a a
ax
2
1
fLxco{Jrx)dx = 2
co{Jrx)IL + - x siJ
1 Jrx)IL = -2(!:_) ;t O
1 L (Jr IL ) L 0 (Jr I L) \ L 0 Jr
rL 3Jrx
XCO{-)dx =
L
1
( 3Jr I L)
3Jrx
2co{-)\
L
L
0
+(
x
3Jr I L
. 3Jrx IL
) SIJ-) =
'\ L
0
-2(-)L
3Jr
2
:;t: 0
Thus µ 2, 1 :;t: 0.
In a similar manner, Ji-J,1= 0.
COMMENT. A general formula for µ fi applicable to all possible particle-in-a-box transitions may be
derived. The result is (n = f,m = i)
µ =_ eL [cos(n-m)ff-1 _ cos(n + m)ff-1]

nm ff2 (n-m) 2 (n+m)2
For m and n both even or both odd numbers, µ nm = O; if one is even and the other odd , µ nm "# 0.
See also Problem 11.22.
Question. Can you establish the general relation for µnm above?
P11.21 (a) Ethene (ethylene) belongs to D 2h. In this group the x, y, and z components of the dipole moment
transform as B3u, B2u, and B 1u, respectively. Then: orbital is B 1u (like z, the axis perpendicular
to the plane) and 7t• is B3g· Since B3g x B 1u = B2u and B2u x B2u = A 1g , the transition is lallowe~
(and is y-polarized).
(b) Regard the CO group with its attached groups as locally C2v. The dipole moment has
components that transform as Ai(z), Bi(x), and B2(y), with the z-axis along the C=O direction
and x perpendicular to the R2CO plane. The n orbital is Py (in the R2CO plane) and hence
transforms as B2. Then:' orbital is Px (perpendicular to the R2CO plane) and hence transforms as
B 1• Since rf x 1; = B 1 x B2 = A2, but no component of the dipole moment transforms as A2, the
transition is [orbidde~.
P11.23 (a) The Beer-Lambert Law is

I
A= log_Q_ = e[J]/
I
The absorbed intensity is
Substitute this expression into the Beer-Lambert law and solve for J abs :
(b) The problem states that I f (vf) is proportional to <A and to / abs (v), so
If (v f) oc <A 10 (v)x(1-10-ec111 )
If the exponent is small, we can expand 1-1 o - e[ JJI in a power series:
10-E[J)/ = ( e!n lO r E[J)/ ""1-£[J]/ ln 10 + •••
P11.25 Fraction transmitted to the retina is

(1-0.30) x (1-0.25) x (1-0.09) x 0.57 = 0.272
The number of photons focused on the retina in 0.1 s is

0.272 x 40mm 2 x0.ls x 4xl03 mm-2 s- 1 = l4.4xl0 3 I
-more than what one might have guessed.
P11 .27 The integrated absorption coefficient is
A= 1 £(ii) d ii [11.5]
and
If we can express £ as an analytical function of ii, we can carry out the integration analytically.
Following the hint in the problem, we seek to fit £ to an exponential function, which means that a
plot of In£ versus ii ought to be a straight line (Figure 11 .6). So if In£= mii + b, then
6
£ = exp( mii) exp( b) and A = ( e I m ){exp( miif ) - exp( mii;)}
5 1 y =l- 38.3:83 + (1.2597 x rn-,3) x

4 I·:·~i::f §9.9.?.······· :········7·········:·········
3
"'
.5
2
Y ............;.
······ ····•·········!······················•····
0 ~~~~~~~~~~~~~~~
31000 32000 33 000 34 000 35 000

ii /(cm- 1) Figure 11.6
We draw up the following table, find the best-fit line, and make the plot of Figure 11.6. The linear
regression fit yields the values of m and b for the computation of the integrated absorption coefficient.
A/nm &/(dm 3 mo1- 1 cm- 1) ii/cm- 1 ln&/(dm 3 moi- 1 cm- 1)
292.0 1512 34248 4.69

296.3 865 33748 4.13
300.8 477 33248 3.54
305.4 257 32748 2.92
310.1 135.9 32248 2.28
315.0 69.5 31746 1.61
320.0 34.5 31250 0.912
So A= e-38.383 [ ex{1 .26xl0- cm ) -exp ( l.26xl0- cm )

3 3
]dmJmo1_, cm -1
l.26 x l0-3 cm 290 x l0-7 cm 320 x l0-7 cm
= lt.24 x l0
5
dm 3
moi- 1 cm-2 I
P11.29 In Figure 11 .7
v=0+--0
0+-- 1 1=1+--0
V = ] +-- ]
liE11 Moo
~~~+--~~~~~~-t-~~~~~~~~~~~t----A
386.4 nm 387.6 nm
Figure 11.7
till11 =~
A he =5.1409xl0- 19 J=3.2087eV
II 386.4nm
and
he he 19
M 00
::i::-:o: ""5.1250x10- Jz3.1987eV
Aoo 387.6nm
Energy of excited singlet, S 1: E 1 (v,J) = v; + (v+ Yz)i\he + J(J + l)B1he

Energy of ground singlet, S0 : E0 ( v, J) = V0 + ( v + Yz)v0 he + J ( J + 1)B0 he
The midpoint of the 0--0 band corresponds to the forbidden Q branch (Al= 0) with J =0 and u = 0 +--- 0.
(1)
The midpoint of the 1-1 band corresponds to the forbidden Q branch (Al= 0) with J = 0 and v = 1 +--- 1.
(2)
Multiplying eqn. 1 by 3 and subtracting eqn. 2 gives

3M00 - M 11 = 2(f'; - V0 )
1
f'; - V0 = -(3ti£00 - M 11 )
2
= .!..{3(5.1250)-(5.1409)}xl0- 19 J
2
= 5.117lxl0- 19 J =13 .1938 evl (3)
This is the potential energy difference between S0 and S1.

Equations (1) and (3) may be solved for v1 -v0 •
i7i -v0 =2{M00 -(v;-Va)}

= 2{5 .1250-5.l 171}xl0- 19 J I he
= l.5800xl0- 21 J = 0.0098615eV=179.538 cm- 1 I
The v1 value can be determined by analyzing the band head data for which J + 1 +--- J.
M 10
(J) = E 1(O,J)-E0 (1,J+1)
1 - -
= v; -V
+-(v1 -3v0 )he+J(J +l)B1he-(J +l)x(J +2)B0 he
0
2
1 - -
M 00 (J) = v; -Va+-( i7i - ii0 )hc+J(J + 1J8ihc-(J + l)x(J + 2)B0 hc
2
Therefore,
M 00
(J)-M10 (J) = v0 he
he - 19
M 00 (Jhead)= =5.1158xl0 J
388.3nm
he - 19
MIO(Jhead) = = 4 .7117x10 J
421.6nm
- Moo(J)-Mw(J)
Vo=
he
(5.1158-4.71l7)xl0- 19 J
he
4 4
= ·0 10xl0-zoJ == 0.25222 eV = !2034.3 cm- 1 I
he
vi =Vo+ 79.538cm- 1
4 .1990 x 10-20 J
= (2034.3 + 79.538)cm- 1 =12113.8 cm- 1
he
11-1 e - £, (1,o)m;ff
1 "" e - E,(O,o) t kr. = e-(£,(i,o)-£,(o,o))tkr.
- <ff <ff
0 0
"" e-h<:V, I kT,ff
ln( 11-1 ) = - hcv1

lo-o kT'.rr
h(c:~-o
4.1990x10-20J =ll321KI
T eff =
kln
) (1.38066 x l 0-23 J K- 1) ln(l 0)
11-1
The relative population of the v = 0 and v = 1 vibrational states is the inverse of the relative
1
intensities of the transitions from those states; hence - - =[ill .
0.1
It would seem that with such a high effective temperature, more than eight of the rotational levels of
the S 1 state should have a significant population. But the spectra of molecules in comets are never
as clearly resolved as those obtained in the laboratory, and that is most probably the reason why
additional rotational structure does not appear in these spectra.
12 Magnetic resonance
012.1 Refer to eqn. 12.13(b), which describes the condition for resonance. The resonance field and
resonance frequency are directly proportional to each other. High magnetic fields imply high
frequencies and vice versa. The intensity of an NMR transition depends on a number of factors, two
of which are seen in eqn. 12.14(a): one is the strength of the magnetic field itself and the other is the
population difference between the energy levels of the a and /3 spins, which is also proportional to
the magnetic field as shown by eqn. 12.14(b). Hence the intensity of the signal is proportional
to B~. Consequently an increase in external field results in an even larger increase in signal
intensity. See Section 12.4 and Justification 12.1 for a more detailed discussion. Chemical shifts as
expressed in eqn. 12.15 are also seen to be proportional to B0 . Finally, as discussed in Section 12.6,
the use of high magnetic fields simplifies the appearance of the complex spectra of macromolecules
and allows them to be interpreted more readily. Although spin-spin splittings in NMR are not field
dependent, strongly coupled (second-order) spectra are simplified at high fields because the
chemical shifts increase and individual groups of nuclei become identifiable again.
012.3 Before the application of a pulse the magnetization vector, M, points along the direction of the static
external magnetic field B0 • There are more a spins than p spins. When we apply a rotating
magnetic field B1 at right angles to the static field, the magnetization vector as seen in the rotating
frame begins to precess about the B, field with angular frequency CVi = yB, . The angle through
which M rotates is e = yB,t , where t is the time for which the B, pulse is applied. When
t =Jr I 2yB,, ()=Jr I 2 = 90°, and M has rotated into the xy plane. Now there are equal numbers of a
and fJ spins. A 180° pulse applied for a time n I yB, rotates M antiparallel to the static field. Now
there are more fJ spins than a spins. A population inversion has occurred.
012.5 For example, at room temperature, the tumbling rate of benzene, the small molecule, in a mobile
solvent may be close to the Larmor frequency, and hence its spin-lattice relaxation time will be
short. As the temperature increases, the tumbling rate may increase well beyond the Larmor
frequency, resulting in an increased spin-lattice relaxation time.
For the large molecule (like a polymer) at room temperature, the tumbling rate may be well below
the Larmor frequency, but with increasing temperature it will approach the Larmor frequency due to
the increased thermal motion of the molecule combined with the decreased viscosity of the solvent.
Therefore, the spin-lattice relaxation time may decrease.
012.7 The basic COSY experiment uses the simplest of all two-dimensional pulse sequences: a
single 90° pulse to excite the spins at the end of the preparation period and a mixing period
containing just a second 90° pulse.
The key to the COSY technique is the effect of the second 90° pulse, which can be illustrated by
consideration of the four energy levels of an AX system (as shown in Figs. 12.11 and 12.12 of the
text). At thermal equilibrium, the population of the aAaX level is the greatest, and that of PAPX
level is the smallest; the other two levels have the same energy and an intermediate population.
After the first 90° pulse, the spins are no longer at thermal equilibrium. If a second 90° pulse is
applied at a time t 1 that is short compared to the spin-lattice relaxation time Ti, the extra input of
energy causes further changes in the populations of the four states. The changes in populations will
depend on how far the individual magnetizations have precessed during the evolution period.
For simplicity, Jet us consider a COSY experiment in which the second 90° pulse is split into two
selective pulses, one applied to X and one to A Depending on the evolution time ti. the 90° pulse that
excites X may leave the population differences across each of the two X transitions unchanged, inverted,
or somewhere in between. Consider the extreme case in which one population difference is inverted and
the other unchanged. The 90° pulse that excites A will now generate an FID in which one of the two A
transitions has increased in intensity and the other has decreased. The overall effect is that precession of
the X spins during the evolution period determines the amplitudes of the signals from the A spins
obtained during the detection period. As the evolution time t1 is increased, the intensities of the signals
from A spins oscillate at rates determined by the frequencies of the two X transitions.
This transfer of information between spins is at the heart of two-dimensional NMR spectroscopy and
leads to the correlation of different signals in a spectrum. In this case, information transfer tells us that
there is a scalar coupling between A and X. If we conduct a series of experiments in which t1 is
incremented, Fourier transformation of the FIDs on t2 yields a set of spectra/(vi. v2) in which the A signal
amplitudes oscillate as a function of t 1• A second Fourier transformation, this time on ti. converts these
oscillations into a two-dimensional spectrum /(vi. v2). The signals are spread out in v1 according to their
precession frequencies during the detection period. Thus, if we apply the COSY pulse sequence to our
AX spin system, the result is a two-dimensional spectrum that contains four groups of signals centred on
the two chemical shifts in v 1 and v2 • Each group will show fine structure, consisting of a block of four
signals separated by JAX. The diagonal peaks are signals centerd on (JA JA) and (Jx Jx) and lie along the
diagonal v1 = v2. They arise from signals that did not change chemical shift between t 1 and t2• The cross
peaks (or off-diagonal peaks) are signals centred on (JA Jx) and (Jx JA) and owe their existence to the
coupling between A and X. Consequently, cross peaks in COSY spectra allow us to map the couplings
between spins and to trace out the bonding network in complex molecules. Fig. 12.47 of the textbook
shows a simple example of a proton COSY spectrum of 1-nitropropane.
012.9 The hyperfine parameter a due to a nucleus in an aromatic radical, which is easily measured from
the splittings of the lines in the EPR spectrum of the radical, as illustrated in Fig. 12.51 of the
textbook, for the benzene anion radical, can be related to the spin density p of the unpaired electron
on the nuclei in the aromatic radical. For the hyperfine splitting due to protons in aromatic systems,
the relationship required is the McConnell equation, eqn. 12.44. The process of obtaining p from the
McConnell equation is illustrated in A Brief Illustration following eqn. 12.44. For nuclei other than
protons in aromatic radicals similar, although more complicated, equations arise; but in all cases the
spin densities can be related to the coefficients of the basis functions used to describe the molecular
orbital of the unpaired electron.
E12.1 (a) Work with eqn. 12.11. y1i = g 1µ N Ii has units J sand µN has units J T- 1 ; therefore y has units
Jr' 1s-1 r1I.
Js
E12.2(a) The magnitude of the angular momentum is given by {I(/+ 1)} 11 2 Ii . For a proton I = 112; hence
magnitude= -J3 Ii= l9.133 x 10- 35 J sl . The components along the z-axis are
2
±_!_Ii= l±5.273xl0-35 J sl. The angles that the projections of the angular momentum make with
2
the z-axis are B = ±cos- 1 ~/ 2 = l±0.9553 rad= ±54.74° 1.

v31i / 2
E12.3(a) The resonance frequency is equal to the Larmor frequency of the proton and is given by
v = VL = rBo[12.9] with r= glflN [12.11]

2tr h
MAGNETIC RESONANCE 273
g 1~[30 (5.5857)x( 5.0508xl0- J

27
r- 1
)x(13.5 T) I I
Hence v = = 34
= 574 MHz
h 6.626x10- J s
E12.4(a)
3 1 1 3
m =- - - - - -
1 2' 2' 2' 2
Em, = (-0.4289)x(5.05lxl0-27 J r 1)x(6.800 Txml) = l-l.473xl0-26 Jxml I
E1 2.S(a) The energy level separation is
fill= hv where v = yBo [12.9]

2;r
So
( 6.73xl0 1 r 1s- 1 )xl5.4 T

v= = l.65xl0 8 s- 1
2;r
8
= l.65xl0 Hz= jl65MHzj
E12.6(a) (a) By a calculation similar to that in Exercise 12.3(a), we can show that a 600-MHz NMR
spectrometer operates in a magnetic field of 14.l T. Thus
fill = yhB0 = hv L = hv at resonance
= (6.626xl0-34 Js)x(6.00xl0 8 s- 1) = l3.98xl0-25 JI
(b) A 600-MHz NMR spectrometer means that 600 MHz is the resonance frequency for protons for
which the magnetic field is 14.1 T. In high-field NMRs, it is the field, not the frequency, that is
fixed, so for the deuteron
v = giµNBo [Exercise 12.3a]

h
= (0.8575) x (5.05lxl0-27 JT- 1) x (14.1T)= 21 6 101 H = 92 I6MH

6.626 x 10-34 J s 9. x z . z
fill= hv = (6.626xl0-34 J s)x(9.216xl0 7 s- 1 ) = j6.l lxl0-26 Jj
Thus the separation in energy is larger for the proton~·
E12.7(a) fill= hv = yhB = g 1 ~B [solution to exercise 12.3a]
34 1
B=~= (6.626xl0- JHz- )x(90.0xl0 Hz) =1 . TI
6
Hence, 6 59
g 1 µN (1.793)X(5.05}XJ0-27 J r- 1)
E12.8(a) In all cases, the selection rule fun 1 = ±1 is applied; hence
l3 =~= 6.626xl0- JHz- x~

34 1
g/~ 5.0508xl0-27 J r- 1 g/
0
= (l.31l9x10-7 )x (v 1 Hz) T = (0.13 l 19)x (v 1 MHz) T

gl gl
Refer to the following table.
80 I T (a)1H (b) 2 H (c) 13 C
gl 5.5857 0.85745 1.4046

(i) 800 MHz 18.8 123 74.9
(ii) 500 MHz 11.7 76.6 46.8
COMMENT. Magnetic fields above 30 T have not yet been obtained for use in NMR spectrometers. So
most of these calculated values have no current significance. As discussed in the solution to Exercise
12.6 (both a and b), it is the field , not the frequency, that is fixed in high-field NMR spectrometers. Thus
an NMR spectrometer that is called a 500-MHz spectrometer refers to the resonance frequency for
protons and has a magnetic field fixed at 11 .7 T.
Question. What are the resonance frequencies of these nuclei in 250-MHz and 500-MHz
spectrometers? Refer to Exercise 12.6.
E1 2.9(a) The ground state has
m1 + 1 =a spm,
.
m1 =- 1 = A
f' spm
.
2 2
Hence, with
oN=Na -N~
oN _
N a -NP _ N a -Na e-wkr
[Justification 12.1]
N- N +N - N +N e-t.Etkr
a p a a
1-e-t.El kr 1-(1-M ! kT)"' M =g1µNB0 [forM=kT]

= l +e t.Etkr "' l+l 2kT 2kT
27 1
That is oN"' g 1µ NBo = (5.5857)x(5 .0508xl0- J r )x(B0 ) "'
3 .4 3 xl0-6B 0 I T
' N 2kT (2) x (l.38066 x l0- 23 J r')x(298 K)
(a) B0 =0.3 T, oN/N= l1x10-6 j
(b) B0 =1.5 T, 0N/N=is.1x10-6 I
(c) B0 =10 T, oN/N=l3.4xlO-s j
Ng Jtr,B0 . Nhv
E12.1 O(a) oN"' I [Exercise 12.9a] = -
2kT 2kT
Thus, oN ex: v
oN(800MHz) = 800MHz = [!JJ

oN(60MHz) 60MHz
This ratio is not dependent on the nuclide as long as the approximation M = kT holds (Exercise
12.9a).
0
E12.11(a) (a) o= v-v

Vo
x l0 6 [12.18]
Since both v and v 0 depend on the magnetic field in the same manner, namely,
v=~ and v0 = g 1 ~Bo [Exercise 12.3(a)]
J is ~ndependenq of both B and v.

(b) Rearranging [12.18], we see v-v 0 = v 0 J x 10-6 and we see that the relative chemical shift is
v-v (800 MHz)= (800 MHz)= [LlJ

0
v-v 0 ( 60 MHz) ( 60 MHz)
COMMENT. This direct proportionality between v - v and v is one of the major reasons for operating
0 0
an NMR spectrometer at the highest frequencies possible.
E12.12(a) Bloc = (1-a-)B0 [12.16]
IdBloc I=! (dO") I B0 ""I [J(CH 3 )-J(CHO)] IB0 [1dO" I"" IV ~0V IJ
= IC2 .20-9.80)lx10-6 B0 = 7.60x10-6 B0
(a) ldB1oc l = 7.60xl0-6 xl.5 T = ll lµTI
(b) B0 =15 T, ldB1oc l = !11oµrl
E12.13(a) v-v 0 = v0 t5 x 10-6 [12.18]
ldvl =(v-v0 )(CHO)-(v-v0 )(CH 3 )
=-= v"[t5(CHO)-t5(CH 3 )]xl0-6
(a) v 0 = 250 MHz, Id vi= 7.60x 10-6 x 250 MHz= 1.90 kHz
The spectrum is shown in Figure 12.1 with the value of I dv l as calculated above.
2.9 Hz
-v Figure 12.1
(b) v0 "" 800 MHz, ldvl = 6.08 MHz
When the frequency is changed to 800 MHz, the Idv l changes to 6.08 kHz. The fine structure (the
splitting within groups) remains the same as spin-spin splitting is unaffected by the strength of the
applied field. However, the intensity of the lines increases by a factor of 3.2 because JN I N oc v
(Exercise 12. lOa).
The observed splitting pattern is that of an AX 3 (or A 3X) species, the spectrum of which is described
in Section 12.6.
E12.14(a) -r"" J2 [12.29, with 8v written as .1 v]

miv
.1 v = v0 (8' -5) xl0-6 [Exercise 12.13a]
'""" _____J2 _
Then
(8' -S)xl0-6
1r11
0
J2 ""3.9x10-4s
(n) x (550x 10 6 Hz)x (4.8- 2.7)x 10-6
Therefore, the signals merge when the lifetime of each isomer is less than about p.39 msl,
corresponding to a conversion rate of aboutl2 .6xl0 3 s- 1 I.
19 10
E12.1 S(a) The four equivalent F nuclei (I= f) give a single line. However, the B nucleus (I= 3, 19.6
percent abundant) splits this line into 2x3+1 = 7 lines, and the
11
B nucleus (I =1, 80.4 percent
11
abundant) splits it into 2x f +1 = 4 lines. The splitting arising from the B nucleus will be larger than
10
that arising from the B nucleus (since its magnetic moment is larger by a factor of 1.5; Table 12.2).
11
Moreover, the total intensity of the four lines due to the B nuclei will be greater (by a factor of
10
80.4/19 .6 "" 4) than the total intensity of the seven lines due to the B nuclei. The individual line
intensities will be in the ratio ix 4
4 = 7 ( the number of lines and about four times as abundant).
The spectrum is sketched in Figure 12.2.
Figure 12.2
E12.16(a) v = gi µ NB [solution to Exercise 12.3a]

h
v(1 9 F) g(1 9 F)
Hence,
v(1H) = g(1H)
5 2567
or v(1 9 F) = · x800MHz=1753 MHz I
5.5857
The proton resonance consists of 2 lines (2xf + 1) and the 19F resonance of 3 lines [2x(2xf) + 1].
The intensities are in the ratio 1:2:1 (Pascal's triangle for two equivalent spin t nuclei; Section
5 5857
12.6). The lines are spaced · = 1.06 times greater in the fluorine region than in the proton
5.2567
region. The spectrum is sketched in Figure 12.3.
I I I
Figure 12.3
E12.1 ?(a) The A, M, and X resonances lie in distinctively different groups. The A resonance is split into a
1:2:1 triplet by the M nuclei, and each line of that triplet is split into a 1:4:6:4:1 quintet by the X
nuclei (with JAM >JAX). The M resonance is split into a 1:3:3:1 quartet by the A nuclei and each
line is split into a quintet by the X nuclei (with JAM > J MX ) . The X resonance is split into a quartet
by the A nuclei and then each line is split into a triplet by the M nuclei (with JAX > J MX ). The
spectrum is sketched in Figure 12.4.
Figure 12.4
E12.18(a) (a) If there is rapid rotation about the axis, the H nuclei are both chemically and magnetically
equivalent.
(b) Since Jcis :/. J,rans, the H nuclei are chemically but not magnetically equivalent.
E12.19(a) Analogous to precession of the magnetization vector in the laboratory frame due to the presence of
8 0 , that is,
VL = yBo [12.9]
2;r
there is a precession in the rotating frame due to the presence of B1, namely,
vL = rBi or m = yBI [OJ= 2JW]

21( ""'!
Since OJ is an angular frequency, the angle through which the magnetization vector rotates is
B = yBt = gifiN Bt
I h I
Bh (f)x(l.055xl0-34 Js) I -4 I
and B1 = - - = 27 1 5
= 5.9xl0 T
g 1 f4.t (5.586)x(5.05lxl0- JY- )x(l.Oxl0- s)
A 180° pulse requires 2x10 µs = I20 µs I·
34
= ~ = (6.626xl0- JHz- )x(9x10 Hz)=1 2 x 10 2 Tl
1 9
E12.20(a) (a) 80
g1µ K (5.5857)x(5.05lxl0-27 JY- 1)
34
B =~= (6.626 x l0- JHz- )x(300xl0 Hz) =llOmTI
1 5
(b) 0 24 1
gcµB (2.0023)x(9.274xl0- JY- )
COMMENT. Because of the sizes of these magnetic fields , neither experiment seems feasible.
Question. What frequencies are required to observe electron resonance in the magnetic field of a
300-MHz NMR magnet and nuclear resonance in the field of a 9-GHz (g = 2.00) ESR magnet? Are
these experiments feasible?
hv
E12.21 (a) g = - [12.41]
µsBo
We shall often need the value

34
h 6.62608xl0- JHz-i = 7.14478 x l0- 11 THz- 1
µ 8 = 9.27402xl0 24 JT 1
Then, in this case,
9
=(7.14478xl0- 11 1
THz- ) x (9.223l x l0 Hz) =l 2 .0022 I
3
g 329.12 x l0- T
E12.22(a) a= B(line3)- B(line2) = B(line2)- B(linel)
B3 - B2 = (334.8 - 332.5) mT = 2.3 mT} I

a= 2.3 mT
I
B2 - B1 = (332.5 - 330.2) mT = 2.3 mT
Use the center line to calculate g.
9 319
· x
109
g =_!:::___ =(7.14478x10- 11
T Hz- 1) x ~2 =J2 .0025 J
µ 8 B0 332.5 x l0- T
E12.23(a) The center of the spectrum will occur at 332.5 mT. Proton 1 splits the line into two components with
separation 2.0 mT and hence at 332.5±1.0 mT. Proton 2 splits these two hyperfine lines into two, each
with separation 2.6mT, and hence the lines occur at332 .5±1.0± 1.3 mT. The s ectrum therefore
consists of four lines of/equal intensity/ at the fields 330.2 mT, 332.2 mT, 332.8 mT, and 334.8 mT .
E12.24(a) We construct Figure 12.5(a) forCH 3 and Figure 12.5(b) forCD 3 • The predicted intensity distribution
is determined by counting the number of overlapping lines of equal intensity from which the
hyperfine line is constructed.
(a) (b)
ao
H{l) D(l)
H(2) 0 (2)
H(3)
II 0 (3)
D 3
~ 1367631 Figure 12.5
hv 7.14478x10- 11 _ •
E12.25(a) B0 = - - = THz 1 xv [Exercise 12.21a] = 35.68mTx(v/GHz)
gµ 8 2.0025
(a) v = 9.313GHz, B0 =1332.3 mTI

(b) v = 33.80GHz, B0 =1206mT = [1.206T[
E12.26(a) Since the number of hyperfine lines arising from a nucleus of spin 1 is 2/ + 1, we solve 21+1=4
and find that 1 = I ·H
COMMENT. Four lines of equal intensity could also arise from two inequivalent nuclei with I =~ .
E12.27(a) The X nucleus produces six lines of equal intensity. The pair of H nuclei in XH 2 split each of these
lines into a 1: 2 : 1 triplet (Figure 12.6a). The pair of D nuclei (I = 1) in XD 2 split each line into a
1: 2: 3: 2: 1 quintet (Fig. 12.6b). The total number of hyperfine lines observed is then 6x3=18 in
XH 2 and 6x5 = 30 in XD 2•
I I
I I
I I
I
t
t
(a) (b) Figure 12.6
P12.1 (a)
Using the formulas
. . . rat10
Sens1tiv1ty . (v) = R,,(nuclide) = -2 (/ + !)[µ(nuclide)]
R,,( 1H) 3 µ( 1H)
Sens1tiv1ty . (B) = .R8 (nuclide) = -l(l+lJ[µ(nuclide)]

. . . rat10 - -
1
RB ( H) 6 I2 µ( 1H)
we construct the following table.

-
Nuclide Spin I µ/µ N Sensitivity Ratio ( v) Sensitivity Ratio (B)
2H l 0.85745 0.409 0.00965

IJC I
0.7023 0.251 0.01590
2
14N l 0.40356 0.193 0.00101
I
'9F 2 2.62835 0.941 0.83350
I
l ip
2 1.1317 0.405 0.06654
I
'H 2 2.79285
(b) µ=rhl=g1µN 111

µ
Hence r= nI
At constant frequency,
Rv oc (I+ l)µw~ or ~ oc (I+ I)µ [Wo is constant between the nuclei.]
Thus
.. . . ( ) Rv(nuclide)
Sens1t1v1ty ratio v = 1
~( H)
= lu + l)[µ(nuclide)J = lu + l)[µ(nuclide) /µ N]
3 µ(' H) 3 µ(' H) !µ N
as above. Substituting Wo = rBo and r= !!__, lUo =µBo' so

hi hi
(I+ 1)µ B~
3
RB oc
12
Sensitivity ratio(B) = Ra (nu,clide) =

RB ( H)
l(I +
6 J
2
1J[µ(nuclide)]
µ(' H)
3
= l(I +
6 12
lJ[µ(nuclide) I µ N]
µ('H) ! µ N
3
as in part (a).
P12.3 The envelopes of maxima and minima of the curve are determined by T2 through eqn. 12.30, but
the time interval between the maxima of this decaying curve corresponds to the reciprocal of the
frequency difference ~ v between the pulse frequency v0 and the Larrnor frequency vL , that is,
~v = lvo-vLI·
1 -I
~v = - - = 8.3s = 8.3Hz
0.12s
Therefore the Larmor frequency is 1400xl0 6 Hz ±8Hzl.
According to eqns. 12.30 and 12.34, the intensity of the maxima in the FID curve decays
exponentially as e- rlT2 • Therefore T2 corresponds to the time at which the intensity has been reduced
to lie of the original value. In the text figure, this corresponds to a time slightly before the fourth
maximum has occurred, or about I0.29sl.
P12.5 (a) The Lorentzianfanction in terms of angular frequencies is
The maximum in this function occurs when W= £i-O. Hence h ,max = S0 T2 and
where dW = ~ d% ; hence 2 = 1+ T22 (dw)2 and dW = 11 T2 • Therefore Id% = ~ I·

(b) The Gaussianfanction in terms of angular frequencies is
The maximum in this function occurs when W= £i-O. Hence JG.max= S0 T2 and
JG (dlil ) - JG ,max -- __Q_1_
-1/ 2 - - -
S T- - s 2( )2
s
- 0 r.2 e-T2 Ill_.-% -- 0r.2 e-T2 Lim)
2( 2
2 2
where dw = _!._ d% ; thus ln2 = T22 (dw) 2 and dW =(In 2f' I T2 .

2
2(1n 2)y,
Therefore dco., = - - -
" T2
(c) If we choose the same values of S0 , T2 , and £i-O for both functions, we can rewrite them as
1 2
Jdw) = L(x) oc - - and JG(w) = G(x) oc e-x wherex = T2(W-%)
l+x 2
These functions are plotted against x in the following Mathcad worksheet. Note that the Lorentzian
function is slightly sharper in the center, although this is difficult to discern with the scale of x used
in Figure 12.7, and decreases much more slowly in the wings beyond the half amplitude points.
Note that the functions plotted in the figure are not normalized but are matched at their peak
amplitude in order to more clearly display the differences in their shapes. If the curves had been
normalized, the areas under the two curves would be equal, but the peak height in the Lorentzian
would be lower than the Gaussian peak height.
x := -5, -4.95 .. 5
1 2
L(x):=-- G(x) := e-x
l+x2
L(x)
0.5
G(x)
''
o._~~....._~ ........
"---_.__--........,.~~...._~~_.
-6 -4 -2 0 2 4 6
x Figure 12.7
P12.7 (a) The Karplus equation [ 12.27] for 3 J HH is a linear equation in cos¢> and cos 2¢> . The experimentally
determined equation for 3 J snsn is a linear equation in 3 J HH . In general, if F(f) is linear inf, and
if f (x) is linear in x, then F( x ) is linear. So we expect 3 J snsn to be linear in cos¢> and cos 2¢>. This is
demonstrated in (b) .
3
(b) J snsn/Hz = 78.86(3 J HH/Hz) + 27.84
Inserting the Karplus equation for 3 JHH we obtain
3
Jsnsn /Hz = 78.86{A + Bcos¢> + C cos 2¢>} + 27.84
Using A= 7, B = -1, and C = 5, we obtain

3
J snsn/Hz=1580 - 79cos ¢>+ 395 cos 2¢1
3
The plot of J snsn is shown in Figure 12.8.
Vicinal tin coupling constant

1200 ~-----------~
1000
800
N
~ 600
'{!
....,"'
"'
400
200
0 ~~~~~-~~~~~-~~
0 ~ W 00 IW l~ IW
<t>fdegrees Figure 12.8
(c) A staggered configuration (Figure 12.9) with the SnMe3 groups trans to each other is the
preferred configuration. The SnMe3 repulsions are then at a minimum.
SnMe3
H H
R SnMe3 H Figure 12.9
24 1 3
P12.9 v = geµ 8 !3 = (2 .00)x(9.274xl0- J T ) x (l.Oxl0 T) = 12 .8 x l0' 3 Hzl
h 6.626xl0- 34 Js
This frequency is in the infrared region of the electromagnetic spectrum and hence is comparable to
the frequencies and energies of molecular vibrations; it is much greater than those of molecular
rotations and far less than those of molecular electronic motion.
P12.11 Refer f°
Figur 12.6 in the solution to Exercise 12.24(a). The width of the CH 3 spectrum is
3aH = 6.9 mT . The width of the CD 3 spectrum is 6an. It seems reasonable to assume, since the
hyperfine interaction is an interaction of the magnetic moments of the nuclei with the magnetic
moment of the electron, that the strength of the interactions is proportional to the nuclear
moments.
and thus nuclear magnetic moments are proportional to the nuclear g-values; hence
0.85745
a0 "' xaH = 0.1535aH = 0.35mT
5.5857
Therefore, the overall width is 6a0 = 12.1 mT I·
57
P12.13 Write P(N2s)= · mT =lo.101 (10percentofitstime)
55.2mT
P(N2pz) = 1.3mT = lo.381 (38 percent of its time)

3.4mT
The total probability is
(a) P(N) = 0.10+0.38 = lo.481 (48 percent of its time).
(b) P(O) = 1-P(N) = lo.521 (52 percent of its time).
The hybridization ratio is
P(N2p) = 0.38=1 3 .8 1
P(N2s) 0.10
The unpaired electron therefore occupies an orbital that resembles an sp 3 hybrid on N, in accord
with the radical' s nonlinear shape.
From the discussion in Section 5.2 we can write
1 +cos¢
I-cos¢
b2 =l-a 2 = -2cos¢
l-cos¢
2
, b' -1 cos¢ . I . h 'A
"" = -;z = , imp ymg t at cos¢ = - -
a l+cos¢ 2+£
Then, since 'A= 3.8, cos¢= -0.66, so ¢ = 1131°1.
P12.15 When spin label molecules approach to within 800 pm, orbital overlap of the unpaired electrons and
dipolar interactions between magnetic moments cause an exchange coupling interaction between the
spins (Figure 12.10). The electron exchange process occurs at a rate that increases as concentration
increases. Thus the process has a lifetime that is too long at low concentrations to affect the "pure"
ESR signal. As the concentration increases, the linewidths increase until the triplet coalesces into a
broad singlet. Further increase of the concentration decreases the exchange lifetime and therefore
the linewidth of the singlet.
When spin labels within biological membranes are highly mobile, they may approach closely and
the exchange interaction may provide the ESR spectra with information that mimics the moderate
and high-concentration signals above.
ESR Spectrum of di-tert-butyl Nitroxide

Low
concentration
Moderate
concentration
Higher
concentration
High
concentration
Figure 12.10
P12.17 The first table below displays experimental De chemical shifts and computed* atomic charges on the
carbon atom para to a number of substituents in substituted benzenes. Two sets of charges are shown,
one derived by fitting the electrostatic potential and the other by Mulliken population anlysis.
Substituent CH 3 H CF3 CN N02

L1 128.4 128.5 128.9 129.l 129.4
Electrostatic charge/e -0.1273 -0.0757 -0.0227 -0.0152 -0.0541
Mulliken charge/e -0.1089 -0.1021 -0.0665 -0.0805 -0.0392
*Semi-empirical, PM3 level, PC Spartan Pro™
In Problem 6.7 we have recalculated net charges at a higher level than the semi-empirical PM3 level
displayed above. The following table obtained from the solution to Problem 6.7 displays both the
experimental and calculated* (HF-SeF/6-311G") De chemical shifts and computed* atomic charges
on the carbon atom para to a number of substituents in substituted benzenes. Three sets of charges
are shown, one derived by fitting the electrostatic potential, another by Mulliken population
analysis, and the other by the method of "natural" charges.
Substituent CH3 H CF3 CN N02
b exo
b calc
. 128.4
134.4
128.5
133.5
128.9
132.l
129.l
138.8
129.4
141.8
Electrostatic charge"/e -0.240 -0.135 -0.138 -0.102 -0.116
Mulliken charge"/e -0.231 -0.217 -0 .. 205 -0.199 -0.182
Natural charge"/e -0.199 -0.183 -0.158 -0.148 -0.135
' Spartan '06™; HF-SCF/6-31 IG'
0.00
0
-0.02
.
v
-0.04
u
~ -0.06 • Mulliken
;a
..c:
u }
•
-0.08 - 0 Electrostatic
-0.10
-
-0.12 •
0
-
~
-0.14
128.0 128.5 129.0 129.5 130.0 130.5
{J Figure 12.11
(a) Neither set of charges correlates well with the chemical shifts; however some correlation is
apparent, particularly for the Mulliken charges.
(b) The diamagnetic local contribution to shielding is roughly proportional to the electron density
on the atom. The extent to which the para-carbon atom is affected by electron-donating or
electron-withdrawing groups on the other side of the benzene ring is reflected in the net charge
on the atom. If the diamagnetic local contribution dominated, then the more positive the atom,
the greater the deshielding and the greater the chemical shift would be. That no good o
correlation is observed leads to several possible hypotheses: for example, the diamagnetic local
contribution is not the dominant contribution in these molecules (or not in all of these
molecules), or the computation is not sufficiently accurate to provide meaningful atomic
charges. See the solution to Problem 6. 7 for additional discussion.
P12.19 Eqn. 12.28 may be written
B = k(l-3cos 2 B)
where k is a constant independent of angle. Thus
Boer (l-3cos B)sinBdB rd¢2
oc r (1- 3x 2 ) cl.xx 2n [x =cos(}, dx =-sin (}d(}]
oc(X-X 3 ) 1-1 =0
1
P12.21 The shape of spectral line /(OJ) is related to the free induction decay signal G(t) by
/(OJ)= a Re r G(t)e;(j)( dt
where a is a constant and Re means take the real part of what follows. Calculate the lineshape
corresponding to an oscillating, decaying function.
G(t) = cosmote-11 '
r
=a Re cos OJote-'''+i(j)( dt
=~aRe r (e-i<>tt +ei"t')e-t/r+i(j)( dt
=~aRe r {ei(<>t+w+i/T)I +e-i(<>t -W-i/T)t}df

when OJ and OJ0 are similar to magnetic resonance frequencies (or higher), only the second term in
1 1
brackets is significant ( because = 1 but may be large if OJ"' Wo ) . Therefore
l (OJo +OJ) (OJo-OJ)
1 1
J(OJ)"'-aRe-----
2 i(OJ0 -0J)+l/r
1 -i(OJ0 -OJ)+l/r 1 llr

=-aRe =-a--2 -
2 (OJ0 - 0J) 2 +1/ r 2 2 (OJo-OJ) +1/r 2
=I (21) aT
l+(OJo-OJ)2Z°2
which is a Lorentzian line centered on OJ0 of amplitude * ar and width

-
~T at half-height.
3
P12.23 JHH =A+ B cos </J+ c cos 2¢ [12.27]
_i._( 3JHH) = -Bsin¢-2Csin 2¢ = 0

d¢
This equation has a number of solutions:
¢=0, ¢=n7r, ¢=Jr-arcos ( 4~ ) =arcos (:C)

The first two are trivial solutions.
If ¢ = arcos (!!_)
4C
then, sin ¢ = ~1- 16C
B 2
. 2.
sm2¢= sm¢cos ¢=2 1 - - -
16C 2
n; (B) 2
-
4C
Bsin¢+2Csin2¢=B n; + 4C 1 - - -
16C 2 ~ (B)
2
-
4C
=0
So !!_ = cos ¢ clearly satisfies the condition for an extremum.

4C
The second derivative is
d2
- 2 (3 JHH) =-Bcos¢-4Ccos2¢ =-Bcos¢-4C(2cos 2 ¢-1)
d¢
B ) 4 (2 B
= - B ( 4C - C l 6C 2
2
-
J B
l = - 4C
2
- 2B
4C + 4 C
2
This quantity is positive if

16C2 > 3B2
This is certainly true for typical values of Band C, namely, B = -1 Hz and C = 5 Hz. Therefore the
condition for a minimum is as stated, namely, kos p= B!4Cj.
P12.25 Methionine-105 is in the vicinity of both typtophan-28 and tyrosine-23, but the latter two residues
are not in the vicinity of each other. The methionine residue may lay between them as represented
in Figure 12.12.
OH
H
I
.... .N
H
I
..... N
...... c~
0
.....c=o Tyrosine residue
Tryptophan residue Figure 12.12
P12.27 See Figure 12.13. Only the H(N) and H(Ca) protons and the H(Ca) and H(Cp) protons are expected
to show coupling. This results in a simple COSY spectrum with only two off-diagonals, one at
(8.25 ppm, 4.35 ppm) and the other at (4.35 ppm, 1.39 ppm).
-
0
2 CpH
I
4
8 I
6
10
8
10 8
NH
6
-
8
4 2 0
Figure 12.13
P12.29 Assume that the radius of the disk is 1 unit. The volume of each slice is proportional to length of slice x '5x .
- x Figure 12.14
length of slice at x = 2 sin B

x=cos B
B = arcosx
ranges from -1 to +1
length of slice at x = 2 sin(arcos x)
1.5
MRI
absorption
intensity
f(x)
-
0.5
0
-l - 0.5 0 0.5 Figure 12.15
x
Plot/(x) = 2 sin(arcos x) against x between the limits -1 and +l. The plot is shown in Figure 12.15.
The volume at each value of x is proportional to j(x) and the intensity of the MRI signal is
proportional to the volume, so the figure above represents the absorption intensity for the MRI
image of the disk.
PART 4 Molecular thermodynamics
13 The Boltzmann distribution
013.1 The molecular partition is roughly equal to the number of physically distinct states thermally
accessible to a molecule at a given temperature. At low temperatures, very little energy is available,
so only the lowest energy states of a molecule are accessible; therefore, as the temperature
approaches absolute zero, the partition function approaches the degeneracy of the molecule's
ground state. The higher the temperature, the greater the Boltzmann weighting factor e-fk and the
more accessible a state of energy e becomes. Thus the number of accessible states increases with
temperature. (The partition function is only "roughly equal" to the number of accessible states
because at any non-zero temperature, each state is accessible with a finite probability proportional
to e-fk. Thus, to state whether or not a given state is "accessible" at a given temperature is somewhat
arbitrary, so an exactly counted number of accessible states is also arbitrary. Because the partition
function is the sum of all of these fractional probabilities, it is a good estimate of this number.) See
Section 13.2.
013.3 The population of a state is the number of molecules of a sample that are in that state, on average.
The population of a state is the number of molecules in the sample times the probability of the state.
The configuration of a system is a list of populations in order of the energy of the corresponding
states. For example, {N-3, 2, 1, 0, ... } is a possible configuration of a system of N molecules in
which all but three of the molecules are in the ground state, two molecules are in the next lowest
state, one is in the next state, and so on. The weight of a given configuration is the number of ways
the configuration can be made up. In our example, the single molecule in the second excited state
could be any of the system's N molecules, so there are N ways to arrange that state alone. The
weight of the configuration {N0 , Ni. N2, ••. } is
N!
'W=------ (13.1)
No!N1!N2!
When N is large (as it is for any macroscopic sample), the most probable configuration is so much
more probable than all other possible configurations that it is the system's dominant configuration.
See Section 13.1.
013.5 Because this chapter focuses on the application of statistics to the distribution of physical states in
systems that contain a large number of atoms or molecules, we begin with a statistical answer: the
thermodynamic temperature is the one quantity that determines the most probable populations of
those states in systems at thermal equilibrium (Section 13. lb). As a consequence, the temperature
provides a necessary condition for thermal equilibrium; a system is at thermal equilibrium only if
all of its sub-systems have the same temperature. Note that this is not a circular definition of
temperature, for thermal equilibrium is not defined by uniformity of temperature: systems whose
sub-systems can exchange energy tend toward thermal equilibrium. In this context, sub-systems can
be different materials placed in contact (such as a block of copper in a beaker of water) or they can
be more abstract (such as rotational and vibrational modes of motion).
Finally, the equipart1t10n theorem allows us to connect the temperature of statistical

thermodynamics to the empirical concept of temperature developed long beforehand. Temperature
is a measure of the intensity of thermal energy directly proportional to the mean energy for each
quadratic contribution to the energy (provided that the temperature is sufficiently high; see
Discussion Question 13.7)
013.7 The equipartition theorem says that the average value of each quadratic contribution to the energy is
the same and equal to (1/2)kT = 11(2/J). This result agrees with the mean energy computed from a
partition function, dqld,8, at sufficiently high temperatures. The partition function yields the general
result for mean energy. Mathematically, evaluating dqld,8 involves summing ov~r states. In
mathematical terms, the equipartition theorem is valid when the temperature is high enough for the
discrete sum to be well approximated by a continuous integral. In physical terms, this corresponds to
temperatures sufficiently high for the difference between energy levels to be small compared to kT.
013.9 Identical particles can be regarded as distinguishable when they are localized as in a crystal lattice
where we can assign a set of coordinates to each particle. Strictly speaking, it is the lattice site that
carries the set of coordinates, but as long as the particle is fixed to the site, it too can be considered
distinguishable.
E1 3.1 (a) The weight is given by
N! 16!
'W= N 'N'N! 0!1!2!3!8!0!0!0!0!2!
0 • 1• 2
This can be simplified by removing the common factor of 8! from the numerator and denominator
and noting that O! = 1! = 1:
'W = 16xl5xl4x13x12xllxl0x9 =1 1
21621600
2 x (3 x 2) x 2
E13.2(a) (a) 8!=8x7x6x5x4x3x2xl=~exactly.

(b) According to Stirling's approximation,
In x! ""x In x -x
so In 8! ""8 In 8 - 8 = 8.636 and 8! ""e8·636 = ~.63 x 10~
(c) According to Stirling's better approximation,
x! ""(2zj 112.x7+ 112e-x so 8! ""(2zj 112 885 e- 8 =13.99 X 104
E13.3(a) For two non-degenerate levels,
N
k~]
- /JE
_2 = ~ = e-P«,-e = e-flt;e = e - 11e1kr
1)
NI e- /JE1
[ 13.7 with ,8 =
Hence, as T ~ oo, N 2 = e-o =[!].That is, the two levels would become equally populated.
N,

N
_2
N
I
- /JE
= ~ = e-P<e,-e = e-/Jt;e = e - 11Etkr
e-/JE1
1)
[13.7 with,8= k~ l
so
N2 !}.£
ln-=-- and T=-~
N, kT kin N2
N,
THE SOLTZMANN DISTRIBUTION 293
34 10 1 1
Thus
T= 6.626xl0- J sx2.998xl0 cm s- x400 cm- = 1
524
Kl
l.38 lxl0-23 J K- 1x In (1/ 3)
E1 3.S(a) See Example 13 .1. The ratio of populations of a particular state at the J = 5 level to the population
of the non-degenerate J = 0 level is
[ 13.7 with ,8 = k~]

Because all the states of a degenerate level are equally likely, the ratio of populations of a particular
level is
The degeneracy of linear rotor energy levels is
g; =(2J+l)
and its energy levels are
c, = hcBJ(J + 1) [Section 10.2(c)]
Thus, using kT/hc = 207.224 cm- 1 at 298.15 K,
N 5 = gs e -5(5+1)hcB/ kT _ (2x5+1) e-5(5+l)x2.7lcm-11207.224cm-1 =17.431

N0 g0 (2x0+1)
[ 13.7 with ,8 = k~]

so, assuming that other states (if any) are negligibly populated,
and
34 1
Thus
10 1
T = _ 6.626x10- J s x 2.998x10 cm s- x540 cm- = 1
354
Kl
1.381x10-23 J K - 1 x ln(lO I 90)
E13. 7(a) (a) The thermal wavelength is
A= h [13.15b]
(2 1 mkT) 112
We need the molecular mass, not the molar mass:
3 1
m= 150x10- kgmoi- =2.49xlo-25 kg
6.022 x 10 23 mol- 1
6.626xl0-34 Js l.43x10- 10 m
So A
(i x2.49xl0-25 kg x l.38l x 10-23 JK- 1xT)11 2 (T I K) 112
(i) T= 300 K: - 1.43x10-10 m=18 .23 x io-12 ml= 18.23 pml

A- (300)1 12
(ii) T = 3000 K: - 1.43x10-10 m=12.60x10-12 ml= 12.60 pml

A- (3000)1'2
(b) The translational partition function is
T V
q = A3 [13.18b]
(i) T= 300 K: T = 1.00 cm

3 2 3
= (l.OOxl0- m) = li. 79 x 1021 1
q (8.23x10- 12 m) 3 (8.23x10- 12 m) 3
(ii) T= 3000 K: T = (l.OOxl0-2 m)3 =15.67x102s l

q (2.60xl 0- 12 m) 3
E13.8(a) qT = -V3 [13.18b], implying that q, = -

A q A
(A') 3
.
3/2
However, A = h ex: ~ so q, = m,
(2 1 mkT) 112 m q (m)
32
Therefore,~
qHe
= ( 2x1.008 )
4.003
'
= I0.35741.
E13.9(a) The high-temperature expression for the rotational partition function of a linear molecule is
R kT - -n 2
q =---[13.2lb], B=-- [10.5], l=µR [Table 10.1]
a'hcB 47rcl
2 2 2
Hence q = 8n k;I = 8n kT µR
(J'h (J'h 2
For 0 2 , µ = f m(O) = f x 16.00 u = 8.00u, and (J'= 2; therefore,

_ (8n 2)x(l.38 lxl0-23 J K- 1)x(300 K)x(8.00xl.6605xl0-27 kg)x(l.2075xl0- 10 m) 2
q- (2)x(6.626xl0-34 Js) 2
=172.21
E13.1 O(a) The high-temperature expression for the rotational partition function of a non-linear molecule is
[Table 13.1]
R 1.027 (T I K) 312 l.027x(T / K) 312 312

q =---;;---(ABC I cm-3 ) 112 (3 . l 752x 0.395 lx o. 3505)1' 2 = l.549x (T / K)
THE BOLTZMANN DISTRIBUTION 295
(a) At25 °C, l =l.549x(298) 312 =l7.97xl0 31.
(b) At 100°c , l = 1.549 x (3 73)312 =Ii .12 x l 04I.
E13.11 (a) The rotational partition function of a non-symmetrical linear molecule is
qR = ~)2J + l)e-hcBJ(J+l)tkT [Example 13 .2 with ,8 = k~]

J
hci3 34 10 1 1
6.626xl0- Jsx2.998x10 cms- x l.93lcm- = . K
Use 23 1
2 778
k l.38lx10- J K -
so qR = L (2J + l)e-2.778 KxJ(J+l)/ T
Use a spreadsheet or other mathematical software to evaluate the terms of the sum and to sum the
terms until they converge. The high-temperature expression is
R kT T
q =-=
hcB 2.778 K
The explicit and high-temperature expressions are compared in Figure 13.1. The high-temperature
expression reaches 95% of the explicit sum at[!]'].
Rotational Partition Function
8
7
6
5
.,.=4
3
2 temperature
1
0 ~~~~~~~~~~~~~~~~
0 5 JO 15 20
T!K Figure 13.1
E13.12(a) The rotational partition function of a spherical rotor molecule, ignoring nuclear statistics, is
qR = Lg1 e-e~ tkr [l3.9b] = L(2J + 1)2e-hcBJ(1+1)tkT [I0.6]

J J
hci3 34 10 1 1
6.626xl0- J sx2.998xl0 cm s- x5.241 cm- = . K
Use 7 539
k l.38lxl0- 23 J K - 1
so qR = L( 2J + l)2e-7.539 KxJ(J+l)/ T
terms until they converge. The high-temperature expression is eqn. 13.22, neglecting cr and with
A=B=C:
l = tr112 kT_ 3/2 = tr112 ( T )3/2

( hcB ) 7.539 K
expression reaches 95% of the explicit sum at~-
Rotational Partition Function
35
30
25
a: 20
"'"' 15
10 Exp licit
tern perature
5
0
0 10 20 30 40 50
T/K Figure 13.2
E13.13(a) The rotational partition function of a symmetric rotor molecule, ignoring nuclear stati stics, is
qR = L gJ,Ke-e~.x lkT (13.9b] = L (21 +

J ,K J=O
l)e - hcBJ(J+ l )/ kT ( 1+2 fK=I e -hc(A - B)K' l kT) (10 .10]
hcB 6.626xl0-34 J sx2.998 x 1010 cm s-1x 0.443 cm-1 = 0.637 K and

Use
k l.38l x l0 23 J K 1
hc(A-B) = 6.626 x l0-34 J s x 2.998 x l0 10 cm s- 1x(S.097-0.443) cm- 1 = . K

6 694
k l.38l x 10-23 J K- 1
so l = ~(21 + l)e--0.637 KxJ(J+l)I T ( l + 2~e-6. 694 KxK'IT)
Write a brief computer program or use other mathematical software to evaluate the terms of the sum
and to sum the terms until they converge. Nested sums are straightforward to program in languages
such as BASIC or FORTRAN, whereas spreadsheets are more unwieldy. Compare the results of the
direct sum with the high-temperature expression, eqn. 13.20(b), with B = C:
l = (~r2 ~:r2 ~ (
expression reaches 95 % of the explicit sum at~-
Vibrational Partition Function
14
12
IO
>
8
"'"' 6
4
2
1000 2000 3000 4000 5000 6000

nK Figure 13.3
E13.14(a) The symmetry number is the order of the rotational subgroup of the group to which a molecule
belongs (except for linear molecules, for which O'= 2 if the molecule has inversion symmetry and 1
otherwise).
(a) CO: Full group C v; subgroup C 1; hence O'= m

(b) 0 2 : Full group D~h; subgroup C2 ; O'= ~
(c) H2 S: Full group C2v; subgroup C2 ; O'= ~
(d) SiH4 : Full group Td; subgroup T; O'= ~
(e) CHCh: Full group C3v; subgroup C3 ; O'= ~
E13.1 S(a) Ethene has four indistinguishable atoms that can be interchanged by rotations, so O' = 4. The
rotational partition function of a non-linear molecule is [Table 13.1]
312 312
R = 1.0270 (T I K) = 1.0270x (298.15) =1 1
660 6
q O' (ABC I cm-3 )1 12 4 x (4.828xl.0012x0.8282)" 2 •
E1 3.16(a) The partition function for a mode of molecular vibration is
V = "'""e-vhcv l kT = 1 - (13.24 With fJ= 1/kT]

q L.,
v
1
-e - hcvl kT
hcii = 6.626xl0-34 J sx2.998xl0' 0 cm s-' x323 .2 cm-' = . K

Use 464 9
k l.38lxl0-23 J K - 1
So V "'"" -vhcli / kT 1
q = L., e = 1- e -464.9 KIT
v
The high-temperature expression is
qv = kT = T [13.25]
hcii 464.9 K
expression reaches 95% of the explicit sum at@500 Kj.
Vibrational Partition Function
14 ~~~~~~~~~~~~~~~~
12
10
8
>,,.
6
4
2
0 ~~~~~~~~~~~~~~~~
0 1000 2000 3000 4000 5000 6000

T/K
Figure 13.4
E13.17(a) The partition function for a mode of molecular vibration is
qV =l ! hcvl kT (13.24 WithfJ= l/kT]

-e
and the overall vibrational partition function is the product of the partition functions of the
individual modes. (See Example 13.6.) We draw up the following table.
Mode 2 3 4
vI cm- 1
658 397 397 1535
hcv I kT 1.893 l.142 1. 142 4.416

v
q mode 1.177 1.469 l.469 1.012
The overall vibrational partition function is
qv mode = 1.177 X 1.469 X 1.469 X 1.012 = J2.57ll
E13.18(a) The partition function for a mode of molecular vibration is
qv =.
-e
!h,rnT [13 .24 with /J= llkT]
and the overall vibrational partition function is the product of the part1t1on functions of the
individual modes. (See Example 13.6.) We draw up the following table, including the degeneracy of
each level.
Mode l 2 3 4
--
v I cm- 1 459 217 776 314
gmode 1 2 3 3
hcv I kT 1.320 0.624 2.232 0.903
v
q mode 1.364 2.15 1.120 1.681
The overall vibrational partition function is
qvmode = 1.364 X 2.15 2 X 1.1203 X 1.681 3 =@2.31
E13.19(a) q= L g i e-/1Ej [l3.9b] = L gJ e -hcv/ kT = 4+ e -hcv1 tkr + 2e-hcv, tkr

levels levels
hcii1 10 -I -
6.626xl0-34 J s x 2.998xl0 cm s x vi = 7.57l x l0-4 x (vJ I cm-1 )
where
kT l.38l x l0 23 J K 1x l900 K
Therefore
q = 4+e-7.571xl0-4x2500 + 2e-7.571xl0-4x3500 = 4+ 0.151+2 X0.0707=14.2921
The individual terms in the last expression are the relative po~ulations of the levels, namely
2 x 0.0707 to 0.151 to 4 (second excited level to first to ground) or .0353 to 0.0377 to ti.
E13.20(a) The mean energy is
L c;e-/IE; ce-/IE
(c) =; ~c;e-/1<; [13.33] = ~>-/IE; 1 + e- fle
where the last expression specializes to two non-degenerate levels. Substitute
c = hcv = 6.626 x 10-34 J sx2.998xl0 10 cm s- 1x500 cm-'= 9.93x10-21 J
and /Jc=_.!._= 9.93x10-21 J =2.41

kT 1.381x10-23 J K - 1 x298 K
so (c) = 9.93 x 110-21 J x e-2.41

+ e-2.41
= 18.16 x 10-22 JI
E13.21 (a) The mean energy is
(c) = ..!_ :~::C;e-P<, [13.33] = ..!.. L g ;c ;e-P<' = ..!.. L(2J + I)cJ e- e, ikr
q states q levels q J
cJ = hcBJ(J + 1) = 6.626 x l0-34 J s x 2.998x10' 0 cm s-' xl.931 cm-' x J(J + 1)
=J(J+l)x3.836xl0-23 J
and cJ = J(J + l)x3.836x10-23 J = J(J + l)x2.778 K

k l.38lxl0-23 J K -'
so (c) = ..!_ LJ(J + 1)(2J + 1) X 3.836X10-23 J X e- J(J+I)x211s KIT

q J
terms until they converge. For the partition function, see Exercise 13.ll(a).
The equipartition value is simply kT (i.e., kT/2 for each rotational degree of freedom) . The explicit
and equipartition expressions are compared in Figure 13.5. The explicit sum reaches 95 % of the
equipartition value at about~·
Mean Rotational Energy
3E-22
2 .5E-22
2E-22
:;;;
l .5E-22
I E-22
5E-23
0
0 5 10 15 20
Figure 13.S
TIK
E13.22(a) The mean energy is
Note that the sum over levels is restricted by nuclear statistics; to avoid multiple counting, we sum
over all J without restriction and divide the result by the symmetry number o:
£1 =hcBJ(J+l)=6.626xl0-34 Js x 2.998 x l0w cms-' x 5.241 cm-'xJ(J+I)
= J(J +l) x l.04l x l0-22 J
22
and £1 J(J+l)xl.04l x 10- J =J(J+l) x 7.539K
k l.38lxl0-23 J K '
so (c) = _l_ L J(J + 1)(2J + 1)2 x 1.041x10-22 J x e-J(J+I)x7539 KIT

<J'q J
terms until they converge. For aq, see Exercise 13.12(a). The quantity evaluated explicitly in that
exercise is aq, because we computed the partition function without taking the symmetry number
into account; in effect, the sum evaluated here and the sum evaluated in the earlier exercise contain
factors of o; which cancel.
The equipartition value is simply 3kT/2 (i .e., kT/2 for each rotational degree of freedom). The
explicit and equipartition expressions are compared in Figure 13.6. The explicit sum reaches 95 % of
the e_quipartition value at about~·
I .2E-21
lE-2 1
8E-22
::::
"' 6E-22
4E-22
2E-22
0
0 10 20 30 40 50 Figure 13.6
T/ K
E1 3.23(a) The mean energy is
(c) = .!.. L E;e -pc, [13.33] = .!.. L g ;E;e -pc,

q states q levels
= _l_L ( 2J
<J'q J=O
+ l)e -hcBJ(J+l)l kT ( i
K=-J
2
E;,K e -hc( A- BJK !kT) [lO. lO]
Note that the sum over levels is restricted by nuclear statistics; to avoid multiple counting, we sum
over all J without restriction and divide the result by the symmetry number a: (See Exercise
13.22a.)
1
£ 1.K = hc {BJ(J + 1) +(A- B)K }
Use hcB = 6.626 x l0- 34 J s x 2.998 x l0 10 cm s- 1 x 0.443 cm- 1 = 8.80 x l0-24 J
24
hcB 8.80 x l0- J = 0.637 K
k = 1.3 81 x l 0 23 J K I
hc( A - B) = 6.626 x l0- 34 J s x 2.998 x l0' 0 cm s- 1 x (5 .097 -0.443) cm- 1
= 9.245 x l0- 23 J
hc(A-B) 9.245x10-23 J = 6.694 K

and
k l.38l x l0-23 J K-1
so (£) =-l-L( 2J + l)e-0.637 KxJ(J + l )I T

CYq J=O
x L J
{J(J + l)x8.80 x l0-24 J + K z x9.245 x 10-23 J}e-6694 KxK
2
IT
K=- J
Write a brief computer program or use other mathematical software to evaluate the terms of the sum
and to sum the terms until they converge. Nested sums are straightforward to program in languages
such as BASIC or FORTRAN, whereas spreadsheets are more unwieldy.
Compare the results of the direct sum with the equipartition value, namely 3kT/2. The explicit and
equipartition expressions are compared in Figure 13.7. The explicit sum reaches 95 % of the
equipartition value at about [I!g.
I .40E-22
~
I .20E-22
l .OOE-22
Equipartition
15 8.00E-23
6.00E-23
4.00E-23 Explicit I
2.00E-23
O.OOEt-00
0 2 4 5 6
Figure 13.7
T/K
E13.24(a) The mean vibrational energy is
(£ v) = hcv
e hcv l kT
. /3
-l [13.39w1th =llkT]
Use hcv = 6.626 x l0-34 J s x 2.998 x l0' 0 cm s-' x 323.2 cm-'= 6.420 x 10-21 J
21
hcv 6.420 x 10- J = . K
and 464 9
k l.38l x l0-23 J K-'
21
so (£v) = 6.420
e464.9
X 10- J
1 KI T _
The equipartition value is simply kT for a single vibrational mode. The explicit and equipartition values
are compared in Figure 13.8. The explicit expression reaches 95% of the equipartition value at~·
Mean Vibrational Energy
9E-20 1- ----- -------

SE-20
7E-20
6E-20
~ 5E-20
4E-20
3E-20
2E-20
I E-20
0
0 1000 2000 3000 4000 5000 6000
Figure 13.8
T/K
E1 3.25(a) The mean vibrational energy per mode is
(£ v) = hcv
ehcii l kT - l (13.39 with
. fJ = llkT]
Mode 2 3 4
v I cm- 1
658 397 397 1535
hcv I (10- 21 J) 13.07 7.89 7.89 30.49
(hcv I k) I K 946 571 571 2208
v) = l.307xlo-20 J + 2 x 7.89xl0-21 J +3.049x10- 20 J

So (£ e946 K I T - 1
------ e571K I T - 1 e2208 K I T - 1
The equipartition value is simply 4kT, that is, kT per vibrational mode. The explicit and
equipartition values are com ared in Figure 13.9. The explicit expression reaches 95% of the
equipartition value at 10500
9E-19
8E-19
7E-19
6E-19
;i 5E-19
4E-19
3E-19
2E-19
IE-19
0
0 5000 10000 15000
Figure 13.9
T/ K
E13.26(a) The mean vibrational energy per mode is
(£ v) = hcv
ehcii l kT -1 (13.39 with
. fJ = llkT]
Mode l 2 3 4
v I cm- 1 459 217 776 314

Degeneracy l 2 3 3
hcv 1 (l 0-21 J) 9.12 4.31 15.42 6.24
(hcv l k) I K 660 312 1116 452
v)= 9.12x10-21 J + 2 x 4.31x10-21 J + 3 x 1.542 x 10-20 J + 3 x -

6.24x10-21 J
So (£
e660KIT -1 e312KIT -1
---
elll6KIT -1 e452KI T -1
The equipart1t10n value is simply 9kT, that is, kT per vibrational mode. The explicit and
equipartition values are compared in Figure 13.10. The explicit expression reaches 95 % of the
equipartition value at ~500 Kj.
::;J
I .4E- 18
.1.2E- 18
IE-1 8
SE-19
,-
I
6E-19
4E-19
2E- 19
0
0 2000 4000 6000 8000 10000
TIK Figure 13.10
1 dq 1 d - 1 -
E13.27(a) (c) =---[13.34) = - - - ( 4+e-fie, +2e fie2 ) =--(-£,e-/ie, -2£2e fie2 )
q d/3 q d/3 q
hcJl
1 1
Use -- =7.57l x 10--4x (V1./ cm - ) and q=4.292 [Exercise 13.19a]
kT
Thus (c) = 6.626xl0-34 J sx2.998xl0' 0 cm s-

1
4.292
x ( 2500 Cm- I X e-7.571xl0--4x2500 + 2 X 3500 Cm- IX e-7 571xl0--4x3500 )
= /4.033 x 10- 21 J/
E13.28(a) The partition function is
q= L e-/ie, = /1 + e- µ.fiB I [energies measured from lower state]

2
The mean energy is [13.34]
Alternatively, if we measure energy with respect to zero magnetic field (rather than to ground-state
energy), then [13.35a]
B +-2"-µ""'0 B_e_
- ~µ·~/i_ 1
2 8
(£) =£gs __!__d_q

q d/3
= -µ
B 1+ e-2µo/JB
We write x = 2µ 8 /38 , so the partition function becomes

q= 1 + e-x
and the mean energy, scaled by the energy separation , becomes
(£) 1 e-x 1 1
--=--+--=--+--
2µBB 2 l+e-x 2 ex +l
The functions are plotted in Figs. 13.11 (a) and (b ). The effect of increasing the magnetic field is to
concentrate population into the lower level.
(a) Partition Function (b) Mean Energy
2 ------------·-------------- 0
1.75
--0.l
I s;
1.5
1.25 --0 .2
I:()
1
"' ::l
--0.3
0.75
0.5
--0.4
0.25
0 --0.5
0 2 3 4 5 0 I 2 3 4 5
x x
Figure 13.11
The relative populations are
N+ = e-f.he[13.7] = e-x
N
24
x= /JB = 2µ 8 8 = 2x9.274xl0- Jr' xl.0 T l.343
2 8
µ kT (1.38lxl0-23 JK-')T TIK
(a) T = 4K, N+ = e-1.3 4314 = lo.711

N
(b) T = 298 K, N+ = e-1.3431298 = I0.9961

N_
E13.29(a) Inclusion of a factor of l/N! is necessary when considering indistinguishable particles. Because of
their translational freedom, gases are collections of indistinguishable particles. Solids are
collections of particles that artdis~inrishable by their rsitions. The factor must be included in
calculations on (a)~. (b) 0 as, and (d) lflzo vapo , but not in (c) solid CO.
51
P13.1 (a) W = N! [13.1] = = [l]
N 0 !N, !N2 ! .. · 0!5!0!0!0!
(b) We draw up the following table.
0 £ 2£ 3£ 4£ 5£ w---;;-r;;r
N!
n,.fli....
4 0 0 0 0 1 5
3 1 0 0 1 0 20
3 0 l 1 0 0 20
2 2 0 l 0 0 30
2 1 2 0 0 0 30
1 3 1 0 0 0 20
0 5 0 0 0 0
The most probable configurations are 1{2, 2, 0, 1, 0, O}I and 1{2, 1, 2, 0, 0, O}I .
P13.3 Listing all possible configurations for a 20-particle system would be very time-consuming and tedious
indeed; however, listing representative configurations for a given total energy is manageable if done
systematically. By "representative," list only one configuration that has a given weight.
For example, consider systems that have a total energy of lOE, where E is the separation between
adjacent energy levels. There are many distinct configurations that have 17 particles in the ground
state and one particle in each of three different states, including configurations in which the singly
occupied levels are (E, 2E, 7 E), (2E, 3E, 5E), and (E, 4E, 5E). Any one of these configurations is
"representative" of all of them, however, because they all have the same weight, namely,
N! 20'
W = - - - - - [13.1] = · = 20xl9xl8 = 6840
N 0 !N 1 !N 2 ! 17!l!1 !l !
So it is sufficient to enumerate just one of the configurations whose occupancy numbers are 17, 1,
1, and l (to make sure that one such configuration exists consistent with the desired total energy). A
systematic way of keeping track of representative configurations is to lower maximum occupancy
numbers. The next set of occupancy numbers to look at would be 16, 4; then 16, 3, 1; 16, 2, 2; 16, 2,
1, l; and 16, 1, 1, 1, 1. We would eliminate 16, 4, because no such occupancy numbers yield a total
energy of 1OE.
Set up a spreadsheet to generate one of each kind of representative configuration, while keeping the
total number of particles constant at 20 and total energy constant (at lOE for the moment). Again,
the most systematic way to do this is to give the highest occupancy numbers to the lowest energy
available states. (This rule also generates the most "exponential" configurations.) For example, out
of several configurations corresponding to occupancy numbers of 16, 3, and 1, the one used is N 0 =
16, N 1 = 3, and N 7 = l.
Next examine systems of total energy lOE, 15E, and 20E. The most probable configurations and
corresponding weights are
20!
lOE: {No= 12, N 1 = 6, N 2 = 2, N3 = 0, ... } w = = 3527160
12!6!2!
20!
15E: {No= 10, N, = 6, N2 = 3, NJ= 1, N4 = 0, ... } w = = 155195040
10!6!3!1!
20!
20E: {No= 10, N, = 4, N2 = 3, N 3 = 2, N4 = 1, N 5 = 0, ... } w = 10!4!3!2!1! = 2327925600
20!
and {No= 9, N, = 6, N 2 = 2, NJ= 2, N4 = 1, N 5 = 0, ... } w = = 2327925600
9!6!2!2!1!
As the total energy increases, the most probable configuration has more occupied levels and
occupancy of higher energy levels.
The Boltzmann distribution would predict the following relative probabilities for equally spaced
energy levels above the ground state:
p j= -fJ.jE
ln -
so
Po
Thus, a plot of the natural log of relative probability vs. the ordinal number of the energy level (j)
should be a straight line whose slope is -/JE. Using the non-zero occupancy numbers from the
configuration, the plots are indeed roughly linear. Furthermore, the value of fJ decreases with
increasing total energy, corresponding to an increase in temperature.
P13.5 According to the "integral" approximation
x (2:rrmkT) 112 X
h [13.15b]
A
and hence for an H atom in a one-dimensional 100-nm box, when l = 10,
T J2
l- x :L!!._
T-
(_
2trmk ) ( X
2
1 10x6.626xl0- 34 J s
[ 27 23 1
= 2trxl.008xl.6605xl0- kgxl.38lxl0- J K - x lOOxlo- 9 m J( )
=I0 .030 Kl
The exact partition function in one dimension is
qT = f 2 2
e - (n - l)h /il8ml
2
= e h /il8ml
2 2
f 2
(e - h /il 8ml
2
r'
n= I n=l
For the H atom,
h2 /J _ (6.626xl0- 34Js) 2
8mL2 - 8xl.008xl.6605xl0- 27 kgxl.38lxl0- 23 J K - 1x0.030 K x (100 x l0- 9m) 2
= 7.9 x l0-3
2 2 2
and 2
e h fii8ml = e79xl0-3 = l.QQ8 ' e - h fi/8ml = e-7.9xl0-3 = Q.992
Then qT = l.008x f (0.992)"' = l.008x(0.992 + 0.969 +0.932+ .. ·)=19.571

n= l
COMMENT. Even under these conditions, the integral approximation is less than 5% from the explicit sum.
P13.7 If the electronic states were in thermal equilibrium with the translational states, then the temperature
would be the same for both. The ratio of electronic states at 300 K would be
N -E, lkT
_ 1 = g 1e =_ix e - L>E1kr = 2e - h&tkr = 2 e-{(I.43ssx4soJ1Joo1 = 0 .23
N o g e- E0 1kT 2
0
The observed ratio is o. 3o = 0.43 . Hence the populations are lnot at eguilibriurrl
0.70
P13.9 (a) First, evaluate the partition function
q = L g i e -P'1 [13.9b] = L g i e - hcfiv1
At 3287°C = 3560 K hc/J= I. 43877 cmK = 4.041x 10-4 cm

' 3560K
q = 5+ 7e-{(4.041xlff-<cm)x(l70cm-')} + 9e-{(4.041xl0-4cm)x(387cm-•)} + 3e-{(4.041xl0-4cm)x(6557cm-')}

= 5 + 7 x (0.934) + 9 x (0.855) + 3 x (0.0707) = 19.444
The fractions of molecules in the various energy levels are

g .e-/IE1 -he/iv
P1 = 1- [13 .8] - g ie '
q q
3 5 ~ 3F) = (7)x(0.934) =lo 3361

p( F2) =- - =&1.TIJ p( 3 19.444 .
19.444
3F ) = (9) x (0.855) =lo 3961 4F) = (3)x(o.0101) =

p( 4 19.444 . p( I 19.444 10 .0111
COMMENT. L i Pi = 1 . Note that the most highly populated level is not the lowest level.
P13.11 The partition function is
q= Lgje-.&j [l3.9b]= Lgje-hcPvj = Lgje-hcv/ kT

j
g is the degeneracy, given by
g=2f+l
where J is the level of the term (displayed as the subscript in the term symbol).
hcv l.43877cmKxvj
At298 K, - -1
K = 4.83 x l0-3x vj I cm- 1
kT 298
so q = 1+3e-4.83xl0-3x557. J + 5e-4.83xJ0-3xl41 0.0 + 5e-4.83xJ0-3x7 125.3 + e-4.83xJ0-3xJ6367.3 = li.2091
hcv
1
l.43877cmKxv . 3
At 1000 K, - - IOOOK J =l.439 x l0- xvj / cm-I
kT
so q =I+ 3e-1.439x10-'x551. 1+ 5e-1.439x10-•x1410.o + 5e-1.439xW-'x1125.3 + e-1.439x10-•x16367.3 = 13 .oo4 1
P13.13 The partition function is
(a)AtlOOK, k/ = l.43877cmKxv
hcv .
lOOK 1 2
=l.44x10- xvj/ cm- 1
so q = 1 + e-0.0J44x213.30 + e-0.0144x425.39 + e-0.0144x636.27 + e-0.0144x845.93 = I1.0491
hcv l.43877cmKxv1.
(b) At 298 K, - - 1
K = 4.83 x 10-3xvj I cm- 1
kT 298
The fractions of molecules at the various levels are
e-,&, e-hcv,lkT
Pv =-[13 .8 ] = - -
q q
So Po =_!_= (a)I0.9531, (b)I0.6451

q
P1 = e-hcv,tkr = (a)I0.0441, (b)I0.2301

q
-hcv2 tkT ~ ~
P2 =-e--=(a)i.Qimj, (b)~
q
COMMENT. Eqn 13.24 gives a closed-form expression for the vibrational partition function, based on an
infinite ladder of harmonic oscillator states. The explicit sum will deviate slightly from this number
because an actual molecule has a finite number of slightly anharmonic vibrational states below the bond
dissociation energy.
P13.15 (a) The probability of finding a molecule in statej is
- PE;
Nj _ e_ [13.8]
Pj =Ji- q
In the systems under consideration, c is both the mean energy and the energy difference between
adjacent levels, so
e -j/JE
pj = -
q
which implies that
-j/Jc= In Nr In N+ In q
Thus, a plot of In~ againstj should be a straight line with slope -tfkT .
and lnNJ. =lnN-lnq-j/Jc=
EH
We draw up the following table using the information in Problem 13.2.
j 0 2 3
l\'J 4 2 2 1 [most probable configuration]
In l\'J 1.39 0.69 0.69 0
These are points plotted in Figure 13.12 (full line). The slope is -0.416, and since L = 50cm- 1 , the
he
slope corresponds to a temperature.
1
T = (50cm- ) x (2.998x10 cm s-
10 1
x (6.626x10- Js)=1
)
163
34
Kl
(0.416) x (1.381x10-23 J K- 1)
(A better estimate, 104 K, represented by the dashed line in Figure 13.12, is found in Problem 13.16.)
1.6
1.2
0.8
O!.....
..s
0.4
......~. \. ··!··
. \ .
.. .... : ,:
: \ :
0 ··-···· · ·· ~··
. . ' .... . .. .. .":: ...\ ,\ . .: ..

·~. ~· ' -~
,:
.\ ..
-0.4
0 2 . 3 4
J I
t
- oo • Figure 13.12
(b) Choose one of the weight 2520 configurations and one of the weight 504 configurations, and
draw up the following table.
J 0 1 2 3 4
'W = 2520 N; 4 3 0
ln l\j 1.39 1.10 0 --00 0
'W= 504 l\j 6 0
ln l\j 1.79 --00 0 0 0
Inspection confirms that these data give very crooked lines
P13.17 Mean values of any variable can be found by weighting possible values of the variable by the
probability of that value. Thus, the mean of the square of energy is
Note that
d -/]< . - /]< d2 - /]< . 2 -/]< .

- - e ' =E .e j so - e ' = E . e '
d/J J d/32 J
Thus and
For a harmonic oscillator, we have a closed-form expression for the partition function,
1
q= 1 -Phcv [13 .24)
-e
~ -hcve-Phcv d2q _ (hcv)2 e-Phcv (1 + e-Phcv )

so and
d/J (1- e-Phcv )2 d/32 - (l-e-Phcv )3
After some algebra, the expression becomes
- - Phcv12
heve hcv
_ -----:-:--=-:--
Li£ =I 1_ e-Phcv - 2 sinh(/Jhcli I 2)
P13.19 Basic thermodynamic relationships will be introduced in Chapters 14 and 15. Among the key
quantities is the internal energy, U, where
U = U(O) + (E) [14.lb]
Here, U(O) is the value of the energy at T = 0. The relationship between the internal energy and
other macroscopic thermodynamic functions is
dU= TdS-pdV[l5.54]
where Sis the entropy, a main topic of Chapter 15. Already we can see a connection between U and
the canonical partition function, Qi on the one hand (via eqn. 13.46), and to macroscopic system
variables like pressure and temperature, on the other. However, the thermodynamic function most
directly related to Q is the Helmholtz energy, A, where
A= U- TS [15.37]
The relationship of A to system variables, therefore, is
dA = dU- TdS-SdT= TdS-pdV- TdS-SdT= -pdV- SdT
so
aA)
(av r,N
=-p
The simple and direct relationship between A and Q is
A = A(O) - kTin Q[15.38a]
Thus p = kT( a ~nVQ)

T .N
= kT (a ln~;/N!)) T,N
= kT(a[Nlnq-lnN!]) = NkT(alnq)
av T,N av T,N
The only contribution to the molecular partition function that depends on Vis translation:
q=qTqRqVqE [13.14]= V3qRqVq E [13.18b]

A
so
= N kT ( a[In v + ln (q R q vq E I A
3
) ] J = N kT ( a1n v )
av r,N av r.N
NkT
v
or lpV = NkT = nRTI
P13.21 If the atmosphere were at equilibrium, then the Boltzmann distribution would apply, so the relative
populations per unit volume would be
N
- ' =--=e }
N
e -/Je,
e - /Je;
-« -E.)l kr
I
[13.7 withfJ= k~]
J
What distinguishes the states and energies of molecules in a planet's gravitational field is the
distance r from the center of the planet. The energy is gravitational, measured from the ground-state
energy.
c(r) = V(r)-V(r0 ) = -GMm(_!__J_)

r r0
(Note that the ground-state energy is literally the energy at the ground--or more precisely, at the
lowest point of the atmosphere, r 0 .)
N(r) -{V(r)-V(r. )}lkT

So --=e '
N( r0 )
Far from the planet, we have
.
,__
hmc(r)=-GMm ( 1)0-- =GMm
--
~ ~
and lim N(r) = e -GMm1r,kT

r-->~ N(r0 )
Hence, if the atmosphere were at equilibrium, the farther one ventured from the planet, the concentration
of molecules would tend toward a non-zero fraction of the concentration at the surface. This is obviously
not the current distribution for planetary atmospheres where the corresponding limit is zero.
Consequently, we may conclude that no planet's atmosphere, including Earth's, is at equilibrium.
P13.23 Each protein-binding site can be represented as a distinct box into which a ligand, L, may bind. All
possible configurations are shown in the following table and the configuration count of i
indistinguishable ligands being placed in n distinguishable sites is seen to be given by the
combinatorial
n'
C(n , i) = ( n -1)1. z.·1
4!
PLo: C(4, 0) (4-0)!0! = 1 configuration
L
L 4!
L PL 1: C(4, l) (4-1)!1! = 4 configurations
L
L L
L L
4!
L L PL2: C(4,2) (4- 2) !2 ! = 6 configurations
L L
L L
L L
L L L
4!
L L L PL3: C(4, 3) (4-3)!3! = 4 configurations
L L L
L L L
4! fi .
L L L L PL4: C(4,4) = =1con1gurat1on
(4-4)!4!
P13.25 (a) According to Impactl13.l , p; = q/qand
_i_ = l + CTs{s"+' -(n + l)s" + l} [l3. 30]

qo (s -1)2
So p0 is just the reciprocal of this quantity. For I > 0,
(n-i+l)CTi
P;
qlqo
(Recall that i = 0 corresponds to the completely helical form, a form with only one possible
configuration and the reference form, so there are no factors of er, s, or n involved in counting its
configurations.) The probabilities for the three different values of stability parameters are plotted in
Figure 13.13.
Probability of Coiled Amino Acids
0.25
0.2
0.15 --+- s = 0.8

,,:.- ---- s= 1
0. 1 • s = l.5
0.05
0 ., l
0
l ~·:z ...-
•
5
.
~·
10 15
~
t
.....
t ~~~-~'
20 Figure 13.13
The fraction of molecules with i coiled residues depends dramatically on the value of s. When s < 1,
low values of i are observed, but large i values are observed when s > 1. Thus, when s < 1, the
polypeptide is largely helical, and when s > 1, it is more of a random coil. The same sort of
distribution can be seen in Fig. 13.15 of the main text, but the smaller value of CT there makes the
completely helical form even more likely than it is here when s < 1.
(b) The mean value of the number of coiled residues is
(i) = IJP;
i=I
This number is plotted against the stability parameter in Figure 13.14. (From left to right, the
curves are for <J'= 0.05, 0.01 , 0.001, and 0.0001, respectively. Plot symbols are shown at the s
values specified in part (a), namely 0.8, 1, and 1.5.) The plot shows that for s < 0.5 the model
polypeptide is helical and little changed as s is varied. At the other extreme, for s > 1.5 the
polypeptide is largely a random coil that changes only slightly with variance of s. The mean
number of coiled residues changes rapidly in the middle range of 0.5 > s > 1.5, giving an overall
sigmoidal dependence on s.
Mean Number of Coiled Residues
20
15
·~ JO
0
0 0.5 1.5 2
Figure 13.14
14 The first law of thermodynamics
014.1 In physical chemistry, the universe is considered to be divided into two parts: the system and its
surroundings. In thermodynamics, the system is the object of interest; it is separated from its
surroundings, the rest of the universe, by a boundary. The characteristics of the boundary determine
whether the system is open, closed, or isolated. An open system has a boundary that permits the
passage of both matter and energy. A closed system has a boundary that allows the passage of
energy but not of matter. Closed systems can be either adiabatic or diathermic. The former do not
allow the transfer of energy as a result of a temperature difference, but the latter do. An isolated
system is one with a boundary that allows the transfer of neither matter nor energy between the
system and the surroundings.
In thermodynamics, the state of a system is characterized by state functions, thermodynamic properties
that are independent of the previous history of the system. In quantum mechanics the state of a system
is characterized by a time-independent wave function.
014.3 A state function is a thermodynamic property the value of which is independent of the history of the
system. Examples of state functions are the properties of pressure, temperature, internal energy,
enthalpy and, as well as the properties of entropy, Gibbs energy, and Helmholtz energy to be
discussed fully in Chapter 15. The differentials of state functions are exact differentials. Hence, we
can use the mathematical properties of exact differentials to draw far-reaching conclusions about
the relations between physical properties and to establish connections that were unexpected but tum
out to be very significant. One practical importance of these results is that we can obtain the value
of a property we require from the combination of measurements of other properties without actually
having to measure the required property itself, the measurement of which might be very difficult.
014.5 When a system is subjected to constant pressure conditions, and only expansion work can occur,
the energy supplied as heat is the change in enthalpy of the system. Thus enthalpy changes in the
system can be determined by measuring the amount of heat supplied. The calorimeters used for
measuring these heats and hence the enthalpy changes of the systems being studied are constant
pressure calorimeters. A simple example is a thermally insulated vessel (a coffee cup calorimeter)
open to the atmosphere: the heat released in the reaction is determined by measuring the change
in temperature of the contents. For a combustion reaction, a constant-pressure flame calorimeter
may be used, as illustrated in textbook Fig. 14.19 where a certain amount of substance bums in a
supply of oxygen and the rise in temperature is monitored. The most sophisticated way of
measuring enthalpy changes is to use a differential scanning calorimeter, described in detail in
Impact 14.1.
014.7 One can use the general expression for 7tr proved in Section 15.7 (eqn. 15.58) to derive its specific
form for a van der Waals gas as given in Exercise 14.29(a), that is, Irr =a IV~. (The derivation is
carried out in Example 15.7.) For an isothermal expansion in a van der Waals gas,
dUm = (a I Vm ) 2 d Vm. Hence !::i.Um = -a(ll Vm,2 -1/ Vm,I) . This derivation is given in the solution
to Exercise 14.29(a). This formula corresponds to what one would expect for a real gas. As the
molecules get closer and closer, the molar volume gets smaller and smaller, and the energy of
attraction gets larger and larger.
THE FIRST LAW OF THERMODYNAMICS 315
014.9 Equations of state can be thought of as expressions for the pressure of a gas in terms of the state
functions , n, V, and T. They are obtained from the expression for the pressure in terms of the
canonical partition function given in eqn. 15.61 in Section 15.9(b ).
=kT(olnQ )
P av T
Partition functions for perfect and imperfect gases are different. That for the perfect gas is given
by Q = qN I N! with q =V I A 3 . There is no one form for imperfect gases. One example is shown in
Self-test 15.5. Another example, which can be shown to lead to the van der Waals equation of state, is
3N / 2
Q =_1_ 2trmkT (V _Nb )eaN 2 t kTV
( 2 )
N! h
For the case of the perfect gas there are no molecular features in the partition function, but for
imperfect gases there are repulsive and attractive features in the partition function that are related to
the structure of the molecules .
E14.1 (a) Cv,m =t(3+v~ +2v~ )R [14.27]
with a mode active if T > ()M
(a) v; = 2, v~ "'1
Hence Cv,m =t(3+2+2xl)R = l1RI [experimental= 3.4R] and the energy is
1RT = 1x8.314 J K - 1 mol- 1 x 298 .15K=8671 J mol- 1 = l8.671 kJ mo1- 1 J
Note that 12 has quite a low vibrational wavenumber, so

34 10 1 1
= hcv = (6.626x 10- Js)(2 .998 x 10 cm s- )(214 cm- ) = K
8 308
v k 1.38lxl0-23 JK- 1
The temperature specified for this exercise is less than this but only slightly. Looking at Fig. 14.16 in
the text suggests that the mode is closer to active than inactive when the temperature is even close to
the vibrational temperature. Thus applying the equipartition theorem may not be adequate in this case.
(b) v; = 3, v~ "'0
Hence Cv,m = l2 (3 + 3 + O)R = [1E} [experimental = 3 .2R] and the energy is
E = 3RT = 3x8.314 J K - 1 mol- 1 x298.15 K =7436 J mol- 1 = J7.436 kJ mo1- 1 J
(c)
Hence Cv,m = t (3 + 3 + 2 x 4 )R =I 7 RI [experimental = 8.8R] and the energy is
E = 7 RT= 8x8 .314 J K - 1 mol- 1 x298.15 K=J17.35 kJ mo1- 1 J
Note that data from G. H. Herzberg, Molecular Spectra and Molecular Structure II. Infrared and Raman
Spectra ofPolyatomic Molecules (Princeton, NJ: van Nostrand, 1945, pp. 364-365) give low vibrational
wavenumbers for four modes of benzene; they are included above. There are 26 more vibrational modes
we have neglected, taking them to be inactive. Slight activity from these modes accounts for the
difference of about 1.8R in the heat capacity between the experimental value and our estimate.
E14.2(a) (a) Pressure, (b) temperature, and (d) enthalpy are state functions.
E14.3(a) The physical definition of work is dw = -F dz [14.5].

In a gravitational field the force is the weight of the object, which is F =mg.
If g is constant over the distance the mass moves, dw may be integrated to give the total work
f"; Fdz=- Jz;f" mgdz=-mg(zr-zi)=-mgh

w=-Jz where h=(zr-zi)
On earth: w=-(60 kg)x(9.81 ms-2 )x(6.0 m)=-3.5xl03 J=l3.5xl0 3 Jneededl
On the moon: w = -(60 kg)x(l.60 ms-2 )x(6.0 m) = -5.7xl0 2 J = 15.7xl0 2 J needed I
E14.4(a) This is an expansion against a constant external pressure; hence w = -p.,l:lV [14.8].
Pex = (1.0atm)x(l.013x 105 Pa atm- 1 ) = 1.01X105 Pa
The change in volume is the cross-sectional area times the linear displacement,
l:lV = (50cm )x(15cm)x(~)

2
3
= 7.5x10-4 m 3
lOOcm
3
so w=-(l.Olxl0 5Pa)x(7.5x10-4m 3)=1-75JI as l Pam =1 J
E14.5(a) For all cases l:lU = 0, since the internal energy of a perfect gas depends only on temperature. From
the definition of enthalpy, H = U + pV, so l:lH = l:lU + l:l(pV) = l:lU + l:l(nRT) (perfect gas). Hence,
l:lH = 0 as well, at constant temperature for all processes in a perfect gas.
(a) lllu = l:lH = ol

w=-nRTln(~) [14.12]
3
= -(1.00mol)x(8.314J K- 1 mor 1)x(293K)xln( 0.0dm:)
10.0dm
3
= -2.68x10 J=1-2.68k11
q = l:lU -w [first law]= 0+2.68kJ = 1+2.68kJI
Cb) lllu = l:lH = ol

w=-p.,llV [14.8) l:lV=(30.0-10.0)dm3 =20.0dm3
Pex can be computed from the perfect gas law

pV=nRT
3 1 1
so = = nRT = (l.00mol)x(0.08206dm atmK- mor )x(293K)=0. 0latm
8
Pex Pr v;. 30.0dm3
w = -(0.80latm)x(l.013xl05 Pa)x(20.0dm3)x( 13m3 3)

latm 10 dm
3
=-l.62xl0 Pam 3 =-l.62xl0 3 J=l-l.62kJI
q = l:lU -w= O+l.62kJ = l+l.62kJI

THE FIRST LAW OF THERMODYNAM ICS 317
(c) liiu = Afl = ol

Free expansion is expansion against no force, so Iw = ol and q = LiU - w = 0- 0 = [Q].
COMMENT. An isothermal free expansion of a perfect gas is also adiabatic.
qp 2291 -I
E14.6(a) CP = LiT [14.33c] = . K = 89.81K
2 55
so Cµ,m = (89.8 1 K- 1)/(3.0mol)=130 1 K- 1 mor 1I
For a perfect gas, Cµ ,m - Cv,m = R [14.35]
Cv,m = Cp,m - R = (30-8.3)1 K - 1 moi- 1 = /221 K- 1 mo1- 1 /
E14. 7(a) For a perfect gas at constant volume,
p nR
- = - = constant,
T V
P2 = ( ~ )xp, = ( ;~~~ )x (l.OOatm) = /1.33atml

LiU = nCv,m liT [2.16b] = (n)x{tR )x(400K-300K)
= (l.00mol)x(~)x(8.3141 K - 1 mor 1 )x(lOOK)

3
= l.25x10 1 = l+i.25k1I
Iw = 0 I [constant volume] q = LiU -w[first law]= l.25kJ-O = l+l.25kJI
E14.B(a) (a) q = Afl, since pressure is constant.
r,
Afl =
i 7:
dH, dH = nC
p,m
dT
d(HI 1) = {20.17 + 0.3665(T!K) }d(T/K)
r,
i
t 73
Li(H! 1) = (H/J) = {20.17 + 0.3665(T/ K)}d(T/ K)
r, 298
0 3 65
·~ )x (~ y
373
= (20.17) x (3 73 - 298) + ( 1
298
3 3 4
= (l.513xl0 )+(9.222xl0 ) = l.07xl0
4
q = Afl = l1.07x10 11=1+10.7 kll for 1.00 mol
w= -pex liV [14.8] where p 0 , =p
w = -pli V = -Li(pV) [constant pressure]= -Li(nRT) [perfect gas]= -nRLiT

= (-l.00mol)x(8.314J K-l mor 1)x(373K-298K) = /-0.624 x l0 3 1/ = l-0.624 kll
LiU = q + w = (10.7 k1)-(0.624k1) =I+ I 0.1kll

(b) The energy and enthalpy of a perfect gas depend on temperature alone; hence it does not matter
whether the temperature change is brought about at constant volume or constant pressure; !:!..H and
11U are the same.
!:!..H=l+10.1k1I, 11u=l+10.ik1I
Under constant volume, w = ~.
q = 11u -w= l+10.n1I
E14.9(a) qP = CPl1T [14.33c] = nCp,ml1T = (3.0mol)x(29.4JK- 1mol- 1)x(25K)=1+2.2 kJI
!:!..H = qp [14.29b] = 1+2.2 k1I
11U = !:!..H - 11(p V) [From H =U + p V] = !:!..H - 11(nRT) [perfect gas] = !:!..H - nRl1T
= (2.2kJ)-(3.0mol)x(8.314JK- 1mol- 1)x(25K) = (2.2kJ)-(0.62kJ) = l+l.6kJI
E14.1 O(a) The partition function is
q = L g1e-Pe1
with degeneracies g1 = 2J + 1
so q = 4+ 2e-Pe [g(2P312) = 4, g(2P112) = 2]
U -U(O) =_ N dq = Nce-/JE
q d/3 2 + e-/JE
Cv=(au) = -k/3
dT v
2 (auJ
d/J V (2+e-PE)
2
= 2R(c/3) e-:E [N =NA]
(a) Therefore, since at 500 K /3c = 2.53 5,
2 2535
(2)x(2.53S) x(e- ) = I0.2361
Cv,m!R ( 2 + e 2.535 )2
(b) At 900 K, when /Jc= 1.408,
C IR= (2)x(l.408)2 x(e-1408) = lo.1931

V,m (2 + e-1.408 )2
COMMENT. Cv,m is smaller at 900 K than at 500 K, for then the temperature is higher than the peak in
the "two-level" heat capacity curve.
E14.11 (a) Assuming that all rotational modes are active, we can draw up the following table for c V,m' cp,m
and r with and without active vibrational modes.
cv,m cp,m r Exp ti
NH 3 (v>o) 3R 4R 1.33 1.31 Icloser I

NH 3 (v>6) 9R IOR 1.11
CH 4 (v>O) 3R 4R 1.33 1.31 lc!oserl
CH 4 (v>9) 12R 13R 1.08
The experimental values are obtained from Tables 14.5 and 14.6 assuming Cp,m = Cv,m + R. It is
clear from the comparison in the above table that the vibrational modes are not active. This is
confirmed by the experimental vibrational wavenumbers (see Herzberg, Molecular Spectra and
Molecular Structure II. Infrared and Raman Spectra of Polyatomic Molecules, Princeton, NJ: Van
Nostrand, 1945) all of which are much greater than kT at 298 K.
E14.12(a) We need to calculate b.c 2 = (c 2 ) - (c) 2 [14.25] . We assume that argon may be treated as a perfect
gas and follow the results of Example 14.1. The root mean square deviation of the molecular energy
is then
E1 4.13(a) For reversible adiabatic expansion,
Tr =I'; ( ~
V ) 'c[14.37a]
1 1
c = Cv,m = Cp,m -R (20.786-8.3145) J K- mol- = l.500
where
R R 8.3145 J K- 1 mol- 1
so the final temperature is

3Jl/l.500
T =(273 .15K)x l.Odm 3 =l131KI
r ( 3.0dm
E14.14(a) In an adiabatic prqcess, the initial and final pressures are related by (eqn. 14.40)
r r
PrVi =Pi Vi
1 1 1
= CP = Cv + nR = 20.8 J K- + (1.0 mol)(8.31 J K- mol- ) = l .40
where
r Cv Cv 20.8 J K- 1
Find Vi from the perfect gas law.

1 1
V = nRI'; = (1.0 mol) x (8 .31 J K- mor )x(300 K) x l atrn
' P; 4.25 atm 1.013xl05 Pa
V; =5 .79x10-3 m 3
11 11 4
so Vr = V; (B...)
Pr
r = (5 .79x10- 3 4 25
m3 )x( · atm)
2.50 atm
1. o = io.00846 m 3 i
Find the final temperature from the perfect gas law.

3 5
T, = PrVr = (2.50 atm)x(0.00846 m ) x 1.013 x l0 Pa
r nR (1.0 mol)x(8 .31 J K- 1 moi- 1) 1 atm
Tr =i257 Ki
Adiabatic work is (eqn. 14.36)

1 3
w = Cvb.T = (20.8 J K- )x(257 -300) K = l-0.89xl0 Ji
E14.1 S(a) Reversible adiabatic work is
w= Cvb.T (14.36] = n(Cp,m -R)x(I'r-I';)

where the temperatures are related by

l/c
Cp ,m -R = 3.463
Tr = 1'; ~
( J [14.37a] where c=R-C V ,m _
R
3 3 \ 1/3.463
( 500 X 10- dm I
So Tr=[(27.0+273 .15)K]XI 3
) =179K
\ 3.00 dm
2 5
and w=( .4 g _1 )x[(37.l l-8.3145)JK- 1mor 1 )x(l79-300)K = l-194JI
44.0gmol
E14.16(a) For reversible adiabatic expansion,
PrV/ = pJI/ [14.40], so Pr = P;( ~)

r ( 0
= (67.4kPa)x / °::
0
3)1.4
=l9.7kPal
E14.1 ?(a) At constant pressure,
q = Afl = nl':i.vap H B =(0.75 mol) x (30.0 kJ mol- =122.5 kJI 1

)
1 1
and w = -pl':i.V ""-pVvapor = -nRT = -(0.75 mol)x(8.3145 J K- mol- )x(250 K)
3
w = -i.6 x 10 J = 1-i.6 k1I
l':i.U = w+q =-I.6+ 22.5 kJ =120.9 kJI
COMMENT. Because the vapor is treated as a perfect gas, the specific value of the external pressure
provided in the statement of the exercise does not affect the numerical value of the answer.
E14.18(a) The reaction is
C6 H 5 C 2 H 5 (1) + 21 0 2 (g) ~ 8 C0 2 (g) + 5 H 2 0(l)

2
l':i.cH tt = 81':i.rH tt (C0 2 , g) +5!':i.rH tt (H 2 0 , l)-l':i.rHtt (C 6 H 5C 2 H 5 ,l)
1
= [(8) x (-393.51) + (5) x(-285.83)-(-12.5)) kJ mo1-
= 1-4564.7 kJ mo1-
1
I
E14.19(a) First l':i. rH[(CH 2 ) 3 , g] is calculated, and then that result is used to calculate l':i.,H for the isomerization.
(CH 2 Mg)+~0 2 (g) ~ 3C0 2 (g)+3H 2 0(l) l':i.cH=-209lkJmol- 1
l':i.rH[(CH 2 ) 3 , g] = -/':i.cH + 31':i.rH(C0 2 , g) + 31':i.rH(H 2 0,g)
= [+2091 + (3) x (-393 .51) +(3)x(-285.83))kJ mol- 1
= 1+53kJmor
1
I
(CHJ 3 (g) ~ C3H 6 (g) l':i. ,H = ?
l':i.,H = l':i.rH(C 3 H 6 ,g)-l':i.rH[(CH 2 ) 3 , g]
= (20.42-53)kJmol- 1 = l-33kJmo1- 1 I
E14.20(a) Because 11rHe (H +, aq) = 0, the whole of 11rH e (HCl, aq) is ascribed to 11rH e (Cl-, aq). Therefore,
11rH e (Cl- ,aq) = 1-167 kJ/mor 1 /.
E14.21 (a) For naphthalene, the reaction is C10 H 8 (s) + 120 2 (g) ~ 10C0 2 (g) + 4H 2 0(1).
A bomb calorimeter gives qv = nl1cUe rather than qP = nl1cH e ; thus we need

11cU e =11cH e -/1ngRT[l4.31], /1ng =-2mol
11cH e = -5157kJmol- 1 [Table 14.5]
t::..pe = (-5157 kJ mol- 1 )-(-2) x (8.3 x 10-3 kJK- 1 mo1- 1)x(298K)
= l-5152kJ mo1- 1 I
3
12
I q I= I qvl =I nl1Pe l = ( 0xl0- g_1 J x(5152kJmol- 1 )=4.823kJ
128.18gmol
When phenol is used the reaction is
i
C6 H 5 0H(s) + 1 0 2 (g) ~ 6C0 2 (g) + 3H 2 0(1)
11cH e = -3054 kJ mol- 1 [Table 14.5]
11cUe = 11cH e -11ngRT, 11ng = -t

= (-3054kJ mor 1) +{t)x(8.314x10-3 kJK- 1 mol- 1)x(298K)
= -3050 kJ mol- 1
3
5
Jql= l 0 x l0- g 1 x(3050kJmor 1)=4.86kJ
94.12gmol-
4 86 1
t::..r=li.L · k =1+3.08KI
C l.58kJK- 1
COMMENT. In this case l'lpe and l'lcH e differed by about 0.1 per cent. Thus, to within 3 significant
figures, it would not have mattered if we had used !1 0 H e instead of l'lpe, but for very precise work it
would.
E14.22(a) (a) reaction(3) = (-2) x reaction(!)+ reaction(2) and /1ng = -1
The enthalpies of reactions are combined in the same manner as the equations (Hess's law).
11,H e (3) = (-2) X 11,He (1) + 11,He (2)
= [(-2) x (-184.62) + (-483.64)]kJ mor 1
= l-l 14.40kJmor 1 I
t::..pe = 11,H e - 11ngRT [14.31] = (-114.40 kJ mol- 1 ) - (-1) x (2.48 kJ mol- 1)
= l-l l 1.92kJmol- 1 I
(b) ~ r H e refers to the formation of one mole of the compound, hence
~rHe (J) = ~,He (J)

VI
~rHe (HCl, g) = -l 8:·62 kJ moi- 1 = j-92.31 kJ mo1- 1 I
~r He (H 2 0 , g) = -4 8~ ·64 kJ mol- 1 = 1-241.82 kJ moi- 1 I
E14.23(a) ~, He = ~pe + ~ng RT [14.31]; ~g = +2
= (-1373kJ mor 1) + 2 x (2.48kJ mor 1) = l-1368kJ moi- 1 I
COMMENT. As a number of these exercises have shown, the use of tl,H as an approximation for tl,U is
often valid .
E14.24(a) (a) ~rH e L..J Products v~ f H e - "L..J Reactants v~ f H e

= " [14.45]
~, He (298 K) = [(-l 10.53)-(-241.82)]kJ moi- 1 =I+ 131.29 kJ mor 1 I

~pe (298K) =~, He (298K)- ~ng RT [14.31]
= (131.29kJmor 1)-(l) x (2.48kJmor 1) = l+128.8lkJmor1 I

(b) ~ , He (478K) =~,H e (298K) + (T2 -1;)~ , CP e [Example 14.6]
~, CP e = Cp.m e (CO, g) + Cp,m e (H 2 , g)-Cp,me (C, gr)-Cp,me (H 20, g)
= (29.14+28.82-8.53-33.58) x l0-3 kJK- 1 mor 1
= 15.85 x l0-3 kJK- 1 mo1- 1
~, He (478K) = (13 l.29kJ mor 1) + (15 .85xl0-3 kJK- 1 mor 1)x(l80K)
= cn 1.29 + 2.85) kJ mor 1

=I+ 134.14kJ moi- 1 I
~p e (478K) = ~, H e (478K)-(l) x (8.31xl0-3 kJ K- 1 mor 1)x(478 K)

1
= (134.14-3.97)kJ moi- = 1+130.17 kJ mo1-
1
I
COMMENT. The differences in both ~, He and ~, ue between the two temperatures are small and justify
the use of the approximation that ~, c: is a constant.
E14.25(a) For the reaction CH 4 (g) + 20 2 (g) ~ C0 2 (g) + 2H 2 0(g),
~ , H e = ~ r H e (C0 2 , g) + 2 x ~ r H e (H 2 0, g)-~r H e (CH 4 , g)
To calculate the enthalpy of reaction at 500 K, we first calculate its value at 298 K using data in
Tables 14.5 and 14.6.
~. H <'> (298 K) = -393.51 kJ mol- +2x(-241.82 kJ mor' )-(-74.81 kJ mor') = -802.34 kJ mor'
1
Then using data on the heat capacities of all the reacting substances, we can calculate the change in
enthalpy, M , of each substance as the temperature increases from 298 K to 500 K. The enthalpy of
THE flRST LAW OF THERMODYNAMICS 323
reaction at 500 K could be obtained by adding all these enthalpy changes to the enthalpy of reaction
at 298 K:
li,HB(500 K) = li,HB(298 K) +/iH(C02, g)+ 2x/iH(HzO, g)-/iH(CH4, g)-2x/iH(02, g)
However, we need not calculate each individual liH value. It is more efficient to proceed as follows
using eqn. 14.47:
500K
li,HB (500 K) = li,HB (298 K) +
f298K
li,C BdT [14.47]
P
We will express the temperature dependence of the heat capacities in the form of the equation given
in Problem 14.20 as data for the heat capacities of the substances involved in this reaction are
available only in that form. They are not available for all the substances in the form of the equation
of Table 14.2.
If c;m =a+ /JT + yT' 2

then li,C: = lia+!i/JT +liyT' with lia =
2
~_>1 a)' etc.
J
Using the data given in Problem 14.20, we calculate
lia = (26.86+ 2x30.36-14.16-2x25.72) J K - 1 mol- 1 = 21.98 J K- 1 mo1- 1
li/3 = (6.97 + 2x9.61-75.50-2xl2.98) mJ K- 2 moi- 1 = -75.27 mJ K- 2 mol- 1
liy=[-0.820+2xl.184-(-17.99)-2x(-3.862)] µJ K - 3 mol- 1 =27.262 µJ K - 3 mol- 1
Integrating eqn. 14.47 between T1(298 K) and Tz(500 K), we obtain
!J.,HB(500 K) = li,HB(298 K)+lia(500 K-298 K)+~li/3[(500 K) 2 -(298 K) 2 ]
+.!.!iy[(500 K) 3 -(298K) 3 ]=1-803.07 kJ mo1- 1I

3
E14.26(a) Since enthalpy is a state function, li,H for the process (see Figure 14.1)
Mg 2+ (g) + 2Cl(g) + 2e- -7 MgCl 2 ( aq)
is independent of path; therefore the change in enthalpy for the path on the left is equal to the
change in enthalpy for the path on the right. All numerical values are in kJ mo1- 1•
Mg2+(g) + 2Cl(g) + 2e-(g)

J' 241.6 (2) x (- 3.78 eV) =-729.4
Mg2+(g) + 2Cl2(g) + 2e-(g) 1
Mg2+(g) + 2Cl-(g)
" 15.035 eV =1450.7

Mg+(g) + 2C12(g) + e- (g)
(2) x (-383. 7) =- 767 .4
'' 7.646 eV = 737.7
Mg(g) + 2Cl2(g)
1 Mg2+(g) + 2Cl-( aq)
J
167.2
Mg(s) + 2Cl2(g)
,,
641.32 =- C:.rff& (MgCl2 , s) C:.hyctH-e-
MgCl2(s) C:.hyctH-e- (Mg2+) =-x

·~
150.5 = -C:., 1H-e- (MgC(i , aq)
0
'~
Figure 14.1
The cycle is the distance traversed upward along the left plus the distance traversed downward on
the right. The sum of these distances is zero. Note that £ 0 • = -t:i. 0 gH . Therefore, following the cycle
up the left and down the right and using kJ units,
-(-150.5)-(-641 .32) + (167.2) + (241 .6) + (737 .7+1450.7)
+ 2 x (-364.7) + 2 x (-383.7) + t:i.hydH(Mg 2+) = 0
which yields t:i.hyd H(Mg 2+) = 1-1892 kJ mor 11.
E14.27(a) The Joule-Thomson coefficient µ is the ratio of temperature change to pressure change under
conditions of isenthalpic expansion. So
µ = -ar ) [14.65] = hm. ( -t:i.r) "'" -t:i.T [µconstant over temperature range]
( dp H t.p->0 t:i.p H t:i.p
-22 K = lo. 7 1 K atm- 1I

µ = -31atm
E14.28(a) See Example 15.6 and Exercise E14.29(a). The internal pressure of a van der Waals gas is
lrr =a I V~. The molar volume can be estimated from the perfect gas equation. We will assume that
the temperature of 298 K given in the statement of the exercise was a typographical error and
instead do the calculation for 398 K. Water is not a vapor at 1.00 bar and 298 K.
3 1 1
RT 0.08206 dm atm K- mor x 39 8 K = 33 .09 dm3 mol-1
vm = - = ( 1.000 atm )
P 1.00 bar x l.Ol3 bar
6 2
a 5.464 atm dm mol- = 4 .99x10-3 atm = 15.06 mbarl
lrr = V2 = (33 .09 dm 3 mol 1) 2
m
E14.29(a) The internal energy is a function of temperature and volume, Um= Um(T, Vm) , so
dU = ( aum) dT+ ( aum) dV [!rr =(dUm / '()Vm)T]

m dT vm avm T m
For an isothermal expansion, dT = O; hence,
d Um = ( aum ) dV=nr dVm =-;dvm

avm T vm
20.0 dm 3 mot-I
d v = -a-I
dm3 mol-I --f-
ti.Um= l .i
m.2
dUm =(
m.1
., V~
~dV =a
m J
QO.O
.oodm3 mol-1 Vm Vm 1.oo dm' mo1-1
a a 19.0a
=- + - - -3- - -1 20.0 dm3 morl = 0.950 a mol dm-3
20.0 dm 3 mor 1 1.00 dm mol-
From Table 8.7, a= 1.352 dm6 atm mor 1.
ti.Um = (0 .950 mo! dm-3) x (l.352 dm 6 atrn mol- 2 )
mor 1 )x(~)
3 5
3
= (1.284 dm 3 atm x(l.Ol xl0 Pa ) = 1+ 130.l J mor 1 I
10 dm atm
where p = -RT- - -a2 for a van der Waals gas. Hence,

vm -b vm
w=- r( __E_Jdvm + s~dV

Jl vm - b v; m =-q+!l.Um
Therefore,
q_
_
3
i20.0dm mol -
1
( RT J _ 120.0dm' mo1-
- - dVm - RTln(Vm b) 1 OOdm' 1
_ 1
-1
l.00dm 3 mol- 1 Vm - b · mo
= (8.314JK- 1 mol- 1)x(298K)xJ 20 · 0 - 3 · 9 xl0~: ) =\+7.52xl0 3 J mo1- 1 \

u.'l i.oo-3.9xlO
and w =-q +fl.Um =-(7.52xl0 J moi- 3 1
) + (130.iJ mol- 1) =\-7.39xl0 J mo1-
3 1
\
E14.30(a) a=(~ )(~~)}14.58];
so a 320 = -
( 1J(av)
-
oT
1!;20 p , 320
= ( 1 )x(l.34x10
1.02611;00
-3 K - 1 V300 )
COMMENT. Knowledge of the density at 300 K is not required to solve this exercise, but it would be
required to obtain numerical values of the volumes at the two temperatures.
E14.31 (a) The isothermal compressibility is
Kr=-(~ )(~;l (14.59] SO (av)

Op r
=-K v
T
At constant temperature,
dV
dv=(av)
op r dp,
so d V =- Kr V dp or -v=-Krdp
Substituting V = m yields dV = - ~ dp; dV = - dp = -Krdp.

p p v p
Therefore, op"" KrOp.

p
3 3
For op= O.lOxl0-2 = l.Oxl0-3 , op"" l.Oxl0- = l.Oxl0- = l2.0xl0 3 atml.
P Kr 4.96xl0-5 atm- 1
E14.32(a) The isothermal Joule-Thomson coefficient is
µT = (fJHm)
dp T
= -µCp ,m [14.69] = (-0.25Katm- 1 )x(29JK- 1 mor 1 ) = l-7.2J atm- 1 mo1- 1I
a
dH=n((JHm) dn=-nµC p,m dp
'P T
.,.,.
fPi
Mi= J, (-nµCp ,m) dp = -nµCp,m (p 2 - p 1 ) [µand CP are constant]
p,
Mi= -(10.0mol) x( +7.2J atm- 1 mol- 1 )x(-85 atm) = +6. lkJ
so q(supplied) =+Mi= 1+6.lkJI.
Assume that all gases are peifect unless stated otherwise. Unless otherwise stated, thermochemical
data are for 298 K.
P14.1 The coefficient of thermal expansion is
~(~~)P
t.V
a=
so t.V"" avt.T
Vt.T
This change in volume is equal to the change in height (sea level rise, t.h) times the area of the
ocean (assuming that area remains constant). We will use a of pure water, although the oceans are
complex solutions. For a 2°C rise in temperature,
t.V = (2.1x10-4 K- 1) x (1.37x10 9 km 3 ) x (2.0 K) = 5.8 x 105 km 3
so t.h = t.V = 1.6x10-3 km= Jl.6mJ

A
Since the rise in sea level is directly proportional to the rise in temperature, t.T = 1°C would lead
to t.h = J0.80 ml and t.T = 3.5°C would lead to M = 12.8 ml.
COMMENT. More detailed models of climate change predict somewhat smaller rises but the same order
of magnitude.
P14.3 To explore which of the two proposed equations best fits the data, we have used PSI-PLOT®. The
parameters obtained with the fitting process to eqn. 14.34, along with their standard deviations, are
given in the following table.
Parameters a b/10- 3 K- 1 c/105 Kz
Values 28.796 27.89 -1.490
Std dev of parameter 0.820 0.91 0.6480
The correlation coefficient is 0.99947. The parameters and their standard deviations obtained with
the fitting process to the suggested alternate equation are as follows.
Parameters a /J/10-3 K- 1 y/10-6 K- 2

Values 24.636 38.18 -6.495
Std dev of parameter 0.437 1.45 1.106
The correlation coefficient is 0.99986. It appears that the ~ltemate form for the heat capacit~
~guation fits the data slightly betteq, but there is very little difference.
P14.5
c v.m = -k,8
2
( ar:,) v
[14.26]
Let x = ,Be; then d,B =t dx.
C
V, m
=-k .::_
( c)
2 :. ( N Ace -x
&.!!..._
ax l+e-x
J=-N kx2 x.!!_:. (_e_
A ax l+e-x
-x ) =R ( x 2 e-x
(l+e-X)2
l
Therefore,
We then draw up the following table.
TIK 100 298 600

1
(kT/hc) I cm- 69.5 207 417
x 1.741 0.585 0.290
Cv,m IR ki.3851 ~ ~.020~
Cv,m I (J K- 1 moi- 1) 3.20 0.654 0.171
COMMENT. Note that the double degeneracies do not affect the results because the two factors of 2 in
q cancel when U is formed. In the range of temperature specified, the electronic contribution to the heat
capacity decreases with increasing temperature.
P14.7 The energy expression for a particle on a ring is
17 2m 2
1
E = -- [Section 3.3]
21
Therefore
q= L- e-m,'ry 2
12lkT
-
= L e-Pm,'ry 121 2
m=--oo
The summation may be approximated by an integration.

112 112 112
q,,,, _!_ [
(]'
e- m,'ry
2
12lkT dm
I
=_!_(2IkT)
(]' 2
[ e-x' dx ""_!_(2trlkT) =_!_(2trf)
(]' ,B
2 (]' 2
17 17 17
U -U(O) =-Nalnq =-Nl_ln_!_( 2trI) 112
=!!._ =}_NkT =}_RT (N =N )

ap ap (]' p 17
2
2,a 2 2 A
Cv,m =(a~m =~R =14.2 J K- l 1

moi-
1
I
P14.9 The vibrational temperature is defined by kBv = hcii, so a vibration with Bv less than 1000 K has a
wavenumber less than
23
__ kBV_ (1.38lxl0- JK-')x(lOOOK) =6952 - I
v- - 34 10
. cm
he (6.626x10- Js) x (2.998x10 ems-')
There are seven such wavenumbers listed among those for C60 : two T1u, a T2u, a Gu, and three Hu.
The number of modes involved, v:, must take into account the degeneracy of these vibrational
energies.
v~ = 2(3) + 1(3) + 1( 4) + 3(5) = [lfil

The molar heat capacity of a molecule is roughly
Cv ,m = !(3 + v; + 2v: )R [14.27] = !(3 + 3 + 2x28)R = 3 IR= 31(8.3145 J mor' K- 1)
= 1258 J mor 1 K- 1 I
v, nRT n2a .
P14.11 w=-
f.v, pdV with p = --- -
V-nb V 2
[van der Waals equat10n]
Therefore,
f 2 d v I- nRTln (-
w=-nRT.iv.f 2- d-V+ n 2 aJv.-= 2
nb -n 2 a ( -1 - -
V2 - - I J J
' v - nb "' V nb v; -
v2 v;
This expression can be interpreted more readily if we assume that V >> nb, which is certainly valid
at all but the highest pressures. Then using the first term of the Taylor series expansion,
x2
ln(l-x) = - x - - · ·· for Ix I« 1
2
ln(V-nb) =Inv +In ( l - nb) nb

v ""lnV-v
and after substitution,
(V
v; J (I v;IJ
w=o -nRTln - 2 +n 2 bRT - - - -n 2 a - - -
v2 v2
(1 v;IJ
(VJ
""-nRTln - 2 -n 2 (a-bRT) - - -
Ii; v2
(I v;IJ
""+w0 -n 2(a-bRT)(_!__J_J =perfect gas value+ van der Waals correction

v2 v;
w 0 , the perfect gas value, is negative in expansion and positive in compression. Considering the
correction term, in expansion V2 > V'i , so (_!_ _J_J < 0. If attractive forces predominate, a> bRT, and
v2 v;
the work done by the van der Waals gas is less in magnitude (less negative) than the perfect gas, the
gas cannot easily expand. If repulsive forces predominate, bRT > a, and the work done by the van
der Waals gas is greater in magnitude than the perfect gas, the gas easily expands. In the numerical
calculations, consider a doubling of the initial volume.
1 1 1 20
(a) w0 = -nRTln(Vr) = (-l.Omol- )x(8.314JK- mol- )x(298K)xln( · dm:)
it; l.Odm
WO= -1.72x10 3J = l-l.7kJI
(b) w= Wo -(l.Omol) 2 x[0-(5.1 lxl0- 2 dm 3mol- 1)x(8.314JK- 1mor 1)x(298K)]

1 1 3 3
x( 3 - 3 )=(-l.72xl0 J)-(63J)=-l.7Sxl0 J=l-1.SkJI
2.0dm l.Odm
6 2 1 1
(c) w= w0 -(l.Omol) 2 x(4.2dm atm mol- )x( - )
2.0dm l.Odm 3
3
w= w0 +2.ldm 3 atm
= (-1.72x103 J)+(2.ldm3 atm)x (~)3x(ll.Olx10s Pa)'\

lOdm latm
=(-l.72xl03J)+(0.2lxl0 3 J)=l-1.5 kJI
Schematically, the indicator diagrams for cases (a), (b), and (c) would appear as in Figure 14.2. For
case (b) the pressure is always greater than the perfect gas pressure, and for case (c) the pressure is
always less. Therefore,
rv,
p dV(c) < r
~
p dV(a) < r v,
p dV(b)
2
2.0
§ (a)
~
t:l.
1.0
50 100 150
3
V/dm Figure 14.2
P14.13 Cr(C 6 H 6 Ms)~Cr(s)+2C 6 H 6 (g) Ang =+2mol
A,Hf} =Apf} +2RT, from [14.31]

= (8.0kJ mol- 1) + (2)x(8.314J K- 1 mol- 1)x(583K) = l+l 7.7kJ mo1- 1 I
In terms of enthalpies of formation,
A,H 6 = (2) x ArH 6 (benzene,583K)-ArH 6 (metallocene,583K)
or A,H 6 (metallocene,583K) = 2ArH 6 (benzene,583K)-17.7 kJ moi- 1

The enthalpy of formation of benzene gas at 583 K is related to its value at 298 K by
~rH B (benzene, 583 K) = ~rHB (benzene, 298 K)
+(Tb - 298K)Cp,m(I)+ ~vapHB + (583K-Tb)Cp,m(g)
- 6x(583K-298K)Cp,m(gr)-3x(583K- 298K)Cp,m(H 2 ,g)
where Tb is the boiling temperature of benzene (353 K). We shall assume that the heat capacities of
graphite and hydrogen are approximately constant in the range of interest and use their values from
Table 14.6.
~rHB(benzene,583K) = (49.0kJmor 1)+ (353-298)Kx(l36.1JK- 1mor 1)

+ (30.8kJ mol- 1) + (583-353)Kx(8L67 JK- 1mor 1)
- (6)x(583-298)Kx(8.53JK- 1 mol- 1)
- (3)x(583-298)Kx(28.82JK- 1 mor 1)
= {(49.0) + (7.49) + (18.78) + (30.8)-(14.59)-(24.64)} kJ mol- 1
= +66.8kJ mor 1
Therefore, ~rHB(metallocene,583K) = (2x66.8-17.7)kJmor 1 =1+116.0kJ mo1- 1 I.

P14.15 (a) and (b), The table displays computed enthalpies of formation (semi-empirical, PM3 level, PC
Spartan Pro), enthalpies of combustion based on them (and on experimental enthalpies of formation
of H2 0(1) and C0 2 (g), -285.83 and -393.51 kJ mor 1, respectively), experimental enthalpies of
combustion (Table 14.5), and the relative error in enthalpy of combustion.
Compound 11rH"' I kJ mor 1 11,H"' I kJ mor 1(calc.) 11,Hf't I kJ mor 1(expt.) % error
CJLi(g) -54.45 -910.72 - 890 2.33

C2H6(g) -75.88 -1568.63 -1560 0.55
C3Hs(g) - 98.84 -2225.01 -2220 0.23
C4H1 o(g) -121.60 -288 1.59 -2878 0.12
CsHdg) -142.11 -3540.42 -3537 0.10
The combustion reactions can be expressed as
C.H 2.+ 2 (g)+ ( -3n +- 1) 0 (g) 2 ~ nC0 2 (g)+(n+ l)H 2 0(l)

2
The enthalpy of combustion, in terms of enthalpies of reaction, is
~cHB = n~rHB (C0 2 ) + (n+ l)~rHB (H 20)- ~rHB (C.H 2n+J
where we have left out ~ rHf't (0 2 ) = 0. The % error is defined as

~ H f't(calc)-~ HB(expt.)
% error = c B c x 100%
~cH (expt.)
The agreement is quite good.

(c) If the enthalpy of combustion is related to the molar mass by
~ c H B = k[M I (g mor
1
)]"
then one can take the natural log of both sides to obtain
lnl~c HB I = lnlkl+ n In M 1
I (g mol- )
Thus, if one plots In I L\H~I against In [MI (g mor 1)], one ought to obtain a straight line with slope
n and y-intercept In lkJ. Draw up the following table.
ln lb.,H~ I kJ mor
1
Compound Ml(g mor 1) t!.,H I kJ mol- 1 In M/(g mor 1) 1
CH4(g) 16.04 -910.72 2.775 6.814

C2H6(g) 30.07 -1568 .63 3.404 7.358
C3Hs(g) 44.10 -2225 .01 3.786 7.708
C4H10(g) 58.12 -2881.59 4.063 7.966
CsHdg) 72.15 -3540.42 4.279 8-. 172
The plot is shown in Figure 14.3.
9
~
~----
~-
~
~
~
6
2 3 4 5
Figure 14.3
The linear least-squares fit equation is
In IL\H~ I kJmoi- 1 1 = 4.30+0.903lnM I (gmor') R2 =1.00
These compounds support the proposed relationships, with
n = ~.903/ and k = -e4·30 kJ mor 1 = t73.7 kJ moi-11
The agreement of these theoretical values of k and n with the experimental values obtained in
P14.14 is rather good.
P14.17 We must relate the formation of DyCI3
to the three reactions for which for which we have information. This reaction can be seen as a
sequence of reaction (2), three times reaction (3), and the reverse of reaction (1), so
ArH~ (DyCl 3,s) = [-699.43 + 3(-158.31)-(-180.06)] kJ mol- 1
= l-994.30 kJ mo1- 1 I
P14.19 (a) The probability distribution of rotational energy levels is the Boltzmann factor of each level,
weighted by the degeneracy, over the partition function
R g(J)e-e,lkT ( 2J + l)e-hcBJ(J+l)/kT
PJ (T) = q
R = L ( J + l)e-hcBJ(J+l)/kT [13.19]
2
J=O
It is conveniently plotted against J at several temperatures using mathematical software. This

distribution at 100 K is shown in Figure 14.4 as both a bar plot and a line plot.
Rotational distributions
0.15 . - - - . - - - - - . - - - - - . - - - . - - - - . - - - . - - - - - - . - - - - - ,
JOOK
0.1
pJ(T)
0.05
5 10 15 20 25 30 35 40
J Figure 14.4
The plots show that higher rotational states become more heavily populated at higher temperature.
Even at 100 K, the most populated state has 4 quanta of rotational energy; it is elevated to 13 quanta
at 1000 K.
Values of the vibrational state probability distribution,
p: (T) =~
q
=
- c, tkT
e-vhcv/kT (1-e-hcv/kT) [13.24)
are conveniently tabulated against v at several temperatures. Computations may be discontinued

when values drop below some small number like 10-1 •
p~(T)
v lOOK 300K 600K lOOOK
0 1 1 0.095 0.956
2.77x10- 14 3.02x10-5 5.47x10-3 0.042
2 9.15x10-IO 3.0lx10-5 1.86x10-3
3 1.65x10-7 8.19x10- 5
4 3.6lx10--0
5 1.59x10- 7
Only the state v = 0 is appreciably populated below 1000 K and even at 1000 K only 4% of the
molecules have 1 quanta of vibrational energy.
(b) The classical (equipartition) rotational partition function is
R (T) = kT =I_ [13 2lb]

qclassical hcB BR ·
where ~ is the rotational temperature. We would expect the part1t10n function to be well
approximated by this expression for temperatures much greater than the rotational temperature.
B = hcB = (6.626 x 10-34 J s) x (2.998x10' 0 cm s-') x (1.931 cm- 1)

R k l.38lxl0-23 JK-'
BR= 2.779K
In fact~ « Tfor all temperatures of interest in this problem (100 Kor more). Agreement between
the classical expression and the explicit sum is indeed good, as Figure 14.5 confirms. The figure
displays the percentage deviation (q:assicat - qR )100 I qR . The maximum deviation is about -0.9% at
100 K and the magnitude decreases with increasing temperature.
Classical partition function error

0
-0.2
c:
0
·~
·;;
., -0.4
.,,,
.,
OJ)
5
.,c: - 0.6
.,I:!
11.
- 0.8
-I
0 200 400 600 800 1000
Temperature I K Figure 14.5
(c) The translational, rotational, and vibrational contributions to the total energy are specified by
eqns. 13.36(b), 13.37(b), and 13.39, respectively. As molar quantities, they are
The contributions to the difference in energy from its 100 K value are t:,.UT (T) =
UT (T)-UT (lOOK), and so on. Figure 14.6 shows the individual contributions to t:,.U(T). Translational
motion contributes 50% more than the rotational motion because it has 3 quadratic degrees of freedom
compared to 2 quadratic degrees of freedom for rotation. Very little change occurs in the vibrational
energy because very high temperatures are required to populate v = 1, 2, ... states (see part a).
Energy change contributions
TIK Figure 14.6
The derivative dUv I dT may be evaluated numerically with numerical software (we advise exploration
of the technique) or it may be evaluated analytically using the equation for Cv in Example 14.2:
2
v dUv fJ. e - 0.,/ 27
C - -R v
v ,m -dT- T { ( 1-e-llv/T]}
where Bv = hcv I k = 3122 K. Figure 14.7 shows the ratio of the vibrational contribution to the sum
of translational and rotational contributions. Below 300 K, vibrational motion makes a small,
perhaps negligible, contribution to the heat capacity. The contribution is about 10% at 600 K and
grows with increasing temperature.
Relati ve contributions to the heat capacity

0.2 ~----~----~-----~----~----~
c~.m 0.1
C~,m + C~. m
0 L.__ _ _ _ ...L-~~======-_J_ _ _ _ _ _L __ _ __ _L__ _ _ __J
0 200 400 600 800 1000

TI K Figure 14.7
P14.21 To calculate the enthalpy of the protein' s unfolding, we need to determine the area under the plot of
Cp,ex against T, from the baseline value of Cp,ex at Ti. the start of the process, to the baseline value of
Cp,ex at T2 , the end of the process. We are provided with an illustration that shows the plot, but
no numerical values are provided. Approximate numerical values can be extracted from the plot, and
then the value of the integral /J.H = r I
Cp,ex dT can be obtained by numerical evaluation of the area
under the curve. The first two columns in the table below show the data estimated from the curve;
the last column gives the approximate area under the curve from the beginning of the process to the
end. The final value, 11889 kJ mod, is the enthalpy of unfolding of the protein. The four significant
figures shown are not really justified because of the imprecise estimation process involved.
8 /° C 1
Cp.exlkJ K- mor' ~HlkJ mo1- 1
30 20 0
40 23 215
50 26 460
54 28 567
56 33 626
57 40 663
58 46 706
59 52 755
60 58 810
61 63 870
62 70 937
63 80 1011
64 89 1096
64.5 90 1141
65 85 1185
66 80 1267
67 68 1342
68 60 1405
69 52 1461
70 47 1511
72 41 1598
74 37 1676
80 36 1889
P14.23
N
We work with eqn. 14.26 in the form C = - - __!.._
(a<>) with
L -t:je-P<,
(£) given by (E) = - -'- -
v kT 2 ap v L ie-PE'
Differentiating this expression with respect to [J, we obtain
a(t:)) which can be rewritten as

( ap v
After substituting into the expression above for Cv, we obtain
kT
(a(c))
Cv = - -N-2 - - = - -N-2 (-~E 2 ) = ,N~t:
CJj3 v kT
2
I .
- -2- , which was to be proved.
kT
P14.25 We begin the derivation with the full expression for the molecular rotational partition function .
1 - hcB J(J+I) 1 __llit_J( J + I ) -

q R =-I(2J+l)e kT [13 .19]=-L(2J+l)e r [BR =hcB / k]
(]' J (]' J
We first note that no single analytical expression for this summation can be obtained that is valid at
all temperatures. The summation process must be continued until additional terms change the sum
to less than some pre-defined limit of accuracy, say 0.2%. However, various approximate analytical
expressions that are valid within certain temperature ranges can be derived. Taken together, these
expressions can give values that are valid within small error limits over the entire temperature
range.
One of these approximations applies the Euler-Maclaurin summation formula to the expression for
qR . We obtain an expression that is accurate to about 0.1 % when BR = .!_::; 0.7.

T x
2 3
qR =__!__{l+.!_ BR +_!_(BR) +__i_(BR) + .. ·}
aBR 3 T 15 T 315 T
qR =~{l+_.!__+_1_+_4_+ ,, ·}
<Y 3x 15x 2 315x 3
However, when .!_=BR :?: 0.7, we must use the full summation expression forqR , but the first five
x T
terms are usually sufficient for better than 0.1 % accuracy. Fewer terms are needed as llx increases.
qR =_!_(l+ 3e-2/x + 5e-6/x + 7 e-1 21x + 9 e-20/x + .. ·)

(]'
The energy is calculated from Um- Um (0) = kT

2 [a :TQ 1,
and the heat capacity is calculated from Cv,m = 2kT[CJlnQ] +kT 2
ar v
[a ar1np] .
2
v
The canonical partition function for a linear rotor is QR = (qR t.

Substituting this expression for
QR into the expression for Cv.mand performing the differentiations term by term, we obtain the
final expressions for Cv,m: (1) using qR from the Euler-Maclaurin expansion,
2 3
C {}, ) +16- ( iB ) + · · ·} I or
= R 1+ 1- ( _s_
V,m { 45 T 945 T '
1 +-
Cvm = R { 1+-- 16- +.. .} (1)
' 45x 2 945x 3
(0.3% accuracy when ..!.. ::; 0.65, or I_~ 1.54 ), and (2) using qR from the full summation
X {)R
C, ,• = R {( ~ J 120'"' (I + !50 ~,' + 200. ,, + 840·'"" + !750_,,,, + I050_,.,, +··))
c,. = R { ( ~ J 120" '' (! + 150~'' + 200• '' + 840' '"'' + !750' '"' + 1050'"'' +· )}Ix =~ (2)
1 T
(0.2% accuracy when - ~ 0.65 or - ::; 1.54 ).
X {)R
Examination of the data in Table 10.2 reveals that only in the case of H 2 and possibly the hydrogen
halides is this latter expression, eqn. (2), needed. The case of H2 is treated separately in Problem
14.33.
An alternative but equivalent approach would be to use the expression derived in Problem 14.32.
Again a decision would have to be made as to when to terminate the summation in order to obtain
the desired level of accuracy.
To complete these calculations and to plot the heat capacity, a spreadsheet program such as Excel or
a computer algebra system such as Mathcad is very useful. See Figure 14.8 for a plot of
cm (x) =-~m'- [eqn. (2) above] against x =-~T .

R
1.2r--~~~~~~~~~~~~~~~~~~~~~~~~
0.8
C(x) 0.6
0.4 C(x) = Cv.m!R
0.2
o~~~~~~~~~~~~~~~~~~~~~~~
0 05 I 1.5 2
x
x =T/ 8 Figure 14.8

P14.27 The partition function for one dimension of vibration of a harmonic oscillator is
1 1 .
qv = l-e-Phcv (13.24] =l-e-0, IT. The energy is calculated from Um-Um(O)=kT
2 [olnQJ
aT v
with Qv =(qvt. Performing the differentiation, we obtain Um-Um(O)=NkBE Ce, i~ _ } The
1
heat capacity is calculated from Cv =

,m
(oUm
oT )v . Performing this differentiation we obtain
~:IT
2
Cv = Nk {(BE) 8 } • For three independent dimensions of oscillation as in one mole of a

,m T (e • -1) 2
crystalline solid, we multiply by 3 and set Nk = R, finally obtaining the Einstein formula
2
(}, ) eo. 1T }
Cv m = 3R { ( ___£_ (), I T 2 • The heat capacity Cv m I 3R is plotted against x =T I B
Ein
· T (e • -1) ·
Figure 14.9.
0.8
Cv (x) = Cv.n/3R
0.6
Cv (x)
0.4
0.2
O"'-"-~~~'--~~~---''--~~~--'~~~~--'
0 0.5 1.5 2
x
Figure 14.9
P14.29 (a) 8v and ~ are the constant factors in the numerators of the negative exponents in the sums
that are the partition functions for vibration and rotation. They have the dimensions of
temperature, which occurs in the denominator of the exponents. So high temperature means that
T » 8v or ~. and only then does the exponential become substantial. Thus 8v and ~ are
measures of the temperature at which higher vibrational and rotational states, respectively,
become significantly populated.
10 1
(}, = hcB = (2.998 x l0 cm s- ) x (6.626 x l0- J s ) x (60.864cm-
34 1
) -1 87 .55 KI
R k (l.38lxl0-23 J K- 1) · ·
and 8
34
= hcv = (6.626 x 10- J s) x (4400.39cm- ) x (2.998 x 10 cm s-
1 10 1
) =1
6330
Kl
v k (l.38lxl0-23 JK- 1)
(b) and (c) These parts of the solution were performed with Mathcad and are reproduced on the
following pages.
Objective: To calculate the equilibrium constant K(T) and Cp(T) for dihydrogen at high
temperature for a system made with n mol H2 at 1 bar.
H 2 (g) ;:::::: 2H(g)
At equilibrium, the degree of dissociation, a, and the equilibrium amounts of H 2 and atomic
hydrogen are related by the expressions
nH = (1- a)n and nH = 2an

2
The equilibrium mole fractions are
xH, = (1-a)n I {(l-a)n+ 2an} = (1-a) / (1 +a)
xH = 2an I {(l-a)n + 2an} = 2a I (1 +a)
The partial pressures are
PH, =(1-a)p / (l+a) and PH =2ap l (l+a)
The equilibrium constant is
K(T) =(pH I p~)2 = 4a2 (p I p~)

2
4a
6 2
- - wherep = p 6 =1 bar
(PH, I P ) (1- a ) (l-a 2 )
The above equation is easily solved for a,
2
/a= (K I (K +4))11 /
The heat capacity at constant volume for the equilibrium mixture is
Cv(mixture) = nHCV,m (H)+ nH, c V,m (HJ
The heat capacity at constant volume per mole of dihydrogen used to prepare the equilibrium
mixture is
Cv = Cv (mixture) I n= {nHCv,m (H) + nH, Cv,m (H 2 )} I n
= /2aCv,m (H) + (1-a)Cv,m (H 2 )/
The formula for the heat capacity at constant pressure per mole of dihydrogen used to prepare the
equilibrium mixture (Cp) can be deduced from the molar relationship.
Cp,m =CV,m +R
CP = {nHCp,m(H) + nH, Cp,m(H 2 )}/n
= ~ {Cv,m (H)+R}+ n:,{Cv,m(Hz)+R}

= nHCv,rn (H)+nH , Cvm(H
, 2 ) +R (nH +nH , )
n n
= Cv +R(l+a)
Calculations
J =joule s = second kJ=lOOOJ

mol= mole g =gram bar = 1 x 105 Pa
h = 6.62608 x 10- 34 J s c = 2.9979 x 108 m s- 1 k = 1.38066 x 10-23 J K- 1
1 23 1
R = 8.31451 J K- 1 mor NA = 60.2214 x 10 mo1- p e =l bar
Molecular properties of H 2
v = 4400.39 cm- 1 B= 60.864 cm- 1

D = 432.l kJ mor'
1 g mo!-'
mH = NA
hcB
8 = hcv
n _
v k UR -
k
Computation of K(T) and cef....T)
N =200 i=O, ... ,N T =SOOK+ i x 5500 K

I N
h h
.f\i; = (2timHkT;) lf 2 .!\i,; = (2tim H, kT) l/ 2 I
See Figure 14.10.

(a)
ff 0.5
0
0 1000 2000 3000 4000 5000 6000
T;/K
(b) 100
80
60
1
40
20
0
0 1000 2000 3000 4000 5000 6000
T; / K Figure 14.10
Heat capacity at constant volume per mole of dihydrogen used to prepare the equilibrium mixture is
(see Figure 14.11).
27
26
25
I
0
s 24
I
~
0 23
---,;.-
\...)
22
21
20
0 1000 2000 3000 4000 5000 6000
T;/K Figure 14.11
Cv(H) = luRI
2
(} e-ce.,;2r,J
Cv(H 2)=/2.5R+ i x e.,;r R CV; = 2a;Cv (H) + (1- a ;)Cv (H 2; )
' [ I; 1- e ']
The heat capacity at constant pressure per mole of dihydrogen used to prepare the equilibrium
mixture is (see Figure 14.12).
CP; =CV; +R(I+a;)
42
40
38
I
0 36
E
I
~
-,
::::::_ 34
\...);;.
32
30
28
0 1000 2000 3000 4000 5000 6000
T;/K Figure 14.12
P14.31 We are given q = L je-,8'\

j j
r
q = Lf3cje-,8Ej ' ij = L(/3cj e-,8Ej. But note that the degeneracy factor,
g = (21+1) , should be included in these expressions. The energy level expression for linear and
spherical rotors is c1 = hcBl(l + 1) . Inserting this expression and the degeneracy factor into the
expression for q above, we obtain for the rotational partition function including the degeneracy
factor
1 - hes J(J+I ) 1 n_, J(J+ I)
___
qR = -
a
L (21 + l)e kT [13.19], which at 298 K becomes qR = -
a
L (21 + l)e 2
01.
22
cm-
1 1
The symmetry number for the molecule must be obtained from the point group of the molecule; it is
equal to the number of distinct pro~r rotations of the molecule plus the identity operation. For HCl
that is 1, but for CH 4 it is 12. For q and ijR we obtain at 298 K
qR = _.!._ L( B -
- l(J + 1) (21 + l)e J ----J(J+l)
8
207.22 cm- 1
a 1 201.22 cm 1
ijR = _.!._ L( -B
- 1(1+1)
J2 (21 + l)e --- 8 -J(J+l )
207.22 cm- 1
a 1 201 .22 cm '
(a) For HCl, B= 10.593 cm- 1 • When this value is inserted into the expressions above, the results of
these summations are
lqR = 19.899, qR = 19.558, and ijR = 576.5361
(b) For CC14 , B= 5.797 cm-'. When this value is inserted into the expressions above along with
a= 12, the results of the summations are
'qR = 3.007, qR = 2.979, and ijR = 118.51
P14.33 The partition functions for the ortho- and para- forms of H2 are
-~J(J+ l )
q:rth 0
=3 L (2l+l)e r
-
[BR=hcB / k=87 .6K]
J=l,3,5 ...
-~J (J+l )
q:ara = L (21 + l)e r
J=0,2,4 ...
To conform to the notation of Problem 14.32, we can rewrite these expressions as
q:rtho = 3 L g(J)e-,Bc(J)
J=l,3,5 ...
with g(l) = 21+1 and c(l) = hcBl(l + 1)
q:.,. = L
g(l)e-,Bc(J)
J=0,2,4...
To simplify the summation process and in order to use the formulas derived in the solution to
Pl4.32, we define a new quantum number K by l = 2K + 1 for the ortho- case and by l = 2K for
the para- case. Then
g 0 (K) = 4K + 3 and c0 (K) = hcB[(2K + 1)(2K + 2)] for ortho-hydrogen and
gP(K) = 4K + 1 and cP(K) = hcB[2K(2K + 1)] for para-hydrogen.
With these modifications the partition functions can now be rewritten as

q:rtho =3 L go(K)e -,BE.(K)
K=O,l,2...
R
qpara = "
L..J gp (K) e -.Bc,(K)
K=O,l,2...
Now the final expression for Cv ,m IR derived in Pl4.32, with Kin place of J, g(K) in place of
g(J), and £(K) in place of £(J), can be used to calculate the heat capacities. With these
substitutions the expression becomes
Cv ,m = ..!_ Lg(K)/32£2(K)e-Pe(K) -~(Lg(K)/3£(K)e-Pe(K))

R q K q K
This expression needs to be evaluated separately for both the para- and ortho- forms of hydrogen. It
is most easily evaluated with a spreadsheet program such as Excel or a CAS system such as
Math cad.
L,g0 b~e-b0 -~(L,g0 b0 e-b0

2
For the ortho- case, C0 = Cv,m = __!_ ) [eqn. I], in which
R qo K qo K
(}
b0 = /3£0 =_B_(2K+1)(2K + 2) = -(2K + 1)(2K + 2)
T x
1
x =-~T
-~(LgPbPe-b' )
2
For the para- case, Cp =Cv,m
R
= __!_ L
qp K
gPb:e-b'
qp K
[eqn. 2], in which
(} 1
bP = /3£P = _B_[2K(2K + l)] = -[2K(2K + l)] x =T I (JR
T x
In the Mathcad worksheet below the notation is as follows: x =T I (JR; for ortho-hydrogen, q0 is its
partition function, C01 and C02 are the first and second terms on the right in eqn (1), and C0 =
Cv ~ I R s its heat capacity in units of R . Similarly, for para-hydrogen, qp is its partition function,
Cp 1 and Cp2 are the first and second terms on the right in eqn. (2), and Cp = Cv 'm I R is its heat capacity
in units of R.
i := 0 .. 24 xstart := 0.2 Xend := 5.0
I
xi := xstart + ( xend - xstart) . 24 xi =T/0
6 [ -+.·{2·K+IH2·K+2) ]
qo, := L
K~ O
(4 · K +3)-e
C0 1, :=
(l [ [ }
q:-
6
·~ (4·K+3) [ ~i(2·K+l)(2 · K+2)]
2 - -{2·K+IX2·K+2)
·e 'iI ]]
o:-( q~ l :t.[(4
2
2 _...!._{2 K+1){2·K+2)
c., K+3)[ :, (2 K+i)(2 K+2) e ., ]]

[
1
co, := col, + co2,

0.8
Co= C v,mlR
0.6
c o,
0.4
0.2
0
0 2 3 4 5
x=TI EJ
q :=
P,
L6 [ (4·K +1)-e -t·(2·K+l)-(2·K)]
K~O
6 2
Cp 1, :=
(
q:-1 ) ·&o [ l ·K+l)(2 ·K) ] ·e_ _1_(2·K+
(4 · K+l) [[ xY 'i l)(2·K)] ]
c.,
l
o=-(;;;:-)2[&, [(4·K+l)k(2 K+!)(2
6 1 __I_(2· K +1)(2K)
K) e " l
]]2
0.5
o'---==='--..L_~~_J_~~--'~~~.J..._~~~
0 2 3 4 5
x=TI EJ
P14.35 The differential equation to be solved is ~ ( e-/Je, ) = 0. We differentiate this quotient with respect
dL q(/J)
to L and obtain
d ( e-/Je, )- 1 d(e-/Je, ) e-/Je, dq

dL q(/J) --q dL 7 dL
In an adiabatic process, fJ changes with L. Thus
d -fJe ae-/Je, d/J ae-/Je, de;

-e , =----+----
dL ap dL aci dL
Performing the differentiations and using t'; = ~ , we obtain

- d e _ ,,e,
R R, d/J
= -£.e _ "°' 2/Jc
- +_ _, e _R,
f'<i
dL I dL L
I
Relative to the lowest level, q = ( ~~; )2 L for a particle in a one-dimensional box.
Differentiating q with respect to L while recognizing again that fJ changes with L , we obtain
(omitting a couple of algebraic steps)
dq q q d/J
-=----
dL L 2/J dL
Putting this all together, we have
!(;~;))=~{-t';e-/Je, ~ + 2~£; e-/Je, }- e;" {z- 2~ ~}

2
By inspection we can see that this equals zero when d/J = /3 .
dL L
Thus d/J = 2 dL and In fJ = 2 ln L +constant or In fJ = In L2 + constant, or In ~ = constant

/J L L
and hence ~ = constant. Since

1
fJ = - - and recognizing that k is a constant, we finally obtain
L kT
1 ~
- = constant or TL2 = constant or LT 2 = constant.
TL2
Q.E. D.
P14.37
Cv = (~~)v
( ~~ ), = (a~ (~a), = (a"r( ~~n I[derivatives may be taken in any o<docJ
( au ) = O for a perfect gas [Section 14.10]

av r
Hence, (acv)
av r
=0
( aa: l = 0 for a perfect gas
Hence, (acp
Op
J =O
T
P14.39 Using the Euler's chain relation and the reciprocal identity [Mathematical Background 8],
Substituting into the given expression for cp -CV'
c p
-c =-r(ap) (av)2
v av
ar P
T
Using the reciprocal identity again,
r(av) 2
oT p
(~~)r
For a perfect gas, p V = nRT, so
nRT
p2
so
P14.41 (a) V= V(p,T);hence, dV= (av) dp+(av) dT.

op r ar p
Likewise p =p(V,T), so dp = (op) dV +(op) dT.

av r ar v
(b) We use a=(~ )(~~)P [14.58] and Kr=-(~ )(~;l [14.50] and obtain
d InV=_!_dv=(_!_)(av) dp+(_!_)(av) dT=l-Krdp+adTI

v op r v ar p v
Likewise d Inp=dp =_!_(
P P
0
PJ
av
dv+_!_( PJ dT
r
0
ar P v
We express (op
av
J in terms of
T
Kr:
KT= _ _!_(avJ 0
= -[v( P) ]-
1
so (
0P)
v op T av T av T KTV
We express (op) in terms of Kr and a:

ar v
op
( ar v
J (avar J (avop Jr __ 1
J (oV I oT)p
ar v cav /op)r
P
so ( op
= .!!...
KT
so dlnp=-~+adT =1-1-(adT-dVJ
pKTV pKT pKT V
P14.43 µ =(ar)
Op H
[14.65]
Use of Euler's chain relation [Mathematical Background 8] yields
(aHm)
Op (14.67)
µ-- T
- cp ,m
(aHm J = (aum J +[o(pVm)] = (aum J (avm J +[o(pVm)]

Op T Op T Op T 0 Vm T Op T Op T
Use the virial expansion of the van der Waals equation in terms of p. Now let us evaluate some of
these derivatives.
(aum)
OVm T -(au) a
- '(JV T = 1lT = V2
m
(Exercise 14.29)
pVm =RT[I+ RlT(b- RaT )p+···]
[o(pVm)] "'b-__!!_, (oVm J "'_ R:

op T RT op T P
Substituting (oHJ
op T
"'(__f!_)x(-RT)+(b-___g_)
v.~ p 2
RT
"' (pVm)
-aRT +(b-___g_)
RT 2
Since ( oH) is in a sense a correction term, that is, it approaches zero for a perfect gas, little error
Op T
will be introduced by the approximation, (pVm) 2 = (R1) 2•
( 2a b)
Thus ( oH)
op T
"'(-___g_)+(b-___g_) =(b-k) and
RT RT RT
µ=RT-
Cp ,m
P14.45 a- 1
- V aT
(av) _V ( aT1 )
P -
[Mathematical Background 8]
av p
a= -x----(--)---
1 1
V ( T ) _ 2na x (V _ nb)
[Problem 14.44]
V-nb RV 3
=1~-~~~-~-~1
(RV 2 )x(V-nb)
(RTV 3 )-(2na)x(V-nb) 2
Kr= _ _!_(~V)
V 'P
= (-I )
V ap T
[<eciprncfil identity]
av r
1 1
Kr = --x ( )
V -nRT
(V-nb) 2
+(2n a) [Problem 14.44]
V3
2
nRTV 3 -2n 2 a(V-nb)2
K V -nb
Then _I_= - - , implying that KrR = ~Ym -b).
a nR
Alternatively, from the definitions of a and Kr above,
-Kr - -( ~ )r - --~~-
-l [rec1proca
. 11"dentity
. ]
a - ( ~~) P - ( i~ l( ~~) P
= (oT)
op v
[Euler chain relation]
V-nb
=--[Problem 14.44],
nR
KR= a(V-nb)
T n
Hence, KrR = l~:Vm - b).
P14.47 (a)
1
µ=-- (aH) 1{T(a;) -vm}
=- [14.67andProbleml4.43]
cp ap cp a p r
V =RT +aT 2
m p
so (avm)
oT P
=R+2aT
p
µ = _l {RT + 2aT 2 _RT _ aT 2 }

cp p p
=I aT'
cp
I
(b) c -aTV (ap)

v
=C
P m aT v
=C
P
-T(avm) (0P)
oT p
oT v
RT
But
p= V -aT 2
m
(~~l
R RT(- 2aT)
2 2 2
Vm -aT
(Vm -aT )
R 2aRT 2 p 2ap 2
= + 2 =-+--
(RT / p) (RT / p) T R
Therefore,
Cv =CP-T ( R
p +2aT ) x T + RJ
2ap (p 2
cp-~(1+~Jx(1+ J
2
= a;TJx ( :
C =C -R( l+ 2apT J2
v P R
P14.49 (a) One major limitation of Hooke' s Jaw is that it applies to displacements from a single
equilibrium value of the end-to-end distance. In fact, if a DNA molecule or any other
macromolecular chain that is susceptible to strong non-bonding intramolecular interactions is
disturbed sufficiently from one equilibrium configuration, it is likely to settle into a different
equilibrium configuration, a so-called "local minimum" in potential energy. Hooke' s law is a good
approximation for systems that have a single equilibrium configuration corresponding to a single
minimum in potential energy. Another limitation is the assumption that it is just as easy (or as
difficult) to move the ends away from each other in any direction. In fact, the intrarnolecular
interactions would be quite different depending on whether one were displacing an end along the
chain or outward from the chain. (See Figure 14.13.)
Figure 14.13
Work is dw = -Fcl.x = +kF x dx. This integrates to
w -- Jorxr kFxctx-
- 1 kFx 2
2
I"-~
0
-~
0.9
\ I
0.8
\ I
0.7
\ I
0.6
-g 0.5
\ I
~
0.4
\ \
I
v
0.3
!\ I
0.2
\ \ I
I
0. 1
!\. I
v
0
- 1 -0.8 -0.6 -0.4 -0.2
"' !'-.....
0
./
0.2 0.4 0.6 0.8

displacement Figure 14.14
(b) One obvious limitation is that the model treats only displacements along the chain, not
displacements that take an end away from the chain. (See Figure 14.13.)
(i) The displacement is twice the persistence length, so
x = 21, n = 2, V= n/N = 2/200 = 1/100

and jFj = kT ln ( l +V J=(1.38lxl0- 23 1
J K - )(298 K) 1n(1.01J=1 9. lxl0_ NI
16
21 l-v 2 x 45xl0-9 m 0.99
(ii) Figure 14.15 displays a plot of force versus displacement for Hooke's Jaw and for the one-
dimensional freely jointed chain. For small displacements, the plots very nearly coincide.
However, for large displacements, the magnitude of the force in the one-dimensional model
grows much faster. In fact, in the one-dimensional model, the magnitude of the force
approaches infinity for a finite displacement, namely a displacement the size of the chain
itself Clvl = 1). (For Hooke ' s law, the force approaches infinity only for infinitely large
displacements.)
s ~~-~~-~~-~~~--~
j- Hooke
4 +--+--+---+--+---+--+---+- - - - 1-D model
3 +->-l---+---+--+---+--+---+--+---+-
2 -t--:;:--f~-+----t--+----t--+----t--+----t-
-----r-::.: -
O.l J---.-r---.
2 0 +----+- +----+-+-"""+=---+----+-+----+-
..£ ----J---.-
-1 +----+-+----+-+----+--t---f~-±----+-
--~r-----..
-2 +--+--+--+--+--+--+--+--+---<t-~
- 3 +--+--+---+--+---+--+---+--+---+~
-4 +--+--+--+--+---+--+--+--+--+~7
- 5 +--+--+---+--+---+--+---+--+---+-
- I -0.8 -0.6-0.4 -0.2 0 0.2 0.4 0.6 0.8

displacement Figure 14.15
(111) . d w = -F dx =kT
.. . Work 1s 1+-
- ln ( - v dx =kNT
- - ln ( - J
1 +-
v dv J
21 l-v 2 l-v
This integrates to
ln (1
- + v Jd v = -kNT iv' [ln(l + v)- ln(l -v)]d v
w=
iv,-kNT
0
2 l-v 2 °
kNT +v) ln(l +v)-v + (1-v)ln(l-v) + v] Iv'

= -[(1 0
2
kNT
= --[(l +vr )ln(l + vr ) + (l-vr) ln(l-vr )]
2
(iv) The expression for work is well behaved for displacements less than the length of the chain;
however, for Vf = ±1, we must be a bit more careful, for the expression above is
indeterminate at these points. In particular, for expansion to the full length of the chain
w = lim kNT [(l + v)ln(l + v) + (l-v) ln(l-v)]

V-+I 2
=kNT
- [ (l+l)ln(l+l)+hm(l-v)ln(l-v)
. =kNT
- [ 2ln2+hm J
. ln(l-v)]_1
2 V-+I 2 V-+I (l-V)
where we have written the indeterminate term in the form of a ratio in order to apply l'Hopital's
rule. Focusing on the problematic limit and taking the required derivatives of numerator and
denominator yields
. -(1- vf' = 1Im

. ln(l - v) = 11IIl . [- (l - )] = O
1Im V
V-+I (1- vr' V-+I (1- Vf2 V-+I
Therefore w = kNT (2 ln 2) = IkNTln 2 I

2
(c) For V<< 1, the natural log can be expanded: ln(l+v) "" vand ln(l-v) "" -v. Therefore,
kT ln (l+v)
IFl=- - kT
=-[ln(l+v)-ln(l-v)]
21 1-v 21
"' kT [ v _ (-v)] = v kT = nkT = xkT

21 I NI Nl 2
(d) Figure 14.15 already suggested what the derivation in part (c) confirms: that the one-
dimensional chain model and Hooke's law have the same behavior for small displacements.
Part (c) allows us to identify k~ as the Hooke's law force constant.

NI
5
P14.51 (a) q=nl1 H 6 = 1. g , x(-5645kJmor')=l-25kJI
c 342.3gmor
(b) Effective work available is "' 25 kJ x 0.25 = 6.2 kJ.

Because w = rngh and rn "" 65 kg,
3
h"' 6.2x10 J
65kgx9.8lms-2 =l9.7ml
(c) The energy released as heat is
25
q=-11,H=-nl1cH 6 =-( · g _,)x(-2808kJmol-')=139kJI
180gmol
(d) If one-quarter of this energy were available as work, a 65-kg person could climb to a height h
given by
~
3
1 q 39xl0 J
-q=w=rngh so h=--= =~
4 4 mg 4(65kg)x(9.8m s-2)
P14.53 (a) The Joule-Thomson coefficient is related to the given data by
µ =-(11 CP)(oH I op)r = -(-3.29xl03 J mor' MPa- 1) / (110.0JK-' mor')
=/29.9 K MPa - 1 /
(b) The Joule-Thomson coefficient is defined as
Assuming that the expansion is a Joule-Thomson constant-enthalpy process, we have
/J.T = µ/J.p = (29.9K MPa -') x [(0.5-1.5)x 10- 1 MPa] = /-2.99 K/

15 The second law of
thermodynamics
015.1 We must remember that the second law of thermodynamics states only that the total entropy of both
the system (here, the molecules organizing themselves into cells) and the surroundings (here, the
medium) must increase in a naturally occurring process. It does not state that entropy must increase
in a portion of the universe that interacts with its surroundings. In this case, the cells grow by using
chemical energy from their surroundings (the medium), and in the process the increase in the
entropy of the medium outweighs the decrease in entropy of the system. Hence, the second law is
not violated.
015.3 Everyday experience indicates that the direction of spontaneous change in an isolated system is
accompanied by the dispersal of the total energy of the system. For example, for a gas expanding
freely and spontaneously into a vacuum, the process is accompanied by a dispersal of energy and
matter. It is easy to calculate the increase in the thermodynamic entropy that accompanies this
v
process. For a perfect gas this entropy change is given by the formula l1S = nRln_f__ [eqn. 15.26],
v;
which is clearly positive if Vi is greater than Vi. The molecular interpretation of this thermodynamic
result is based on the identification of entropy with molecular disorder. An increase in disorder
results from the chaotic dispersal of matter and energy, and the only changes that can take place
within an isolated system (the universe) are those in which this kind of dispersal occurs. This
interpretation of entropy in terms of dispersal and disorder allows for a direct connection of the
thermodynamic entropy to the statistical entropy through the Boltzmann formula S = k ln W, where
W is the number of microstates, the number of ways in which the molecules of the system can be
arranged while keeping the total energy constant. The concept of the number of microstates makes
quantitative the more ill-defined qualitative concepts of "disorder" and "the dispersal of matter and
energy" used above to give a physical feel for the concept of entropy. A more "disorderly"
distribution of energy and matter corresponds to a greater number of microstates associated with the
same total energy.
015.5 It was demonstrated in Justification 13.5 that for distinguishable particles the relationship between
the canonical, Q, and the molecular, q, partition functions is Q = qN. But if all the molecules
are identical and free to move through space, we cannot distinguish between them and the relation
N
Q = qN is not valid. The correct relationship is instead Q = L. This can be demonstrated as
N!
follows. Suppose that molecule 1 is in some state a, 2 in b, and 3 in c. Then one member of
the ensemble of these three molecules has energy E = c0 +ch +cc . If the molecules are
indistinguishable, this member of the ensemble is indistinguishable from one in which molecule 1
is in state b, 2 inc, and 3 in a, or some other permutation. Altogether in this case there are 3! = 6
indistinguishable such permutations, and in general for N molecules, there are N! such
indistinguishable permutations. Hence the number of products of molecular partition functions that
must be included in the canonical partition function is reduced by the factor 1/N!
THE SECOND LAW OF THERMODYNAMICS 353
In general, the entropy is given by S = U -U(O) + k ln Q. For distinguishable particles using

T
Q =q N the entropy becomes S = U -U(O) + Nk ln q. For indistinguishable particles, using Q = q N ,

T N!
the entropy becomes
S = U-U(O) +Nklnq-klnN!
T
015.7 See Justification 13.2 for the derivation from the Boltzmann distribution of the formula for the
partition function of a perfect gas, which is given by q =-;,

A
with A = h Y: . The general
(2trmkT) 2
expression for the entropy is S = U -U(O) +klnQ [15.4]. For indistinguishable, non-interacting
T
N
particles, Q = g_ . After insertion of this expression for Q, we obtain for the entropy [see
N!
Justification 15.1] S = U - U(O) + Nk ln qe [15 .2b] . From this expression, we derive the Sackur-
T N
12
v__
Tetrode equation, Sm = R In _m es ) [15 .5a], for the entropy of a perfect gas. See Justification 15.2
( N AA
3
for the derivation. Because the molar volume appears in the numerator, the molar entropy increases
in proportion to the natural log of the molar volume. In terms of the Boltzmann distribution, this is
natural: large containers have more closely spaced energy levels than do small containers, so more
states are thermally accessible. Because temperature appears in the numerator (the denominator of A),
the molar entropy increases with temperature. The reason for this behavior from the point of view of
the Boltzmann distribution is that more energy levels become accessible as temperature increases.
015.9 Because solutions of cations cannot be prepared in the absence of anions and vice versa, in order to
assign numerical values to the entropies of ions in solution, we arbitrarily assign the value of zero to
the standard entropy of H+ ions in water at all temperatures, i.e., Se (H+, aq) = 0 . With this choice,
the entropies of ions in water are values relative to the hydrogen ion in water; hence they may be
either positive or negative. Ion entropies vary as expected to the degree to which the ions order the
water molecules around them in solution. Small, highly charged ions induce local structure in the
surrounding water, and the disorder of the solution is decreased more than for the case of large,
singly charged ions.
015.11 All the thermodynamic properties of a system that we have encountered, U, H, S, A, and G, can be
used as the criteria for the spontaneity of a process under specific conditions. The criteria are
derived directly from the fundamental relation of thermodynamics, which is a combination of the
first and second laws, namely,
-dU - Pext dV + dwnon-pV + TdS ~ 0
The inequality sign gives the criteria for the spontaneity of a process; the equality gives the criteria
for equilibrium.
The specific conditions we are interested in and the criteria that follow from inserting these
conditions into the fundamental relation are the following:
(1) Constant U and V, no work at all
dSu,v ~ 0
(2) Constant Sand V, no work at all

dUs,v :::; 0
(3) Constant Sand p, no work at all
dHS ,p $ 0
(4) Constant T
dAr $dw
(5) Constant T and V, only non-p V work
dAr,v $ dwnon-pV
(6) Constant T and V, no work at all
dAr,v:::;; 0
(7) Constant T and p, p = Pext
dGT,p $ dwnon-pV
(8) Constant Tandp, no non-pV work

dGT ,p $ 0
Assume that all gases are perfect and that data refer to 298.15 K unless otherwise stated.
E15.1 (a) All spontaneous processes are irreversible processes, which implies through eqn. 15.19, the
Clausius inequality, that M,01 = M,ys + Msurr > 0 for all spontaneous processes. In this case,
M,01 = 0. Therefore, the process is ~ot spontaneous.I
E15.2(a) lh{g2I willhave the higher standard molar entropy at 298 K primarily because Mfus and Mvap are
greater for 12 . At 298 K, 12 is a solid in its standard state.
E15.3(a)
m
52
Sf}= Rln(e ' k;) [15.5b withp =pf}]
pf}A
h 6.626xl0-34 J s
(a) A
(2rrmkT) 112 [(2rr)x(4.003)x(l.6605x10-27 kg)x(l.38lx10-23 J K- 1T)] 1'2
8.726xl0- 10 m
- (TI K)1' 2
Sf}= Rln( (es'2)x(l.38lxl0-23 J K-1r) )x(!_J312 = Rln(2.499x(T I K)s12)

m (l.013x105 Pa)x(8.726x10- 10 m)3 K
T = 298.15 K, s:: = (8.314 J K-1 mor1)xln(2.499x(298) 512)

I= 126 J K-I mor 1I
A= _h 6.626x 10-34 J s
(b)
(2rrmkT)112 [(2rr)x (13 l.29)x (1.6605 xl0-27 kg)x (1.38lx10- 23 J K- 1T)] 112
l.524xl0- 10 m
(TI K) 112
s:: =Rln( (1 .013xl0

(es' 2)x(l.38lxl0-23 JK-1 T) ) (TJ312
5 Pa)x(l.524x10-'°m)3 x K
512
= R ln( 469.lx(T I K) )
T = 298.15 K , s: = (8.314 J K - 1 mor 1)xln(469.lx(298}512 )

I= 169 J K- 1 mo1- 1 I
E15.4(a) From the solution to exercise El5.3(a) we have for helium
s:: = (8.314 J K- 1
mor 1 )xln(2.499x(T) 512 ) = 169 J K- 1 mor 1 •
We solve for T: /T = 2.35x10 3 K/
E15.S(a) The rotational partition function of a non-linear molecule is
312
R 1.0270 (T I K)
q =-- [Table 13.l]
<5 (ABC I cm-3 ) 112
1 0270x 298 312
= · " [<5=2fromTablel3 .3J=l43.ll
(2) x (27.878 x 14.509 x 9.287) 2
. h . . . 1·d .f {) h {) hc(ABC)1n
T he h1g -temperature approx1mat10n is va 1 1 T > u R, w ere uR = - - - -
k
113
hc(ABC)
B=----
R k
(6.626xl 0-34 J s)x(2.998xl 010 cm s- 1 ) x[(27.878) x (l4.509)x(9.287) cm-3 J"3
l.38xl0-23 JK- 1
= l22.36KI
Thus the high-temperature approximation is valid.

l = 43 .1 [Exercise 15.5(a)]
All the rotational modes of water are fully active at 25°C [Exercise 15.5a]; therefore,
= ~ R + Rln43 .l = 143.76 J K-I mor 1 I

2
COMMENT. Division of qR by N) is not required for the internal contributions; internal motions may be
thought of as localized (distinguishable). It is the overall canonical partition function, which is a product
of internal and external contributions, that is divided by N)
E15.6(a) We assume that the upper nine of the (2x1+1) = 10 spin-orbit states of the ion lie at an energy
much greater than kT at 1 K; hence, since the spin degeneracy of Co 2+ is 4 (the ion is a spin quartet),
q =4. The contribution to the entropy is
R In q = (8.314 J K- 1mor 1 ) x (In 4) = 11 i.5 J K- 1 mo1- 1 I
E15.7(a) thl = nRin(~) [Example 15.1]

=( lSg Jx8.314JK- 1
44 g/mol
mol- 1 xln (~l
1.0)
=l3.1JK- 1 I
E1 5.8(a) The molar entropy of a collection of oscillators is given by
Sm= um -~m(O) +klnQ (15.4]= NA)c) +Rlnq
hcv B q= 1 - 1
where ( c) = Phc:V = k~ [13.39], 1- e - Phcv - 1- e - 8/T [13.24]
e -1 e -1
and Bv is the vibrational temperature hcv/k. Thus
R((J I T) - R ln(l- e - 8t r)
Sm= e8/T -1
The vibrational entropy of formic acid is the sum of contributions of this form from each of its nine
normal modes. The table below shows results from a spreadsheet programmed to compute Sm!R at a
given temperature for the normal-mode wavenumbers of formic acid.
T=298 K T=500 K
vI cm- 1
fJv/K 11Bv Sm!R JlfJv Sm!R
638 918.0 0.324635 1.624247 0.544689 4.340205
1033 1486.3 0.200501 0.341767 0.33641 1.769583
625 899.3 0.331387 1.707377 0.556019 4.471129
ll05 1589.9 0.187436 0.254961 0.31449 1.500608
1229 1768.3 0.168525 0.153044 0.28276 1.127318
1387 1995.6 0.149327 0.079118 0.250549 0.779719
1770 2546.7 0.ll7015 0.015427 0.196334 0.312684
2943 4234.4 0.070376 8.53E-05 0.118081 0.016529
3570 5136.5 0.058016 4.95E-06 0.097342 0.003239
4.176032 14.32101
(a) At 298 K, Sm = 4.l 76R = 134.72J mol-'. K- 1 1.
(b) At 500 K, Sm= 14.32R = 1119.06 J mol- 1 K - 1 I.
COMMENT. These calculated values are the vibrational contributions to the standard molar entropy of
formic acid . The total molar entropy would also include translational and rotational contributions, but
without knowledge of the rotational constants, the total molar entropy cannot be calculated.
E15.9(a) (a) For H 2 we need to evaluate the expression for the rotational partition function term by term
since B is a significant fraction of kT at 298 K; hence the high-temperature approximation is not
valid at that temperature.
l hcB J (J+l )
qR=-°L(2J+l)e kT (13.19], 0"=2forH2
(}" J
At 298.15 K, kT I he= 207.22 cm- 1 and qR can be rewritten
1
qR = - L (2J + l)e ___ B__
207.22cm- 1
J(J+ I ) 1
=- L (2J + l)e--0.29372J(J+l)
2 J 2 J
qR as a function of J converges rapidly to the value 1.8794.

U -U (0) U -U (0)
WecannowuseSm= m Tm +klnQ[l5.4]= m Tm +RlnqR
Um-Um(O)=NA(E
R
)=-71 (OqR
o/J ) v
um-Um (0) = 2 JR N Ahcii])v + l)[J(J + l)]e- PhcBJ(J+ I)
q J=I
um -Um(O)= NA xl.2090 x 10-21 Jx_L(2J+l)[J(J+l)]e--0 29372 J(J+I)

2Xl.8794 J=I
U -U (0) = NA x l.2090 x 10-21 Jxl 1.5162 = 2.2307 kJ/mol- 1

m m 2xl.8794
S =Um -Um(O) + RlnqR = 2230.7 J/mol-1 +8.314 J K-1 mor1 x ln1.8794

m T 298.15 K
= li2.73 J K- 1 mo1- 1I
(b) For C}z, the high-temperature approximation is valid at 298 Kand we can write
1 1
kT 207.22 cm- = 207.22 cm- = .
424 5
qR = CYhcB = 2B 2 x 0.2441 cm- 1
We can now use Sm= Um -~m (O) +klnQ [15.4] =Um -~m(O) +RlnqR with Um -Um(O) = 2RT.
Therefore,
2
Sm = ;T +RlnqR =2x8.314JK- 1 mor 1+8.314JK- 1 mol- 1xln424.5=l66.94JK- 1 mo1- 1I
COMMENT. In the solution to part (a) above we have used the symmetry number approach in treating
the case of H2 • This effectively assumes that hydrogen is a 50/50 mixture of the nuclear ortho- and
para- forms. If the calculation had been done separately for the para- and ortho- forms , the results
would have been
12.61JK- 1 mol- 1 and12.86JK _, moi- 1
respectively. In actuality, equilibrium H2 is not a 50/50 mixture of the ortho- and para- forms. Instead it is
approximately a 3/ 1 mixture. See the solutions to Problems 14.26, 14.29, and 14.33 for further analysis
of the H2 case.
E15.10(a) Efficiency, rJ , is
work performed lwl
= - [15.15]=
3.00 kJ . .
=0.300. For an ideal heat engme we
heat absorbed qh 10.00 kJ
haven =1- T., [15.17] =0.300=1-

'/rev Th
T.,
273 .16 K
. Solving for Tc, we obtain .Ire = 191.2 -KJ as the
temperature of the organic liquid.
E15.11 (a) Assume that the block is so large that its temperature does not change significantly as a result of the
heat transfer. Then
rrd rf
!J.S= J; ~ev [15.lO]=tJ;dqrev [constantT]=qTv
(a) !J.S = 1OOx103 J =1366 J K-11 (b) !J.S = lOOx 103 J = 1309 J K-11
273.15K 323.15K
E15.12(a) Trouton' s rule in the form f.,. vapHB =Tbx 85 J K- I mor 1can be used to obtain approximate
enthalpies of vaporization. For benzene,
f.,. vapHB = (273.2+80.l)Kx85 J K- 1 moi- 1 = l3o.o kJ/moi- 1I

E15.13(a) Sm(I'r) = Sm(J;)+ Jr,( ' C~m dT[15.30, with Cv,m in place of Cp]
If we assume that neon is a perfect gas, then Cv,m can be taken to be constant and given by
Cv,m = Cp.m- R.
Cp,m = 20.7861K- 1 mol- 1 [Table 14.6]
= (20.786-8.314) 1 K- 1 mo1- 1
= 12.472 1 K- 1 mol- 1
Integrating, we obtain
T
Sm (500 K) =Sm (298 K) + Cv,m In~
I
= (146.221 K- 1 mor 1)+ (12.4721 K- 1 mor 1) ,JSOOK)

u\298K
= (146.22+6.45)1 K- 1 mol- 1 = I152.67 1 K- 1 moi- 1 I
E15.14(a) Since entropy is a state function, f..S may be calculated from the most convenient path, which in this
case corresponds to constant-pressure heating followed by constant-temperature compression.
f..S=nCp,m~~) [15.30,atp;] +nR~~) [15.24, atI'r]

vr p.
Since pressure and volume are inversely related (Boyle's law), - =_!_.Hence,
~ Pr
398
f..S = nC
p,
miJTrJ; )-nR u\
u\ iJ Pr)=
Pi
(3.00mol)xix(8.3141K-
2
1
mol- 1)xlJ
'\ 298K
KJ
_1 1 1J5 .00atrn)
-(3.00mol)x(8.3141K mol- )Xu\ l.OOatrn
= (18.04-40.14)1K- 1 =-22.lJK- 1
Though f..S (system) is negative, the process can still occur spontaneously if f..S (total) is positive.
E15.1 S(a) For an adiabatic reversible process, q = qrev = [QJ.
f,,S = ( dqrev = [Q]

Ji T
E1 5.16(a) Since the container is isolated, the heat flow is zero and therefore I/),]{ = 0 I; since the masses of the
blocks are equal, the final temperature must be their mean temperature, 25°C. Specific heat
capacities are heat capacities per gram and are related to the molar heat capacities by
c
=___!!!_
Cs M [Cp,m "'CV,m = Cm ]
So nCm = mC, [nM = m]
f..S = mC, ~~ }15.30]

3
Ml = (1.00xl0 g)x(0.3851K-I g- 1 )X~ ~~~~) = -31.0lK-I
M 2 = (1.00xl0 g)x(0.3851K-I g-
3 1 )x~ ~~~~) = 33.71K- 1
COMMENT. The positive value of ~S 101 corresponds to a spontaneous process .
148
E15.17(a) (a)M(gas)=nRlnV.Vr [l5.24]=( _ Jx(8.314JK- 1mor 1)x(ln2)
; 28.02gmol 1
= 1+2.9JK- 1I
M(surroundings) = 1-2.9 J K- 1I [overall zero entropy production]
M(total) = [Q] [reversible process]
(b) M(gas)=l+2.9JK- 1I [Sisastatefunction]
M(surroundings) = [Q] [surroundings do not change]
M(total) = 1+2.9J K- 1I
(c) M(gas) = [Q] [qrev = 0)
M(surroundings) = [Q] [no heat is transferred to surroundings]
M(total) = [Q]
E15.18(a) (a) ~ S = ~vapH = 29.4X103J mol-1 = 1+87.8J K-1 mo1-1 I

vap Tb 334.88 K
(b) If the vaporization occurs reversibly, M ,01 = 0, so M surr = l-87.8JK- 1moi- 11.
E15.19(a)
n= lO.O g = 0.555 mol

18.02 g moi- 1
1
~S = 0.555 molx38.02 J K- 1 mol- 1x ln 273 · 15 + 0.555 molx 6 ·008 kJ/mol -
263.15 273.15 K
373 15
+0.555 molx75.291 J K - 1 mol- 1xln ·
273 .15
44 016 1
+0.555 molx · kJ/mol- +0 .555 molx33.58 J K - 1 mol- 1xln 388 · 15
373.15 K 373.15
IM= 92.2 J K- 1I
COMMENT. This calculation is based on the assumption that the heat capacities remain constant over
the range of temperatures involved and that the enthalpy of vaporization at 298.15 K given in Table 14.3
can be applied to the vaporization at 373.15 K. Neither assumption is strictly valid. Therefore, the
calculated value is only approximate.
E15.20(a) In each case, Sm = R In s where s is the number of orientations of about equal energy that the
molecule can adopt. Therefore,
(a) Sm =R In 3 = 8.3145 J K- 1 mor 1 xIn3 =~. 13 J K 1 moI 'I

(b) Sm= R In 5 = 8.3145 J K- 1 mor 1 x In 5 = l13.4 J K- 1 mor 1I
(c) Sm=R In 6 = 8.3145 J K- 1 mor 1 xIn6 =l14.9 J K 1 mol 11
E15.21(a) IneachcaseA,S 6 = L vs:;- L vS! [l5 .32]

Products Products
with Sm values obtained from Tables 14.5 and 14.6.

(a) A,S = 2S!(CH3COOH, l)-2S! (CH3CHO, g)-s: co2, g)
= [(2 x l59.8)-(2 x 250.3)-205.14]JK-I mor 1 =1-386.lJK-I mor 1 I
(b) A,S 6 = 2S! (AgBr, s)+s: cc12, g)-2S!(AgCI, s)-S! (Br2, I)

= [(2 x l07. l) + (223.07)-(2x96.2)-(152.23))JK- 1 mor'
= 1+92.6JK- 1 mo1- 1 J
(c) A,S 6 = S! (HgCl2 , s)-S! (Hg, l)-S!(Cl 2 , g)

= [146.0-76.02-223.07)JK- 1 mor 1 =.-1--1-53_.l_J_K___I m_o_l__,, I
E15.22(a) In each case we use
A,0 6 = A,H 6 -TA,S 6 [Example 15.6)
along with
A,H
6
= L
Products
vArH
6
- L
Reactants
6
vArH [14.43b]
(a) A,H 6 = 2ArH 6 (CH 3COOH, 1)- 2ArH 6 (CH 3CHO, g)

= [2 x (-484.5)-2 x (-166.19)]kJ mor' = -636.62kJ mo1- 1
A,G6 = -636.6lkJmol- 1 -(298.15K)x(-386.1JK- 1 mor') = l-521.5kJmo!- 1 J
(b) A,H 6 = 2ArH 6 (AgBr, s)-2ArH 6 (AgCI, s)

= [2 x (-100.37)-2x(-127.07)]kJ mo1- 1 = +53.40kJ mor'
A,G6 = +53.40kJmol-I -(298.15K)x(+92.6)JK-I mor' = l+25 .8kJmor 1 I

(c) A,H 6 =ArH 6 (HgCl 2, s)=-224.3kJmor'
A,G6 = -224.3kJ mol- 1 -(298.15K) x (-153.l J K- 1 mol- 1) = J-l 78.7kJ mor 1 J
E15.23(a) In each case A,G

6
= L
Products
vArG 6 - L
Reactants
vArG6 [15.51)
with ArG6 (J) values from Tables 14.5 and 14.6.

(a) A,0 6 = 2ArG6 (CH 3COOH, 1)- 2ArG6 (CH 3CHO, g)
= [2 x (-389.9)- 2x(-128.86)]kJ mol- 1 = J-522.lkJ mo1- 1 J
(b) b..,G& = 2b..rG& (AgBr, s)-2b..rG& (AgCl, s) = [2x(-96.90)-2x(-109.79)]kJ mol- 1
= 1+25.78kJ mo1-
1
I
COMMENT. In each case, these values of ilpe agree closely with the calculated values in Exercise
15.22(a).
E15.24(a) b..,G& =b..,He -Tb..,S& [Example 15.6] b..,H& = L vb..rH& - L vb..rH& [14.43b]
Products Reaclanls
b..,Se = L vs:- L vs;[15.32]

Products Reactants
b..,He = 2b..rH&(H 2 0, l)-4b..rH&(HI, g) = {2x(-285.83)-4x(+26.48)}kJmol-1

= -677.58kJ mol- 1
b..,S = 2s:(I 2 , s) + 2s:(Hp, l)-4S:(HI, g)-S:(o 2 , g)

= [(2xl 16.135) + (2x69.91)-(4x206.59)-(205.14)]JK- 1 mol- 1
= -659.41 JK- 1 mol- 1 = -0.65941 kJK- 1 mol- 1
b..,G& = -677.58kJ mol- 1 -(298.15K)x(-0.6594lkJK- 1 mol- 1 ) = l-480.98kJmol- 1 I
Question. Repeat the calculation based on b..rG data of Table 14.6. What difference, if any, is there
from the value above?
E15.25(a) The formation reaction for ethyl acetate is
4C(s) + 4H 2 (g)+0 2 (g) ~ CH 3 COOC 2 H 5 (1)
b..rG& =b..rH& -Tb..rS& [Example 15.6]
b..rHe is to be obtained from b..cHe for ethyl acetate and data from Tables 14.5 and 14.6.
Thus
b..cH & =4b..rH&(C0 2 , g)+4b..rH&(Hp, l)-b..rH&(CH 3 COOC 2 H 5 (1))
b..rH&(CH 3 COOC 2 H 5 (1)) = 4b..rH& (C0 2 , g) + 4b..rH& (H 2 0, 1)- b..cH&
= [4x(-393.5 l) + 4x(-285.83)-(-223 l)]kJ mo1- 1
= --486.4 kJ moi- 1
b..,SB = L vs:- L [15.32]

Products Reactants
= [259.4-(4x5.740)-(4x130.68)-(205.14)]JK- 1 mol- 1
=-491.4JK- 1 mor 1
Hence t,.p& = -486.4kJ mol-I -(298.15K)x(-491.4JK-I mor 1 ) = l-340 kJ moi- 1 I

E15.26(a) CH4(g) + 202(g)-7 co2(g) + 2H20(1)
11,G =
6
L vt1rG 6 - L vt1rG6 [15 .51]
Products Rectants
6 6
11,G =11rG (C0 2, g)+211rG 6 (Hp, l)-t1rG 6 (CH 4, g)
= {-394.36+ (2x-237.13)-(-50.72)} kl mol- 1 = -817.90kJ moi- 1
Therefore, the maximum non-expansion work is is17.90kJ moi- 1 since lwactctl = lt1GI. I
E15.27(a) 11G = nRTin( ~J [15.66] = nRTin( ~) [Boyle's law]
/1G = (2.5xl0-3 mol)x(8.314 J K- 1

60
mol- 1 )x(300K)xln( ~2 ) = J-17 Jj
E15.28(a) ( -aa) =-S[15.60]; hence (aa

_r ) =-Sr, and (aa)
- ' =-S;
ar p ar p ar p
t1S = s
r
-s, =-(aar
ar
) +(aG;) =-(a(Gr -GJ)
ar ar
p p p
=-( aT
a11a) P =- aT ( -85.40J+36.5JxK
r)
0
= l-36.5JK- 1 I
E15.29(a) dG = -S dT + V dp [15.59]; at constant T, dG = V dp; therefore
pf
11G = f Vdp
p.
I
The change in volume of a condensed phase under isothermal compression is given by the
isothermal compressibility (eqn. 14.59).
Kr= _ _!_(oVJ
V Op r
= 76.8x10- atm- 6 1
[Table 14.7]
This small isothermal compressibility (typical of condensed phases) tells us that we can expect a
small change in volume from even a large increase in pressure. So we can make the following
approximations to obtain a simple expression for the volume as a function of the pressure:
IC ,,, _ _!_(V-f';),,, __!_(V-f';J so V=~(l-Krp)

r v p- Pi V; p
where Vi is the volume at 1 atm, namely, the sample mass over the density, m Ip.
3000atm m
11G= -(1-Kr P) dp
J atm p
m( J 3000atm l OOOatm
=- dp -Kr pdp )
p
l
atm latm
= m 13000atm _ IC f!_213000atm
(
p latm r 2
P latm
35
g (2999 atm -(76.8xl0-6 atm- 1)x(9.00xl0 6 atm 2) / 2)
0.789 g cm-3
= 44.4cm 3 x( 10~~m J 5 1
x2653atmx(l.013xl0 Paatm- )
= l.2xl0 4 J = J12kJj
E15.30(a) b.G = nVmf,p [15.65] = V f,p
b.G = (1.0 dm 3 )x lm
3
( 103 dm 3
J
x(99 atm)x(l.013xl0 5 Pa)=10 kPa m 3 = /+lOkJj
E15.31(a) !iGm =RTln.EI._[15.66]=(8.314 J K- 1mor 1)x(298K)xln(lOO.O)=J+11 kJmor 1J

Pi 1.0
E15.32(a) In each case the contribution to G is given by

G - G(O) = -nRT In q [15.40; also see Comment to the solution to Exercise 15.5a]
Therefore, we first evaluate qR and q v
0 6950
qR= · _TIK_I [Tablel3.l,a=2]
a Blem
= 0.6950x(298) =
265
(2) x (0.3902)
= (~)x(~)
2
qv
1-e 1-e
x(~)
1-e
[Table 13.1]
with
a= (1.4388) x (1388.2) = _ 2
6 70
298
b= (l.4388)x(667.4) = _ 2
3 22
298
c = (1.4388) x (2349.2) = 11.34

298
Hence
2
v I ( 1 ) 1 _
q = l-e-6.102 x l-e-J.222 xl-e-11.34 =l.086
Therefore, the rotational contribution to the molar Gibbs energy is
-RTlnqR =-8.314 J K- 1 mol- 1x298 Kxln 265

= J-13.8 kJ mo1- 1J
and the vibrational contribution is
-RT In q v = -8 .314 J K- 1 mol- 1 x 298 K x In 1.086 = J-0.20 kJ mo1- 1I
E15.33(a) The partition function is
q= z:g
j j
e
-/k
j
with degeneracies g1 = 2J + 1
so q=4+2e-lk[g(2P312 )=4, g(2P112 )=2]
(a) At 500 K
/3£ = ei.4388cmK)xe881cm- 1) = .
2 535
SOOK
Therefore, the contribution to Gm is
Gm - Gm eo) =-RT ln q [15.40; also see the Comment to Exercise 15.5(a)]
-RT ln q = -e8.3 l4 J K- 1 mor 1 )xesOOK)xln e4 + 2xe-2535 )

=-e8.314 J K- 1 mol- 1)xesoOK)xeln4+0.158) = l-6.42kJmoi- 1 I
(b) At 900 K,
/3£ = e1.4388cmK)xe88lcm- 1 ) = l .40S

900K
Therefore, the contribution to Gm is
Gm - Gmeo) =-RT lnq
-RT ln q = -e8.314 J K- 1 mol- 1)xe900K)xlne4+2xe- 1408 )

=-e8.314 J K- 1 mol- 1)x(900K)xeln4+0.489)=1-14.0kJmol- 1 I
P15.1 The absorption lines are the values of differences in adjacent rotational terms. Using eqns. 10.6,
10.7, and 10.8,
F(J + 1)-F(J) = E(J + l)-E(J) = 2i3e1+1)

he
for J = 0, 1, .... Therefore, we can find the rotational constant and reconstruct the energy levels
from the data of Problem 13.12. To make use of all of the data, one would plot the wavenumbers,
which represent F(J + 1) - F(J), versus J; the slope of that linear plot is 2 B . However, in this case,
plotting the data is not necessary because inspection of the data shows that the lines in the spectrum
are equally spaced with a separation of 21.19 cm- 1, so that is the slope:
I - - - I
slope= 21.19 cm- = 2B and hence B = 10.595 cm-
The partition function is

~
q= L (21 + l)e -PE(J ) -
where E(J) =he B 1e1 + 1) [10.6]
J=O
and the factor (21 + 1) is the degeneracy of the energy levels. Making these substitutions into the
partition function q, we obtain
_ hcB J(J+l) -~J(J+I) _
qR =.Lev+ l)e kT [13.19] =.Lev+ l)e r [OR = heB 1k]
J J
For HCI, OR = heB I k = 15.244 K. Defining x =.!._, qR can be rewritten

OR
qR = .L:e2J+l)e-J(J+l)/x
J
At temperatures above about 30 K, the high-temperature approximation for l

would be adequate to
calculate the molar entropy, but at lower temperatures the summation needs to be performed.
The molar entropy is calculated from Sm= Um -~m(O) +klnQ [15.4] =Um -~m(O) +RlnqR and
the molar energy from
Substituting into the expression for the entropy we obtain
1 1 -J(J +1)t x
Sm = R R-L,(2J+l)[J(J+l)]e +RlnqR
q X J= I
Sm and qR are best evaluated with a spreadsheet program such as Excel or a CAS system such as
Mathcad. Here we have used Mathcad. See the Mathcad worksheet that follows. Sm!R is plotted as a
function of x =.!_
{)R
in Figure 15 .1.
i :e=0 .. .47
x start := 0.2 x end :e= 9.6
X; =T/0
30
S; = S.,IR
25
20
S; 15
10
2 4 6 8 10
X;
xi= T/ 0 Figure 15.1

P15.3 f..Sm= ( ' Cp,mdT [15 .29] = f.'(a+bT)dT = aln(T,_ )+b(T2 -I;)
Jr, T T
I I;
1
a= 91.47 J K- mol- , 1 2 2
b = 7.5x10- J K- mor 1
1 1
f..S = (91.47 JK- mol- ) x 1n (
m
30
°
K)+(0.075JK-2 mor 1)x(27K)
273 K
= 110.7 JK- 1mo1- 1 I

P15.5 First, determine the final state in each section. In section B, the volume was halved at constant
temperature, so the pressure was doubled: Pa,r = 2pa,i· The piston ensures that the pressures are equal
in both chambers, so PA.f = 2pa,i = 2pA,i· From the perfect gas law,
3
TAr PA.rVA,r (2pA)x(3.00dm )
- ' =---= ' 3 =3.00 so TA,f =900 K
TA,i p A,i vA,i (pA_)x(2.00dm)
(a) f..SA = nCv,m1n (~A,f J [15.30] + nRln( ~A,f J[l5 .24]

A,1 A,1
f..SA = (2.0mol) x (20JK- 1mor 1)xln3.00

3 00
+(2.00mol) x (8.314JK- 1mol- 1)xin ( · dm: J
2.00dm
1
=150.7 JK- I
f..88 = nRln ( ; .r J = (2.00mol)x(8.314JK- 1mol- 1)xln( l.OOdm: J

B,i 2.00dm
=l-11.5JK-1I
(b) The Helmholtz free energy is defined as A = U - TS [3.29). Because section B is isothermal,
t:,.U = 0 and fl(TS) = Tf..S , so
~ =-T8 f..S8 =-(300 K)(-11.5 JK- 1) = 3.46x 103 J = /+3.46 kJ/

In section A, we cannot compute fl(TS) , so we cannot compute t:..U. M Iis indeterminat~ in both
magnitude and sign. We know that in a perfect gas, U depends only on temperature; moreover, U(T)
is an increasing function of T, for '(JU = C (heat capacity), which is positive; since t:,.T > 0,
ar
t:,.U > 0 as well. But fl(TS) > 0 too, since both the temperature and the entropy increase.
(c) Likewise, under constant-temperature conditions,

t:,.G = l1H -Tf..S
In section B, 11H8 = 0 (constant temperature, perfect gas), so
1 3
t:,.GB =-TBf..SB =-(300K)x(-11.5JK- )=/3.46xl0 J/
t:,.GA is ~ndeterrninat~ in both magnitude and sign.
(d) f..S(total system)= f..SA + f..88 = (50.7 -11.5)J K- 1 =/+39.2 J K - 1/
If the process has been carried out reversibly, as assumed in the statement of the problem, we can
say
f..S(system) + f..S(surroundings) = 0
Hence, f..S(surroundings) = /-39.2J K- 1I
Question. Can you design this process such that heat is added to section A reversibly?
P15.7 q w 1'1 U =till l'1S /';.Ssur /';.Stot
Path (a) 2.74 kJ - 2.74 kJ 0 9.13 J K- 1

-9.13 J K- 1 0
Path (b) 1.66 kJ - 1.66 kJ 0 9.13 J K- 1 -5.53 J K- 1 3.60 J K- 1
Path (a)
w =-nRTln ( ~ }14. 12]=-nRT!n ( ;~ J [Boyle's law]

1 1
=-(1.00mol) x (8.314JK- mol- ) x (300K) x ln ( 3.00atm
l.OOatm J =-2.74 x l0 3 J
= 1-2.14k1I
f:.H = !:lU = [QJ [isothermal process in perfect gas]
q = !:lU - w = 0-(-2.74kJ) =1+2.74kJj
2 74 3
!J.S= qrev [isothermal]= · x l0 J =1 +9.13 JK- 1 1
T 300K
!J.S,01 = [QJ [reversible process]
tJ.Stot =thlsur =tJ.Stot -tJ.S=0-9.13JK- 1 =1-9.131K- 1 I
Path (b)
w=-p.x (Vr -V;)=-pex( nRT _nRT ) =-nRT ( Pex _Pex )

Pr Pi Pr Pi
=-(1.00 mol) x (8.314 JK- 1 ) x (300 K) x( l.OO atm _LOO atmJ

1.00 atm 3.00 atm
=-l.66 x 103 1 = l-1.66 k1I
f:.H = !:lU = [QJ [isothermal process in perfect gas]
q = !:lU - w = O-(-l.66kJ) =1+1.66kJI
A<'
D.LJ = -qrev [·1sothermal] = 2.74xl03J = I+913JK-ll
.
T 300K ~--~
(Note: One can arrive at this by using q from Path (a) as the reversible path, or one can simply use
tJ.S from Path (a), realizing that entropy is a state function.)
t:,.S = q sur = -q = -1.66 X103J = 1-5.53 J K -1 1

sur T
sur
T
sur
300K
t:,.S tot = t:,.S + t:,.Ssur = (9.13-5.53)J K- 1 =1+3 .60J K- 1 1

P15.9 !lS depends on only the initial and final states, so we can use !lS = nC In 1'r [15.30] .
p,
m
r;
q 1 2 Rt
Since q = nC (Tr -T), Tr = T + - - = T + - - [q = 1tV = 1 2 Rt]
p,m ' ' nC ' nC
p ,m p,rn
12
That is, !lS = nCp,m1n[1 +--R_t_)
nCp,mT;
Since 500 g = 7.87 mol

n = 63.5 g morl
!lS = (7.87 mol)x(24.4 J K-1 mol-1 )xln ( l + (1.00 A)2 x(lOOO Q)x(l5.0 s))
(7.87)x(24.4 J K-1)x(293 K)
= (192JK- 1)x(lnl.27)=1+45.4 J K- 1j
[lJ=lAVs=lA 2Qs]
For the second experiment, no change in state occurs for the copper; hence, !lS(copper) = 0. However,
for the water, considered as a large heat sink,
2 2
!lS(water) = !L = 1 Rt= (1.00 A) x(lOOO Q)x(l5 .0s)=1+5 1. 2 J K-i j
T T 293 K
P15.11 Consider the temperature as a function of pressure and enthalpy:
T = T(p ,l{) so dT = (aT) dp+(

ap H
aT)
aH p
dH
The Joule-Thomson expansion is a constant enthalpy process (Section 14.11). Hence,
dT = ( ar) dp =µdp
ap H
Pf
!J.T =
L µ dp = µJ¥J
P1
[µ is constant]
= (0.21Katm- 1)x(l.00atm-100atm) = l-21 Kj
~ = T; +!J.T = (373-2l)K = 352K [Mean T = 363K]
Consider the entropy as a function of temperature and pressure: S = S(T, p ).
Therefore, dS= ( ~~) PdT+ ( ~;) rdp
(~:)p =? ( as) r =- ( av) p

ap ar [Table 15.5]
For V =RT (l+Bp)

m p
(avm)
aT P
= R (l+Bp)
p
c
Then dSm = ;m dT-~(l+Bp)dp
Cpm R
or dS = -' dT--dl[J-RBdlfl
m T p
On integration,
=.iRLn(
2
352
373
)-Rln(-
1
100
)-R( 0.525 atm-1) x(-99atm)
363
=1+35.9JK- 1 mo1- 1 I
P15.13
From the data, draw up the following table.
TIK 10 15 20 25 30 50
c;:'" I (J K-2 mol- 1) 0.28 0.47 0.540 0.564 0.550 0.428
TIK 70 100 150 200 250 298
~I (J K-2 mol- 1) 0.333 0.245 0.169 0.129 0.105 0.089
Plot Cp,mlT against T (Figure 15.2). This has been done on two scales. The region 0 to 10 K has
been constructed using Cp,m= aT 3, fitted to the point at T= 10 K, at which Cp,m = 2.8 J K- 1 moi- 1, so
1
a= 2.8x10-3 J K-4 mor • The area can be determined (primitively) by counting squares. Area A=
38.28 J K- mol- • Area B up to 0°C = 25.60 J K- 1 mor 1; area B up to 25°C = 27.80 J K- 1 moi- 1•
1 1
0.6
0.5
I
0 0.4
E
N
I
::..: 0.3
~
:;::,,
h 0.2
----E
v"- 0.1
··!·· .... ?···
0 ·'· ········· · ····' ........ ..•
0 20 40 60 80 100 200 300
T /K Figure 15.2
Hence,
(a) Sm (273K) =Sm (0) + 163.881 K- mo1-

1 1I
(b) Sm (298K) =Sm (0) + 166.08J K - mo1-

1 1I
( C dT
P15.15 Sm(T) =Sm(0) + .lo p,~ [15.29]
Perform a graphical integration by plotting Cp,m I T against T and determining the area under the
curve. Draw up the following table. (The last two columns come from determining areas under the
curves described below.)
~ Cp,m/T s: -s: co) H : -H: (O)

TIK J K- 1 mol- 1 J K-2 mor 1 JK- 1 mol- 1 kJmor 1
--
0.00 0.00 0.00 0.00 0.00
10.00 2.09 0.21 0.80 0.01
20.00 14.43 0.72 5.61 0.09
30.00 36.44 l.21 15 .60 0.34
40.00 62.55 l.56 29.83 0.85
50.00 87.03 l.74 46.56 l.61
60.00 111.00 l.85 64.62 2.62
70.00 131.40 l.88 83.29 3.84
80.00 149.40 l.87 102.07 5.26
90.00 165.30 l.84 120.60 6.84
100.00 179.60 l.80 138.72 8.57
110.00 192.80 l.75 156.42 10.44
150.00 237.60 l.58 222.91 19.09
160.00 247.30 l.55 238.54 21.52
170.00 256.50 l.51 253 .79 24.05
180.00 265.10 l.47 268.68 26.66
190.00 273.00 l.44 283.21 29.35
200.00 280.30 l.40 297.38 32.13
Plot C p,m against T (Figure 15.3a). Extrapolate to T = 0 using C p,m = aT 3 fitted to the point at T =
10 K, which gives a= 2.09 mJ K-2 moi- 1• Determine the area under the graph up to each T and plot
Am against T(Figure 15.3b).
(a) 2.0
1.8
,.-....._. I
1. 6
/ ~ I (b) 300
:-
!;;
1.4 l ----._ 1
j I 250
J' 1. 2 I
Ci
~
~ 1. 0
I I
)G
E
200
f...
- .. 0.8 I 0
>- 150
80.
0.6
t 8
~
'?
0.4
I ~
IC'
100
j t?,
50
v
0.2
0.0 0
0 50 100 150 200 0 50 100 150 200
TIK T/K
Figure 15.3
The molar enthalpy is determined in a similar manner from a plot of Cµ,m against T by determining
the area under the curve (Figure 15.4).
300
250
I 200
0
E
I
::.<: 150
.....,
~
v°" 100
50
0
0 50 100 150 200
TIK Figure 15.4
P1 5.17 The entropy at 200 K is calculated from
f200 Kc dT
S!(200K)=S!(lOOK)+ ~ooK p,~
The integrand may be evaluated at each data point; the transformed data appear below. The
numerical integration can be carried out by a standard procedure such as the trapezoid rule (taking
the integral within any interval as the mean value of the integrand times the length of the interval).
Programs for performing this integration are readily available for personal computers. Many
graphing calculators will also perform this numerical integration.
TIK 100 120 140 150 160 180 200

1 1
Cp,mI (JK- mol- ) 23.00 23.74 24.25 24.44 24.61 24.89 25 .11
c
~ / (JK- 2 mor 1 ) 0.230 0.1978 0.1732 0.1629 0.1538 0.1383 0.1256
T
Integration by the trapezoid rule yields
S!(200K)=(29.79+16.8l)JK- 1 mol- 1 =[46.60JK- 1 mor 1 [
Taking Cµ,mconstant yields
S!(200K)= S!(lOOK)+ Cp ,m ln(200K/100K)

= [29.79 + 24.44 ln(200 1100 K)]J K- 1 mol- 1 = [46.60 J K- 1 mor 1 I
The difference is slight.
P15.19 The Gibbs-Helmholtz equation [15.62b] may be recast into an analogous equation involving !!.G
and !lH since
( o!!.G)
ar p
= (aGr)
ar
-(aGi)
p ar p
and b.H = Hr - Hi
_Q_ A, GB ) A HB
Thus, - r
( ar r Ti
p
d ( ~ = a~r P dT [constantpressure]=-~dT
A GB ) ( A GB ) A HB
A( A,~B) = _ ( A,HB dT
,,,, -A HB ( dT = A HB
r Jr, T2 r
(_lT __l_)
T.,
(A HB assumed constant]
r
Therefore,
A,GB (T) A, GB (I;,) "" A HB (l_ __l_)

T I;, 'TT.,
so A,GB (T) = f A,GB (I;,)+( 1-f )A,HB (T.,)
= m, GB (I;,)+ (I - i")A,HB (I;,) where 'X' =~

c
For the reaction N 2 (g)+3H 2 (g) ~ 2NH 3 (g), A,GB = 2ArGB(NH 3 ,g).
(a) At 500 K 'X'= 5oo = 1.678

, 298
so A,GB (500K) = {(l.67S)x2x(-16.45) +(I- l.67S)x2x(-46.l l)} kJ mol- 1
l=-7kJmol- 1 j
(b) At 1000 K 'X'= lOOO = 3.356

' 298
so A,GB (lOOOK) = {(3.356)x2x(-16.45) +(l-3.356)x2x(-46.l l)} kJ mol- 1
I= +107kJmoi- 1 j
P15.21 The molar entropy is given by
S =Um -Um(O) +R(ln~-1) where Um -Um(O) =-N (alnq)

m T NA T Aap V
where Um -Um(O) =-N (alnqJ and !fm_ - qm T R V E
r A ap v
N -Fq q q
A A
The energy term Um - Um (0) works out to be
um -Um(O) = NA((cT)+(cR)+(cv)+(cE)J
Translation:
T~
qm = 2.56lxl0-2(T I K) 512x(M I gmol- 1)312 [Table 13.1]

NA
= 2.561x10-2 x(298) 512x(38.00) 312 = 9.20xl0 6
and ( c T) = t kT
Rotation of a linear molecule:
qR = 0.6950 x _T/ K [Table 13.1]

a B/ cm- 1
The rotational constant is

- h h
B = - - = - - -2
4nc! 4ncµR
(1.0546xl0-34 J s)x(6.022xl0 23 mol- 1)
=~~~~~-'---~~~~----'----'-~~~~~---'-~~~~~
4n(2.998xl0 10 cms- 1)x(1xl9.00x10-3kgmoi- 1)x(190.0 x l0- 12 m) 2

= 0.4915cm- 1
so R = 0.6950 X ~ = 210 .7
q 2 0.4915
Also
Vibration:
l - e -hcvtkT
l -exp
-1.4388(v/cm- 1 )J 1-exp (
-1.4388(450.0))
( T!K 298
= 1.129
34
c v )= hcv = (6.626xl0- Js)x(2.998xl0 10 cms- 1)x (450.0cm- 1)
(
ehcvl kT - l ( 1.4388( 450.0))
exp 298 -1
= l.149xl0- J 21
The Boltzmann factor for the lowest-lying excited electronic state is
23 1
19
ex (-(1.609eV)x(l .602x10- J ev-
1
= x _28
6 10
)J
p (1.38lxl0- J K- )x(298K)
so we can take l to equal the degeneracy of the ground state, namely 2, and ( c E) to be zero.
Putting it all together yields
um -Um(O) =NA (~kT+kT+l.149x10-211)=2-R+ NA(l.149x10-21J)

T T 2 2 T
= (2.5)x (8.3145 J mol-1 K-1 ) + (6.022x1023 mol-1 )x (1.149 x10-21 J)
298K
= 23.1 lJmoi- 1 K- 1
R( In~: -1 J= (8.3145J mol-1K-1)x {ln[(9.20xl0 )x(210.7)x(l.129)x(2)]-1}

6
=176.3Jmoi-1K- 1 and S~ =l199.4Jmol- 1 K- 1 I

P15.23 wadd. max = !J.,G [15.49b]
/J.,GB(37°C) =r /J.,GB(TJ+(l-r)/J.,HB(TJ [Problem 15.19, r= ~]
3 3
=( lOK Jx(-6333kJmor 1)+ (1- lOK Jx(-5797kJmol- 1)
298.15K 298.15K
=-6354kJmol- 1
The difference is
/J.,Ge (37°C)-/J.,Ge (J;J = {-6354-(-6333)}kJmor 1 = l-2lkJmo1- 1 I
Therefore an additional 21 kJ moi- 1 of non-expansion work may be done at the higher temperature.
COMMENT. As shown by Problem 15.18, increasing the temperature does not necessarily increase the
maximum non-expansion work. The relative magnitude of llPB and ll,HB is the determining factor.
P15.25 In effect, we are asked to compute the maximum work extractable from a gallon of octane,
assuming that the internal combustion engine is a reversible heat engine operating between the
specified temperatures, and to equate that quantity of energy with gravitational potential energy of a
1000-kg mass. The efficiency is
17=M[15.15]=M=TJrev =1-
Iqh I I /J.H I Th
[15.17] ~ SO lwJ=ltJ.Hl(l- ~)
Th
3
3 00
ltJ.Hl=5512xl0 3 Jmor 1 xl.OOgaJx · xl0 gx lmol =l.44xI08 J
1 gal 114.23 g
so -
lwl=l.448xl0 8
Jx ( 1- 1073 K) =7.642xl0
- 7
J
2273 K
If this work is converted completely to potential energy, it could lift a 1000-kg object to a height h
given by lwl = mgh, so
1
h=M= 1.642x10 J 3
mg (1000 kg)(9.81 m s-2 ) = 7.79xl0 m = 17.79 kml
P15.27 The partition function for a two-level system with energy separation e is
q=l+e-elkT =l+e-/Je
The entropy is calculated from

E
S =-+Nk lnq = k/JE +Nklnq
T
E- N dq _ Ne
--q dj3 - 1+ e,BE
S=Nk[ /3£,, +ln(l+e-.BE)]
1+ e"E
We now plot __§__ = §_ (for N =NA) against x

NkR
=/3£ =_!___and
kT
against y =_!_ = kT . These plots are
x £
shown in the following Mathcad worksheets.
x :=-10,-9.95 ... 10 y :=-10,-9.95 ... 10
S(x) (-x-)+ +
:=
1+ex
In (1 e-x)
0.8r-------.------..-----..-------.
S(x)=SI R
0.6
S(x) 0.4
0.2
oi.---==~~~~J..._~~---L-==-----i
-10 -5 0 5 10
x
x = /Je Figure 15.5(a)
0.8 ........---~----.-----....--------.
0.6
S(y) 0.4
0.2 S(y)=SI R
o~---...___---~---~--~
-10 -5 0 5 10
y
y = 11/Je = kT/e Figure 15.5(b)
Physically, the increase in entropy for T > 0 corresponds to the increasing accessibility of the upper
state, and the decrease for T < 0 corresponds to the shift towards population of the upper state alone
as more energy is packed into the system.
P15.29 Let us write Newton's law of cooling as follows:
dT =-A(T-T)
dt
where A is a constant characteristic of the system and Ts is the temperature of the surroundings. The
negative sign appears because we assume that T > T5 . Separating variables ~ = -Adt, and
T-T:,
integrating, we obtain ln(T -Ts) = - At+ K , where K is a constant of integration.
Let Ti be the initial temperature of the system when t = 0. Then
K = ln(Ij - Y's)
Introducing this expression for K gives
In _T-T:
_ J
s =-AtorT=T:,+(T;-T:,)e-A'
( T;-T:,
dS= -
- d ( Cln-
T J =-(ClnT)
d
dt dt T; dt
From the above expression for T, we obtain In T = In T5 - At ln(Ij -Y's) . Substituting ln !, we obtain
dS =-CA ln(T - T5 ) , where now T; can be interpreted as any temperature T during the course of
df I
the cooling process.
P15.31 The Otto cycle is represented in Figure 15.6. Assume l mole of air.
Pl C
(2)
B D
(4)
V Figure 15.6
_ I wlcycle [15 .15J

rt - Iq2 I
wcycle =WI + w3 = !1U1+ !1U3 [qi = q3 = O] = Cv(TB -TA)+ Cv(TD -Tc ) (14.36]
We know that
lie
and TD = Ve [14.37a]
( )
Tc VD
Since Ve= Ve and or T = TATc

D T
B
TATC -T
T. A TA V, )lie
then 17=1- ;, -T. =1-- or 17=1- ( _..!!_
c B TB VA
Given that Cµ,m = 7/ 2R, we have C v,m = 512R [14.35] and c = %-
25
For vv: =10, 11=1- (1o

1) '
=lo.411
M 1=M3=M sur,1 =M sur,3 = '~

o1 [adiabatic reversible steps]
At constant volume, ( ~:) = (~:) = 5.0.
M 2
1
= (%)x(8.314JK- mol- )x(ln5.0)=1+33JK- 1
1
I
P15.33 Einstein solid: Cv,m (T) = 3RfE (T) /E (T) = ( ;

{) )2 (e~'r _ 1J2
(J / 2T
-1 ) { e(J / T
= 3R
1 -
T ( {)E )
T
(
T (l-e111r)2
}
dT
Set x = ()E I T, then dT = -T 2 dx I ()E ; hence Sm = r xe x

3R J0r 1r lc1-ex) 2
r Jdx .This integral can be evaluated
analytically. The result is Sm =
3R ex -1
[-x-- ln(l-e-x)]with x = ()E .
T
A more instructive alternative derivation starting from the partition function follows . The partition
function or one dimension of vibration of an harmonic oscillator is
qv
1-e-/Jhcv [13.24] l-e-o. 1r
The energy is calculated from
Um -Um(O)=kT 2 [()JnQ] with Qv=(q v t

()T v
Performing the differentiation we obtain
um -Um (0) = RBE C0r1;_J

We have used N =NA and NA k = R. The molar entropy is calculated from
Um -Um(O) +klnQ [15.4] =Um -Um(O) +Rlnq v

Sm
T T
Substituting for Um - Um (0) and q v and multiplying by 3 for the 3 dimensions of vibration in a
crystal, we obtain Sm =
3R ex -1
[-x-- ln(l - e-x)] with x =BTE . Note that this is the same expression
obtained above. We now plot this result against y =.!. = ..!.___.
X E)E
S(y) 2 S(y ) = Sm/ 3R
2 4 6 8 10
y
y =T/ E) E Figure 15.7(a)

3
T o!T x 4 ex
Debye solid: Cv m (T) = 3Rf0 (T) / 0 (T) = 3 -
( J r8 dx
' eD 1 (ex -1) 2
Sm = r (Cv,m I T)dT = 3R r[/ 0 (T) I T]dT
The function / 0 (T) can be integrated only numerically, not analytically, the integration yielding a
(},
table of numbers, one for each value of ___.£_ • The
entropy requires a second integration, which would
T
be the area under a plot of Cv ,magainst T. This double integration can certainly be accomplished
rather easily with available software such as Mathcad, and we do this below. However we could
again proceed as we did in the alternative derivation of the entropy equation for the Einstein
solid, starting from the partition function for the Debye solid. This derivation is complex, but in
essence it is conceptually the same as the calculation above for the case of the Einstein solid. The
derivation finally yields an equation for the entropy that involves only a single numerical
integration.
~ =i_ '[-X--ln(l-e-x)} 2 dx With U:: eD

3R u 3 1 ex -1 T
In Figure 15.7b, we plot this function against y =.!.. =..!___.

U 80
S(y) 2
2 4 6 8 10
y
y = TIGD Figure 15.7(b)
The entropy can be calculated by double integration of the equation
S z[
___..!!!...-
3R - r Y3
y
YI x 4 ex
LY (ex -1)2
dx } .
!Y
The plot obtained in Figure 15.7(c) is identical to the one in Figure 15.7(b). Also note that the
Debye plots are not much different from the Einstein plot. It is a little steeper at low values of y .
S(y) 2
S(y) = Sm / 3R
2 4 6 8 10
y
y = TI GD Figure 15.7(c)
P15.35 H=U+pV
dH =dU + pdV + Vdp =TdS- pdV [3.43]+ pdV + V dp =TdS+Vdp

Since His a state function, dH is exact, and it follows that
(()HJ
as p
=T and
(~JP =(*l
Similarly, A =U -TS
dA = dU -TdS-S dT = TdS- pdV [3.43]-TdS-SdT =-pdV-SdT
Since dA is exact,
as) -(apJ v
(a-vT--ar
P15.37 If S= S(T,p)
then dS =(as()T Jp dT + (asdp JTdp

T dS =T (as()T Jp d T + r (asdp JTdp
Use (as()T J -( ()Has J(aH
P P()T
J __!_T x c [(~~JP= T, Problem 15.35
P P
l
(asJ
-dp T=-(avJ .
-()T p [Maxwell relation]
Hence, TdS=CpdT-T(~;Jp dp=ICpdT-aTVdpl
For reversible, isothermal compression, TdS = dqrev and dT = O; hence
dqrev = -aTV dp
qrev = J:' - aTV dp = j-aTV!l.p I [a and V assumed constant]

I
For mercury,
qrev = (-l.82 x 10-4 K - 1) x (273K) x (l.00 x 10-4 m-3)x(l.Oxl08 Pa)=j-0.50kJI
P15.39 (a)
S= U-~(O) +nRln(q+l) = nR ( %+ln(eq))
Note that division of q by N in the expression for the entropy is not required for internal degrees of
freedom; division of q by N is required only for the total molecular partition function, which
includes translational degrees of freedom.
(b) At 5000K, kT = 3475cm- 1. We form the sums

he
q= L e-Pcj = 1+e-2185013475 + 3e-218101J475 + . .. = l.Ol 67
q. = L..,,
" t:j -/JE1
- e = -he "L..,, v-1.e-pc
1
j kT kT j
1 2185013475 2187013475
= ( --) x {O + 21850e- + 3x 21870e- +A}= 0.1057
3475
= ( - l -)2 x {O + 218502 e-21s5013475 + 3x 218702e-2181013475 +A}= 0.6719

3475
The electronic contribution to the standard molar entropy is
0 1057
S =R (1+1n(eq)) =8.314 JK- 1 mo1- 1x( · +ln(2.71828xl.0167))
m q 1.0167
P15.41 Begin with the partition function of an oscillator (Table 13.3).
1
q=- - x = Bv = hev/J = nOJ 11
1-e-x ' T '!-'
The molar internal energy, molar entropy, and molar Helmholtz energy are obtained from the
partition function as follows:
S = U-U(O) +nRlnq = Nlo£ x -Nkln(l-e-x )

T 1-e-x
= 1Nk ( -x--ln(l-e-x ))
ex -1
A-A(O) = G- G(O) = -nRTlnq= INkT ln(l-e-x )I
The functions are plotted in Figure 15.8.
100
4
-«
~
"1
2
J
~ 50 0
e 0.0 1 0.1 x
::::i
I 0 1 ... ..... . ...... 1...
~ h :
~ : .............. . ........ .
...._ .
0'-2 i.
~I
:
: ..... _ ..
0
""<: :
0.0 1 0.1 1.0 ~ -4 ;..
x
Figure 15.8
P15.43 We evaluate f3 by comparing calculated and experimental values for thermodynamic properties. The
calculated values are obtained from the theoretical formulas for these properties, all of which are
expressed in terms of the parameter /J. So there can be as many ways of identifying f3 as there are
thermodynamic properties. One way is through the energy, as shown in Section 13.l. Another is
through the pressure, as demonstrated in Section 15.9. Another yet is through the entropy, Section
15.2, and this approach to the identification may be the most fundamental.
When plotted against T in model systems such as a two-level system, q and U show sharp
discontinuities on passing through T = 0. Only Sis continuous. However, when plotted against /J, all
three are continuous on passing through f3 = 0. See the solution to Problem 14.48. Hence f3 seems a
more natural variable than T. Another way of looking at this is to consider r, defined as r = 11/3 = kT,
to be the fundamental temperature, and then the "fundamental" constant k appears merely as a scale
factor.
P15.45 S = k In W [also see Exercises 15.20(a) and (b)]
so S = k In 4N = Nk In 4
= (5xl0 8 )x(l.38 x l0-23 J K- 1)xln4=19.57xl0- 15 J K- 1 I
Question. Is this a large residual entropy? The answer depends on what comparison is made.
Multiply the answer by Avogadro 's number to obtain the molar residual entropy, 5.76 x 109 J K- 1
mor' , surely a large number-but then DNA is a macromolecule. The residual entropy per mole of
base pairs may be a more reasonable quantity to compare to molar residual entropies of small
molecules. To obtain that answer, divide the molecule's entropy by the number of base pairs before
multiplying by NA. The result is 11.5 J K- 1 mor 1, a quantity more in line with examples discussed
in parts (a) and (b) of Exercise 15.20.
P15.47 (a) At constant temperature,

!l.H-!l.G
!l.G=!l.H-T!l.S so /l.S= r r
r r r r
T
and !l.,S = [-20-(-3 l)) kJ morl = +0.035 kJ K -I mor 1 =1+35 J K -l mor 1 I

310 K
(b) The power density Pis
Ill.G i n
P=~'--
V
where n is the number of moles of ATP hydrolyzed per second
6 1
N 10 s- - -18 -1
n=- = = l.66xl0 mol s
N A 6.02xl0 23 mol- 1
and Vis the volume of the cell
3 1 18 1
Thus p = I!l.,G In= (31x10 J mol- ) x (1.66x10- mol s- ) = 112 W m-31
15 3
V 4.19x10- m
This is orders of magnitude less than the power density of a computer battery, which is about
R = 15 W x(lOO cm)3 = li.5xl04 W m-3 1

battery 100 cm3 1m
(c) Simply make a ratio of the magnitudes of the free energies.
14.2 kJ (mol glutaminer1 = 0.4 mol ATP

6
31 kJ (mol ATPf 1 mol glutamine
P15.49 The Gibbs-Helmholtz equation is
a (!l.G)
()T T =- i1.H
T 2
so for a small temperature change,
t,.(!l.,Ge J= !l.,He !l.T and

T T2
so and
t,. r Ge
190 = t,. r Ge 7;90 + t,. r H e (l - T7;90
220 T J
220 220
For the monohydrate,
~GB
r
190 =(46.2kJmol- 1) x(
19
220K
19
°K ) +(l27kJmol- 1) x(1- °K )
220K
~rG-;:0 =\57.2kJ mo1- 1 \

For the dehydrate,
~GB
r
190 =(69.4kJmor 1)x (
19
220K
19
°K ) +(l88kJmol- 1) x(1- °K )
220K
~rG1!i = \s5.6kJ mo1- 1 \

For the trihydrate,
~GB
r
190
9
220K
9
= (93.2kJmor 1) x( I 0K ) +(237kJmol- 1) x(1- i oK )
220K
~rGl~O = 112.SkJ moi- 1I

f
16 Physical equilibria
016.1 Vapor pressure curve of water
Exploration
pathp( T )
221.2 bar
647.4 K
T Figure 16.1
Refer to Figure 16.1 above and Fig. 16.6 in the text. Starting at point A and continuing clockwise on
path p(T) toward point B, we see only a gaseous phase within the container with water at pressures and
temperatures p(T). On reaching point B on the vapor pressure curve, liquid appears on the bottom of
the container and a phase boundary or meniscus is evident between the liquid and the Jess dense gas
above it. The liquid and gaseous phases are at equilibrium at this point. Proceeding clockwise away
from the vapor pressure curve, the meniscus disappears, and the system becomes wholly liquid.
Continuing along p(T) to point C, at the critical temperature no abrupt changes are observed in the
isotropic fluid. Before point C is reached, it is possible to return to the vapor pressure curve and a
liquid-gas equilibrium by reducing the pressure isothermally. Continuing clockwise from point C
along path p(T) back to point A, no phase boundary is observed even though we now consider the
water to have returned to the gaseous state. Additionally, if the pressure is isothermally reduced at any
point after point C, it is impossible to return to a liquid-gas equilibrium.
When the path p(l) is chosen to be very close to the critical point, the water appears opaque. At
near-critical conditions, densities and refractive indices of the liquid and gas phases are nearly
identical. Furthermore, molecular fluctuations cause spatial variations of densities and refractive
indices on a scale large enough to strongly scatter visible light. This is called critical opalescence.
016.3 The fundamental equation of chemical thermodynamics (eqn. 16.5) is a general expression that
describes how the Gibbs energy changes with conditions (i.e., with pressure, temperature, and
composition). Although eqn. 16.5 is general with respect to the behavior of the Gibbs function, the
Gibbs function is only an indicator of spontaneous change under conditions of constant temperature
and pressure. Under those conditions, the behavior of the Gibbs function is given by eqn. 16.6. At
constant temperature and pressure, a system' s Gibbs function decreases when the system undergoes
spontaneous change, and it remains constant when the system is at equilibrium.
016.5 The Clapeyron equation (eqn. 16.12) is exact and applies rigorously to all first-order phase
transitions. It shows how pressure and temperature vary with respect to each other (temperature or
pressure) along the phase boundary line, and in that sense, it defines the phase boundary line.
The Clausius-Clapeyron equation (eqn. 16.14) serves the same purpose, but it is not exact; its
derivation involves approximations, in particular the assumptions that the perfect gas Jaw holds and
that the volume of condensed phases can be neglected in comparison to the volume of the gaseous
phase. It applies only to phase transitions between the gaseous state and condensed phases.
Eqn. 16.13 is an exact corollary of the Clapeyron equation for a first-order phase transition, for it
substitutes t:..1, 5H/T for l:..1r5S, quantities that are equal when two phases are at equilibrium. Enthalpy
of transition and temperature are quantities easily measured in the laboratory.
016.7 Mathematically, the reason is clear. The dependence of chemical potential on pressure, expressed in
eqn. 16.10, follows from the chemical potential's status as a molar Gibbs energy and from the
dependence of the Gibbs energy on conditions as expressed in the fundamental equation of
chemical thermodynamics (eqn. 16.5).
The question implies that the dependence of chemical potential on pressure is not intuitive for an
incompressible phase. Perhaps the dependence is more comprehensible for a compressible phase,
because increasing pressure does work on a compressible phase. In that case, one can imagine a
compressible phase (a vapor, for example) in equilibrium with an incompressible phase (say, a
liquid) in a closed container. As the pressure increases, the chemical potential of the vapor
increases, yet the chemical potentials of the two phases in equilibrium remain equal; therefore, the
chemical potential of the liquid must also increase with pressure.
016.9 A regular solution has excess entropy of zero but an excess enthalpy that is non-zero and dependent
on composition, perhaps in the manner of eqn. 16.32. We can think of a regular solution as one in
which the different molecules of the solution are distributed randomly, as in an ideal solution, but
have different energies of interaction with each other. The parameter q is a measure of the
difference between A-B interactions and A-A interactions. If q < 0, A-B interactions are
energetically more favorable than A-A interactions; in that case, mixing is exothermic and even
more spontaneous in all proportions than for an ideal solution. If, on the other hand, q > 0, A-B
interactions are energetically less favorable than A-A interactions. In this case, mixing is
endothermic. If qis not too large, mixing can still be spontaneous in all proportions. If qis larger,
mixing is only spontaneous when one component dominates the composition. (See eqn. 16.33.)
016.11 Phase: a state of matter that is uniform throughout, not only in chemical composition but also in
physical state.
Constituent: any chemical species present in the system.
Component: a chemically independent constituent of the system. It is best understood in relation to
the phrase "number of components," which is the minimum number of independent species
necessary to define the composition of all the phases present in the system.
Degree of freedom (or variance): the number of intensive variables that can be changed without
disturbing the number of phases in equilibrium.
E16.1 (a) See Figure 16.2.
JI] t1=1 F-Tl

140
130
Solid ~ : S~lid AB i l i Li~uid A ~nd B
.Li uid A and B Li uid A and B ········f .. ·····+ Solid B
f:l~il'
120
~
11 0 ' ' ' ! I
100
90
x(B 2H6) Figure 16.2

PHYSICAL EQUILIBRIA 387
E16.2(a) Refer to Fig. 16.50 of the text. At the lowest temperature shown on the phase diagram, there are two
liquid phases, a water-rich phase (x8 = 0.07) and a methylpropanol-rich phase (x8 = 0.88); the latter
phase is about 10 times as abundant as the former (lever rule). On heating, the compositions of the
two phases change, the water-rich phase increasing significantly in methylpropanol and
the methylpropanol-rich phase more gradually increasing in water. (Note how the composition of
the left side of the diagram changes more with temperature than does the composition of the right.)
The relative proportions of the phases continue to be given by the lever rule. Just before the isopleth
intersects the phase boundary, the methylpropanol-rich phase (x8 = 0.8) is in equilibrium with a
vanishingly small water-rich phase (x 8 = 0.28). Then the phases merge, and the single-phase region
is encountered with x 8 = 0.8.
E16.3(a) At equilibrium, the chemical potential of a substance is the same throughout a sample, regardless of
how many phases are present [Section 16.3(b)] . Thus
/µw(s)=µwO)/ and /µE(s)=µE(l)/
E16.4(a) The Gibbs-Duhem equation relates changes in the chemical potential of a mixture's components to
the composition:
For a small macroscopic change,
n
<JµE = _ _:!!._<JµW 0.60
= ---X0.25 I
J mor' =-0.38 J mor' I
nE 0.40
E16.S(a) The temperature dependence of the chemical potential is given by
(~~)p =-Sm [16.9]
For a small macroscopic change,

'5µ=-Sm8I'= (-69.91 J moi- 1 K- 1) x (5 K) =l-3x10 2 J mo1- 1I
E16.6(a) The pressure dependence of the chemical potential is given by
(aµdp ) T
= vm[16.10]
So
r'oo kbar ( aµ) r'oo kbar
11µ = J1.o bar dp T dp = J1.o bar Vmdp = Vm/1p
3
· gx cm x(~) x99kbarx
3
18 0 103 5
= xl0 Pa=IL79xl05 Jmo1-'I.
mol 0.997 g 100 cm 1 kbar
E16. 7(a) The Clausius-Clapeyron equation gives the variation of vapor pressure with temperature if the vapor
is a perfect gas.
11 H
d ln p = 11vapH [16.14]
dT RT 2
SO
fdln p = f~dT
RT 2
Assume that 11varfl is independent of temperature.

1 1
__!_ =_!_ _ _R_ln p 2 = 1 + 8.3145 J K - moi- xln(80.0 )
3
T2 T; 11vapH p 1 297.25K 28.7xl0 Jmor' 53.3
3 1
=3.247xl0- K - ,
1
Tz 3.247xl0-3 K - 1 = 308.0K = !39°cl
E16.8(a) The Clapeyron equation relates the pressure and temperature of phase boundaries to state functions:
11
dp = ""S [16.12]
dT 11,lll V
SO
dp) !lp
/),fusS = 11fus V X ( dT "" 11fusV X 11T
where the approximation holds if 11rusS and 11ru, V are independent of temperature.
5
11ru,S = [(163 .3-161.0)x(lo-2 m)J mol- ']x((l00-1) atmx(l.013xl0 Pa atm- '))
(35 l.26-350.75)K
1
= 1+45JK- ' moi- 1.
11ru,H = I'r11rusS = (350.75K)x(45JK- ' mor')

4 1
= I+ 1.59x10 J mo1- ' I= l+l5.9kJ mo1- I.
E16.9(a) The Clausius-Clapeyron equation gives the variation of vapor pressure with temperature if the vapor
is a perfect gas.
dlnp _ 11 vapH [16.14]

dT- RT2
11 H 11vapH
= f~dT
so
fdln
p RT 2
and In p = constant - - -
RT
1
Therefore, 11varf/ = (1501.8 K) x R = (1501.8 K) x (8 .3145 J mor' K- )
11v.rf/ = ~ 12487 1 mor'I = ~ 12.487 kJ mo1- 'I
E16.1 O(a) Use eqn. 16.13(a) and assume that 11ru,H and 11ru, Vare independent of temperature:
dp 11ru,H !lp
-=--""-
dT Trl1ru,V 11T
Thus
7:11
11T ""~x!lp
v
11ru, H
Because the change in molar volume upon fusion (melting) is
11ru, V = (78.11 g mol- 1) x ( 0.879 ~ cm _ l) x(lO:cmJ
= l.20xl0-6 m3 mor'
the change in melting temperature is

6 3 1 5
l1T"" (278.65 K)x(l.20xl0- m mol- ) x(lO.Oxl0 3 -l) barx 10 Pa
10.59xl03 J mor' bar
= 31.5 K.
Therefore, at 10.0 kbar, Tr = (5.5 + 31.S)°C = l37°CI

E16.11 (a) Assume perfect gas behavior.
mRT pVM
pV=nRT=-- so m=--
M RT
where V = 4.0 m x 4.0 m x 3.0 m = 48 m3
3 3
m = (3.2x10 Pa)x(48 m )x(18.02 gmol- ) = jl.lxlOJ I=~
1
(a) 1 1
(8.3145 J K- mol- )x(298.15K) g g
3 3
m = (13.lxl0 Pa)x(48 m )x(78.l l gmoi- ) = j2 .0xl04 I=~
1
(b) 1 1
(8.3145 J K- moi- )x(298.15K) g g
E16.12(a) (a) According to Trouton's rule (Section 15.3b),
!lvapH = (85JK-1 moi- 1)xTb = (85JK- 1mol- 1)x(76.8+273.15) K
= J2.97 x10 4 Jmo1- 1 I=129.7 kJ mo1- 1I
(b) The Clausius-Clapeyron equation [16.14] integrates to
P2 =
ln- /lvapH
--(- 1 --
1 J [Exercise 16.7(a)]
P1 R I; Ti
Let T1 be the normal boiling temperature, 350.0 K; then p 1 = 1 bar. Thus at 25°C,
ln 12 = 2.97x10
- 3 Jmol - I x 1 J(__l_ =-1.7?6 J
bar ( 8.3145 J K- 1 moi- 1 350.0 K 298 K
so P2 = k}.169 ba!i
At 7ooc lnll=( 2.97x103 Jmol-1 Jx( 1 __ l_J=-0.203

' bar 8.3145 J K- 1 mol- 1 350.0 K 343 K
so P2 = k).82 ba!i
E16.13(a) !lT"'
T,!1
r ruH
v
, x!lp [Exercise 16.lO(a)],
!lfus
_3 Jx(~J
3
1 1 1
where .:1ru,V=(18.02gmor )x( _ -
1.00 g cm 3 0.92 g cm 100 cm
=-1.57x10--{j m3 moi- 1
3 1 5
so llT"' (273.15 K)x(-1.57 xlO--{j m moi- ) x( 50- l) barx 10 Pa = _ 0 _35 K
6008 J mol- 1 bar
Therefore, at 50 bar, Tr= b().35°Q = (273.15 - 0.35) K = ~72.80 KJ.
E16.14(a)
The mole fractions are equal, so xA = x 8 = 0.50. Because the gases are perfect, p V = nRT. Therefore,
!lmixG = (pV)x(0.50ln0.50+0.50ln0.50) = pVln0.50
= (1.5 bar)x -
( bar
J - -
Pa xlO.Ox(lO 1m) 3x(ln0.50) = -1.04x10 3 J = I-1.04 kJ I
105 -
-l.04xl03 J
L'lmixS=-nR(xAlnxA +x 8 lnx8 ) [16.20]= -L'lmixG =
298K
= 1+3.5 J K- 1I
E16.15(a) llmixG = nRT(xA In xA + x 8 In x 8 +Xe In Xe) [16.18 with three components]

We need to determine mole fractions from the given mass percentages. Assume a 100-g sample:
76g =2.7lmol 23 g = 0.72 mo!

nN = 28.02 g moi-· no = 32.00 g moi-·
1g =0.03 mo! and n10ra1 = 3.46 mo!

nAr = 39.95 g mol-1
Thus XN = nN I n10,31 = 2.71 I 3.46 = 0.78; similarly x 0 = 0.21 and XAr = 0.007, and for 1 mole of air at
298 K,
L'lmixG = (8.3145 J mor 1 K- 1) x (298 K)
x (0.78 In 0.78 + 0.21 ln 0.21 + 0.007 In 0.007)

3 1 1
L'lmixG=tl.37xl0 J mor i=t1.37 kJ mor i
A . s = -L'lmixG [E
Limix ~
. 16 . 14(a )] =
xerc1se '°'"o v J mol-1 = 1+4 . 6 J K-1 mo r' I
-l.37 x103
For a perfect gas, 14mixH = tj [no intermolecular interactions before or after mixing].
E16.16(a) Hexane and heptane form nearly ideal solutions, therefore eqn. 16.20 applies.
llmixS = -nR(xA In XA + Xs In Xs)

(a) To maximize L'lmixS, differentiate the equation with respect to xA and look for the value of xA
which makes the derivative vanish. Since x 8 = l - XA, we need to differentiate
llmixS = -nR {xA In XA + (1 - XA) ln (1 -xA)}

This yields
dllmi,S =-nR{lnxA + xA -ln(l-xA)_ (1-xA)}= -nRln~

dxA XA (l-xA) 1-xA
which is zero when x A = rn = X9. Hence, the maximum entropy of mixing occurs for the preparation
of a mixture that contains equal mole fractions of the two components.

(b) An equimolar mixture still maximizes the entropy of mixing; we only have to express the
concentrations by mass fraction rather than mole fraction:
mA = mB _ mtotal - mA
nA=ns so
MA MB MB
Solve for mA in terms of mtota1:
mA = mtotai( MA:AMJ
But mA I m10,.1is just the mass fraction of A (hexane, say). So the mass fractions are
1
mhex = 86.17 gmol- =I0.4 624 1 and mhep =l - 0.4624=10.53761
m, 01• 1 (86.17+100.20) g mo!- 1 mtotal
E16.17(a) Check whether PHci I XHcI is constant; if so, that is the Henry's law constant [16.26a].
XHCI 0.005 0.012 0.019

(pHc1 I kPa) I xHcl 6.4 x 103 6.4 x 103 6.4 x 103
Hence, Ka= ~.4x10 3 kP~.
E16.1 B(a) The vapor pressures of components A and B may be expressed in terms of their compositions in the
liquid (mole fractions xA and x 8 ) or in the vapor (mole fractions YA and y 8 ). The pressures are the
same whatever the expression; hence the expressions can be set equal to each other and solved for
the composition.
PA= YAP= 0.350p =XNJA* =xA x (76.7 kPa)
Pa = YaP = (1 - YA)P = 0.650p = xapa • = (1 - xA) x (52.0 kPa)
Therefore , YAP= xApA'

YsP XsPs
.
0.350 76.7XA
Hence - - = --~~
0.650 52.0(1-XA)
which solves to xA = R.2681 and x8 = 1 -xA = R.7321.

Also, since 0.350p = XNJ A*,
= xApA' = (0.268)x(76.7kPa)= .6 kPal

158
p 0.350 0.350
E16.19(a) In Exercise 16.17(a), the Henry's law constant, K8 , was determined for concentrations expressed in
mole fractions. To use that value, Ks = 6.4 x 103 kPa, we must express the molality given here as a
mole fraction. For convenience, assume a sample with 1 kg solvent (GeCl4 ). Thus
IOOOg
n(GeC1 4 ) = = 4.663 mol and n(HCI) = 0.15 mol
214.44 g mol- 1
0.15 mol
Therefore, xttci = = 0.031
0.15mol +4.663mol
PHCI = (0.031) X (6.4 X 103 kPa)=12.0 X 102 kP~
E16.20(a) We assume that the solvent, benzene (A), is ideal and obeys Raoult's law; then
nApA
.
Hence p A = ; which solves to
nA +ns
n = nA(pA' - PA)
B PA
Then, since n8 = ' ;8 , where m 8 is the mass of B (solute) present,

B
mBMApA
mA (pA' - PA)
From the data,
1
M
8
= (19.0g)x(78.ll gmor )x(51.5 kPa) =1 85 ri/
(500g)x(53.3-51.5)kPa g mo
E16.21 (a) With concentrations expressed in molality, Henry' s law is p 8 = baf(.8 [16.26b].
Solving for b, the solubility, we have b8 = .!2_ _

Ka
(a) b 0.10 atm x 101kPa=1 3 .4xl0_3 mol kg-' I

3.0lxl0 3 kPa kg mor' 1 atm
(b) b 1.00 atm x 101kPa=1 3 .4xl0_2 mol kg-' I

3.0lxl0 3 kPa kg mol- 1 1 atm
E16.22(a) The best value of the molar mass is obtained from values of the data extrapolated to zero
concentration, since it is under this condition that the van't Hoff equation applies.
n RT rn RT RT
II= [B]RT = - 8- [16.28] so II= - 8 - = _c_ where c = rn
v MBV MB v
At the same time, the osmotic pressure is the hydrostatic pressure:
II=pgh , so h= pgMa (__BI_)c

4.0
3.0
E
~ 2.0
..:;:
1.0
0
0 4 8 12
ca/ gdm-3 Figure 16.3
Thus, a plot of h against c should be a straight line with slope __BI_. Figure 16.3 shows the plot.
pgMB
The slope of the best-fit line is
2
RT 0.2854 cm 0.2854x(I0- m) = 2.854x10-3 m 4 kg -'
pgMs gdm-3 (10-3 kg)x(lO I m ) 3
Therefore,
RT
Ma= (pg)xslope
1
- (8.3145 J K- mor')x(298 .15K) = 188.2 kg mo1- 1 I
E16.23(a) (a) The number-average molar mass is
( ~)M +(!!'l_)M
Mo= N,M;,, ::,,M,= M(~)+(~) ' (i):f~)
Assume 100 g (a convenient sample size for mass percent information).
-
Mn=(
100 g I
=18kgmol
-I I
30 g 70 g
30 kg mol- 1 J+(15 kg mor' J
(b) The weight-average molar mass is
M w = m1M 1 + m2M 2 = (30)x(30) + (70)x(l5) kg mol-1 =1 20 kg mol-1 j

m1 +m 2 100
20
(c) The heterogeneity index is M w = =[OJ .
Mn 18
E16.24(a) The excess enthalpy in a regular solution is

J-f =n$.TxAXB =n$.TxA(l -xA)
The maximum value occurs at the composition where xA(l - xA) is at a maximum. That maximum
occurs at xA = xs =\.Now we can find q-.
1
q = H!ax I n = 700 J mol- = (O]
RTxAxB 1 1
(8.3145 J K- mol- )(298 K)(0.500) 2 •
Phase separation occurs if q> 2, so ~o phase separatio~ occurs at this temperature.
E16.25(a) For A (Raoult's law basis; concentration in mole fraction),
2 50 Torr
QA = p:p [l 6·35J= 300Torr
A
=&&Th
rno::;-::;i
For B (Henry's law basis; concentration in mole fraction),
Qa = i: [16.42) = ~~01;0: = lo.1251

For B (Henry's law basis; concentration in molality), we use an equation analogous to 16.42 but
with a modified Henry's law constant K~:
Q = --1!.L_ with PB = bs K 8' analogous to PB = xsKs

B K' bf}
B
K~ and Ks are related by equating the two expressions for ps:
PB= bsK~ =xsKs so K~ = x 8 K 8 = O.lx200 Torr= 9 .0 Torr kg mol-1

b8 2.22 mol kg- 1
Ya= bs ~abB = 2~2~ = 11.251

Then Qs = 25Torr =12.sl
9.0Torr
COMMENT. The two methods for the "solute" B give different values for the activities. This is reasonable
since the reference states are different and therefore the chemical potentials in the reference states are
also different.
Question. What are the activity and activity coefficient of B in the ideal solution (Raoult's law)
basis?
E16.26(a) Activities and activity coefficients on the ideal-solution (Raoult's law) basis are defined by
and
So we need partial pressures. Dalton's law relates the vapor-phase mole fractions to partial
pressures.
- PA PA
YA - lQl.3kPa=0.516
PA +pM
So PA= 0.516 x 101.3 kPa = 52.3 kPa and PM= (101.3 - 52.3) kPa = 49.0 kPa
PM
P:
a A =PA = 52.3kPa
lOSkPa = lo.4981 a = -.--
M PM
49.0kPa = lo.6671
73.5kPa
r A=GA = 0.498 GM 0.667 r;-;-;l

XA 0.400 = \1.241 rM= XM = 0.600 = t.Ll!J.
E16.27(a) The excess enthalpy in a regular solution is
J-t- = n;RTxAXB = n;RTxA(l - XA)

1
The maximum excess enthalpy occurs at x A = x 8 = /
2
[Exercise 16.24(a)].
H!ax / n 800 J mol-

1
=
~ = RTxAxB 1 1 2 1 31
(8 .3145 J K - mol- )(293 K)(0.500) ·
The Margules equations [16.45] give the natural logarithms of activity coefficients:
lnyA= ;x~ and lny8 = ;x~

2
Because XA =Xe, In r A =In }B = 1.31 x (0.500) = 0.328 and YA= }B = 1.39.
Finally, a A = xArA = 0.500 x 1.39 =~=as.
E16.28(a) l=~L(b) be- )z;2 [16.57]

I
For a salt of formula MpXq , bM = pb and bx = qb ,
so l=~(pz~ +qz~ ) (b: )

/(KC!)= _!_(lxl + lxl)(bKCI) = bKCI
2 be- be-
J(CuSO 4 ) = _!_(lx22 + l x 22) ( bcuso,) = 4 ( bcuso,)

2 be- be-
! =/(KC!)+ J(CuS04) = ~K;I +4 ( b~~o,) = 0.15+4 x 0.35 = lusl

E16.29(a) The ionic strength of the original solution is J(KN0 3) = 0.250 [ b I be- for a singly-charged salt] . So
the added salt must contribute an additional ionic strength of 0.200.
(a) /(Ca(NOJJ = -21 (2 2 +2 x l 2) : =3 : = 0.200

b b
0 200
so b= · be- = 0.0667molkg- 1
3
1
and m(Ca(N0 3) 2) = 0.0667 mo! kg- 1 x 0.800 kg x 261.32gmoi- =18 .75 gj
(b) An additional 0.200 mo! NaCl must be added per kilogram of solvent, so
m(NaCI) = 0.200 mol kg- 1 x 0.800 kg x 58.44 g moi- 1 =[ill
E16.30(a) The solution is dilute, so use the Debye-Hi.ickel limiting law.
log Y± = -iz+Z-1AI1 [16.56]

12
I=~ ~ z; (:~ ) = ~ {(2 2 x 0.0050) + (l x 0.0050 x 2)+ (l x 0.0040) + (lx0.0040)}

= lo.01901
CaCl 2 : log Y± =-2 x 1 x 0.509 x (0.0190) 112 =-0.140 so Y± =[llJ
log Y± =-1 x 1 x 0.509 x (0.0190) =-0.070 so Y± = ~

112
NaF:
E16.31 (a) The extended Debye-Hiickel law (eqn. 16.59), with the parameter C set equal to zero, is
lo - A Iz+z- I1"2
gy± -- l+B/" 2
Solve for B.
B ( 1 A I Z+Z- ') ( 1 0.509)

=- fl/2+ logy± =- (bfb-&) 112 +logy±

b I (mol kg- 1) 5.0 x 10-3 10.0 x 10-3 20.0 x 10- 3
Y+ 0.930 0.907 0.879
B 2.01 2.01 2.02
The values of B are constant, illustrating that the extended law fits these activity coefficients with B = [Ql].
P16.1 The data are plotted in Figure 16.4. From the graph, the vapor in equilibrium with a liquid of
composition (a) xM = 0.25 is determined from the tie line labeled a in the figure extending from xM =
0.25 to ~M = 0.3~, (b) x 0 = 0.25 is determined from the tie line labeled b in the figure extending
from xM = 0.75 to kM = 0.811.
126
124
122 ---- - -- -- --: vapor - --.-- -- -- -- -- -
120 __ ,JI (ll)~t_l)yl_~nzi;ne) _____ _
u
!!.. 118
CI>
116
114 ---- -- --- -'. Liquid-- -- -- -:-
112 - _________ ; x_(me_thy_lben~ene~ _
110 +----~---~---__,_ _ ____,

0 0.25 0.5 0.75
Mole fraction of methylbenzene Figure 16.4
P16.3 The phase diagram is shown in Figure 16.5. Point symbols are plotted at the given data points. The
lines are schematic at best.
llOO ~-----------------
1050
1000
950
u
~ 900
850
800
750
700 1 - - - - - - + - - - - ' - - - - - -- - ----<

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
x(ZrF4) Figure 16.5
At 860°C, a solid solution with x(ZrF4 ) = 0.27 appears. The solid solution continues to form, and its
ZrF4 content increases until it reaches x(ZrF4) = 0.40 at 830°C. At that temperature and below, the
entire sample is solid.
P16.5 The phase diagram is drawn in Figure 16.6.

95 -r - - - - - - -, - - - c -
: I
1
- - -. - - - ,- - - -. - - - ' - - - - - - - ,- -
i ! I
1
: 1
-1
___ ~ ___ L___:____ :_ __ 1___ :___ ~ ___ ~ ___ ~ __ _
: : : ; : : : : :
93 -+- --:- --t- --;- --~ --~- --~ ---:- ---:- --~ ---
: : : Li'quid1 : : : •
---~--,---~---~---~--,---~---~--~---
: I
1
~ I : :
91 -k- - - ~ - - -:- - ,_ - - ~- - -~ - - - - - - "' - - - ~ - - -:- - -
--r-----
:
:
1
:
: ; : : : : :
--,· ----~---+ --
1Twolhas~
- -L
:
- - , -- - - - , - - -- ... - - -
, • :
89 --l-- :_ -~---~~!~--~---.!.-- ~---:---~---
' : : : I : I '
~ --~---.!.---~---~---!---.!. --~---1 __ _
I I I I I I
I I
87 ---t---;- --~ --~ --- ~ ---:- -
\ I I '
\ I I I 1 I
I I ,
: l :solid CH4, and CF.
:_-_-r--r_-~t--1---t-~+--+v---
_ _ _1_ , , '
85
83 -+--'
I ' II '' y--L---'
I ' ,- - - •' - - ' ''
. I : : : - : E
'
0 x(CF.) Figure 16.6
P16.7 (a) The Clapeyron equation [16.12] is
dp = ~vap S _ ~ vap H
dT ---
~ vapV Tb~ vapV
= 22.0xl0 3J mo1- 1 3 1
(380K)x(l3.5x10 3 _ l.20xl0-4)m3 mol-1 1+4.33xl0 Pa K- I
(b) The Clausius-Clapeyron equation is
dlnp = ~vapH [16.14]

dT RT 2 '
3 1
dp = P~vap H X= (10 Pa)x(22.0x10 Jmol- ) = +1.& xl03 PaK-1
5
so 3
dT RT 2 (8.3145 J K- 1 mol- 1)x(380K) 2
The percentage error is J().7 percenij.
P16.9 The Clausius-Clapeyron equation,
dlnp _ ~vapH [16.14]

dT- RT2
yields upon indefinite integration
~ vap H
In p = constant - - -
RT
Therefore, plot Jn p against l!T and identify -~vapH IR as the slope of the best-fit line. Construct the
following table.
TIK 250 270 280 290 300 310 330

IOOOK/T 4.00 3.70 3.57 3.45 3.33 3.23 3.03
lo I kPa 0.036 0.514 1.662 4.9 18 13.43 34.1 182.9
In (p I kPa) - 3.32 -0.666 0.508 1.593 2.597 3.529 5.209
6
5
4
3
"-:r.i 2
l
""
.5 0
-I
-2
In (p!kPa) =-8800 KIT+ 31.9
-3
-4
3 3.2 3.4 3.6 3.8 4
1000 KIT Figure 16.7
(a) The points are plotted in Figure 16.7. The slope is -8800 K, so
/:;.varf! =-8.3145 J mor' K- 1 x (-8800 K) = ~7.32 x 104 J mor1j = ~73.2 kJ mo1- 1 J
(b) The normal boiling point occurs at p = 1 bar= 100 kPa. Solving the equation of the best-fit line
for Tyields
T= 8800 K = 8800 K = 1322 Kl

31.9-ln(p / kPa) 31.9-ln(IOO)
P16.11 Refer to Example 16.3, using eqn. 16.29 with [J] =cl Mand fl= pgh:
JI= RT(l+~c+· ··) = RT+ RTE c+ ...

c M M M M2
where c is the mass concentration of the polymer. Therefore, plot II I c against c. They-intercept is
RT IM and the slope is RTE I M 2 . The transformed data to plot are given in the following table.
c I (mg cm-3) 1.33 2.10 4.52 7.18 9.87

fl/ Pa 30 51 132 246 390
(fl/ c) I (Pa mg- 1 22.6 24.3 29.2 34.3 39.5
= l.98x + 20.1
Y ·--
40.0 ·------
38.0
36.0
~ 34.0
'5 32.0
~ 30.0
:::. 28.0
~
!; 26.0
24.0
22.0
20.0
0 2 4 6 8 10
c/(mg cm-3) Figure 16.8
The plot is shown in Figure 16.8. They-intercept is 20.1 Pa mg- 1 cm 3. The slope is 1.98 Pa mg- 2
cm6 • Therefore,
=8.3145JK-I mol- x303Kxl0- gx(~)

1 3 3
M= RT
20.l Pamg- 1 cm 3 20.1 Pamg- 1 cm 3 1 mg 10-2 m
= li.2sxl0 5 gmo1 -
1
I
M2
B=-xl.98
RT
Pa mg-
2 6
cm = (
RT
M) xl.98 Pa mg- 2
cm
6
M
5 1
_ l.25xl0 g mol- xl.98 Pa mg-2 cm 6
- 20.1 Pa mg- 1 cm3
3
1 10 1
= l.23xl0 4 gmol- 1 mg- 1 cm 3 x :g x( - dmJ = li.23xl0 4 dm 3 moi- 1 I
10 g I cm
P16.13 The partial pressure of a solvent is related to its activity by

PA= apJJ/ [16.35] = YAXNJA• [16.37]
so rA =~= YAP
XAPA. XAPA.
(Note: Here x and y are mole fractions. In the table in the statement of the problem, x and y are mole
percentages.)
Sample calculation at 80 K:
y(O 80K) = 0.1 lxlOOkPa x 760Torr = l 079

2
' 0.34x225Torr 101.325kPa ·
Summary:
T/K 77.3 78 80 82 84 86 88 90.2

r(02) - 0.877 1.079 1.039 0.995 0.993 0.990 0.987
To within the experimental uncertainties, the solution appears to be ideal (y"'" 1). The low value at
78 K may be caused by non-ideality; however, the larger relative uncertainty in y(0 2 ) is probably
the origin of the low value. A temperature-composition diagram is shown in Figure 16.9(a). The
near ideality of this solution is, however, best shown in the pressure-composition diagram of
Figure 16.9(b). There the liquid line is essentially straight, as predicted for an ideal solution.
92
"" ~.... •••••·•·••r.•••i••~:t,~

{.. r ! _;1>~} E
i i Liquid : ' i
~
..... 84
300 L--·······jr:r·········-;--······ : Vapor !
~-2l.. ~--! ········i············i············t··········

76 JOO
0 20 40 60 80 JOO 0 20 40 60 80 JOO
x(Oi) or y(Oi) x(0 2) or y(02)
(a) (b) Figure 16.9

P16.15 (a) On a Raoult's law basis, the following relations apply to both components:
p 1 = a1p/ [16.35] = '}5X1p/ [16.37] so Yi = __f!J__

XiPi.
The vapor pressures of the pure components are given in the table of data. p 1• is the value of p 1 at
x1 = 1: p/ = 47.12 kPa and PA*= 37.38 kPa.
(b) On a Henry's law basis, the following relations apply to the solute (in this problem,
iodoethane):
_Pa [16.42) so Pa
QB - KB Ya= XaKa
(The solvent activity remains based on Raoult's law, so YA would remain as in part a.) Henry's law
constants are determined by plotting the data and extrapolating the low concentration data (i.e., the
best straight line in the neighborhood of x 8 = 0) all the way across the plot to x8 = 1. The data are
plotted in Figure 16.10, which also displays p/, PA*, Ki. and KA . K 1 = 64.4 kPa.
70
50
20
10
0
0 0.2 0.4 0.6 0.8
Figure 16.10
x, p 1/kPa PAlkPa ]f(Raoult) YA(Raoult) !f(Henry)
0 0 37.38t - l 1
0.0579 3.73 35.48 1.367 1.008 1.000
0.1095 7.03 33.64 1.362 1.011 0.997
0.1918 11.7 30.85 1.295 1.021 0.947
0.2353 14.05 29.44 l.267 1.030 0.927
0.3718 20.72 25.04 1.183 1.066 0.865
0.5478 28.44 19.23 1.102 l.138 0.806
0.6349 31.88 16.39 1.066 1.201 0.779
0.8253 39.58 8.88 1.018 1.360 0.744
0.9093 43.00 5.09 1.004 1.501 0.734
1.0000 47.12:j: 0 1 - 0.731
tValueofpA* :j:Value of p 1*
Question. In this problem both I and A were treated as solvents, but only I was treated as a solute.
Extend the table by including a column for YA(Henry).
P16.17 (a) The volume of an ideal mixture is
so the volume of a real mixture is
V= Videal + v£
We have an expression for excess molar volume in terms of mole fractions. To compute partial
molar volumes, we need an expression for the actual excess volume as a function of moles.
V E -(
- n1 +n2 )VE
m
=_!Yi_ ( ao a (n -n
+~~-~
1 1 2 )J
n, +n2 n1+n2
so V -- nl Vm I + n2 Vm 2 +n,n2
- - ( Go+~~-~
a1(n1 -n2)J
, , n1+n2 n1+n2
The partial molar volume of propionic acid is
The partial molar volume of oxane is
Iv2 = vm,2 + QoX12 +al (xi - 3x2 )x~ I

(b) We need the molar volumes of the pure liquids
V = M1 74.08 g mor1 = 76.23 cm3 mol-1

m,I P1 0.97174 g cm-3
and 86.13 g mol-1 = 99.69 cm3 mol-1

vm.2 0.86398 g cm 3
In an equimolar mixture, the partial molar volume of propionic acid is
v; = 76.23+(-2.4697)x(0.5) 2
+(0.0608)x{3(0.5)-0.5}x(0.5) 2 cm 3 mo1- 1
= 175.63 cm mo1-
3 1I.
and the partial molar volume of oxane is
V2 = 99.69 + (-2.4697)x(0.5) 2 + (0.0608)x {0.5-3(0.5)}x(0.5) cm3 mo1- 1

2
= 199.06 cm 3 mo1- 1I
P16.19 According to the Debye-Htickel limiting law,
b )1/2
log Y± = -0.509 I z+z- I1112 [16.56] = -0.509 ( b~
We draw up the following table:

b I (mmol kg- 1) 1.0 2.0 5.0 10.0 20.0
1"2 0.032 0.045 0.071 0.100 0.141
Y±(calc) 0.964 0.949 0.920 0.889 0.847
/'±(exp) 0.9649 0.9519 0.9275 0.9024 0.8712
log Y±(calc) -0.0161 -0.0228 -0.0360 -0.0509 -0.0720
log /'±( calc) -0.0155 -0.0214 -0.0327 -0.0446 -0.0599
The points are plotted against Iw in Figure 16.11. Note that the limiting slopes of the calculated and
experimental curves coincide. We use the extended Debye-Htickel law (eqn. 16.59) with C = 0. A
sufficiently good value of B in the extended law may be obtained by assuming that the constant A in the
extended law is the same as A in the limiting law. Using the data at 20.0 mmol kg- 1 we can solve for B.
0 l ...... , ..... , ...... ,. ., .... ·: ..... , ...... , .....
:··".··:- ..... : ..... ;....
--0.02 ;.... ;.....

...... .:····
~
Oil ......:...... ; ..
..2
~
·E~p;;iim~~i .. .,
--0.06 ~- .... 0.04

0.08 0.12 0.16
11 12 Figure 16.11
B=--A___l_=- 0.509 _l_=l. 40S

logy± 1" 2 (-0.0599) 0.141
Thus,
0.509/1 12
logy± =
l+l.405!' 12
To determine whether or not the fit is improved, we use the data at 10.0 mmol kg- 1
lo = -(0.509) x (0.100) = _ .0446

0
gy± (1) + (1.405) x (0.100)
which fits the data almost exactly. The fits to the other data points will also be almost exact.
P16.21 Consider two phases a and /3, in mechanical contact with each other, constituting an isolated
system. Making the system isolated allows us to confine ourselves to interactions between the
phases and to neglect any surroundings external to those phases. The general condition of
equilibrium in an isolated system is dS = 0. Hence,
(a) dS=dSa +dSp=O
Energy may be transferred between phases and the volumes of the phases may also change;
however, Ua +UP = constant and Va +VP = constant. Hence,
(b) dUp =-dUa
(c) dVp= -dVa
For each phase, eqn. 15.54 applies:
so
Using this result for both phases as well as conditions (b) and (c), condition (a) becomes
[l ll
dS= - - - dU + [ -Pa - -Pp ) dV =0
Ta Tp a Ta Tp a
The only way in which this expression may, in general, equal zero is for
and
Therefore, /Ta = Tp and Pa = Pp/·
P16.23 The barometric formula gives the variation of pressure with height:
p(h) = p 0e -.MghlRT [Problem 13.20]
In Exercise 16.7(a), we obtained from the Clausius-Clapeyron equation

so, letting T1 be the normal boiling point Tb, so p 1 = 1 bar, we have an expression for the variation of
vapor pressure with temperature:
/),.vapH ( 1 _ _!_)
p(T) =p 1e-z, where X =-R- T Tb
In this expression, let Th be the boiling temperature at altitude h. Boiling occurs when the vapor
pressure is equal to the ambient pressure, that is, when p(h) = p(Th). Setting the two expressions
equal to each other, with p 0 =p 1 = 1 bar, implies that
e-Mgh/Rr =exp[- !:!.;H x[~ -~)}
It follows that _!_ = _!_ + Mgh where T is the ambient temperature and M the molar mass of the
J;, J;, T ,1 vap H
1
air. For water at 3000 m, using M = 29 g mor ,
1 1 29xl0-3 kgmor 1 x9.81ms-2 x3.000xl0 3 m

~=--+---~---------~
3 1
I;, 373 K 293Kx40.7xl0 Jmor
=-1 · ·+ 1.-4-0x_l_0-4K-
373K 1 = 2.75xl0- 3
K-1
Hence, Th = ~63 K (90°C) I.
P16.25 The question asks us to express derivatives 0f the chemical potential in statistical thermodynamic
terms, so we start with the chemical potential itself, which is the partial molar Gibbs function .
G = G(O)-nRTinJ_ [15.40]
N
so µ =(aG) =aG(O) -RTinJ_-nRT~(1nJ....)

an p ,T an N an N
How does q IN depend on n (at constant p and T)? N = nNA. q depends on molecular parameters and
temperature and (in the translational partition function) volume. Recall that
T V
q = A 3 [13.18b]
q qTlqVqE VqRqVqE kTqRqVqE

so
N = N = NA = 3 pA 3
where we used the perfect gas law in the form p V = NkT in the last step. Thus, for a perfect gas, the
partial derivative of In q IN with respect to n at constant p and T vanishes, and
-(aG) =aG(O) -RTinJ_

µ- an p ,T
an N
(a) We are to show that eqn. 16.9,
oµ) = -S
( OT p,n m
is consistent with eqns. 15.40 and 15.2,
S= U-U(O) +Nkln qe = U-U(O) +nR+nRlnJ....

T N T N
We differentiate our statistical-thermodynamic expression of the chemical potential:
oµ) =~(oG(O) _RTlnJ....) =-R(mJ....)-Rr~(mJ....)

( oT p,n oT on N p.n N oT N p,n
=-R1nJ....-Rr( 01nq)
N oT p,n
We must show that this equals Sin. To bridge the gap between our expressions, we need a
statistical-thermodynamic expression for internal energy. For a collection of independent particles,
U-U(O)=N(c)=-N(olnqJ [13.35b]=-N(olnq) ( 0 TJ
o/3 v oT v o/3 v
=-N(olnq)
oT v oT
(0/3)- = NkT2 (olnq)
1
oT v
Note that what is held constant here is volume, not pressure as in the chemical potential derivative,
so we need the following property of partial derivatives based on eqn. MB 8.3:
(
olnq) =(otnq) +(olnqJ (op)
or v or p op r or v
= (olnq) +{1-(1n nRTqRqV qE )} {~(nRT)}

oT p op 3
pA r or v v
=( o1n q) __!_ x nR = ( o1n q) __!_

oT P p V oT P T
Thus U-U(O) = nRT(olnq) -nR

T oT P
which allows us to identify our statistical-thermodynamic expression for oµloT:
oµ) =-RlnJ__- U-U(O) +R =-~=~

( oT p,n N nT n m
(b) We are to show that eqn. 16.10
oµJ
( Op = Vm
T,n
is consistent with statistical thermodynamic results based on eqn. 15.40. So we differentiate
((Jµ) =~(dG(O) _RTinJ_) =-RT (~(Inq-InN))

dp T n dp dn N T ,n dp T,n
=-RT(dlnq ) =-RTx(-_!_) = V =~
dp T.n p n
P16.27 GE = RTx(l-x){0.4857 -0.1077(2x- l) +0.0191(2x-1) 2 }
A regular solution is defined by :!- = 0. Thus, a solution is regular if GE = FF . Because an ideal

solution has zero enthalpy of mixing, FF = limixH; therefore, FF is readily measured experimentally
by calorimetry. Thus, the test of whether the solution is regular amounts to measuring limixH and
determining how closely it matches the expression for GE.
To test whether the given expression is consistent with the regular solution model given by eqn.
16.32, we must compare the above expression for GE with the model expression for FF:
FF= ;R.Tx(x - 1)
Begin the comparison by plotting GE/RT against x, shown as the solid curve in Figure 16.12, which
resembles the curves shown in Figs. 16.38 and 16.39 of the text. The resemblance suggests that the
given GE is consistent with the model regular solution. To make the comparison more salient, plot
the model FF/RT against x on the same graph, selecting ~so that the two curves have the same
maximum. The maximum in the model function is ,;14, and it occurs at x = 0.5. So let i; = 4GE(max) =
4 x 0.123 = 0.497.
0.14
0.12
0.1
Empirical
... 0.08
~ "· Model
"'\,;, 0.06
0.04
0.02
0
0 0.2 0.4 0.6 0.8
x Figure 16.12
IGE is reasonably consistent with the model regular solutio~ over the entire range of composition.
P16.29 The analogous integral is
V. (x )-V. (0) =- f 1<x1) ~dV:

p T p JvT(0) 1- Xy T
We should now plot xTI( 1 - xT) against VT and estimate the integral. We must integrate up to xT = 0.5,
which corresponds to x'fl'(l - xT) = 1. So draw up the following table including all data points with xT <
0.5 and one point beyond so as to define the plot of the integrand over the interval of integration.
XT 0 0.194 0.385 0.559

VT (cm3 moi- 1) 73 .99 75.29 76.50 77.55
XA/(1-XA) 0 0.241 0.626 1.266
The points are plotted in Figure 16.13. To estimate the upper limit, we draw a smooth curve through
the data points. The value of VT where XT = 0.5 is 77 .1 cm 3 moi- 1•
I .4
1.2
10.
....
8
j 0.6
0.4
0.2
0
73 74 75 76 77 78
Figure 16.13
The integral is the area under the curve. Applying the trapezoid rule yields 1.39 cm 3 mor' for the
integral, so
Vr(xT= 0.5) = Vr(xT= 0)- 1.39 cm3 moi- 1
We need Vr(XT = 0), that is, the partial molar volume of propanone in a "mixture" containing no
trichloromethane. Vr(XT = 0) is the partial molar volume of pure propanone, i.e., the molar volume
of propanone.
1
vm (propanone) =-M = 58.08 g mol--3 =73 .92 cm 3

mol
-1
p 0.7857 g cm
Vr(xT= 0.5) = (73.92 - 1.39) cm3 mo1- 1 =ln.53 cm3 mo1- 1I
P16.31 Retrace the argument in Justification 16.3. Exactly the same process applies with GA in place of xA.
At equilibrium,
which implies that, with µ = µ · +RT In G for a real solution,
For an incompressible solution, the integral evaluates to IlVm, so llVm =-RTlnGA.

Thus, the osmotic coefficient </J, defined in Problem 16.30 as </J= -(xA!x 8 ) In GA,
nvm = XB </JRT = !!Ji_</JRT

XA nA
For a dilute solution, nAVm "'V, so llV "' n8 </JRT,
and therefore, with [B] = ~ , Jn= </J[B]RTj .
P16.33 At the boiling point of the solution (Tb) the chemical potential of the liquid solvent is equal to that
of the solvent vapor:
Substituting the ideal-solution expressions for these chemical potentials yields
µ : (! ,Tb)+ RTb ln xA = µ : (g, Tb) + RTb ln(pA I p B- )

The last term vanishes because PA = p 0 at the boiling point of the solution. We are interested in
comparing Tb to Tb*, the boiling point of the pure solvent, so we apply eqn. 16.9 to both pure-
substance chemical potentials:
(oµ)
aT p
=-Sm so µ(Tb)"" µ(Tb*) - (Tb-Tb*)Sm if Tb - Tb* is small
Thus we can express chemical potential at the boiling point of the solution (Tb), in terms of
differences from the chemical potential at the boiling point of the pure substance (Tb*):
µ.!7(1,Tb')-('Z;,-Tb*)Sm(I)+RI;, lnxA = µ.!'(g,Tb')-(Tb -Tb')Sm(g)
Now µ.!'(I, :z;, •) = µ.!' (g, Tb•) [pure liquid and vapor are in equilibrium at Tb'], so eliminating them
from the equation and gathering the entropy terms on the left, we have
(Tb- Tb*){Sm(g)-Sm(l)} ""-RTb In XA = -RTb In (1 -Xs) ""RT-r;xs [xs small]
The differences on the left side of the equation are simply D.Tb and liva~, so we have
2
RTb RTb' • IR(Tb') I •
!iJ;, " " - - x8 " " - - x 8 [Tb ""Tb]"" - - x8 [!ivapH =Tb !ivapS]
!ivapS !ivapS !ivapH
P16.35 In this case it is convenient to rewrite the Henry's law expression as

mass ofN 2 = PN, xmass ofH 2 0 xKN,
At 4.0 atm air, PN, = 0.78x4.0 atm = 3.1 atrn
so mass ofN 2 = 3.1 atmxlOO g H 2 0x0.18 µg N 2 I (g H 2 0atm)=156 µg N 2 I
At 1.0 atm air, pN 2 = 0. 78 atm and mass of N2 = 114 µg Nd.

In fatty tissue the increase in N 2 concentration from 1 atm to 4 atm is
4x(56-14)µgN 2 =l1.1x10 2 µgN 2 I
P16.37 (i) Below a denaturant concentration of 0.1, only the native and unfolded forms are stable; the
l"molten globule" form is not stabl~.
(ii) At a denaturant concentration of 0.15, only the native form is stable below a temperature of
about 0.65. At temperature 0.65, the native and molten-globule forms are at equilibrium.
Heating above 0.65 causes all native forms to become molten-globules. At temperature 0.85,
equilibrium between molten-globule and unfolded protein is observed, and above this
temperature only the unfolded form is stable.
P16.39 (a) The phase boundary is plotted in Figure 16.14.
10
&:
~
"'-
0.1
0.01
80 100 120 140 160 180 200
T!K Figure 16.14
(b) The normal boiling point is the temperature at which the liquid is in equilibrium with the
standard pressure of 1 bar (0.1 MPa). Interpolation of the plotted points gives lrb = 112 KJ.
(c) The slope of the liquid-vapor coexistence curve is given by
d ~ H
...Y!_ = -
va_p - [16.13b], so
dT T~ vapV
The slope can be obtained graphically or by fitting the points nearest the boiling point. Then
dp I dT = 8.14 x 10-3 MPaK- 1 , so
~ vap H
3 1
8 89 38
= (112K) x( ( · -0.0 0)dm mor Jx (8.14kPaK- 1)= 18.07 kJmo1- 1I
1000dm3 m-3
P16.41 By the van't Hoff equation [16.28],
II = [B]RT = cRT
M
Division by the standard acceleration of gravity, g , gives
JI= c(R / g )T
g M
(a) This expression can be written in the form
JI'= cR'T
M
which has the same form as the van't Hoff equation, but the new "osmotic pressure," II: has the
dimensions of II I g : ·
force area - t (mass length time-2 )(area- 1) mass

length time-2 length time -2 area
This ratio can be specified in units of g cm-2, as specified in the problem. Likewise, the proportionality
constant, R', would have the dimensions of RI g:
energy temperature- 1 amounC 1 (mass length 2 time-2 )temperature- 1 amounC 1

length time-2 length time-2
=mass length temperature- 1 amounC 1•
This result may be specified in units of~ cm K- 1 mo1- 1I.
1 1
R' = R = 8.31447 JK- mol-
(b)
g 9.80665ms-2
= 0.847840kgmK- mor
1 1
x(1~~g Jx ( 10c_i;im J
= 184 784.0gcmK- 1 mo1- 1 I
We will drop the primes, giving
II= cRT
M
and use the II units of g cm- 2 and the R units of g cm K- 1 mor' .
Polyiso butylene in chlorobenzene

a t low concentra tions
500
Intercept: 230 gcm- 2 / gcm- 3
450
7 400
5Oil
---
'IE 350
..
u
~
;:::::
§: 300
250
200 ~-~-~-~-~-~-~-~~
0.000 0.0 10 0.020 0.030 0.040
c/(g cm- 3 ) Figure 16.15(a)
We extrapolate the low-concentration portion of the plot of II I c versus c to c = 0 (in effect, employing
the virial analogue of the van' t Hoff equation, eqn. 16.29, as in Example 16.3). They-intercept is 230 g
cm-2 I g cm- 3 (Figure 16.15a). In the limit of small c, the van't Hoff equation is valid so
RT= intercept
M '
(84784.0gcmK- 1 mor 1 )x(298.15K)
and M=__Jf[_
intercept (230 g cm-2 ) I (g cm-3 )
= juxl0 5
g mo1- 1 j
(c) The plot of II I c versus c for the full concentration range (Figure 16.l 5b) is highly nonlinear.
We can conclude that the solvent is good due to the nonpolar nature of both solvent and solute.
CH1
0--CI tCH 2 -
I
C
I "
CH3
t
Polyiso butylene in chlorobenzene
7000 ~~~~~~~~~~~~~~~-...,
6000
•
5000
..
E
~ 4000 I / .
§:
3000
2000
1000
0.050 0. 100 0.150 0.200 0.250 0.300

c/(gcm- 3 ) Figure 16.15(b)
(d) The virial analogue to the van't Hoff equation (eqn. 16.29) rearranges to
ll I c =(RT I M)(l + B'c+ C'c 2 + · · ·)
Since RT I M has been determined in part (b) by extrapolation to c = 0, it is best to determine the
second and third virial coefficients by a linear regression fit.
{(ll I c) ! (RT I M)}-1 = B' +C'c

c
That is, call the left side of this ex ression 17, c) and plot it against c. The best linear fit in the
resulting plot (Fig. 16.15c) gives '= 21.1 cm - and = 212 cm 6 IC'
The plot shows a fair g-3.
amount of scatter.
JOO
y =2J2x +2 1.1
90 2
R =0.96
•
80
70
<:; 60
c 50
~ 40
30
20
JO
0
0 0.05 0. 1 O.J 5 0.2 0.25 0 .3
c I (g cm-3) Figure 16.lS(c)
(e) Using 1/4 for g and neglecting terms beyond the second power, we may write
2
2 2
ll = RT ( l+B'c+ B' c ) = RT(i+ B'c)
c M 4 M 2
J
12 112
so ( -ll
c
) ' - ( -RTJ
M
( 1 ,
l+-Bc
2
We can solve for B' and then evaluate g(B') 2 = C'.
B' = '!:_ {( ll / c )
c RT I M
112
- l}
RT I Mhas been determined above as 230 g cm- 2 I g cm-3 • We analytically solve for B' from one of
the data points, say, ill c = 430 g cm- 2 I g cm- 3 at c = 0.033 g cm- 3 .
B'= 2 430gcm / gem -2 -3 Jl/2_ 1}= 22 .l cm3 g-1

0.033 g cm-3 1( 230 g cm-2 I g cm-3
1/ 2
1
Better values of B' and C' can be obtained by plotting (
fl c )
against c. This plot is shown in
RT I M
Figure 16.15(d). The slope is 14 cm3 g- 1
B' = 2 x slope= 128 cm3 g- 1 I and C' = g(B') 2 = 1196 cm 6 g-2 I
6.0 . - - - - - - - , , - - - - - - - - , - - - - - - : - - - - - - . , - - - - - - , - - - - - .
5.0
--.
N
4.0
,.---.....
~ I~
.....___,,
......._____ 3.0
N
--.
,.---.....
q \ <>
.....___,, 2.0
1.0
0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
c/ (gcm- 3 ) Figure 16.15(d)
The intercept of this plot should theoretically be 1.00, but it is in fact 0.915 with a standard
deviation of 0.066. The overall consistency of the values of the parameters confirms that g is
roughly 114 as assumed.
17 Chemical equilibrium
017.1 The position of equilibrium is always determined by the condition that the reaction quotient, Q,
must equal the equilibrium constant, K. If the mixing in of an additional amount of reactant or
product destroys the equality, then the reacting system will shift so that equality is restored. That
implies that some of the added reactant or product must be removed by the reacting system and the
amounts of other components will also be affected. These adjustments restore the concentrations to
their (new) equilibrium values.
017.3 See Justification 17.2 for a derivation of the general expression (eqn. 17.17b) for the equilibrium constant
in terms of the partition functions and difference in molar energy, D.,E0 , of the products and reactants in a
chemical reaction. The partition functions are functions of temperature, and the ratio of partition
functions in eqn. 17.17(b) will therefore vary with temperature. However, the most direct effect of
temperature on the equilibrium constant is through the exponential term e -t:.,Eo ' RT. The manner in which
both factors affect the magnitudes of the equilibrium constant and its variation with temperature is
described in detail for a simple R r:= P gas phase equilibrium in Section 17 .3(b) and Justification 17 .3.
017.5 (1) Response to change in pressure. The equilibrium constant is independent of pressure, but the
individual partial pressures can change as the total pressure changes. This will happen when there is
a difference, D.ng, between the sums of the number of moles of gases on the product and reactant
sides of the balanced chemical reaction equation:
J=product gases J=reactant gases
The requirement of an unchanged equilibrium constant implies that the side with the smaller number
of moles of gas is favored as pressure increases. To see this, we examine the general reaction equation
0= L v1 J (17.8] is in the special case for which all reactants and products are perfect gases. In this
J
case, the activities of eqn. 17 .12 equal the partial pressure of the gaseous species, and therefore
a1 (gasJ = P1 I p & = x1pl p&
where x 1 is the mole fraction of gaseous species J. Substitution into eqn. 17.12 and simplification
yield a useful equation:
K= (If a;' tuilibnum = (If r x;' (p I p& tuilibnum
=(If x;' ) equilibrium (If ( r =(If

p I p& lquilibnurn x;' tuilibnum ( p I p & t·
=Kx (p ! p&t'• where K
x
=(IJxv')
J
1
equilibrium
Kx is not an equilibrium constant. It is a ratio of product and reactant concentration factors that has a
form analogous to the equilibrium constant K. However, whereas K depends on temperature alone,
the concentration ratio Kx depends on both temperature and pressure. Solving for Kx provides an
equation that directly indicates its pressure dependence.
Kx =K(p 1P&rlln·
This equation indicates that, if f1ng = 0 (an equal number of gas moles on both sides of the balanced
reaction equation), Kx = K and the concentration ratio has no pressure dependence. An increase in
pressure causes no change in Kx and no shift in the concentration equilibrium is observed upon a
change in pressure.
However this equation indicates that, if f1ng < 0 (fewer moles of gas on the product side of the
balanced reaction equation), Kx =K(p / p&)llln, . Because pis raised to a positive power in this
1
case, an increase in pressure causes Kx to increase. This means that the numerator concentrations
(products) must increase while the denominator concentrations (reactants) decrease. The
concentrations shift to the product side to reestablish equilibrium when an increase in pressure has
stressed the reaction equilibrium. Similarly, if f1ng > 0 (fewer moles of gas on the reactant side of
the balanced reaction equation), Kx =K(p I p&f1Lln• 1• Because pis raised to a negative power in this
case, the concentrations now shift to the reactant side to reestablish equilibrium when an increase in
pressure has stressed the reaction equilibrium.
(2) Response to change in temperature. Equation 17 .26(a) shows that K decreases with increasing
temperature when the reaction is exothermic; thus the reaction shifts to the left, the opposite occurs in
endothermic reactions. See Section 17.5(a) for a more detailed discussion.
Failure of Le Chatelier' s principle is very unusual. The expected response to pressure may prove
wrong should the gas components be non-perfect, real gases. Should the gases of the reaction side that
is favored by Le Chatelier' s principle strongly repel while the gas molecules of the other side strongly
attract, a compression may shift the reaction in the direction opposite to that expected for perfect
gases. This is reflected in the analysis of eqn. 17.12 for the special case in which all products and
gases are real gases having activity coefficients that do not equal 1. Coefficients greater than 1 are
observed when intermolecular repulsions dominate, and they are less than 1 when attractive forces
dominate. In this case, aJ (gas) =Yi Pi I p&= YiXiP I p& where y1 is the activity coefficient of gas J.
Substitution and simplification yields
K x=K(p / p&flln•/ Kr where Kr =IJr;'

J
If f1ng < 0 (fewer moles of non-perfect gas on the product side of the balanced reaction equation), a
pressure increase will not shift the reaction equilibrium toward the products, which is predicted by
Le Chatelier's principle, provided that the pressure increase causes Ky to increase to the extent that
the ratio (p/p &f lln'/K r decreases.
01 7.7 A galvanic cell uses a spontaneous chemical reaction to generate a potential difference and deliver
an electric current to an external device. An electrolytic cell uses an external potential difference to
drive a chemical reaction in the cell that is by itself non-spontaneous. In their essential features,
these two kinds of cells can be considered opposites of each other, in the sense that an electrolytic
cell can be thought of as a galvanic cell operating in the reverse direction. For some electrochemical
cells, this is easy to accomplish. We say they are rechargeable. The most common example is the
lead-acid battery used in automobiles. For many other cells, however, this kind of reversibility
cannot be achieved. A fuel cell, like the galvanic cell, uses a spontaneous chemical reaction to
generate a potential difference and deliver an electric current to an external device. Unlike the
galvanic cell, the fuel cell must receive reactants from an external storage tank. See the text on
engineering, Impact 17 .2, Fuel cells.
017.9 The electrochemical series lists metallic elements and hydrogen in the order of their reducing power as
measured by their standard potentials in aqueous solution (see Table 17.3). It is used to quickly
determine whether one metal can spontaneously displace another from solution at 298 K. Application
rule: A low element in the series will displace the cation of a high element in the series. For example,
zinc is lower than hydrogen in the series, so zinc will spontaneously react with the hydronium cation,
W(aq), to form the zinc cation and hydrogen gas: Zn(s) + 2W(aq) ~ Zn2\aq) + H2(g).
CHEMICAL EQUILIBRIUM 413
017.11 Eqn. 17.41,
d H 6 =-vF(E 6 -Td.E!uJ (17.41]

' ~ dT
provides a non-calorimetric method for measuring d,H 6 . £!11 must be measured over a range of
temperatures so that the temperature derivative, d.E! 1 I dT, may be evaluated by curve fitting the
E!1(T) data. Substitution of the £!1 and d.E!1 I dT values into eqn. 17.41 yields the standard
reaction enthalpy. The procedure is illustrated in text Example 17.5. In the special case for which
d.E! 1 I dT is negligibly small, we may conclude that d,S 6 0 (see eqn. 17.40) and d,H 6 := =
d,G 6 = -vFE!1•
E17 .1 (a) Eqn. 17.12 provides equilibrium constants in terms of activities for part (i) with the activities of
pure solids and liquids being equal to 1. For part (ii), substitute a,0 1ute = Ysolutehsoluiefb 6 and assume
perfect gas behavior with the substitution agas = Pga/ p 6 .
a a
(a) (i) K = COCl(g) Cl(g) (ii) K = Pcoc1Pc1
aco(g) ac1 2 (g) Pc0Pc1 2
2 2 B
(b) (i) K = QS03(g)

(ii) K = P~o, p
2
aso 2 (g) ao, (g) Pso, Po,
a (") K =YFeS0
(c) (i) K = FeSO,(aq) 11 - - xbFeS0
-- 4 4
QPbSO,(aq) YrbSO, brbso,
a2 ~ b2 B
(d) (i) K = HCl(aq) (ii) K = HCl(aq) ,HCl(aq) X _P
__
2
6
aH , (g) PH, (g) (b )
a (") K =Ycuc1 b b6
(e) (i) K = C2uCl 2 (aq) 11 - -2x Cuc1 2
QCuCl(aq) fcucJ b~uCI
E17 .2(a) vHg,ci, = - l, vH , = -1, vHci = 2, vHg =2 (dng = -1)
E17.3(a) Let B = bomeol and I= isobomeol; B ~I.
d,G=dG 6 +RTlnQ [17.9] where Q=.f!J_ [17.5°]

Pe
0.15 mo!
Pe = XeP = x 600 Torr= 200 Torr; p 1 = p- Pe= 400 Torr
0.15 mo!+ 0.30 mo!
Q = 400 Torr= 2.00

200 Torr
d,G = (+9.4 kJ mol- 1)+(8.314 J K- 1 mor 1)x(503 K)x(ln 2.00) = 1+12.3 kJ moi- 1 I
This mixture reacts spontaneously to the left (toward the formation of borneol).
E17.4(a) The formation reaction is 2Ag(s) + Y2 0 2(g) ~ Ag 20(s).
1/ 2
K= a1 ~ = p&
[ )
(a Ag(s) = a Ag,O(s) = 1, and assuming perfect gas behavior, a0 2 (g) = Po, Ip &.)
o2<•> Po,
= 10 Pa
5 Jl/2=
9 1. 86
( 11.85 Pa
!1,G& =-RTlnK [17.13]

= -(8.3145 J K- 1mor 1)x(298 K)x(ln91.86)
= l-1 i.20 kJ mor 1I
E17.5(a) The reaction equation is PbO(s)+CO(g) ~ Pb(s)+C0 2 (g).
YPb =1 Yeo, = 1 YpbQ = -1 Yeo= -1
(a) !1,G& = ~)i llrG&(J) [17.lOb]
!1,G& =llrG&(Pb, s)+l1rG&(C0 2 , g)-llrG&(PbO, s, red)-llrG&(CO, g)

= (-394.36 kJ mol- 1)-(-188.93 kJ mol" 1)-(-137.17 kJ mor 1)
= l-68.26 kJ mo1- 1I
l1 G& 3 -I
ln K = - ' [17.13] = +68.26xl0 J mol = 27.55· K = l9.2xl0111
RT 1 1
(8.3145 J K- mol- )x(298 K) '
(b) !1,H& = llrH& (Pb, s)+l1rH&(C0 2 , g)-llrH&(PbO, s, red)-llrH&(CO, g)
= (-393.51 kJ mol- 1)-(-218.99 kJ mol- 1)-(-110.53 kJ mor 1)

= l-63.99 kJ mo1- 1 I
1
lnK(400 K) = lnK(298 K)- !1 ,H& ( - - - -
R
1
400 K 298 K
-J
[17.28]
= 27.55- ( -63 .99xl03 J mol-1)x(-8.557xl0-4 K-1) = 20.96

8.314 J K- 1 mor 1
K(400 K) = lux10 9 I
l1,G&(400 K) =-RTlnK(400 K) [17.13] =-(8.3145 J K- 1 mol- 1)x(400 K)x(20.96)

= -6.97xl0 4 J mol- 1 =I-69.7 kJ mo1- 1I
E17.6(a) CaF2 (s) ~ Ca 2+(aq) +2F- (aq) K = 3.9x10- 11
!1,G& =-RT ln K
= -(8.3145 J K- 1 mor 1)x(298.15 K)xln(3.9xl0- 11 ) = +59.4 kJ mol- 1
= !1p& (CaF2 , aq)- llrG& (CaF2 , s)
llrG&(CaF2 ,aq) = !1,G& + llrG& (CaF2 ,s)

1I
= [59.4-1167] kJ mor 1 = ,....l--1-10_8_kJ_m_o_l_-..
E17.7(a) Draw up the following equilibrium table for the reaction equation: 2 A+ B ~ 3 C + 2 D.
A B c D Total
Initial amounts/mo! 1.00 2.00 0 1.00 4.00
Stated change/mo! +0.90
Implied change/mo! -0.60 - 0.30 +0.90 +0.60
Equilibrium amounts/mo! 0.40 1.70 0.90 1.60 4.60
Mole fractions 0.087 0.370 0.196 0.348 1.001
(a) The mole fractions are given in the table.
(b) K x =fixJ v,
J
K = (0.196)ix(0.348)2 =0.326=10.331
x (0.087) 2 x (0.370)
(c) p 1 =x1p p=l bar p B =l bar
Assuming that the gases are perfect, a1 = p 1 I p B. Hence,
K =(Pc I p B)J x(po I p B)2

(pA I p B)2 x(ps I P B )
32 (
= x;xo x ~ )2 = Kx whenp = 1.00 bar= I0.33!
XAXB p
(d) 11,GB =-RTlnK =-(8.3145 J K- 1 mor 1)x(298K)x(ln0.326)=1+2.8 kJ mor' I
E17.8(a)
The biological standard state applies to the state where aH. = 10-1 and all other activities are 1
(i.e., the biological standard state, EB, has pH= 7). Hence Q$ = lxl0- 7 •
11,G $ = 11,GB +RT ln Q$ (17.9]
= 10 kJ mol- 1 +(8.3145 J K- 1 mor')x(298 K)xln(lxl0- 7 )
= l-30 kJ mo1-
1
I
E17 .9(a) For the chemical reaction I2 (g) ~ 2 I(g), we use eqn. 17. l 9a with X = I, X 2 = 12, and 11,£0 = D 0 (I-I)
where D 0(I-I) is the dissociation energy of the I-I bond.
D 0 = D _ _!_v = 1.5422 eVx 8065 ·5 cm -' 107.18 cm-'

e 2 1 eV
= l.2331xl0 4 cm- 1 =1.475xl0 5 J mol- 1

q!(I 2) = 2.561 x 10-2(T / K) 512 x (M I gmoi- 1) 312 [Table 13.1]

NA
= 2.561 x 10-2 x1000 5n x 253.8 312 = 3.27 x 109
q! (I) =2.561x10-2 x 10005nx 126.9312 =1.16x10 9

NA
R(I ) = 0.6950 x T IK =1- x 0.6950x 1000 = 9316

q 2 a Blcm-1 2 0.0373
V 1 -; -I
q 0 2) = - --- a = 1 4388 v cm
1-e-a ' . T/ K
1
1-e-I.4388x214.36/IOOO = 3.77
9 2
K (1.16x10 x 4) e-1.41sx10' 1s314s11000 = l3.70x10-3J
9
(3 .27 x 10 ) x (9316) x (3.77)
E17 .1 O(a) For the reaction H2CO(g) ~ CO(g) + H2(g), 11ng = 1.

Assuming that all reactants and products are perfect gases, the activities of eqn. 17.12 equal the
partial pressure of the gaseous species, and therefore,
aJ (gasJ =Pi /p ft = xJp l p ft
where x 1 is the mole fraction of gaseous species J. Substitution into eqn. 17 .12 and simplification
yield a useful equation:
K = (If a;' ) equilibrium = (If x;' ( p I p ft )v, ) equilibrium
=(If x;' ) equi librium (If ( pIp ft )"' ) equilibrium = (If ft

x;' ) equilibrium ( p I p t •
=Kx (p ! p ftt• where Kx =(IT x;')

1 equilibrium
Kxis not an equilibrium constant. It is a ratio of product and reactant concentration factors that has a
form analogous to the equilibrium constant K. Therefore,
Kx= K(: f} r6n·

Since K depends on temperature alone,
K x(pi) K(p2 I p: )~=· = (p)-6n,

2
K x(P1) K(p 1 I p ) ' Pi
K x(3 .0 bar)= ( 3.0 bar )-I = 0.

33
Kx (1.0 bar) 1.0 bar
Thus, IKx is reduced by 67%1 when the pressure is increased from 1.0 bar to 3.0 bar. This is
quantification of the Le Chatelier principle that the equilibrium shifts to the left (side that has
smaller number of gas moles) to reduce the stress of increased pressure.
CHEMICAL EQUILIBRIUM .u i
E17.11 (a) At 1280 K, ~,GB = +33xl0 3 J mol- 1; thus
~GB 3 1
lnK (1280K) = - - ' - = 33xl0 J moi- =-3.10
I RT (8.3145 J K- 1 mor 1)x(l280 K)
Kl =I0.0451
lnK2 =lnK -~'HB(_!_

R T T
_ _!_) [17.28]
I
2 I
We look for the temperature T2 that corresponds to In K2 = ln(l ) = 0. This is the crossover
temperature. Solving for T2 from eqn 17.28 with In K2 = 0, we obtain
1 1
_!_ = RlnK1 +l.. = ((8.3145 J K- mol- )x(-3.10)J+( 1 )
T2 ~,HB I; 224x10 J moi- 1
3
1280 K
= 6.66xl0-4 K- 1
2
E17.12(a) Given lnK = -1.04- 108; K + 1. 51 x;?s K ,
. dlnK -~ HB
and smce - - = ' [17 .26b],
d(l!T) R
2
-~,HB =-1088 K+ (2)x(l.5lxl0 K )
5
R T
Then at 450 K,
2
~,HB = (1088 K- 3 .o~~bo~ K )x(8.3145 J K- 1mol- 1)=1+3.47 kJ moi- 1 I
2
~,GB= -RTlnK [17.13] = RTx(l.04+ 10~ K l.5lx;2os K )
5 2
= (8.3145 J K- 1mor 1)x(450K)x(l.04+ 1088 K _ l.5lxl0 K 2 ) = +10.15 kJ mo1- 1
450 K (450 K)
=~,HB -T~,SB [15.50]
~ HB - ~ GB -I -I
Therefore ~SB= r r =3.47kJmol -10.15kJmol =l-l 48 JK-1 moi-11
' ' T 450 K . .
E17.13(a)
T2 = 308 K; hence, with the substitution K 2/K1 = K,

1 1
~ HB =- (8.3145 J K- mor )x(ln K) = 76 _3 kJ mol_1xln K
' ( 1 I )
308 K 298 K
Therefore,
(a) K= 2, 11,HB = (76.3 kJ mor 1)xln2=1+53 kJ moi- 1I
(b) K= .!., 11,HB = (76.3 kJ mor 1)xlnt = l-53 kJ mo1- 1I

2
E17.14(a) The decomposition reaction is CaC0 3(s) ~ CaO(s) + C0 2 (g).
For the purposes of this exercise we assume that the required temperature is the temperature at
which K = 1, which corresponds to a pressure of 1 bar for the gaseous product. For K = 1, ln K = 0
and 11,GB = 0.
11 r GB = /1 r H B - T 11 r S B = 0 when /1 r H B = T 11 r S B
Therefore, the decomposition temperature (when K = 1) is
T= 11,HB
11,SB
11,HB = {(-635.09)-(393.51)-(-1206.9)} kJ mor 1 = +178.3 kJ mor 1
11,S B = {(39.75) + (213.74)-(92.9)}1 K - 1mol- 1 = + 160.6 J K - 1 moi- 1
T = l 78.3xl03 J mor1 = 11110 Ki (840 oq

160.6 J K - 1mol- 1
E17 .15(a) The cell notation specifies the right and left electrodes. Note that for proper cancelation we must
equalize the number of electrons in half-reactions being combined. To calculate the standard cell
potential (emf) of the cell, we have used E B = E: - E:! , with standard electrode potentials from
Table 17.2.
EB
(a) R: 2Ag+(aq)+2e- ~2Ag(s) +0.80 v
L: zn+(aq) + 2e- ~ Zn(s) -0.76 v
(b) Overall (R- L): 2Ag+(aq) + Zn(s) ~ 2Ag(s) + Zn +(aq) 2
+l.56 v
R: 2H+(aq)+2e- ~H 2 (g) 0
L: Cd 2 + (aq)+2e- ~Cd(s) -0.40 v
(c) Overall (R- L): Cd(s) + 2H+(aq) ~ Cd +(aq) + H 2 (g)
2
+0.40 v
R: Cr 3+(aq)+3e- ~ Cr(s) -0.74 v
L: 3[Fe(CN) ] 3-(aq)+3e- ~ 3[Fe(CNU 4- (aq)
6 +0.36 v
(d) Overall (R- L): Cr 3+ (aq) + 3[Fe(CN) 6 ]4- (aq) ~ Cr(s) + 3[Fe(CN) 6 ] 3-(aq) -1.10 v
R: Sn 4+(aq)+2e- ~Sn 2+ (aq) +0.15 v
L: 2 Fe 3+ (aq) + 2 e- ~ 2 Fe 2+(aq) +0.77 v
Overall (R-L): Sn 2+(aq) + 2Fe 2+(aq) ~ Sn 2+(aq) + 2Fe 2+(aq) -0.62 v
COMMENT. Cells for which E" > 0 may operate as spontaneous galvanic cells under standard
conditions. Cells for which E" < 0 may operate as non-spontaneous electrolytic cells. Recall that E"
informs us of the spontaneity of a cell under standard conditions only. For other conditions we require E.
E17 .16(a) The conditions (concentrations, and so on) under which these reactions occur are not given. For the
purposes of this exercise we assume standard conditions. The specification of the right and left
electrodes is determined by the direction of the reaction as written. As always, in combining half-
reactions to form an overall cell reaction, we must write the half-reactions with equal numbers of
electrons to ensure proper cancellation. We first identify the half-reactions and then set up the
corresponding cell. To calculate the standard cell potential (emf) of the cell, we have used
E B = E: - E~ , with standard electrode potentials from Table 17 .2.
EB
(a) R: Pb + (aq)+2e- ~Pb(s)
2
-0.13 v
L: Fe 2+(aq)+2e- ~ Fe(s) -0.44 v
Hence the cell is
Fe(s) I FeS0 4 (aq) II PbS0 4 (aq) I Pb(s) +0.31 v
(b) R : Hg 2 Cl 2 (s)+2e- ~2Hg(l)+2Ci-(aq) +0.27 v
L: H+(aq)+e- ~ tH 2 (g) 0
and the cell is
PtlH 2 (g)IH+(aq)IHg 2 Cl 2 (s)IHg(l)
or PtlH 2 (g)IHCl( aq)IHg 2 Cl 2 ( s)IHg(l) +0.27 v
(c) R: 0 2 (g)+4W(aq)+4e- ~ 2H 2 0(1) +l.23 v
L: 2H+(aq)+2e- ~H 2 (g) 0
and the cell is
PtlH 2 (g)IW (aq) I 0 2 (g) I Pt +l.23 v
COMMENT. All these cells have E" > 0, corresponding to a spontaneous cell reaction under standard
conditions. If E" had turned out to be negative, the spontaneous reaction would have been the reverse
of the one given, with the right and left electrodes of the cell also reversed.
1
E17.17(a) AglAgBr(s)IKBr(aq, 0.050 mo! kg- 1)11Cd(N03)2(aq, 0.010 mo! kg- )1Cd(s)
(a) R: Cd2+(aq) + 2 e- ---+ Cd(s) E B = -0.40 V (Table 17.2)

L: AgBr(s) + e- ---+ Ag(s) + Br-(aq) EB= +0 .0713 v
R - L: l¢d 2+(ag) + 2Br-(ag) + 2 Ag(s)---+ Cd(s) + 2 AgBr(s)I E! 1
= -0.47 V
The cell reaction is not spontaneous toward the right under standard conditions because E! 1 < 0.
(b) The Nernst equation for the above cell reaction is
B RT
E cell = E cell --lnQ [17.32]
vF
where v=2 and
bed,. = 0.010 mol kg- 1 for the right-hand electrode and bsr- = 0.050 mol kg- 1 for the left-hand electrode.
(c) The ionic strength and mean activity coefficient at the right-hand electrode are
I R =t ~:>; (b;f bB ) [16.57] =H4(0.010) + 1(.020)} =0.030
log r±R =- I Z+ Z- [16.56] =-2 x (0.509)x (0.030) =-0.176

12 112
I Af
Y±,R = 0.666
The ionic strength and mean acitivity coefficient at the left-hand electrode are
IL = fLz ; (b) bB) [16.57] =t{l(0.050) + 1(.050)} =0.050 ·
log Y±,L =- I z+z- I A/ 112 [ 16.56] =-1 x (0.509) x (0.050)1'

2
=-0.114
Y±,L = 0.769
Therefore,
=( 1 )x( 1 ) = 1 02x10 5
Q (0.666)x(0.769) 2 (O.OlO)x(0.050) 2 ·
and
25 693 3
Ecen = -0.47 V-( · ;lo- V )ln(l.02xl05)
=l-0.62 vi
E17.18(a) We calculate the standard Gibbs energy with Li,G!11 =-vFE!11 [17.30].
~.G!, I kJ mor
1
v E!11 /V
(a) 2 +1 .56 -301

(b) 2 +0.40 -77
(c) 3 -1.10 +318
(d) 2 -0.62 +120
E17 .19(a) We first recognize the reduction and oxidation processes within the reaction equation and calculate
E!11 using EB = EB(reduction couple)-EB(oxidation couple)[l 7.34] with the standard reduction
potentials of Table 17 .2. Inspection of the balanced reaction equation and comparison with the
redox couples also gives the stoichiometric coefficient of the electrons transferred, v. The
equilibrium constant is calculated with
K=evFE"IRT [17.33] where RT I F=25.693.mVat25°C
(a) EB =EB(Sn 4+ / Sn 2+)-EB(Sn 2+ / Sn) and v=2
EB= +0.15 V-(-0.14 V) = +o.29 v

K = e2x(0.29)/(0.025693) = l6.4x109 I
(b) EB =EB (Hg 2+ I Hg)- EB (Fe 2+ I Fe) and v=2
EB= +0.86 V-(-0.44 V) = +l.30 v

K = e1x(uo)1(0.025693) = ls. 9 xl043 I
E17.20(a) If half-reaction (c) is the direct sum of half-reactions (a) and (b), the generalization of text Example
17.4 gives
EB(c) = v. EB(a)+vbEB(b)
Ve
Thus,
EB(Ce4+ / Ce)= EB(Ce4+ / Ce3+)+3EB(Ce3+ / Ce)
4
(+1.61 V)+3(-2.48 V)
4
=l-1.46 vi
E17.21(a) Zn is lower than mercury in the electrochemical series of Tables 17.2 and 17.3. Consequently,
metallic zinc displaces the mercury(II) cation from aqueous solution and ~lemental mercury cannoq
~pontaneously displace the zinc(II) cation from solution under standard conditions.I
An alternative view observes that, since E 6 (Zn 2+ I Zn)-E 6 (Hg 2+ I Hg)< 0, the reaction Hg(l) +
Zn2+(aq)--+ Hg2+(aq) + Zn(s) is not spontaneous.
E17.22 (a) +0.80V}

E 6 =ER & -EL6 = 0.9509 v
L : Agl(s) + e- --+ Ag(s) + r(aq) -0.15 v
Overall: Ag+(aq) + r(aq)--+ Agl(s) v=l
lnK = vFEe [17.33] = 0.9509 V = 37.010

RT 25 .693xl0-3 V
K = l.1Sxl0 16
(a)
In the above equation, the activity of the solid equals 1, and since the solution is extremely dilute,
the activity coefficients of dissolved ions also equal 1. Solvin for the molar ion concentration gives
[Ag+]= [r] = 9.2 x 10-9 M. Agl has a solubility equal to .2 x 10-9
(b) The solubility equilibrium is written as the reverse of the cell reaction. Therefore,
Ks =K" 1 =1Il.1Sxl0 16 =l8.5x10- 1 ~
E17.23(a)
Within this small 10°C temperature range we can assume that the standard reduction potential is
linear in temperature. The two-point method provides the slope.
slope: a=dE! 1 =M!1 =(0.2669-0.2699)V =-3 .0xl0-4 VK_1

dT !lT (303 - 293)K
The linear expression is
E:11 (T) = E~ +ax(T-7;) = 0.2699 V +ax(T-293 K)

= aT+b where a =-3 .0xl0-4 V K- 1 and b = 0.3578 V
Thus,
ll,G 6 (298 K) = -vFE!1(298K)

=-2x(96485 C mol- 1 )x{(-3.0x10-4 V K- 1)x(298 K)+0.3578 V}
= l-52 kJ moi- 1 I
!!. S 6 = vF dE!i [17.40]
' dT
= 2x(96485 C mol- 1 )x(-3 .0xl0-4 V K- 1)
= l-58 J K- 1 mo1- 1 I
!J.rHB = t:,.pB + T !J.rSB [17.41]
= (-52 kJ mol- 1)+(298 K)x(-58 J K - 1 mol- 1)
1
= l-69 kJ moi- I
P17.1 (a) t:,.pB =-RTlnK [17.13]
=-(8.3145 J K - 1mol- 1)x(298 K)x(ln0.164) = 4.48xl0 3 J mol- 1
1
= 1+4.48 kJ moi- I
(b) Draw up the following equilibrium table.
I2 Br2 IBr
Amounts - (1-a)n 2an
Mole fractions - (1-a) 2a
--
(l+a) (l+a)
Partial pressure - (1-a)p 2ap
P1=X1P (l+a) (1 +a)
( I B)2
K = IJa~i [17 .12] = Prnr p B [perfect gases]
J p Br I P
2
- {(2a)2P I P B} - (4a2P I PB )= 0 164

- - 2 •
(1-a)x(l+a) 1-a
2
With p=0.164atm, 4a =l-a 2 a 2 =1 / 5 a= 0.447
Prnr =-2-a- x p = ( 2) x (0.4 47 ) x(0. 164 atm) = .-I0-.1-0l_a_tm~I

l+a l+0.447
(c) The equilibrium table needs to be modified as follows.
P = P1 2 +Par, + P mr Par, = XBr2 P Pmr =XmrP Pr, =x1, P
(1-a)n
with Xar, = (1 + a)n + n1, [n = amount of Br2 introduced into the container]
2an
and Xmr = (1 + a)n + nr,
K is constructed as above (17 .12] but with these modified partial pressures. To complete the
calculation, additional data are required, namely, the amount of Br2 introduced, n, and the equilibrium
vapor pressure of 12(s). nr, can be calculated from a knowledge of the volume of the container at
equilibrium, which is most easily determined by successive approximations since Pr 2 is small.
What is the partial pressure of IBr(g) if 0.0100 mo! of Br2 (g) is introduced into the container? The
partial pressure of 12 (S) at 25 °C is 0.305 Torr.
P17.3 11,G 6 (298 K) = +118.08 kJ mol- 1 at 2300 K
K = e-e..,a" ! RT [17.13]
= e-(118080 kJ rnol- 1 )/(8.3145 J K - 1 rnol- 1 )x(2300 K)
= 0.002082
Draw up the following equilibrium table.
H20(g) H2(g) 02(g) Totals

Amounts at start n n
Amounts at equilibrium (I - a)n an Vian (I + l/2a)n
(1-a) a ,Vi a
Mole fractions at equilibrium
(I+ ,Via) (I+ ,Vi a) (I+ ,Vi a)
( I e)( I e)112
K =IJa~' [17.12] = Ptt, p Po, p
6
[perfect gases]
J (Ptt,o IP )
& & 112
(x 8 p Ip )(x0 p Ip )
2 2 [p - x p]
( xtt,oP I P &) J - J
= (xH, )(xo, )112 [p =Pe = 1 bar]

(xtt,o)
112
11 )112 a 312 x ( -1-)
= ( 72 x ( -1-) (i)
1+ ,Vi a 1-a
The equilibrium constant is small, and consequently it is reasonable to estimate that a << 1. In this
case, the factors 1+Yi a and 1- a in eqn. (i) are approximately equal to 1.
K:::: (,Yi)112 a 312
112 2/3
a= { (Yir K}
2/3
={(rir112 ( 0.002082)}
=lo.02os41
Alternatively, the numeric solver of a scientific calculator or software package like Mathcad can be
used to acquire the numeric solution to eqn. (i). It is a= 0.02033.
P17.5 H 20(g) + DCl(g);::::: HDO(g) + HCl(g)
6 6
(HDO)
(HCl)
K = q6 q6
e -flEo l RT [17.14a· N factors cancel]
q (H20)q (DCI) , A
Use partition function expressions from Table 13.1. The ratio of translational partition functions is
312 32
q~(HDO)q;(HCl) = (M(HDO)M(HC1)) = (19.02x36.46) ' = l.04 l
qm(H 2 0)qm(DCI) M(H 2 0)M(DCI) 18.02x37.46
The ratio of rotational partition functions is
qR (HDO)qR (HCl) _ o-(H 20) (A(H 20)B(H 20)C(H 20) I cm-3)'12B(DCl) I cm-'
qR (H 20)qR (DCl) - l (A(HDO)B(HDO)C(HDO) I cm-3)' 12 B(HCl) I cm-'
12
= x (27.88xl4.5lx9.29)' x5.449 = 1.
2 707
(23.38x9.102 x6.417) 112 xl0.59
(O"= 2 for H20; O"= l for the other molecules)

The ratio of vibrational partition functions (call it Q) is
qv (HDO)q v (HCl) = q(2726.7)q(1402.2)q(3707.5)q(2991) = Q

qv (H 0)q v (DCl) q(3656.7)q(1594.8)q(3755.8)q(2145)
2
1
where q(x) = l -e-1.43 88x t(T t K)
Mo = !{(2726.7+1402.2 + 3707.5+2991)-(3656.7+1594.8 +3755.8 + 2145)}cm- 1

he
= -162cm-'
So the exponent in the energy term is

-M I RT=_ M 0 =_hex M 0 x_!_ = l.4388x(-162) = + 233
0
kT k he T TIK TIK
Therefore, K = 1.041x1. 707 x Q x e 2331<TtKl = 1. 777 Qe 2331<r 1K>_
We then draw up the following table (using a computer).
Tl K 100 200 300 400 500 600 700 800 900 1000
K 18.3 5.70 3.87 3.19 2.85 2.65 2.51 2.41 2.34 2.29
Specifically, (a) K = 13.891at298 Kand (b) K =12.411 at 800 K.
P17.7 CH 4(g) ~ C(s) + 2 H 2(g)

This reaction is the reverse of the formation reaction. Consequently,
!i,GB = -tirGB = -( t'l.rHB -T t'l.rSB)
=-{-74.85 kJmoi- 1- (298 K)x(-80.67 JK- 1 mol-')}

= +50.81 kJ mol-'
(a) K = e -tJ.,G" t Rr [17.13]

= e-(5.08 IxI04 Jmol-1 )/(8.3145JK-1 mol- 1x298K)
= li.24 x 10-9 1
(b) !i,HB = -/'J.rHB = 74.85 kJ mor'
1 1
lnK(50°C)= lnK(298K)-ti,HB(-- - -- ) [17.28)
R 323 K 298 K
7 4
= -20.508-( .4 85 0xl0 J mo!-' )x(-2.597xI0-4) = -18.170
8.3145 J K -' mol- 1
K(SO 0 C)=/1.29x10-8 /
P17.9 co 2 (g) ~ co(g) +Yi 0 2 (g)

Draw up the following equilibrium table and recognize that, since <Xe << 1, <Xe may be neglected
when compared to 1 within mole fraction factors.
C0 2 co 02
Amounts (1-ac)n a.n .Yiacn
I-a. a. .Yi ac
Mole fractions
I+ .Yi a. 1+ ,Yi ac I+ .Yi a.
Approximate mole fractions a. .Yia.
K = IJ a;; [17.12] = ( Pco I p e)( Po,eI p e)112 [perfect gases]

J Pco, I P
112
XcoXo ~ 1 12
=-- ' (pl P~ ) [P1 =X1P]
Xco,
x x 1122 [
=co- 0- p=pe]
Xco,
1/2
=a. ( ,Via. )
3
= (Yia. )1'2 (i)
A,G 6 =-RTlnK [17.13] (ii)
The calculated values of Kand A,G 6 are given in the table below.
T/K 1395 1443 1498

a c I 10-4 1.44 2.50 4.71
KI 10""° 1.22 2.80 7.23
6 1
6.,G I kJ mor 158 153 147
6.,S 6 I J K- 1 mor' 102 102 102
A,He can be calculated from any two pairs of K and T.
1n K 2 = 1n K - A,He
I R T2
(_!_ __!_J
T
[17 .28]
I
Solving for A,H 6 ,
R1 J ~2 J (8.3145 J K- 1 mor 1)xlJ7.23x10:)

A,He= ll\ i = '\l.22x10 =1300.kJmor1j
(~ -JJ (13i5K-14i8K)
(iii)
K, A,G 6 , and A,S 6 are calculated with eqns. (i), (ii), and (iii).
COMMENT. 6.,S 6 is essentially constant over this temperature range, but it is much different from its
6
value at 25°C. A,H , however, is only slightly different.
Question. What are the values of A,H 6 and A,S 6 at 25°C for this reaction?
P17.11 A, G 6 (H 2CO, g) = A, G 6 (H 2CO, I)+ Avap G 6 (H 2CO, I)
For H 2CO(l) r:= H 2CO(g), K(vap) = Pe where p = 1500 Torr= 2.000 bar andp 6 =1 bar.
p
Avap G 6 =-RTlnK(vap) = -RTln 1:

p
uJ\ .000
2
= -(8.3145 J K- 1 mor 1) x (298 K) x 1 bar ) = -1. 72 kJ mor 1
1 bar
Therefore, for the reaction CO(g) + H 2(g) r:= H 2CO(g),
A,G 6 ={(+28.95)+(-1.72)} kJmoi- 1 =+27.23 kJmo1- 1

Hence, K = e(-27.23xI03 J mo1- 1)1(8.3145 J K- 1mo1- 1)x(298 K) = e-I0.99 = li.69 x 10-s 1.
P17.13 Draw up the following table for the reaction H 2(g) + 12 r:= 2Hl(g) K = 870.
H2 I2 HI Total
Initial amounts/mo! 0.300 0.400 0.200 0.900
Change/mo I -x -x +2x
Equilibrium amounts/mo! 0.300- x 0.400- x 0.200+2x 0.900
0.300-x 0.400- x 0.200+2x
Mole fraction ---
0.900 0.900 0.900
K - (Pm I p e )2
- (p Pe)( 6 ) [perfect gases]
H, 1 P1, 1 p
2 2
= (xm) [ - ] (0.200+2x)
P1 - X Jp = 870 [ .
( xH, )( x1, ) (0.300- x)(0.400- x) = given]
Therefore,
(0.0400) + (0.800x)+ 4x 2 = (870)x(0.120-0.700x + x 2 ) or 866x 2 -609.80x+104.36 = 0
which solves to x = 0.293 x = 0.411 is excluded because x cannot exceed 0.300] . The final
composition is therefore 0.007 mol H 2 , I0.107mol1 2 I, and lo.786 mo! ml .
P17 .15 If we know A,H 6 for the reaction CJiO(g) + H20(g) ~ 2 HOCl(g), we can calculate ArH 6
(HOCl) from
A,H 6 = 2 ArH 6 (HOCl,g)-ArH 6 (Cl 2 0 ,g)-ArH 6 (H 2 0 ,g)
We can find A,H 6 if we know A,G 6 and A,S 6 since
A,G 6 = A,H -T A,S
And we can find A,G 6 from the equilibrium constant.
K = exp(-A,G 6 !RT) so A,G 6 =-RTlnK
A,G 6 =-(8.3145 x l0-3 kJ K- 1mol- 1)x(298 K)ln(8.2 x l0-2 )

= 6.2 kJ mol- 1
Ar H 6 =A r G 6 +TA r S 6
= 6.2 kJ mol- 1 +(298 K) x (16.38xl0-3 kJ K- 1 mol- 1) ,
1
= 11.l kJ mor
Finally,
.£\,He(HOCl,g) = Yi[L\,He +.£\,He(Cl 2 0,g)+.£\,He(H 2 0,g)]
= Yi[l l.1+77.2 +(-241.82)) kJ mor'

= 116.8 kJ mor' I
P17.17 L
Products-Reactants,i
vi =vNH, +vN, +vtt, =l-Yi-Yi=-l
This is the ammonia formation reaction for which we find the standard reaction thermodynamic
functions in the text appendix (Table 14.6) .
.£\,He (298 K) = -46. l l kJ and .£\,Se (298 K) = -99.38 J K- 1
Use appendix information to define functions for the constant-pressure heat capacity of reactants
and products (Table 14.2). Define a function L\,C: (T) that makes it possible to calculate L\,CP at
1 bar and any temperature (eqn. 14.48). Define functions that make it possible to calculate the
reaction enthalpy and entropy at 1 bar and any temperature (eqns. 14.47 and 15.29) .
.£\,He (T) = .£\,He (298) + fr .£\, Cp~ (T) dT

Ji98.15K
.£\ Ce(T)
.£\ Se (T) = .£\ Se (298) + ( ' P dT
r r Ji9S.15K T
(i) For a perfect gas reaction mixture, L\,H is independent of pressure at constant temperature.
Consequently, L\,H(T, p) =.£\,He (T) . The pressure dependence of the reaction entropy may
be evaluated with the expression
L\,S(T,p)=L\,S~(T)+ L viJ:ar [asm.i) dp

Products-Reactants,1 dp T
= .£\,Se (T) - L .vi r:ar [aarvm,i) dp

Products-Reactants,t p
(Table 15 .5)
= L\,Se(T)- L
V; r
bar
R dp
P
= L\,S~ (T)-[ L V;] R ln (_.!!_) = L\,S~ (T)-(-1) R ln (_.!!_)

Products-Reactants,i 1 bar 1 bar
= .£\,Se (T) + R ln (_.!!_)

1 bar
The above two equations make it possible to calculate L\,G(T,p).
L\,G(T,p) = L\,H(T,p)-TL\,S(T,p)
Once the above functions have been defined on a scientific calculator or with mathematical
software on a computer, the root function may be used to evaluate pressure where L\,G(T,p) =
-5001 at a given temperature.
(a) and (b) perfect gas mixture:
For T = (450+ 273.15)K = 723.15 K, root(.£\,G(723 .15 K,p) + 500J)=1156.5 bar!.
For T = (400+ 273.15)K = 673.15 K, root(.£\,G(673.15 K,p)+ 500J)=181.8 barJ.

(ii) For a van der Waals gas mixture, li,H does depend upon pressure. The calculation equation is
li,H(T,P)=li,HB(T)+ L viJ:,(a~m.i ) dp
Products-Reactants.i 'P r
[The sum involves the i =I, 2, 3 gases (NH 3 , N 2 , or H 2 ) ]
=Ii r Hf}(T)+ "L..J

v1.Jib
fP
ar
[v -r(avm,iJ
a
m,1
] T
p
dp
[The equation of this substitution is proven below. *]
where (CJVm.JoT)P = R(Vm,i -bS'(RT(Vm,i -bS -2aY~.: r' for each gas i (NH 3 , N 2 , or H 2 ) and
2
Vm)T,p)=root [ p V.RT a )
-b +-'
2
m,1 I vm,i
The functional equation for li,S calculations is
Ii S(T,p) = li,SB(T)-
r
L
Products-Rcactants,i
vi~fP
bar
(avaT .)
~
P
dp
where (aVm)aT)P and Vm,i (T,p) are calculated as described above. As usual,
li,G(T,p) = li ,H(T,p)-Tli,S(T,p)
(a) and (b) van der Waals gas mixture:
For T = 723.15 K, root(li,G(723.15 K,p)+500 J) = /132.5 bar/ .

For T = 673.15 K, root(li,G(673.15 K,p)+500 J) =/73.7 bar/.
van der Waals gas approximation

1000
500
I
0
E
..... 0
-""
.....
'i.
<l
-500
-1000
60 80 100 120 140 160 Figure 17.1
p/bar
(c) li,G(T,p) isotherms (see Fig. 17.1) /confirm/ Le Chatelier's principle. Along an isotherm, li,G
decreases as pressure increases. This corresponds to a shift to the right in the reaction equation and
reduces the stress by shifting to the side that has fewer total moles of gas. Additionally, the reaction is
exotherrrtic, so Chatelier's principle predicts a shift to the left with an increase in temperature. The
isotherms confirm this as an increase in Ii, G as temperature is increased at constant pressure.
*Many thermodynamic equations are very useful when deriving desired computation equations.
One of them (used above) is (~;J =-T(~;)P +V. To prove this relationship, first use an
identity of partial derivatives that involves a change of variable:
( oH)
ap T
= ( aH \
as (as) + (
JP ap T
oH)
ap S
We will be able to identify some of these terms if we examine an expression for dH analogous to
the fundamental equation of thermodynamics [15.54]. From the definition of enthalpy, we have
dH = dU + pdV +Vdp = TdS- pdV [15.54]+ pdV +V dp = TdS+ V dp
Compare this expression to the exact differential of H considered as a function of Sand p:
Thus, (~~)P =T, (~;)s =V [dHexact].
Substitution yields (~;)r =T(~;)r +V= -r(~)P +V [Maxwell relation].

P17 .19 The electrode half-reactions and their potentials are
Ef}-
R: Q(aq)+2W(aq)+2e- -7QH 2 (aq) 0.6994 v

L: Hg 2Cl 2 (s)+2e- -72Hg(l)+2Cr(aq) 0.2676 v
Overall (R-L): Q(aq)+2W(aq)+ 2Hg(l)+ 2Cr(aq)-7 QH 2 (aq)+ Hg 2 Cl 2 (s) 0.4318 v
Q(reaction quotient)= ~(QH 2 ) 2

a(Q)a (W)a (Ci-)
Because quinhydrone is an equimolecular complex of Q and QH 2 and m(Q) = m(QH 2 ), and their
activity coefficients are assumed to be I or to be equal, we have a(QH 2 ) "'a(Q). Thus,
1 25 7
and E = Ef}- - · mV In Q [17.32, 25°C]
Q = a 2 (H+)a 2 (Ci-) v
lnQ=v(Ef}--E)=(2)x(0.4318-0.190)V =l 8.82 and Q=l.49 x 10s

25.7 mV 25.7xl0-3 V
For HCI(aq), b+ = b_ = b , and if the activity coefficients are assumed equal, a 2 (H+) = a 2 (Ci-); hence
1
Q= a 2 (W)a 2 (Ci-) = a 4 (H+)
114 114
1 3
Thus, a(W)=(_!_) =( ) =9x10-
Q 1.49x108
pH= -log a(H+) = 12.ol
P17.21
E = Ef}- - RT In a(W)a(Cr) [17.32]

F
a(W) = Y+b+ = r+b; a(Cr) = y_b_ = y_b [b = b I bf}- here and below]
E = Ef} - 2RT In b - 2RT In r (i)

F F ±
Converting from natural logarithms to common logarithms (base 10) in order to introduce the
Debye-Htickel expression, we obtain
f} (2.303)x2RT l b (2.303)x2RT l
E=E - og ogy±
F F
=Ef} -(0.1183 V)logb-(0.1183 V)logy±
=Ef} -(0.1183 V)logb-(0.1183 V)[-1 z+z-1 AJ 112 J

112
= Ef} -(0.1183 V)logb+(0.1183 V)xAxb [I =b]
Rearranging,
E+(0.1183 V)logb = Ef} +constantxb 112
Therefore, plot E + (0.1183 V) log b against b 112 , and the intercept at b = 0 is Ef} I V . Draw up the
following table.
bl(mmol kg- 1) 1.6077 3.0769 5.0403 7.6938 10.9474

112
(b l bf}) 0.04010 0.05547 0.07100 0.08771 0.1046
EIV +(O.l 183)logb 0.27029 0.27109 0.27186 0.27260 0.27337
The points are plotted in Figure 17.2. The intercept is at 0.26840, so Ef} = +0.26840 V. A least-
squares best fit gives Ef} = l+0.26843 vi and a coefficient of determination equal to 0.99895.
For the activity coefficients, we obtain from equation (i)
In = Ef} -E -In_£_= 0.26843-E I V In_£_

Y± 2RT I F bf} 0.05139 bf}
and we draw up the following table.
b I (mmol kg- 1) 1.6077 3.0769 5.0403 7.6938 10.9474

E IV 0.60080 0.56825 0.54366 0.52267 0.50532
In Y± -0.03465 -0.05038 -0.06542 -0.07993 -0.09500
Y± 0.9659 0.9509 0.9367 0.9232 0.9094
0.274
¢ 0.272
..,,
....._
..,,
00
.2
.....
~
-~ 0.270
>
~
0.268
0 O.D2 0.04 0.06 0.08 0.10
(bj bB) l /2 Figure 17.2
P17 .23 The cells described in the problem are back-to-back pairs of cells each of the type
M,Hg(s)IMX(b2 )IAgX(s)IAg(s)
R: AgX(s)+e- ~ Ag(s)+X-(!Ji)
L: M+ (b.z)+e- ~ MxHg(s) (reductionofM+ and formation of amalgam)
R-L: MxHg(s)+AgX(s)~Ag(s)+M+(b2 )+X-(b2 ) and v=l
Q = a(M+)a(X-)
a(MxHg)
E = E-e - RT 1n Q
F
For a pair of such cells back to back,
Ag(s) I AgX(s) IMX(b1)IM,Hg(s) I MX(b2 ) IAgX(s) I Ag(s)
(Note that the unknown quantity a(MxHs) drops out of the expression for E.)
With L = (1) and R = (2), we have
E= 2RT lnli_+ 2RT 1n Y±(l)

F b2 F Yt(2)
1
Take b2 = 0.09141 mol kg- (the reference value), and write b = b1 I b-&.
E = 2RT {1n b + 1n____2i_}

F 0.09141 Y±(ref)
For b = 0.09141, the extended Debye-Htickel law gives

AJ1'2
logy± = +CI with A= 1.461, B = 1.70, C = 0.20, and I= b I b-&
l+BI 112
2
lo (ref)= (-l. 46 l)x(0.09 l 4 l)1' +(0.20)x(0.09141) =-0.2735
gy± (l)+(l.70)x(0.09141)1 12
Y± (ref) = 0.5328
Then E = (0.05139V){ln b +ln--1!_}

0.09141 0.5328
1n = E -ln b
Yt 0.05139V (0.0914l)x(0.05328)
We then draw up the following table.
b/(mol/kg·1) 0.0555 0.09141 0.1652 0.2171 1.040 1.350

EI V -0.0220 0.0000 0.0263 0.0379 0.1156 0.1336
Y± 0.572 I0.5331 0.492 0.469 0.444 0.486
A more precise procedure is described in the original references; for the temperature dependence
of EB(Ag, AgCl, Cl-), see Problem 17.24.
P17.25 Electrochemical cell equation: ,ViH 2 (g,l bar)+AgCl(s)~W(aq)+Cl- (aq)+Ag(s) with a(H 2 )=
l bar= PB and ac,- = rc,- b
Weak acid equilibrium: BW ~ B + H+ with bsH• = bs = b
and K. = aSaH. I asH• = rs b aH. I rsH+ b = rs aw I rsH•
or aH. = rsH•K. I rs
Ionic strength (neglect bH. because bH. << b) : I =Yi {z!H• bsH' + z:r be,- } = b
According to the Nemst equation [17.32),
E =EB_ RT
F
1n( p(Hz)
aH. ac,- ) - EB RT ln(lO)
I PB - - F log(aH. ac,- )
---F ( E - E B )=-log(a . yc-b)=-log (K•ysH•Yc1-b) =pK. -log(b)-2log(y±)

1
RTln(lO) H Ys
F 2Afb
--(E-EB) = pK. -log(b)+ fh 2kb where A = 0.5091
RT ln(l 0) l+B b
The expression to the left of the above equality is experimental data and is a function of b. The
parameters pK., B, and k on the right side are systematically varied with a mathematical regression
software until the right side fits the left side in a least-squares sense. The results are
jpK. = 6.736j, Is= l.9971, and lk = -0.1211

112
-A/ )
( --1 !2+kb
The mean activity coefficient is calculated with the equation r± = 10 i+si for desired values of
1
band I. Figure 17.3 shows a Y± against! plot for b = 0.04 mol kg- and 0 $.I$. 0.1.
13
12
Y±
1J
0.9
0 0 _02 0.04 0.06 0.08 OJ

I Figure 17.3
P17.27 aA(g) + bB(g) ~ cC(g) + dD(g)
c d
= PcPo (p fY fl>n' where flrz =c+d-a-b
p~ p; 8
where
P17.29 MX(s) ~ M+(aq)+X- (aq)
The concentration of the soluble salt, b(M+) = S' , is very low compared to the concentration of the
freely soluble salt, [NX] = C. Consequently, b(X- ) = S' + C = C and the ionic strength depends on
C alone.
I= Yz( b(W)+b(X- )) [16.57] = C
1n Y± = 2.303logy± =-2.303AI 112 [16.56) where A= 0.509

Y± = e-2.JoJA1 112
and y; = e-4.606A1'"
Hence ' K s = s'c e -4.606 A1'" or S' = K ,e4'606 AI"' I C.
P17.31 The fractional saturation, s, the fraction of Mb molecules (or Hb molecules) that are oxygenated, is
related to the partial pressure of oxygen, p (= p/1 Torr), through the Hill equation,
l/ v
s (p / KHiur
log--= vlogp-vlogKHm
1-s
or
( J
p=KHmX _s_
1-s
or s=-----
l+(p / KHmr
where v and Kttin are the Hill coefficients.

(a) Letpv, be the oxygen pressure whens= Y2. Then
Yz )llv
Py, = KHiu x ( 1- Yz
=KHill
Thus, measurement of p v, directly yields KHin· The plots of Pl 7 .30 give p v, =20.0 Torr for Mb and
pv, =35.0 Torr for Mb and we conclude that IKHm(Mb) =20.tj and IKHin(Hb) =35.tj.
The fractional saturation of Mb and Hb at a given p is calculated with the equation
(p l KHmr
s= l+(p / KHiuf
The values of KHin are reported above and the values of v are given as v(Mb) = 1 and v(Mb) =2.8.
We draw up a table.
s
p/kPa pf Torr Mb Hb
1.0 7.5 0.27 0.01
1.5 11.3 0.36 0.04
2.5 18.8 0.48 0.14
4.0 30.0 0.60 0.39
8.0 60.0 0.75 0.82
(b) Using the KHin value for Hb reported above and the value v = 4 in the Hill equation,
(p / KHmr
s= l+(p / Kttm r
yields the fractional saturations reported in the following table.
p/kPa p /Torr s(Hb)

1.0 7.5 0.002
1.5 11.3 0.01
2.5 18.8 0.08
4.0 30.0 0.35
8.0 60.0 0.89
P17.33 !:J.,G=!:J.,Gf} +RTlnQ [17.9]
In Equation 17.9, molar solution concentrations are used with 1 M standard states. The standard
state(&) pH equals zero in contrast to the biological standard state(E9)of pH 7. For the ATP
hydolysis
ATP(aq) + H20(1) ~ ADP(aq) + pi-(aq) + H3o•(aq)
we can calculate the standard-state free energy given the biological standard free energy of about -31
kJ mor 1 (Impact on biology 17.1).
!:J.,Gfl! = !:J.,Gf} +RT In Qfl! [17.9]
!:J.,Gf} = !:J.,Gfl! - RT In Qfl!
=-31 kJ mor' -(8.3145 J K-' mor')x(310 K)ln(lo-7 Mil M)
= +11 kJ mor 1
This calculation shows that under standard conditions, the hydrolysis of ATP is not spontaneous! It
is endergonic.
The calculation of the ATP hydrolysis free energy with the cell conditions pH= 7 and [ATP]= [ADP] =
[P;-] = 1.0xl0-6 Mis interesting.
11 G = 11 Ge + RT In Q = 11 Ge + RT!n([ADP]x[P;- ]x[H+])
' ' ' [ATP]x(l M) 2
= +11 kJ mo1- 1 +(8.3145 J K- 1 mor 1 )x(310 K)ln(lO~ xl0-7 )
=-66 kJ moi- 1
The concentration conditions in biological cells make the hydrolysis of ATP spontaneous and very
exergonic. A maximum of 66 kJ of work is available to drive coupled chemical reactions when a
mole of ATP is hydrolyzed.
P17 .35 Yes, a bacterium can evolve to utilize the ethanol/nitrate pair to exergonically release the free
energy needed for ATP synthesis. The ethanol reductant may yield any of the following products:
CH 3CH 2 0H ~ CH 3CHO ~ CH 3COOH ~ C0 2 + H 2 0

ethanol ethanal ethanoic acid
The nitrate oxidant may receive electrons to yield any of the following products:
nitrate nitrite dinitrogen ammonia

Oxidation of two ethanol molecules to carbon dioxide and water can transfer 8 electrons to nitrate
during the formation of ammonia. The half-reactions and net reaction are
2 [CH 3 CH 2 0H(l) ~ 2C0 2 (g) + H 2 0(1) + 4 H+ (aq) + 4e- ]
NOJ"(aq)+9 H+(aq)+8 e- ~ NH 3 (aq)+3 H 2 0(1)
11,Ge = -2331.29 kJ for the reaction as written (a Tables 14.5 and 14.6 calculation). Of course,
enzymes must evolve that couple this exergonic redox reaction to the production of ATP, which
would then be available for carbohydrate, protein, lipid, and nucleic acid synthesis.
P17.37 The half-reactions involved are
R : cytox + e- ~ cyt,cd
L: D 0 x +e - ~D red
The overall cell reaction is
R-L: cytox + Dred ~ cyt ,cd + Dox
(a) The Nemst equation for the cell reaction is
At equilibrium, E = 0 ; therefore,
In [ cyt rcd]eq [D o.Jeq = _£._ (Ee _Ee )

[cyt 0 J eq [ D,cd ]eq RT cyt D
Thus, a plot of In ([g:t) against In U~~i: ) is linear with a slope of 1 and an intercept of
_f_ (Ee -Ee ).

RT cyt D
(b) Draw up the following table.
1nCDo. ~ J -5.882 -4.776 -3.661 -3.002 -2.593 -1.436 -0.6274

[Dred~
1n( [cytox~
[cytred~
J -4.547 -3.772 -2.415 -1 .625 -1.094 -0.2120 -0.3293
The plot of 1n[[~::1:)against 1n[t~;:t}s shown in Figure 17.4. The intercept is -l.2124.
Hence,
RT
E! =-x(-l.2124)+0.237V
F
= 0.0257Vx(-l.2124)+0.237 V
=l+o.206 vi
o~~~~~~~~~~~~~~~~~~~~
0
-I f- ................ i..................i. ............ ····-'·················-'··
- -y =-1.2124+ l.0116x R=0.99427
8- -2
~
-
B
~
~
-3
B -4
c
-5
-6~~~~~~~~~~~~~~~~~~~~
-5 -4 -3 -2 -1 0
In([ cyt0 xleq I [CYlredleq) Figure 17.4
P17.39 (a) Thecellreactionis H 2 (g)+ ,Vi 0 2 (g)~ H 2 0(l) v=2
t:..,G 6 = t:..rG 6 (Hp,l) =-237.13 kJ mol-1 [Table 14.6]
Ee= t:..,Ge [l 7.30] = +237.13 kJ mo1-1 - l+I.23 vi

vF (2)x(96.485 kC mol- 1)
(b) C6 H 6 (1)+ 1% 0 2 (g) ~ 6 C0 2 (g)+3 H 20(l)
!:..rG 6 =6 !:..rG&(C0 2 ,g)+3 !:..rG&(Hp,l)-t:..rG&(C 6 H 6 , l)

= (6)x(-394.36)+(3)x(-237.l3)-(+124.3.03)] kJ moi- 1 [Tables 14.5 and 14.6]
= -3201.58 kJ mo1- 1
To find the value of v for this reaction, recognize that a carbon atom in benzene has a -1 oxidation
state while a carbon atom in carbon dioxide has a +4 oxidation state. This is a change of +5 per
carbon or +30 per benzene molecule. Thus, v = 30 for the reaction equation. Alternatively, to finp v
we break the cell reaction down into half-reactions as follows.
R: 1Yi 0 2(g)+30 e- +30W(aq)--t15 H 20(l)
L: 6 C0 2(g)+30 e- +30 W(aq)--t C6H 6(1)+12 H 20(l)
R - L: C6H6(I)+ 1Yi 0 2(g) --t 6 co2(g) + 3 H20(1)
Once again, we find that v = 30.
1
Therefore E 6 = -t:i.Ge [17.30) = +320 1.5 8 kJ moi- = l+l.11 vi.
' vF (30) x (96.485 kC mol- 1)
P17.41 A reaction proceeds spontaneously if its reaction Gibbs function is negative.
!:i.,G=!:i.,G6 +RTlnQ [17.9]
Note that under the given conditions, RT= 1.58 kJ mol- 1•
(i) !:i.,G I (kJ mol- 1) = {!:i.,G 6 (i)- RT In Ptt,o }/kJ moi- 1 = - 23 .6-1.58 ln(l.3x 10-1 )
=+1.5
(ii) !:i.,G I (kJ mol- 1) = {!:i.,G6 (ii)-RT In Ptt,oP HNo, } I (kJ moi- 1)
= -57.2- l.58ln[(l.3 x 10-7 ) x (4.lx 10 10 ))
=+2.0
(iii) !:i.,G I (kJ moi- 1) = {!:i.,G6 (iii)- RTln Ptt,o2 PHNo) I (kJ mol- 1)
= -85 .6- l.581n[(l.3x 10-1 ) 2 x (4. lxl0- 10 ))
=-1.3
(iv) t:i.,G I (kJ mol- 1 ) = {!:i.,G6 (iv)- RT In Ptt,o3 PHNo, } I (kJ mol- 1 )
= - l 12.8-1.58ln[(l.3 x 10-1 ) 3 x (4.lx!0- 10 ))
=-3.5
So both the dihydrate and trihydrate form spontaneously from the vapor. Does one convert
spontaneously into the other? Consider the reaction
which may be considered as reaction(iv) - reaction(iii). t:i.,G for this reaction is

t:i.,G = !:i.,G(iv)- !:i.,G(iii) =- 2.2 kJ mol- 1
We conclude that the dihydrate converts spontaneously to the ltrihydratel, the most stable solid
(at least of the four we considered).
PART s Chemical dynamics
18 Molecular motion
018.1 The assumptions of the kinetic model of gases are presented in text Section 18.1. The following
critique emphasizes conditions for which the fundamental assumptions may not be applicable:
The gas consists of molecules of mass m in ceaseless random motion obeying the laws of
classical mechanics. Critique: The laws of classical mechanics include the conservation of
particulate total energy, linear momentum, and angular momentum. These laws are predicated
on the assumption that gaseous matter exhibits the particulate behavior alone to the exclusion
of electron wave behavior that is required to explain chemical reactions that may occur during
particle collisions. Furthermore, the assumption of ceaseless random motion means that the
simple kinetic model does not include a description of convective flow or diffusion. (This
restriction is relieved by dividing the gas into very small adjacent volumes in which each
separate volume is characterized by its own temperature, pressure, and composition.)
The size of the molecules is negligible, in the sense that the diameters of the molecules are
much smaller than the average distance traveled between collisions. Critique: A molecular
gas at low molar volumes occupies a significant percentage of available space. The negligible
molecular volume restriction limits the applicability of the simple kinetic model to the limit of
zero pressure and prevents formation of a description of the van der Waals constants. However,
the restriction can be relieved by treating each molecule as a ball bearing or billiard ball of fixed
radius a and diameter d (= 2a) . The resultant hard-sphere model, which is a kind of central-force
model, allows for the estimation of the collision frequency and mean free path (see Section 8.lb
and c); it does not account for collision effects from dipole forces that are not centered on the
center-of-mass.
The molecules interact only through brief elastic collisions (collisions in which the total
translational kinetic energy of the molecules is conserved). Critique: This assumption is
inherent in the analysis of collision frequency, mean free path, and the collision frequency with
walls and surfaces. The model does not account for unevenness of surfaces, which creates surface
pockets that may trap a gas molecule during collision, or cause a gas molecule to reflect at an
angle other than the collision angle. The successful description of the simple kinetic model to
wall collisions and effusion does suggest that it describes these phenomena as an average of
many possibilities. This basic assumption of the model does not account for inelastic collisions
in which molecule collisions at high temperature can exchange energy between translational,
vibrational, and rotational degrees of freedom . This complication becomes important when the
mean translational energy is comparable to the energy difference between the ground and the first
excited state.
018.3 Diffusion is the migration of particles (molecules) down a concentration gradient. Diffusion can be
interpreted at the molecular level as being the result of the random jostling of the molecules in a
fluid. The motion of the molecules is the result of a series of short jumps in random directions, a so-
called random walk.
In the random walk model of diffusion, although a molecule may take many steps in a given time, it
has only a small probability of being found away from its starting point because some of the steps
442 STUDENT SOLUTIONS MANUAL FOR QUANTA. MATTER, AND CHANGE
lead it away from the starting point but others lead it back. As a result, the net distance traveled
increases only as the square root of the time. There is no net flow of molecules unless there is a
concentration gradient in the fluid. Also there are just as many molecules moving in one direction
as there are molecules moving in another. The rate at which the molecules spread out is
proportional to the concentration gradient. The constant of proportionality is called the diffusion
coefficient.
On the molecular level in a gas, thermal conduction occurs because of random molecular motions in
the presence of a temperature gradient. Across any plane in the gas, there is a net flux of energy
from the high-temperature side because molecules coming from that side carry a higher average
energy per molecule across the plane than do those coming from the low-temperature side. In
solids, the situation is more complex as energy transport occurs through quantized elastic waves
(phonons) and also, in metals, by electrons. Conduction in liquids can occur by all the mechanisms
mentioned.
At the molecular (ionic) level, electrical conduction in an electrolytic solution is the net
migration of ions in any given direction. When a gradient in electrical potential exists in a
conductivity cell there will be a greater flow of positive ions in the direction of the negative
electrode than in the direction of the positive electrode; hence there is a net flow of positive
charge toward the region of low electrical potential. Likewise, a net flow of negative ions in
the direction of the positive electrode will occur. In metals, only negatively charged electrons
contribute to the current.
To see the connection between the flux of momentum and the viscosity, consider a fluid in a state of
Newtonian flow, which can be imagined as occurring by a series of layers moving past one another
(Fig. 18.11 of the text). The layer next to the wall of the vessel is stationary, and the velocity of
successive layers varies linearly with distance, z, from the wall. Molecules ceaselessly move
between the layers and bring with them the x-component of linear momentum they possessed in
their original layer. A layer is retarded by molecules arriving from a more slowly moving layer
because the molecules have a low momentum in the x-direction. A layer is accelerated by molecules
arriving from a more rapidly moving layer. We interpret the net retarding effect as the fluid's
viscosity.
018.5 In the one-dimensional random walk model (Section 18.11) a particle jumps a fixed distance A. to
either the right or the left in each r unit of time with the probability of a jump to the left being equal
to the probability of a jump to the right and the sum of these two probabilities being equal to 1
because no other event is possible. This model concludes that the probability of a particle being at a
distance x from the origin after a time t is
1/ 2 1/ 2
~; ) ff~ )
2
P(x) =
(
e-x'•12142 [18.58] or P(n) =
(
e- n 12N
where th= N is the number of steps taken in time t and x!A. = n is the net number of steps traveled
from the origin.
In the freely jointed chain model of a random coil (see Further Information 18.2), the individual
polymer residues occupy zero volume and connecting bonds are free to make any angle with
respect to the previous one. In the one-dimensional freely jointed chain, the angle between
neighbors is either 0° or 180° with all residues aligned in a non-realistic straight line. The
probability that the ends of a one-dimensional freely jointed chain composed of N units of length
I are at the distance nl is
112
P(n) =
(
ff~ ) e - n' l l N [18. 73]
Since the above two equations are identical, the one-dimensional random walk model and the one-
dimensional freely jointed chain are completely analogous: the number of steps in one model are
MOLECULAR MOTION 443
analogous with the number of residue units in the other, and the number of steps traveled from the
origin are analogous to the number of unit lengths separating the chain ends in the other. The
number of left/right steps is even analogous to the number of 0° /180° residue orientations.
However, whereas there would not seem to be a limitation on a step being either to the left or to the
right, the 180° residue orientation unrealistically places one residue on another. Nonetheless, the
concepts and mathematical forms of the one-dimensional freely jointed chain can be usefully
modified and extended to more realistic random coil models.
018.7 The thermodynamic force 'Fis defined in eqn. 18.39.
'F = -( µ)
0
OX p ,T
[18.39]
This expression is a summary of the second thermodynamic law that molecules move in the
direction that minimizes the chemical potential of the molecules when p and Tare local constants. 'F
is not one of the "real" forces, such as gravity or electromagnetism; it is the negative gradient of the
chemical potential, which has a balance of terms involving enthalpy and entropy:
µ1 =(oGJ
On T ,
[16.2]=(~J
On T ,
(H-TS)
1 p , ,n 1 p, ,n
Thus, the thermodynamic force moves molecules so as to minimize the enthalpy, to which
molecular interactions provide a great contribution, while simultaneously attempting to maximize
entropy. Often one or the other of these tendencies predominates. For an ideal solution, the gradient
of the molar enthalpy is zero, so the force represents the spontaneous tendency for molecules to
disperse so that entropy is maximized.
018.9 The processes by which ions are transported across hydrophobic biological membranes are
described in a section on biochemistry, Impact on biochemistry 18.2. Passive transport involves
the spontaneous tendency for a chemical species to move down concentration and membrane
potential gradients. In active transport, the flow of a species is driven by an exergonic process,
such as the hydrolysis of ATP. The passive transport of an ion across a membrane must be mediated
by a carrier molecule that has favorable interactions with both the hydrophobic membrane and the
hydrophilic ion. The hydrophobic character is expected to lie on the periphery of the carrier, the
surface in contact with the membrane, with the hydrophilic character toward the interior, the surface
of the ion channel, so that the ion and membrane are distinctly separate. The ion may be transported
through a channel former, a protein that spans the membrane and creates a hydrophilic pore
through which the ion can pass. Ion channels are proteins that are highly selective to the
transported ion; their activity may be triggered by potential differences across the membrane or by
the binding of an effector molecule. The activity of ion pumps is endergonic and therefore requires
the coupling of an exergonic metabolic process. Selectivity filtering strips an ion of its hydration
sphere and allows passage of ions of only a specific size.
1/ 2
E18.1 (a) c= ( ~~ ) [18.8]
mean translational kinetic energy, (EK) m =(Yi mv 2

) NA =Yi mN
A ( v
2
) =Yi Mc =Yi RT.
2
The ratios of species 1 to species 2 at the same temperature are

l/ 2
~ = (~~ J and
(a)
- =( 200.6 Jl/2=19.975 1
CH,
CHg 2.016
(b) The mean translation kinetic energy is independent of molecular mass and depends on
temperature alone! Consequently, because the mean translational kinetic energy for a gas is
proportional to T, the ratio of mean translational kinetic energies for gases at the same
temperature always equals[!].
E18.2(a) c=(v2)112 =(3RT)112

M [18.3]
1 1 112
3x(8.3145 J mol- K- )x( 293 K) (1J=1 kg m 2 s-2)
cH, ={ 2.016xl0 3 kg mol i }
= h904 m s- 1I
1 1 112
c ={3x(8.3145Jmol- K- )x(293K)}
02
32.00x10-3 kg mol- 1
=1478 m s-11
3/2
E18.3(a) The Maxwell distribution of speeds is f(v) = 41l' ( __!!__ ) v'e-Mv' 12 Rr [18.4].
21l'RT
The factor M/2RT can be evaluated as
M - 28.02x10-3 kg mo1-1 = 4.2lxl0-6 m-2s2

-2RT - 2x(8.3145 J KI mor 1)x(400 K)
Though.fly) varies over the range 200 to 210 m s- 1, the variation is small over this small range and
we estimate its value to be a constant equal to its value at the center of the range.
-6 2 2)3/2 2
/(295 m s-1) = (41l')X 4 .llxl01l' m- s x(205 m s- 1) 2xe<-4·21 xio-6Jx<205 > = 6.86xl0-4 m- 1 s
(
Therefore, the fraction of molecules in the specified range is
f'"' f
low
dv [18.6] = f C'' dv = fx!1v = (6.86x10-4 m-
low
1
I
s)x(lO m s- 1) = l6.86x10-3
corresponding to 0.69 percent.
COMMENT. This is a rather small percentage and suggests that the approximation of constancy of f(v)
1
over the range is adequate. To test the approximation, !(200 m s- ) and !(210 ms-') could be evaluated.
2
E18.4(a) c*--(2RT)"
M [18.9]
112
1 1
-{2x(8.3145 J moi- K- )x( 293 K) (1J=1 kg m2 s-2)
- 44.0lxlO 3 kg mo! 1 }
= 1333 m s- 1 I
112
c= ( ~~ ) [18.8]
In
= 8x(8.3145 J mol- 1 K- 1)x(293 K)
{ JX'x( 44.0lxl0-3 kg mol- 1) }
ere!= 2112c (18.10]
= i1 12 x(375 m s- 1) = /530 m s- 1/
112
E18.S(a) (a) c = ( ~~ ) (18.8]
=/475 m s- 1/
(b) A= 11k2T (18.14] = }T 2 [er= 1X'd 2 ; see Fig. 18.9 of text]

1
2 erp 2 JX'd p
(1.38lxl0-23 J K- 1)x(298 K)
(1 atm = 1.01325 bar= l.01325xl0 5 Pa]
l1121X'x(395xl0-12 m)2x(I.01325xl0 5 Pa)
=l.84xl0-7 m [1 Pa=1Jm-3]=/184nm/
c
(c) z="I (18.13]
475 m s-1 = /2.58xl09 s-1 j

l.84xl0-7 m
E1 8.6(a) The volume and radius of a spherical container are related by
113
Thus, r ={3x( 1.00-4 m3) I 41£} = 0.0288 m.
The pressure at which the mean free path is comparable to the container diameter 2r is given by
eqn. 18.14.
kT
A.=___E_ (18.14] or p = ii12erA.
i1'2erP
P= (l.38lxl0-23 J K-1)x (293 K) = lo.138 Pa/ (1J=1 Pa m3]

(l112)x(0.36xl0- 18 m 2)x2x(0.0288 m)
E18.7(a) _ _!:!_ [18.14]

1- i '2ap
(l.38lxl0-23 J K- 1)x(217 K)
(i' )x(0.43xl0- 18 m 2)x(0.050)x(l.013xl05 Pa)
2
= 19.7x10-7 ml
E18.8(a) The collision frequency, z, is given by z = i 12 dcp I kT [18.12b and 18.10]. Since the mean speed
depends on temperature, not pressure, it can be calculated once and used in all parts of this exercise.
112
c= ( ~~ ) [18.8]
1 1 112
={8x(8.3145Jmor K- )x(298K)}
nx(39.95x10- 3 kgmoi- 1)
=J397 m s- 1J
112 - O]
_ 2 acp [18.12b and 18.l
z- kT
- i '2x(0.36x10-1s m2)x(397 m s-1) x(l.01325x10s PaJxp [Table 18.1]

- (1.381 x10-23 J K- 1)x(298 K) 1 atm
=(4.98xl09 s-1)x(p / atm)
We need only to plug in the pressure in atm to calculate z at that pressure.
(a) z =J5.0xl0 10 s-1Iwhenp=10 atm
(b) z=l5.0xl09 s- 11whenp=1 atm
(c) z = l5.0xl03 s-1I whenp = 10-6 atm
E18.9(a) A= (5.0 mm)x(4.0 mm)= 2.0xl0-5 m 2
The collision frequency of the Ar gas molecules with surface area A equals ZwA
ZwA= (2nMkTP I NA )112 A [18.15; m =M I NA]
(25 Pa)x(2.0xl0-5 m 2)
In
{ 2n(39.95xl0-3 kg mol- 1)x(1.38l x10-23 J K- 1)x(300 K) ! (6.022xl0 23 mol- 1)}
= l.2xl019 s-1
The number of argon molecule collisions within A in time interval t equals ZwAt if p does not
change significantly during the period t.
ZwAt = ( l.2xl0
19 s-1)x(lOO s) = Ji.2x 10 21 I
(rate of effusion )H
E18.10(a) If p does not change significantly during the period t, t0 = ( . ) ' !H .
' rate of effusion 02 '
112
The rate of effusion at constant temperature, pressure, and molecule count is proportional to M
[18.17]. Consequently, the above expression conveniently simplifies to
1/ 2
32 00
=( · x(135s)=l537sl
2.02 )
E18.11 (a) If p does not change significantly during the period t, the mass loss equals the effusion mass loss
multiplied by the time period t: mioss =(rate of effusion) x t x m =(rate of effusion) x t x MI NA.
mloss =[ PAoNA 1/ 2 x -
(2;rMRT) NA
l [M!J [18.17]
M )112
=pAotx ( - -
2;rRT
1/ 2
3 0.300 k moi- 1
2
=(0.735 Pa)x{;r(0.75xl0- m) }x(3600 s)x { g )
( 2;r 8.3145 J moi- 1 K- 1 x(500 K) ]
=116 mgl
E18.12(a) The pressure of this exercise changes significantly during time period t, so it is useful to spend a
moment finding an expression for p(t). Mathematically, the rate of effusion is the derivative -dN/dt.
Substitution of the perfect gas law for N, N = pVNAIRT, where V and Tare constants, reveals that
the rate of effusion can be written as -(NAVIR'I')dpldt. This formulation of the rate of effusion, along
with eqn. 18.17, is used to find p(t).
- -NAV)dp
- - pAoNA [18.17)
( RT dt - (2;rMRT(
112
dp -
- _ -PAo
-( -RT
-)
dt V 2;rM
dp dt i- = I_ ( 2;rM )112
-=-- where
p 1' Ao RT
r
Po p
dp = _.!_ dt f
i-o
where Po is the initial pressure
The nitrogen gas and unknown gas data can be used to determine the relaxation time, r, for each.
t° - fN, = 45 S = 34 S
N, - ln(p0 / p)N ln(74/20)
2
t'unk = funk = 152 S =116 S

ln(p 0 / p)unk ln(74/20)
This definition of r shows that it is proportional to M' 12 • Since the ratio of the relaxation times
cancels the constant of proportionality,
1/2
Munk = runk
[ MN ,
)
t"N ,
2
M unk = [t"unk ) M N 2
t"N,
11
2
=(
34.4
~) 1
x(28.02gmoi- )=1319 g mo1-
1
I
E18.13(a) In El8.12(a) it is shown that
p t
ln-=-- or p(t)=p0e-' 1' where
V
r = - _!!____
(2
M)1 12
Po 1" 4i RT
The relaxation time, r, of oxygen is calculated with the data.
r =[ 3.0 m
3
l{ 3 12
2;r( 32.00xl0- kg mol-1) } '
;r(O.lOxl0-3 mf x (8.3145Jmor1 K-1)x(298K) =8.6xl0s s=lO.Odays
The time required for the specified pressure decline is calculated with the above equation.
t = rln(p0 / p) = ( 10.0 days )x In (80 I 70)=11.3 days I

12
E18.14(a) K=,XILcCvm[A] [18.24], c= ( -8RT) ' [18.8]

. ;rM
and
2 C!p
-(18.14]= 112 1
IL=-1-12kT
2 CJNA[A]
[p-=NA[A]
kT
J
cCvrn
Therefore, K = •
3x2 112 CJNA
For argon M = 39.95 g mol- 1•
c= 8x(8.3145 J K-1mol-1)x(298 K) )1/2= ms-1

( 397
;rx(39.95xl0-3 kg mol- 1)
1
(397ms- )x(l2.5JK- 1mo1- )
1
/ /
k"= = 5.4x10-3 J K -1 m - 1 s - 1
112 18 2 23 1
3x2 x(0.36xl0- m )x(6.022xl0 mor )
COMMENT. This calculated value does not agree well with the value of K listed in Table 18.2.
Question. Can the differences between the calculated and experimental values of K be accounted
for by the difference in temperature (298 K here, 273 Kin Table 18.2)? If not, what might be
responsible for the difference?
c=(~1Z'r
2
E18.1 S(a) D=,XILc [18.23], [18.8], and _ __!:I_ [18.14]

IL- i '2CJp
For argon M = 39.95 g moi- 1 and a= 0.36 nm 2 [Table 18.l]. We draw a table (below) of mean
speed, mean free path, and diffusion coefficient calculations at 293 K and various pressures.
The flux due to diffusion is J = -D( d:) [18.20] where '.N is the number density and z is the
direction of the pressure gradient. Dividing both sides by the Avogadro constant converts '.N to
molar concentration c while converting the flux to number of moles per unit area per second. Thus,
de d(n ! V) D dp
J =-D - =-D = - - - [perfect gas law]
dz dz RT dz
The negative sign indicates flow from high pressure to low.
For a pressure gradient of 1.0 bar m- 1 (= 1.0 x 105 Pa m- 1) ,
5 1
( l.Oxl0 Pa m- )xD
J= =41 molm-2 s- 1xD / (m 2 s- 1)
( 8.3145 J mol- 1 K- 1)x(293 K)
The mole flux due to diffusion toward low pressure is calculated with the above equation and added
to the exercise summary table.
pl Pa c Im s- 1 A. Im DI m2 s- 1 JI mol m-2 s- 1
(a) 1.00 394 7.95 x 10- 3 1.04 43
(b) 1.00 x 105 II
7.95 x 10--S 1.04 x 10-5 4.3 x 10-4
(c) 1.00 x 107 II
7.95 X 10-IO 1.04 x 10- 1 4.3 x 10--0
E18.16(a) The flux is
dT [18.21]=-))AC'Cv,m [A ] &
J=-K-;J; dT [18.24]= }) A-cCv mP dT
RT . & [perfect gas, [ A ] =p l RT]
where the negative sign indicates flow toward lower temperature and
c=(~1Z}
12
kT RT
[18.8] and A, =-1-
/2- [18.14] =-112_ __
2 ap 2 NAap
J =_ x(
3 112RT
2 NAap
Jx(8RT) ' x(Cv,mPJx dT
trM RT dz
12
=- %x -
RT-)
( trM
112
(C J
x ~ xdT
NAa dz
For argon, M = 39.95 g mol-

1
, a= 0.36 nm2 [Table 18.l], and Cv,m = 12.5 J K- 1 mol- 1[given in
E18.14a] .
1 1 12 1
1 ((8.3145JK- mor )x(280K)) ' {
2/ 12.5JK- mol-1 } 1
=- x73 3
trx(39.95xl0- kg mol 1) 23 1
x (6.022 x l0 mor ) x (0.36x10- 18 m2) x (lO.S Km- )
=J-0.055 Jm-2 s- 1J
Note: We have used the Cv,m value provided in E18.14(a). It can, however, be calculated with the
perfect gas relationship Cv,m = Cp,m - R and the Cp,m value provided in Table 14.6 (20.786 J K- 1
mor ). This gives Cv,m = 12.471 J K- 1 mor 1•
1
E18.17(a) The thermal conductivity, K, is a function of the mean free path, ..1, which in tum is a function of
the collision cross-section, a . Hence, reversing the order, a can be obtained from K.
12
K= }) AC'Cv m[A] [18.24], c= ( -8RT) ' [18.8]
' trM
and A=-1-12kT
-[18.14]= 112 1 [p-=NA[A]J
2 ap 2 aNA[A] kT
cCv,m
Therefore, K= 3x2 112 aNA or
1 1 112
Forneonat273K, c={8x(8.3145 JK - mor )x(273K)} _1
1l'X(20.18xl0 J kg mol-1) = 535 ms .
From Table 18.2, "= 0.0465 J K- 1 m- 1 s- 1•

The Cv,m value is calculated with the perfect gas relationship Cv,m = Cp,m - R and the Cp,m value
provided in Table 14.6 (20.786 J K- 1 mol- 1). This gives Cv,m = 12.472 J K- 1 moi- 1• Alternatively, the
Cv,m value is calculated with the equipartition theorem: Cv,m = 3!2R = 12.472 J K- 1 mol- 1•
(535 m s- 1)x(12.472 J K- 1 moi- 1)

(J = -----'--------'-----'--------'----
3x i 12 x ( 6.022x 1023 mo1- 1)x(0.0465JK- 1 m- 1 s- 1)
= 5.62x10-20 m 2 = lo.0562 nm 2I
The experimental value is 0.24 nm 2.
Question. What approximations inherent in the equation used in the solution to this exercise are the
likely cause of the factor of 4 difference between the experimental and calculated values of the
collision cross-section for neon?
E18.18(a) The thermal energy flux ('heat' flux) is described by J(energy) = -K dT [18.21] where the negative
dz
sign indicates flow toward lower temperature. This is the rate of energy transfer per unit area. The
total rate of energy transfer across area A is
¥t = AJ(energy) =-KA1jf
To calculate the temperature gradient with the given data, we assume that the gradient is in a steady
state. Then, recognizing that temperature differences have identical magnitude in Celsius or Kelvin
units,
dT - !lT {(-15)-(28)} K =-4.3xl03 Km-1

&-& l.OxlO 2 m
We now assume that the coefficient of thermal conductivity of the gas between the window panes is
comparable to that of nitrogen given in Table 18.2: K ~ 0.0240 J K- 1 m- 1 s- 1.
Therefore, the rate of outward energy transfer is
dE ~ - ( 0.0240 J K- 1 m- 1 s-1)x(l.O m 2)x(-4.3xl03 K m- 1)

dt
~ 103 J s- 1 or 1103 wl
A 103 W heater is needed to balance this rate of heat loss.
E18.19(a) 'T/ = X MA:cp I RT (18.25, [A]= p l RT for a perfect gas]
We begin by substituting kinetic theory relationships for A [18.14] and c [18 .8].
112 112
RT ) (8RT) ( p ) ( M ) (8RT)
'T/=XMx ( 2"20"NAp x ;rM x RT = 3x2'120"NA x ;rM
We now solve and compute the collision cross-section for neon at 273 Kand 1 atm (1.01325 x 105 Pa).
From Table 18.2, 'T/ = 298xl0-6 P = 298xl0-7 kg m- 1 s- 1•
112
1 1
20.18xl0-3 kg moi- 1 } {8(8.3145 J K- mol- )x(273 K)}
O"= { 3x2 x(6.022xl0 23 mo1- 1 )x(298xl0-7 kgm- 1 s- 1 ) x
112
;r(20.18xl0-3 kgmoi- 1 )
=l.42xl0- 19 m 2 =I0.142 nm 2 I
E18.20(a) Taking air to be composed of 20% oxygen and 80% nitrogen, we estimate the average molar mass
of air to be M = (0.20 x 32 + 0.80 x 28) g mor' = 29 g mor'.
112
'T/ = -1 mAc°""NA[A] (18.25, with M = mNA] = ( .!!!_) x (4RT)

-
3 30" ;rM
27 1 1 112
= ((29)x(l.6605xl0- kg))x((4)x(8.3145 J K- mol- )xT)
(3)x(0.40xl0- 18 m 2 ) ;rx(29xl0-3 kgmol- 1)
= (7.7xl0-7 kg m- 1 s- 1 )x(T I K) 112
(a) At T = 273 K, 'T/ = 1.3xl0-5 kg m- 1 s- 1 or 1130 µPl.

(b) AtT = 298 K, 'T/ = J130 µPJ .
(c) At T = 1000 K, 'T/ = J240 µPJ.
E18.21 (a) We take the natural logarithm of eqn. 18.26, evaluate the resultant constant with a specific ( T], T) 0
data pair, and solve for the activation energy, E •.
'T/ oc eE,I RT [18.26]

In 'T/ = constant + E. I RT
constant = In 'Tio - E. I RTa
Therefore,
R In ( TJ I TJo )
E, = (f-;J
(8.3145 JK- mo1- )xin(l.002 / 0.7975) I -ij
1 1
= ( - l_ _ _ l _ ) =_16.8Jmol .
293 K 303 K
E18 22(a) Molar ionic conductivity is related to mobility by
A= zuF [18.37]
= lx(7.9lxl0-8 m 2 s- 1 y -I )x(96485 c mor 1 )
= l7.63xl0-3 S m 2 mo1- 1 J
E18.23(a) s = u'E. [18.35] and 'E. = fl.¢ [18.31].

l
Therefore,
s =u( ~</J)
2 25.0V )
= (7.92xlo-s m s-i y -i)x ( 7.00xlO 3 m
= 2.83x10-4 m s- 1 or 1283 µm s- 1I
E18.24(a) The basis for the solution is Kohlrausch's law of independent migration of ions (eqn. 18.30).
Switching counterions does not affect the mobility of the remaining other ion at infinite dilution.
0
A,,, = V+A+ +V_A_ [18.30)
A,,, (Nal) = A.(Na+)+A-(i-) = 12.69 mS m 2 moi- 1

0
A,,, 0 (NaN0 3 ) = A.(Na +) + A.(NO~) = 12.16 mS m 2 mol- 1
A,,, 0 (AgN0 3 ) = A.(Ag+)+A.(NO~) = 13.34 mS m 2 mol- 1
Hence,
A,,, Agl) =A,,, AgN0 3 ) +A,,, (Nal)-A,,, (NaN0 3 )

0
(
0
(
0 0
=(13.34+12.69-12.16) mSm 2 mol- 1 =l13.87mSm 2 moi- 11
Question. How well does this result agree with the value calculated directly from the data of Table
18.5?
A.
E18.25(a) u = - [18.37];z= 1; 1 S=l n-1 =1 cv-1 s- 1
zF
u(Li+) = 3.87 mS m2 moi-1 = 4.0lxlO-s mS c-1m2=14.0lxlO-s m2 y -1 s-1 I

9.6485xl0 4 Cmoi- 1
u(Na+) = 5.01 mS m2 moi-1

9.6485x104 Cmo1-1 = l5.19x10-s m2 y-1 s-1 I
+ 7.35 ms m2 mol-1 = l7.62X10-8 m2 v I S 11

u(K ) = 9.6485xl0 4 Cmoi- 1
uRT
E18.26(a) D =- [18.45]; z = 2; 1 CV= 1 J
zF
D=
(8 .19x10-8 m 2 v-1s- 1)x(8.3145JK-1 mo1- 1)x(298K) I _ _
= 1.05xl0 9 m 2 s 1
1
4
2x9.6485xl0 C mol- 1
E18.27(a) Eqn. 18.57, (x 2) = 2Dt, gives the mean square distance traveled in any one dimension in time t.
We need the distance traveled from a point in any direction. The distinction here is the distinction
between the one-dimensional and three-dimensional diffusion. The mean square three-dimensional
distance can be obtained from the one-dimensional mean square distance since motions in the three
directions are independent. Since r 2 = x 2 + y2 + z 2 [Pythagorean theorem],
(r2 ) = ( x 2 ) + (y2 ) + ( z 2 ) = 3 ( x 2 ) [independent motion]
= 3 x 2Dt [18.57 for (x )J = 6Dt

2
2
(r
Therefore, t = - - =
) (5.0x 10- m)
3
J
2
J
=6.2xl0 3 s .
6D (6)x(6.73xl0- 10 m 2 s- 1 )
E18.28(a) a=
6:J;D [18.49] ; 1P=10- 1
kg m- 1 s- 1
(1.38lxl0-23 J K- 1 )x(298 K)
a= = 4.2x10- 10 m or J420pmJ
6n-x(1.00 x l0-3 kg m- 1 s- 1 )x(5 .2x10- 10 m 2 s- 1 ) · ·
E18.29(a) The Einstein-Smoluchowski equation [18.59) relates the diffusion constant to the jump distance A.
and jump time r.
42
D = A.2 [18.59] SO T=-
2-r 2D
If the jump distance is about 1 molecular diameter, or 2 effective molecular radii, then the jump
distance can be obtained by use of the Stokes-Einstein equation [18.49) .
A. = 2a = 2( _!:!__) [18.49] = __!:!__

6m?D 3m-JD
'f= 2~xC;D )
2
2
23 1
1 { (1.38lxl0- J K- )x(298 K) )
= x [Table 18.4]
2x(2.03 x l0-9 m 2 s- 1 ) 3n-x(0.89l x l0- 3 kgm- 1 s- 1 )x(2.03x10-9 m 2 s- 1 )
= l.44 x l0- 11 s = J14.4 psJ
COMMENT. In the strictest sense we are again dealing with three-dimensional diffusion here (cf. E18.27a
and b). However, since we are assuming that only one jump occurs, it is probably an adequate
approximation to use an equation derived for one-dimensional diffusion. For three-dimensional diffusion,
the equation analogous to eqn. 18.59 is r = ).2/60.
Question. Can you derive the equation? Use an analysis similar to that described in the solution to
El8.27.
E18.30(a) The diffusion equation solution for these boundary conditions is provided in eqn. 18.54 with
1 mo! sucrose) _
n0 = (20.0 g)x
( = 5.84 x l0 2 mol sucrose
342.30 g
c (x,t) =
n0 e-x' 14 D' [18.54]
2
A(n-Dt(
2
5.84X10- mol -(0.10 m) 2 /4x(5.216xl0-9 m 2 s-1)xt
c (10 cm,t ) = u2 e
(5 .0xl0-4 m 2)x{.1l'(5.216x10-9 m 2 s- 1)} t 112
= (9.12x10 5 mo! m-3)x(t/sr112e-(4.79x10'Jt(1tsJ
(a) t= 10 s:
c(lO cm,10 s) = (9.12xl05 mo! m-3)x(lor 112e-l479 x10' J1<10> = lo.oo mol drn-31
(b) t= 24 x 3600 s = 8.64 x 104 s:
c(lO cm,8.64x104 s) = (9.12x10s mo! m-3)x(8.64xlo4r112e-(4.79x1o')t(8.64xIO'J
= 12.1 mol m- 3 = lo.0121 mol dm-31
E18.31 (a) For a random coil, the root mean square separation is
Rrms = N 112 l [18.76] where N is the number of jointed chain units of length l
= (900) 112 x(l.05 nm)= \381.5 nml
E18.32(a) The repeating unit (monomer) of polyethylene is (-CH2-CH2- ) , which has a molar mass of
28 g mo1- 1• The number of repeating units, N, is therefore
1
N = 300 000 g mol- = 1.0 7 xl04
28 g mol- 1
and l = 2R(C-C) [add half a bond-length on either side of the monomer].

Since R(C-C) = 154 pm, l = 308 pm.
Therefore,
4 6
Re= Nl [18.75] = (1.07Xl0 )X(308 pm)= 3.30xl0 pm=13 .30 µml
4
Rrms = N lf 2 [ = (1.07xl0 )1/2 x(308 pm)= 3.19Xl0 4 pm= I0.0319 µml
P18.1 The time in seconds for a disk to rotate 360° is the inverse of the frequency . The time for it to
advance 2° is (L]x.!_ .
360° v
This is the time required for slots in neighboring disks to coincide along
the atomic beam. For an atom to pass through all neighboring slots, it must have the speed
1
vx =disk spacing/alignment time= (1.0cm) / {[L)x.!.}=180vcm = 180x(v I Hz) cm s- .
360° v
Hence, the distributions of the x-component of velocity are as follows.
vi Hz 20 40 80 100 120
1
vxl cm s- 3600 7200 14400 18000 21600
fexp (40 K) 0.846 0.513 0.069 O.Gl5 0.002
fexp (100 K) 0.592 0.485 0.217 0.119 0.057
Theoretically, the velocity distribution in the x-direction is

112
f(vJ=
(
;T
)
e-mv;r 2kT [18.SwithMIR=mlk]
2
Therefore as I oc f I oc T- 112 e-mv; I 2kT

' '
83.80x( l.6605x 10-27 kg )x{ l.80x (v!Hz) m s- 1
2
Since mv I 2kT = - - - - - - - - - - - --,------
r( l.63x 10-2 )x( J.1Hz )
2
x 2x(l.381xl0-23 J K- 1 )xT TIK
we can write I oc (T /Kf1 12 e-1. 6Jxw-'x<>1ttzJ'r(T1KJ and draw up the following table, obtaining the
constant of proportionality by fitting I to the value at T = 40 K, v = 80 Hz.
vi Hz 20 40 80 100 120
fcalc (40 K) 0.80 0.49 (0.069) 0.016 0.003
fcalc (100 K) 0.56 0.46 0.209 0.116 0.057
The calculated values are in fair agreement with the experimental data.
P18.3
K
and -= -
K
(T')
T
112
(C'vm)
x --
·
Cv,m
The molar heat capacities at the two temperatures are estimated with the equipartition theorem.
At 300 K there are three translational degrees of freedom and two rotational degrees of freedom,
which gives Cv ,m "'(3 + 2)+R = f R. At 10 K the rotational degrees of freedom are not significantly
populated, so there are three translational degrees of freedom alone, which gives Cv,m "'f R.
Therefore, 300)1/ x (5)

~ = (IO "3 =[TI.
2
P18.5 The time constant for the exponential mass loss is
112
T = (21t'M) V
RT A
21t'X (137.33x10-3kg mo!- l) }1 12 10ox10-6 m3

= x =8.12s
{(8.3145JK- 1
mo1- 1 )x(1573K) (o.lOxl0-6 m 2 )
The expression for the exponential pressure decay is

p ( t) = p 0 e- irr or t = T In (Po I p) where p 0 is the initial pressure
Thus, the time required for the pressure to drop to 10% of the initial value is
t=(8.12 s)xin(10)=l18.9 sl
P18.7 We take the natural logarithm of eqn. 18.26,
'17 oc eE, I RT [18.26)

In 1l =constant+ E. I RT
and recognize that a plot of In TJ against l/T has a slope equal to E.IR. Thus, a linear regression fit of
In T/ against l/T, shown in Figure 18.1, yields the slope from which we calculate E. with the
expression E. = slope x R.
1
E. =(1222 K) x (8.3145 JK- 1 moi-')=110.2 kJmoi- 1
0 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
- 0.2
)" = 1221. 7.Y- -L'\ 953
R Z=0.9994
- OA
~
5-0.6
.s
- 0.8
- 1
- 1.'.!
0.00'.!8 0.003 0.0032 0.003-1 0.0036
K rr Figure 18.1
P18.9 The molar conductivity, Am, is related to the conductivity, K , by Am Kie [18.28], and the
Kohlrausch law [18.29) indicates that molar conductivity is linear in c 112 •
-'\n = -'\n ° -'l{s: 112 [ 18.29]
We draw a data table and calculate values for a plot of Am against c 1n.
c I (mol dm-3) 1.334 1.432 1.529 1.672 1.725

KI (mS cm- 1) 131 139 147 156 164
c 112 / (mol dm- 3) 112 1.155 1.197 1.237 1.293 1.313
AmI (mS m2 moi- 1) 9.82 9.71 9.61 9.33 9.51
The plot, shown in Figure 18.2, is linear and the linear regression fit yields the Kohlrausch
parameters:
-'\n ° =112.78 mS m2 mor' I

1( = j2.57 mS m 2 (mo! dm-'r3' 2 I
9.9 ,.--- - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
9.8 _v =-2.572:2.Y+ 12.782

RZ=0.8 103
£' 9.7
a
NS 9.6
""
5
)
'•
9.5 •
9A
9.3 •
l.14 1.1 6 1.1 8 1.2 l. 2 2 1.24 l.2 6 1.28 l.3 U2 l. 34
c 111 i (mo! chu-3)112 Figure 18.2
P18.11 The molar conductivity, Am, is related to the conductivity, K, by Am= Kie [18.28] = C!Rc where the
cell constant is C = 0.2063 cm- 1• The Kohlrausch law [18.29] indicates that molar conductivity is
linear in c 112 •
A,.= A,. 0 -'1({: 112 (18.29)
We draw a data table and calculate values for a plot of Am against c 112 •
c I (mol dm- 3 ) 0.00050 0.0010 0.0050 0.010 0.020 0.050

R/Q. 3314 1669 342.1 174.1 89.08 37.14
c 1n I (mol dm- 3)tn 0.0224 0.0316 0.0707 0.100 0.141 0.224
Am I (mS m2 mol- 1) 12.45 12.36 12.06 11.85 11.58 11.ll
The plot, shown in Figure 18.3, is linear, and the linear regression fit yields the intercept and slope.
The intercept is the limiting molar conductivity and the slope is the negative of the Kohlrausch
parameter'](:,
A,. = li2.6 mS m 2 mo1-1I

0
'1( = 16.66 mS m 2 (mol ctm- 1 r 2I

3
'
12.5
y =-6.655lx + 12.556
R0 =0.99-n
11
0 0.05 0.1 0.15 0.2 0.25
Figure 18.3
c112 I (mo! dnrl) 112
(a) A,. =((5.01+7.68)-6.66x(0.010) 112 ) mSm 2 mo1- 1

= 112.02 mS m 2 mo1- 1 I
(b) K= c.A,. = (10 mol m-3 )x(l2.02 mS m2 mol- 1)=120 mS m2 m-3 =1120 mS m- 1I
(c) R = C = 20.63 m-1 = iI 72 ni

K 120 mS m- 1
P18.13 The diffusion constant of a C60- ion in solution is related to the mobility of the ion and to its
hydrodynamic radius a in eqn. 18.36, the Stokes formula:
a=___!!__ (18.36)
61fT/U
(l)x(1.602 x 10- 19 c) I
= 1 = 8.3x10- 10 m = 0.83 nml
3 1 8 2 1
6n( 0.93xl0- kg m -i s- )x ( l. lxl0- m v- s- )
This is substantially larger than the 0.5 nm van der Waals radius of a Buckministerfullerene (C 60)
molecule because the anion attracts a considerable hydration shell through the ion-dipole attraction
to water molecules. The Stokes radius reflects the larger effective radius of the combined anion and
its hydration shell.
P18.15 p =- RT x de [18.40b] with the axis origin at the center of the tube.
c d.x
RT= 2.48xl03 J mor 1 = 2.48xl0 3 Nm mol- 1
c = c(x) = c0 e-ax' where c0 = 0.100 mol dm-3 and a= 0.10 cm-2
-de =- 2axc0 e- ax' = -2axc

d.x
Thus, the thermodynamic force per mole is given by the expression

1
P = 2aRTx = 1(50. kN cm- mor )xl
1
while the force per molecule is given by
P = 2aRTx I NA= lc8.2xl0-23 kN cm- 1 molecule- 1)xl
A plot of the absolute force per mole against xis shown in Figure 18.4. It demonstrates that mass is
pushed by the thermodynamic force toward the ends of the tube where the concentration is lowest; a
negative force pushes toward the left (i.e., x < 0), positive force pushes toward the right (i.e., x > 0).
250
200
-._
~ 150
~
:::.. 100
~
50
0 -
-5 -4 -3 -2 -1 0 2 3 4 5
x /cm Figure 18.4
D = uRT [18.45] ze
P18.17 and a= - - [18.36]
zF 6.1lllU
( 8.3145 J K-1 mol-1 )x(2~8.15 K )xu = 2.569x10-2 Vxu

D= 96485 C mol
1
2
So Dl(cm s- 1) = (2.569x10-2 )xu/(cm 2 s- v- 1)
l.602xl0- 19 C
a=~~~~~~~~~~-
(6;r)x(0.89lxl0-3 kg m- 1 s- 1)xu
18 1
= 9.54xl0- C kg - ms= (1 J = l c v , 1J=1 kg m 2 s-2 )
u
aim= 9.54x1o-14
so
ulcm 2 s-1 y-i
2
and therefore a/pm= 9.54x10-
2 1
ulcm s- V
We can now draw up the following table using data from Table 18.5.
Li+ Na+ K+ Rb+

u / (10-4 cm s-1 v-1)
2
4.01 5.19 7.62 7.92
D !l o-s cm 2 s- 1 1.03 1.33 1.96 2.04
a / pm 238 184 125 120
The ionic radii themselves (i.e. their crystallographic radii) are
Li+ Na+ K+ Rb+

r+ ! pm 59 102 138 149
and it would seem that K+ and Rb+ have effective hydrodynamic radii that are smaller than their
ionic radii. The effective hydrodynamic and ionic volumes of Li+ and Na+ are 3 and ¥-1ra ¥-!!r;,
respectively, so the volumes occupied by hydrating water molecules are
4
(a) Li+: LiV = ( ; ) x(238 3 -59 3)x l0-36 m 3 = 5.56xl0-29 m 3
4
(b) Na+: t.V= ( ; ) x(l84 3 -102 3)xl0-36 m 3 =2.16 x I0-29 m 3
4
The volume occupied by a single H 20 molecule is approximately ( ; ) x(150pm) 3 = l.4xl0-29 m 3.
Therefore, Li+ has about !four! firmly attached H 20 molecules whereas Na+ has only lone or two I
(according to this analysis).
P18.19 c(r,t) = no 312 e-r' 140' [18.55] where n0 = (10.0 g)x(l mol/342.3 g) = 0.0292 mol
8(7!Dt)
Using D = 5.22 x I0--0 cm2 s- 1 = 5.22 x 10-s dm2 s- 1 and r = IO cm, the working equation becomes
7 3
- 5.50xl0 mo! dm- -4.79xto6 1(11s)
c (lo cm,t ) - 312 e
( t I s)
(a) 1 hr= 3600 s
c(lO cm, l hr)= 5.50xl01 m~~ dm-3 e-4 79x10• 1(3600) = lo.oo mo! dm-31
(3600)
(b) 1 wk= 6.048 x 105 s
c(lO cm, 1 wk)= 5.50xl07 mo! ?~-3 e-4 79x10• 1(604sxw') = l4.25xl0-s mol dm-3 1
(6.048xl0 5 )
P18.21 The most probable speed of a gas molecule corresponds to the condition that the Maxwell
distribution be a maximum (it has no minimum); hence we find it by setting the first derivative of
the function equal to zero and solving for the value of v for which this condition holds.
f(v) = 4,. ( _!!!__)312 v2e-mv' 12kr [18.4] = constxv2e-mv' 12kr [M I R=m l k]

2;rrkT
d~~) =O when(2-:~ ) =o
~r
2
~J
2
So Iv( most probable)= c* = ( =( [ 18.9).
The average kinetic energy corresponds to the average of Yi mv 2 • The average is obtained by
3/ 2
2
determining (v 2 )= rv 2f(v)dv [18.7]=4tr ( ;T ) fo~ v4 e-mv m r dv [18.4) .
2
3 1/2 (
The integral evaluates to ...!!...._ _!!!_
)-5/2 . Then (v 2 ) = 4tr ( __!!!:__ ) 3/ 2 x ...!!...._
3 1/ 2 (
_!!!_
) -5 / 2 3kT
8 2kT 2trkT 8 2kT m
Thus, (c) = Yim(v 2 ) = Yz kT.
P18.23 We proceed as in Justification 18.2 except that to get the three-dimensional distribution, instead of
taking a product of three one-dimensional distributions, we take a product of two one-dimensional
distributions.
f(vx, vy)dvxdvy = f(v; )J(v~ )dvxdvy = (_!!!_)e-mv' t2kr dvxdvy

2trkT
where v = v; + v~ . The probability f(v)dv that the molecules have a two-dimensional speed, v,
2
in the range v to v + dv is the sum of the probabilities that it is in any of the area elements dvxdvY
in the circular shell of radius v . The sum of the area elements is the area of the circular shell of
radius v and thickness dv, which is tr(v+dv) 2 -trv2 = 2trvdv. Therefore,
f(v) =(~ }e-mv'mr I [~ =:]

The mean speed is determined as
c= fo~vf(v)dv= ( ; ) fo~ v 2e-mv't2krdv= ( ; )x( tr~ )x(2:rr

2 2
[standard integral]
112 12
__1 (trkT)
- or ( -
trRT)
- '
2m 2M
P18.25 Rewriting eqn. 18.4 with M I R= m I k,
~
3/ 2
2
f(v) = 4 _!!!____ v2e-mv mr
2trkT )
The proportion of molecules with speeds less than c is

3/ 2
p= ref(v)dv = 4tr( _!!!____ ) rev2e-mv2m rdv
Jo 2trkT Jo
Defining a =m I 2kT,
P = 4tr( fi )
a 3/2
fv e
0
c 2 -av2
dv = -4tr
( a )3 / 2 d
fi da f e-av2 dv
0
c
Defining z 2 =av 2 • Then dv = a- 112 dz and

3/ 2 112
- a d 1 ca -z2
P - -4tr( tr ) da L1 12 fo e dz}
-- -4tr( -a )
312 {
- -1 -1
( ) 3/ 2 ica 112
e-z2 dz+ -1 - d
( )112
e -x2 ica"' dz}
1l" 2 a o a da o
112
Thenweuse J
ca
0
2
e-x dz=(n 112 / 2)erf(ca 112 )
112
-d Ica"' e-z2 dX--(dca
- - ) x ( e-c2a ) -
_ -1 ( - C ) e-c2a
112
da 0 da 2 a
where we have used /z J: f(y)dy = f(z).

20
Substituting and canceling, we obtain P = erf (ca 112 ) - ( 2ca 112 I n 1'2) e-c .
112 112 112 21 12 2

Now, c = (3kT I m) , so ca = (3kT I m) x( ml 2kTt = (3 / 2t , and
I I
Therefore, (b) 61 % of the molecules have a speed less than the root mean square speed and
(a) 139%1 have a speed greater than the root mean square speed. (c) For the proportions in terms of
2 2
the mean speed c, replace c by c = ( 8kT I nm yi = ( 8 I 3n yi c, so ca 112 = 2 I n 112.
20
Then P= erf(ca1'2)-(2ca 1'2 I n 1'2)x(e-< ) = erf(2 / n 112)-(4 / n)e-4'" = 0.889-0.356 = I0.5331.
That is, 153%1 of the molecules have a speed less than the mean, and 147%1 have a speed greater
than the mean.
2;T r
3/ 2
2 2
P18.27 (v")= rv"f(v)dv [18.7]=41C ( )
v"+ e-ml- t kT dv [18.4]
The integral of the above expression must be handled in a manner that depends on whether n is odd
or even. When n is an odd, positive integer (n = 1, 3, 5, ... ),let n + 2 = 2p + 1 where p = 0, 1, 2, 3, ...
and the integral is given by
[standard integral]
Thus,
12
= 2 (-n +-1) !(--;;;-
i'2 2kT )" . an odd, pos1t1ve
when n 1s . . mteger
.
2
When n is an even, positive integer (n = 0, 2, 4, ... ),let n + 2 = 2p, where p = 0, 1, 2, 3, ... , and the
integral is given by
1- vn+2e-mv212kT dv = 1- V2pe-mv2 12kT dv = ( 2p- l) !! ( 2kT )P ( 2rckT )112 [standard integral]

Jo Jo 2p+1 m m
= rt
112
( n + 1) !! ( 2kT
n+4 m
)2 n+3
2 2
Thus,
3/ 2 J/2 ( n+3
(vn) = 47t _!!!_ X 7t n + 1)!! (2kT)2
( 27tkT ) n+4
22 m
12
( n + 1) !!( 2kT )n
= 1
2n 12
--
m
I when n is an even, positive integer
P18.29 The rate constant, k" for a transport process in which a molecule and its hydration sphere move a
single step is governed by the activation energy for the step, E 0 , where the general definition of
activation energy is
E. = RT ( ~
2 dlnk) [see Sect10n
. 20.1)
We expect that larger viscosities should retard the rate constant, so let us assume that k, is inversely
proportional to the viscosity. Then,
ln k, = constant - ln (TJ)
dlnk, 1 d'T]
--=---
dT TJ dT
2
E =-RT dTJ
• TJ dT
dTJ _ (E• )dT

---;,--- Ii: T2
In the case for which £ 3 is independent of temperature, the above working equation can be
integrated. We choose the lower integration limit to be the viscosity at a reference temperature Trer.
'llrer. The upper integration limit is the viscosity at temperature T, TJ.
( , dTJTJ =-( ~) ( ~~
ln(_!J__J=(E·)x(_!_ __
l J or ITJ=AeE,IRT whereA=TJ,.re-E,IRT~rj
TJref R T T.er
Thus, we see that, when E. is a constant, the pre-exponential factor A is a constant and
TJ oc eE,IRT [18.26]. This demonstrates that the general definition E. = RT 2 ( d:/') is compatible
with eqn. [18.26] when the activation energy is a constant.
We explore the possibility that the Problem 18.8 empirical equation for the viscosity of water
reflects an activation energy that has a dependence on temperature by applying the above working
equation prior to the constancy assumption. The reference temperature is 20° C and from the CRC
Handbook (71st ed., 1990-1991), 1120 = 1002 µPa s = 1.002 x 10-3 kg m- 1 s- 1 (the value is not
actually necessary in the following calculations).
TJ ( O) = T/zo lO{a<zo-iw CJ-b( 20-lll° CJ')i<ei• c+cJ [P 18.8) where a= l.3272, b = 0.001053, and c = 105
2
TJ(x) = TJ 20 10f(x) where x = () 1° C and f(x) ={a(20-x)-b(20-x) } ! (x+c)
-dTJ = TJ20 -(10J<xl

d d d
) = TJ20 l0f<xl xln(lO)x-(f(x)) = TJ(x)xln(lO)x-(f(x))
dx dx dx dx
2
() ( )
=TJXXlnlOx
-a+2b(20-x) a(20-x)-b(20-x)
2
}
1 x+c (x+c)
2
E =- RT2 d17 = Rx(x+273 .15) K d17(x)
• 1J dT ri(x) d(x)
2
2
=- { Rx ( x+273.15 ) K xln 10 x
} () i-a+2b(20-x) - a(20-x)-b(20-x) }
x+c (x+c) 2
This equation is used to make the lot of Ea a ainst 81° C (i.e., x) shown in Fig. 18.5. The activation
energy drops from 17.5 kJ moi- 1 at 20° C to 12.3 kJ moi- 1 at 100° C. This decrease may be caused
by the density decrease that occurs across this temperature range because the increased average
intermolecular distance may cause a decrease in the hydrogen bond strength between water
molecules. There may also be a decrease in the hydration sphere of a molecule, thereby making
movement easier.
18
17
16
"o
s
-. 15
~
.
""'
"l
14
13
12
20 30 40 50 60 70 80 90 100
Figure 18.5
8 1° C
02
P18.31 . d d.ff
The genera1ize . . .
l us1on equat10n lS at
oc = D ox2c - v OX
oc [18 .53] .
2
W e confiirm th at c ( x, t) -_ a e - b(x- x0- v1) /1, where a = Co
an db = - 1 , is
· a so1ut1on
· to th e
112
t (4.nD) 112 4D
generalized diffusion equation by taking the partial derivative w/r/t time and both the first and
second partials w/r/t position to find whether they are related by eqn. 18.53.
oc = -(!Jx(_g_)e-b(x-Jeo -vr)' /1+ (_g_)x {b (x- Xo -vt) }x{ 2 v+ ( X-Xo - vt )}e-b(x-x -v1)' /1 0
ot 2 t 312 tv 2 t t
c {b(x-x0 -vt)} x { 2v+ (x-x0 -vt)} xc
=--+
2t t t
oc = (_!!._Jx{-2b(x- x0 -vt) }e-b(x- x. - vi)' / 1 = {-2b (x- X0 - vt )}xc

112
OX t t t
2
o c = j_ OC = j_[{-2b(x-Xo -vt)}xc]
ox 2 ox ox ox t
-2b
=-Xe+
{-2b(x-x0 -vt)} X-
oc
t t ~
-2b
=-xc+
{-2b(x-x0 -vt)} x {-2b(x-x0 -vt)} xc
t t t
2
-2b
=-Xe+
{2b(x-x0 -vt)} xc
t t
Thus,
2
ac
2
de
D--v-==D -Xe+ {2b(x-x0 -vt)} Xe } -v {-2b(x-x0 -vt)} Xe
{-2b
dX 2 dX t t t
-1 x-x -vt 2b x-x -vt

== 2J xc+b (
{
; ) 2 x c+ v{
}
( t 0
) } x c [ D == 1/ 4b]
-c {b(x-x0 -vt)} x { 2v+ (x-x0 -vt)} Xe

==-+
2t t t
== ~~ as required
Initially the material is concentrated at x == x 0 because c == 0 for Jx - x 0 J> 0 when t == 0 on

t 1~ 2 J.
2
account of the very strong exponential factor ( e-b(x-x, ) / 1 -7 0 more strongly than -7 oo
The term x0 + vt in the concentration expression is the movement of the centroid due to fluid flow,
To prepare a very general set of concentration profiles at a series of times without
Xcentroid·
specifying x0 , v, or D, define z and C as follows.
C= c and Z = x-xcentroid
2
C0 I ( 41tD h )1'2 (4D h}1'
The hour (h) has been chosen for the unit because of the slow pace of diffusion activity. With these
definitions, the concentration expression becomes
C(z t) == 1 e-z' i (1 1h)
' (t ! ht2
Concentration profiles as C against tat various times (1, 5, and 20 h) are displayed in Figure 18.6.
0.8
0.6
\..)
0.4
0.2
0
-5 -4 -3 -2 -I 0 I 2 3 4 5
Figure 18.6
z
x
P18.33 P(x)==
{!cN +s)} ! {!cN
N!
-s)} ! 2 N [Justification 18.7], s==1
N!
P(6A) == {!cN +6)},HcN-6)}' 2N
(a) N == 4, P(6A) ==IQ] [m! == oo form< OJ
(b) N == 6 P(6A-) ==-6_!-6 :::: ...L == ..l._ == /0.016/ [O!:::: l]
' 6! O! 2 2 6 64
(c) N==12 P(6A)==~==

2
12
xllxl0
12
==I0.0541
' 9!3!i 3x2x2
P18.35 P= N!
{Yi(N +n)}!{Yi(N-n)}! 2N
The intermediate mathematical manipulations of Justification 18.7 begin with the above expression.
Simplification of the expression proceeds by taking the natural logarithm of the expression,
applying Stirling's approximation to each term that has the ln(x!) form, checking for term
cancelations, and simplifying using basic logarithm properties.
Stirling's approximation: ln x! = ln(2n')" 2 + ( x +Yi) ln x- x

Basic logarithm properties: ln(xxy) =lnx + lny
ln(xly) = lnx - lny
ln(xY) =y lnx
Taking the natural logarithm and applying Stirling's formula gives
lnP=ln{ N! }
{Yi(N +n)}!{Yi(N-n)}! 2N
= lnN!-ln({Yi( N + n)}!)-tn({Yi( N -n )}!)- ln2N
= ~ +(N +Yi)lnN-J{
-[~ +{Yi(N +n)+Yi}In{Yi(N +n)}-11i(J( + J)]
-[ ln(2nf 2 +{Yi(N-n)+Yi}ln{Yi(N-n)}-Yi(J( -J)]-tn2N
lnP =(N + Y2)lnN -ln(2.nf 2 -ln2N
+ +Yi} ln{Yi (N +n)}-{Yi( N -n) +Yi} In{Yi( N -n)}

-{Yi( N n)
=In! (N ~:ty, }-Yi{N +n+l}ln{ ~ (1+; )}-Yi{N-n+l}ln{ ~ (1-; )}

=In! (N ~:ty, }-Yi{N +n+l}{1n( ~)+1n(1+; )}-Yi{N-n+I}{1n( ~)+1n(1-; )}
=In! (N ~:ty, }-Yi{N +ft +1}1n( ~)-Yi{N +n+l}ln(l+;)
-Yi{N-} +1}1n( ~)-Yi{N-n+l}ln(l-;)
=In! (N ~:t+Y, }-{N +l}ln( ~)-Yi{ N +n+ l} 1n(1 +; )-Yi{N -n+ l}ln(l-;)
=lnl (N(N12)/ ~~+v,
+ 1r
112
}-Yi{N +n+l}tn(1+~)-Yi{N-n+l}In(1-~)
N N
P18.37 For a three-dimensional, freely jointed chain of N repeating units each of length /, the probability
that the ends lie in the ranger tor+ dr isj(r)dr where
a 2 -a2r2
3
3 )1/2
f(r)=4Jr ( Jr 112) re a= ( 2N/ 2 [18.74)
(R
2
) = r r
2
f (r) dr
= 4Jr(Jr~2 Jr 4
r e-a'r' dr = 4;r(Jr~2 J ~~ J
x(
3 2
[standard integral]
=-3-=N/2
2a 2
Thus,
Rrms = (R2 r 2 = INl /2"
P18.39 (a) Each hydrogen atom contributes one electron and one proton to the "free" particle plasma.
Consequently, the number of electrons in volume V equals the number of protons and the total
number of free particles is given by N = NP + N0 = 2Np or, alternatively, n = np + n0 = 2np. Since the
perfect gas law is applicable and because the mass of an electron is negligible compared to the
mass of a proton,
nRT 2n RT 2m RT 2p RT
p = - - = _ P _ = __P - = __P - where pP is the mass density of the protons
v v VMP Mp
2
= pRT where total mass density, p, equals pP because electron mass is negligible
MP
3 3 1 1 6
= 2(1.20xl0 kg m- )x(8.3145 J moi- K- )x(3.6xl0 K) = _ xl0 13 Pal
17 2
l.Oxl0-3 kg moi- 1
(b) From Justification 18.1, p = nM ( v;)I V and ( v;) = ){ c 2.

Thus,
m~;) =~~ =~e~ ~c )=iXPkl where P k = ¥

2 2
p=
(c) p k = Yi p=Yix(7.2xl013 Pa)=l.lxl014 Jm-3 =ll.lxl02 TJm-31

This is about 1 billion times larger than the translational energy density of the Earth's
atmosphere on a warm day.
(d) Each carbon atom contributes 6 electrons and 1 nucleus to the "free" particle plasma.
Consequently, the number of electrons in volume V equals 6 times the number of carbon nuclei
and the total number of free particles is given by N =Ne+ 6N0 = 7Ne or, alternatively, n = ne +
6n0 = 7ne. Since the perfect gas law is applicable and because the mass of the electrons is
negligible compared to the mass of carbon nuclei,
nRT 7n RT 7m RT 7P, RT . . .
p = - - = _ c__ = c = __c - where Pc 1s the mass density of carbon nuclei
V V VMc Mc
7
= pRT where total mass density, p, equals Pc because electron mass is negligible
Mc
=
3 3 1 1
7(1.20xl0 kgm- )x(8.3145 Jmoi- K- )x(3500K)
= 2.0xl0 10 Pa
I I
12xl0-3 kg moi- 1
(e) p = pRT where p is the mass density

M
3 3
(1.20xl0 kgm- )x(8.3145 Jmol- K - )x(3500 K)
1 1
I I
= 3 1
= 2.9x10 9 Pa
12.0xl0- kg moi-
P18.41 Dry atmospheric air is 78.08% N 2 , 20.95 % 0 2 , 0.93% Ar, 0.03%C0 2 , plus traces of other gases.
Nitrogen, oxygen, and carbon dioxide contribute 99.06% of the molecules in a volume with each
molecule contributing an average rotational energy equal to kT. The rotational energy density is
given by
= 0.9906 kTpNA = 0. 9906

RT p
= 0.9906(1.013xl0 5 Pa)= 0.1004 J cm- 1
The total energy density (translational plus rotational) is
Pr= PK+ PR= 0.15 J cm-3 +0.10 J cm-3 = 0.25 J cm-3 l l

P18.43 ;: ;:
c(x,t) = c0 + (c, -c0 ){l -erf(~)} where ~ (x, t) = x I (4Dt)
1/ 2
and ;:
erf(~)
2 f~ eY2 dy
= l- -----v2
1t q
For c(x, t) to be the correct solution of this diffusion problem, it must satisfy the boundary
condition, the initial condition, and the diffusion equation (eqn. 18.50). At the boundary,
Jo~ e-y2 dy = 1- ( 1!2112 ) x ( 2

12
x = 0, r; = 0, and erf(O) = 1- 1!~ 2 tt ' ) = 0.
Thus, c(O, t) = c0 + (c, - c0 ){1- O} = c, . The boundary condition is satisfied. At the initial time
(t=O), r;(x,O)=oo and erf(oo)=l. Thus, c(x,O)=c0 +(c, -c0 ){1-l}=c0 . Theinitialconditionis
satisfied. We must find the analytical forms for (Jcf(Jt and CJ 2 c I CJx 2 .If they are proportional with a
constant of proportionality equal to D , then c(x, t) satisfies the diffusion equation.
dc(x,t) =
CJx
n[l (c, -Co)X e-x 2 !4Dt]
2 f;i(Dt) 312
The constant of proportionality between the partials equals D and we conclude that the suggested
solution satisfies the diffusion equation. Diffusion through alveoli sites (about 1 cell thick) of
oxygen and carbon dioxjde between lungs and blood capillaries (also about 1 cell thick) occurs
through about 0.075 mm (the diameter of a red blood cell). So we will examine djffusjon profiles
for 0 5 x 5 0.1 mm. The largest djstance suggests that the longest tjme that must be examined is
estimated with eqn. 18.56.
Figure 18.7 shows oxygen concentration distributions for times between 0.01 sand 4.0 s. We set c0
equal to zero and calculate Cs with Henry's law [16.26b].
Po 2 2lkPa
b0 2 = - [16.26b]= [Table 16.1]=2.9xl0-4 molkg- 1
K0 2 7.9xl0 kPakgmor 1
4
So Cs= 2.9 x 10-4 mol dm-3
Oxygen concentration profiles at t

3.....-~~~----.-~~~~~~~~~-.-~~~~..,..-~~~--.
2.5
"''E
-0
<.> I o 1.5
E
~
0.5
0.02 0.04 0.06 0.08 0.1 Figure 18.7

xlmm
19 Chemical kinetics
019.1 The time scales of atomic processes are rapid indeed: according to the following table, a
nanosecond is an eternity. Note that the times given here are in some way typical values for times
that may vary over two or three orders of magnitude. For example, vibrational wavenumbers can
range from about 4400 cm- 1 (for H2) to 100 cm- ' and even lower (for Ji), with a corresponding
range of associated times. Radiative decay rates of electronic states can vary even more widely:
Times associated with phosphorescence can be in the millisecond and even second range. A large
number of time scales for physical, chemical, and biological processes on the atomic and molecular
scale are reported in Figure 2 of A. H. Zewail, "Femtochemistry: Atomic-Scale Dynamics of the
Chemical Bond," Journal ofPhysical Chemistry A 104, 5660 (2000).
Process t Ins Reference

Radiative decay of electronic excited state lxl0 1 Section 11.5
Molecular rotational motion 3x 10-2 B""' 1 cm- 1
Molecular vibrational motion 3x10-5 v ""' lOOOcm- '
Proton transfer 0.3 Zewail 2000
Initial chemical reaction of vision• 2x l0-4 Impact 11.1
Energy transfer in photosynthesis t lx10- 3 Impact 19.1
Electron transfer in photosynthesis 3x 10-3 Impact 19.1
Collision frequency in liquids 4xl0-4 Section 18. l(b)t
•Photoisomerisation of retinal from 11-cis to all-trans

1Time from absorption until electron transfer to adjacent pigment
1Use the formula for gas collision frequency at 300 K, the parameters for benzene from the data
section, and the density of liquid benzene.
Radiative decay of excited electronic states can range from about 10-9 s to 10-4 s--even longer for
phosphorescence involving "forbidden" decay paths. Molecular rotational motion takes place on a
scale of 10- 12 s to 10-9 s. Molecular vibrations are faster still, about 10- 14 s to 10- 12 s. Proton transfer
reactions occur on a timescale of about 10- 10 s to 10-9 s, although protons can hop from molecule to
molecule in water even more rapidly (1.5 x 10- 12 s, Section 18.7a). Impact on biochemistry 11.l
describes several events in vision, including the 200-fs photoisomerization that gets the process
started. Impact on biochemistry 19.1 lists time scales of several energy-transfer and electron-
transfer steps in photosynthesis. Initial energy transfer (to a nearby pigment) has a time scale of
around 10- 13 s to 5x10- 12 s, with longer-range transfer (to the reaction center) taking about 10- 10 s.
Immediate electron transfer is also very fast (about 3 ps), with ultimate transfer (leading to
oxidation of water and reduction of plastoquinone) taking from 10- 10 s to 10- 3 s. The mean time
between collisions in liquids is similar to vibrational periods, around 10- 13 s. One can estimate
collision times in liquids very roughly by applying the expression for collisions in gases (Section
18.lb) to liquid conditions.
019.3 The overall reaction order is the sum of the powers of the concentrations of all of the substances
appearing in the experimental rate law for the reaction (eqn. 19.7); hence, it is the sum of the
individual orders (exponents) associated with a given reactant (or, occasionally, product). Reaction
order is an experimentally determined, not theoretical, quantity, although theory may attempt to
predict or explain it. Molecularity is the number of reactant molecules participating in an elementary
reaction. Molecularity has meaning only for an elementary reaction, but reaction order applies to any
reaction. In general, reaction order bears no necessary relation to the stoichiometry of the reaction,
with the exception of elementary reactions, where the order of the reaction corresponds to the number
of molecules participating in the reaction, that is, to its molecularity. Thus, for an elementary reaction,
overall order and molecularity are the same and are determined by the stoichiometry.
019.5 The rate-determining step is not just the slowest step: it must be slow and be a crucial gateway for
the formation of products. If a faster reaction can also lead to products, then the slowest step is
irrelevant because the slow reaction can then be side-stepped. The rate-determining step is like a
slow ferry crossing between two fast highways: the overall rate at which traffic can reach its
destination is determined by the rate at which it can cross on the ferry.
If the first step in a mechanism is the slowest step with the highest activation energy, then it is rate-
determining, and the overall reaction rate is equal to the rate of the first step because all subsequent
steps are so fast that once the first intermediate is formed, it results immediately in the formation of
products. Once over the initial barrier, the intermediates cascade into products. However, a rate-
determining step may also stem from the low concentration of a crucial reactant or catalyst and need
not correspond to the step with highest activation barrier. A rate-determining step arising from the
low activity of a crucial enzyme can sometimes be identified by determining whether or not the
reactants and products for the step are in equilibrium: if the reaction is not at equilibrium, the step
may be slow enough to be rate-determining.
019.7 Simple diagrams of Gibbs energy against reaction coordinate are useful for distinguishing between
kinetic and thermodynamic control of a reaction. For the simple parallel reactions R ~ P 1 and R ~ P2,
shown in Figure 19.1 as Cases I and II, the product P 1 is thermodynamically favored because the
Gibbs energy decreases to a greater extent for its formation. However, the rate at which each product
appears does not depend on thermodynamic favorability. Rate constants depend on activation energy.
In Case I the activation energy for the formation of P 1 is much larger than that for formation of P2 . At
low and moderate temperature, the large activation energy may not be readily available and P1 either
cannot form or forms at a slow rate. The much smaller activation energy for P2 formation is available,
and consequently P2 is produced even though it is not the thermodynamically favored product. This is
kinetic control. In this case, [P2] I [Pi]= k2/k 1 > 1 [19.32].
Case I Case II Case III
GI I
P1
n
\
P2
Gil\
I P1 P2
G R
Y\_
P2
Reaction coordinate Reaction coordinate Reaction coordinate Figure 19.1
The activation energies for the parallel reactions are equal in Case II, and consequently the two
products appear at identical rates . If the reactions are irreversible, [P2] I [Pi] = k2/k 1 = 1 at all times.
The results are very different for reversible reactions. The activation energy for P 1 ~ R is much
larger than that for P2 ~Rand P 1 accumulates as the more rapid P2 ~ R ~ P1 occurs. Eventually
the ratio [P2] I [Pi] approaches the equilibrium value.
[P2]) = e -(l1G,-l1G,) I RT < 1

[ [P1] eq
This is thermodynamic control.

Case ID in Figure 19.1 represents an interesting consecutive reaction series R ~ P1 ~ P2• The first step
has relatively low activation energy and P1 rapidly appears. However, the relatively large activation
CHEMICAL KINETICS 471
energy for the second step is not available at low and moderate temperatures. By using low or
moderate temperatures and short reaction times, it is possible to produce more of the
thermodynamically less favorable P 1• This is kinetic control. High temperatures and long reaction
times will yield the thermodynamically favored P2.
The ratio of reaction products is determined by relative reaction rates in kinetic controlled reactions.
Favorable conditions include short reaction times, lower temperatures, and irreversible reactions.
Thermodynamic control is favored by long reaction times, higher temperatures, and reversible
reactions. The ratio of products depends on the relative stability of products for thermodynamically
controlled reactions.
019.9 In the analysis of stepwise polymerization, the rate constant for the second-order condensation is
assumed to be independent of the chain length and to remain constant throughout the reaction. It
follows, then, that the degree of polymerization is given by
(N)=l+k,t[A] 0 [19.49b]
Therefore, the average molar mass can be controlled by adjusting the initial concentration of
monomer and the length of time that the polymerization is allowed to proceed.
Chain polymerization is a complicated radical chain mechanism involving initiation, propagation,
and termination steps (see Section 19.8(b) for the details of this mechanism). The derivation of the
overall rate equation utilizes the steady-state approximation and leads to the following expression
for the average number of monomer units in the polymer chain:
(N) = 2k,[M][Ir1' 2 [19.58]
where k. = (l/2)kp(fk;k1f 112 , where kp, k,, and k1 are the rate constants for the propagation, initiation,
and termination steps respectively, and where/is the fraction of radicals that successfully initiate a
chain. We see that the average molar mass of the polymer is directly proportional to the monomer
concentration and inversely proportional to the square root of the initiator concentration and to the
rate constant for initiation. Therefore, the slower the initiation of the chain, the higher the average
molar mass of the polymer.
019.11 The shortening of the lifetime of an excited state is called quenching. Quenching effects may be
studied by monitoring the emission from the excited state that is involved in the photochemical
process. The addition of a quencher opens up an additional channel for the deactivation of the
excited singlet state.
Three common mechanisms for bimolecular quenching of an excited singlet (or triplet) state are
Collisional deactivation s· +Q ~S+Q
Energy transfer s· +Q ~S+Q·
Electron transfer s·+Q~s+ +Q- or s - +Q+
Collisional quenching is particularly efficient when Q is a heavy species, such as an iodide ion,
which receives energy from s • and then decays primarily by internal conversion to the ground state.
Pure collisional quenching can be detected by the appearance of vibrational and rotational excitation
in the spectrum of the acceptor.
In many cases, it is possible to prove that energy transfer is the predominant mechanism of
quenching if the excited state of the acceptor fluoresces or phosphoresces at a characteristic
wavelength. In a pulsed laser experiment, the rise in fluorescence intensity from Q* with a
characteristic time that is the same as the time for the decay of the fluorescence of s • is often taken
as an indication of energy transfer from S to Q.
Electron transfer can be studied by time-resolved spectroscopy (Section l 1.7f). The oxidized and
reduced products often have electronic absorption spectra distinct from those of their neutral parent
compounds. Therefore, the rapid appearance of such known features in the absorption spectrum
after excitation by a laser pulse may be taken as an indication of quenching by electron transfer.
E19.1 (a) Let the initial amount of IC! be n 1c 1 and the initial amount of H2 be nH; the initial amounts of Ii and
HCI are assumed to be zero. Thus, the initial total quantity of gas is n 1c 1 + nH. Let the amount of I2
formed at any given time be n. In that case, the amount of HCI is 2n, that of H2 is nH - n, and the
amount of IC! is n1c1 - 2n. At any given time, then, the total quantity of gas is
n101al = n1c1 - 2n + nH - n + n + 2n = n1c1 + nH = ninitial
COMMENT. Measuring the pressure would not be a practical way of monitoring the progress of this
reaction .
E19.2(a) v=_!__ d(J] (19.3b) SO d[JJ =VJV

VJ dt dt
Rate of formation of C = 3v = 18.l mo! dm- s- 1
3 1
Rate of formation of D = v = ~.7 mo! dm- 3 s- 11

Rate of consumption of A= v = ~.7 mo! dm- 3 s- 11
Rate of consumption of B = 2v = ~.4 mo! dm-3 s- 11
E19.3(a) v = _!__ d[J] [19.3b] = .!. d[C] = lx(2.7mol dm-3 s- 1)=11.35 moldm-3 s- 1 I
VJ dt 2 dt 2
Rate of formation ofD = 3v =14.05 mo! dm-3 s- 1 I
Rate of consumption of A= 2v = ~.7 mo! dm- 3 s- 1

1
Rate of consumption of B = v =11.35 moldm-3 s-' I

E19.4(a) The rate is expressed in mo! dm-3 s- 1; therefore,
mo! dm-3 s- 1 = [k,] x (mo! dm-3) x (mo! dm- 3)
1
where [k,] denotes units of k., requires the units to be Hm 3 moi- 1 s- 1.
(a) Rate of formation of A= v = /k,[A)[BJI
(b) Rate of consumption of C = 3v = j3Jc..[A][BJI
E19.5(a) Given d[C] = k,[A][B][C] , the rate ofreaction is [19.3b]

dt
1 d[J] _ _!_ d[C] = .!.k,[A][B][C]

v = -;-Tt- 2 dt L.!:2:..___ __
J
The units of k., [k,], must satisfy

mo! dm-3 s- 1 = [k,] x (mo! dm-3 ) x (mo! dm-3 ) x (mol dm-3 )
1
Therefore, [k,] = ldm 6 moi-2 s- 1.
E19.6(a) (a) For a second-order reaction, denoting the units of k, by [k,],

mol dm-3 s- 1 = [k,] x (mol dm-3) 2 ; therefore J[Jc..] = dm3 moi- 1 s- 11
For a third-order reaction,
mol dm-3 s- 1 = [k,] x (mol dm-3) 3 ; therefore j[k,] = dm6 moi-2 s-'I
(b) For a second-order reaction,

kPa s- 1 = [k,] x kPa2 ; therefore l[k.] = kPa-1 s- 11
For a third-order reaction,
kPa s- 1 = [k,] x kPa3; therefore l[k,] = kPa-2 s- 1)
E19.7(a) Theratelawis
v = k.(A]° oc p/ = {PA,o(l- f)}°

where f is the fraction reacted. That is, concentration and partial pressure are proportional to each
other. Thus we can write
0
3._ _ Pt1 -( 1- J; )
V2 P1.2 1- /2
Taking logarithms,
= a 1J =
1
1J
u\ 3._)
V2 u\ 1 hJ; )
ln(3._) ln (lQZ_)
so a= V2 = 0.76 =l.99
m(l-J;)
/2
1-
tn(0.95)
0.80
Hence, the reaction is ~econd-ordeq.

COMMENT. Knowledge of the initial pressure is not required for the solution to this exercise. The ratio of
pressures was computed using fractions of the initial pressure.
E19.8(a) Table 19.3 gives a general expression for the half-life of a reaction of the type A~ P for orders
other than 1:
2•-I 1
1 - - oc [A]'-• oc p'-•
112 - (n-l)k,[A]~-1 o o
where the proportionality constants may be functions of the reaction order, the rate constant, or even the
temperature, but not a function of the concentration. Form a ratio of the half-lives at different initial
pressures:
1112 (Po,1) = [fu)I-n = [ Po,2 )n-l
1112(Po,2) Po,2 Po,1
Hence, ln[ 1112 (Po,1)) = (n -1) ln[ Po,2)

1112(Po,2) Po.1
J 410 s)
1
or (n-1)= u\SSOs =0.999='1

1J169 Torr)
u\363 Torr
Therefore,~=~ in agreement with the result of Exercise 19.7(a).
E19.9(a)
Therefore, rate of consumption of N 20 5 = 2v = 2k,[N20 5].
d[N20s] = -2k [N 0 ] so
di r 2 5
Solve this fort:
t = _l_ln [N20 s]o

2k, [N 2 0 5 ]
Therefore, the half-life is

1
t112 =-ln2= m2 4
=l.03x10s I I
2k, (2) x (3 .38 x l0-5 s- 1)
Since the partial pressure of N 20 5 is proportional to its concentration,
p(N20 s) = Po(N 20 s)e-2k,1
(a) p(N 2 0 5 ) = (500Torr) x (e-< 2x3·3sxio-' /sJx(so •l )= j498 Torri

(b) p(N20 s) = (500Torr) x (e-<2x338x10-'1sJx(2ox6-0sJ ) = 1461 Torri
COMMENT. The half-life formula in Table 19.3 is based on a rate constant for the rate of change of the
reactant; that is, the formula based on the assumption that
- d[A] = k [A]
dt r
Our expression for the rate of consumption has 2k, instead of k,, and our expression for t,12 does
likewise.
E19.1 O(a) The integrated rate law is
1
kt= ln ( [B] / [B]oJ [19.17]
' [B] 0 -[A] 0 [A] / [A] 0
(a) The stoichiometry of the reaction requires that when

~[B] = (0.020 - 0.050) mol dm- 3 = -0.030 mol dm-3
then ~[A]= -0.030 mol dm- 3 , as well.

Thus [A] = 0.075 mol dm-3 - 0.030 mol dm-3 = 0.045 mol dm-3
When [B] = 0.020 mol dm- 3 . Therefore,
k 1_ 1 ln ( -0_
.0_20_/_0_.0_5_0)
' - (0.050-0.075) moldm- 3 0.045 I 0.075
k, x l.O h = 16.2 dm 3 moi- 1
k, = l16.2dm mol- h- lx(

1 1
3 ;0~ J =14.5 x 10- dm mol- s- I
so
3 3 3 1 1
(b) The half-life with respect to A is the time required for [A] to fall to 0.0375 mol dm- 3 (and [B] to
0.0125 mol dm- 3) . We solve eqn. 19.17 fort.
(A) ( 1 ) ln ( 0.0125 / 0.050 )
= (16.2dm 3 moi- 1h- 1) x (-0.030moldm-3 ) x
1111
0.50
=l.4lh= l5.l x l0 3 sl
Similarly, the half-life with respect to B is the time required for [B] to fall to 0.025 mol dm- 3 (and
[A] to 0.050 mol dm-3) .
(B) ( 1 ) ln ( 0.50 )
= (16.2dm3 mo1- 1h- 1) x (-0.030moldm-3 ) x
1112
0.050 / 0.075
3
= 0.59h = l2.lxl0 sl
COMMENT. This exercise illustrates that there is no unique half-life for reactions other than those of the
type A-t P.
E19.11 (a) The integrated second-order rate law for a reaction of the type A+ B ~ products is
1
kt= ln([B] / [Blo) [19.17]
r [B]o -[A]o [A] / [A]o
Introducing [B] = [B] 0 - x and [A] = [A] 0 - x and rearranging, we obtain
kt=( 1 )1n([A] ([B] -x))0 0
' [B] 0 -[A] 0 ([A] 0 -x)[B] 0
Solving for x yields, after some rearranging,
[A]o[B]o ( e*«lBJo -[AJo)1 -1) (0.060) x(0.110 moldm-3)x( e<o i 10-0 060)xo i 1x11s -1)
x- -----------------
- [B]oe([BJo-[AJo)k,1 -[A]o - (O. llO) x e<o. 110-0.060)xo. 11x11s -0.0 6 0
(0 .060moldm-3) x (e 0005511 ' -1)

e0.00551/s - 0.55
(a) After 20 s,
(0.060moldm-3) x (e 00055xio -1) _3
x= e 00055 x2o _ . = 0.0122 moldm
0 55
which implies that
[CH3COOC 2 H 5] = (O.l 10-0.0122)moldm- 3 = \o.098moldm- 3 \
(b) After 15 min= 900 s,
x = (0.060moldm-3 )x(eooo55x900 -1) = 0.060moldm-3
e0.0055x900 - 0.55
so [CH 3COOC 2 H 5] = (O.l 10-0.060)moldm-3 = \o.050moldm-3 \
E19.12(a) The rate of consumption of A is
- d[A] =2v=2k [A]2 [v =-2]

dt r A
1 1
which integrates to - - - -- = 2k t [19.13b with k, replaced by 2k,].
[A] [A]o r
Therefore t = - 1 ( - 1 - -1- )
' 2k, [A] [A] 0
1
= ( 2x4.30xlO_}dm 3 mo1- 1s- 1 Jx(-o-.o-1_0_~-o-ld_m___3 0. 210~oldm-3 )
5
= \1.11x 10 s\ = \1.28 days I
E19.13(a) The reactions whose rate constants are sought are the forward and reverse reactions in the following
equilibrium.
k,
NH 3(aq)+H 2 0(l) -;( NH; (aq)+Off(aq)
The rate constants are related by

where the concentrations are equilibrium concentrations. (We assign units to Kb, which technically
is a pure number, to help us keep track of units in the rate constants. Keeping track of the units
makes us realize that k, is a pseudo first-order protonation of NH 3 in excess water, for water does
not appear in the above expression.) We need one more relationship between the constants, which
we can obtain by proceeding as in Example 19.4:
_!_ = k, +k;([NH/ ]+[Off])

"
Substitute into this expression
k, =Kb k; and [NH/] = [Off] = (Kb[NH 3]) 112
112
Hence, _!_ =Kbk: + 2k: (Kb [NH 3])
112
= k; {Kb + 2(Kb [NH 3]) }
"
So the reverse rate constant is
k' = 1
, -r{ Kb+ 2(Kb[NH3])1'2}
7.6lxl0-9 s{ l.78xl0-5 mol dm-3 + 2(1.78xl0-5 x0.15)1' 2 mol dm-3}

= l4.0xl010 dm-3 mol s- 1I
and the forward constant is

k, =Kb k; = l.78xl0-5 mol dm-3 x 4.0xl0 10 dm3 mol- 1 s- 1 = [7.lxl0 5 s- 11
Recall that k, is the rate constant in the pseudo first-order rate law.
d[NH3] = k [NH ]
dt r 3
Let us call k the rate constant in the bimolecular rate law.
d[NH3] = k[NH 3][Hz0]

- dt
Setting these two expressions equal to each other yields
k=_!s_= 7.lxlOs s-1 =l1.28xl04 dm3 mol-1 s-11

[H 20] (1000 g dm-3)/(18.02 g mol- 1)
E19.14(a) The rate of the overall reaction is
d[P] = k 2 [A][B]
v=-
dt
However, we cannot have the concentration of an intermediate in the overall rate law.
(i) Assume a pre-equilibrium with
~~~ ],
2
112
K = implying that [A]= K [A 2 ]1'2
112 2
and v = hK [A2J1'2[BJI = keff[A 2]1' [B]
112
where keff = k2K •
(ii) Apply the steady-state approximation:
d[A] "'O = 2k1[A 2]-2k;[A]2 -k2[A][B]

dt
This is a quadratic equation in [A].
A _ -b±.Jb -4ac _
2
k2 [B]±~k/ [B]2 +16k;k,[A 2 ] _ k2 [B][ l+ 16k;k,[A 2 ] -l)
[ ]- 2a - -4k; - 4k; k2 2 [B]2
(In the last step, choose the sign that gives a positive quantity for [A].) Thus the rate law is
This is a perfectly good rate law, albeit a complicated one. It is not in typical power-law form, but it
is a function of reactant concentrations only, with no intermediates. This law simplifies under
certain conditions. If 16k1k1'[A 2] >> k/ [B]2, then
l+ 16k;k,[A 2 ] _ ,,,, 4~k;k,[A 2 ]

1
k/ [B] 2 k2 [B]
and
k2
2
[B]
2
4 1k,'k,[A2] k [A 2 ] I 1/2 1/2 I
V ""~ X Vk1[B] =
k [B] _!__k'
2 I
= k 2K [A 2 ] [B]
. .
recovering the pre-equilibrium rate law. If, on the other hand, 16k1k1' [A2] << k/[B] 2 , we expand
the square root
and
COMMENT. If the equilibrium is "fast," the latter condition will not be fulfilled. In fact, this special case
amounts to having the first step rate-limiting. Note that the full (messy) steady-state approximation is
less severe than either the pre-equilibrium or the rate-limiting step approximations, for it includes both
as special cases.
1 k' 1
E19.15(a) - = -·- + - - [analogous to 19.46]
k, kakb k. p A
Therefore, for two different pressures we have
-1 - - -1- - - 1(1
--- lJ
k,(p1) k, (P2) k. P1 P2
_ 1__ l
Pi P2 -----~~~-Pa
12Pa l.30xl0
3
I I
1 1
so k. = --1~-~1- ~--=1.9xl0-{j Pa-' s- 1
--- --
k, (p,) k, (P2) 2.lOxl0-5 s-' 2.50xl0-4 s-'
or /1.9 MPa- 1 s- 1/
E19.16(a) The degree of polymerization is [19.49b]
(N) = 1+k,t[A]0
= 1+(1.39 dm-3 mol- 1 s-') x 5.00 h x 3600 s h- 1 xl.OOxl0-2 mo! dm-3
= /251/
The fraction condensed is related to the degree of polymerization by
1 (N)-1=251-1 =I0.9961
(N) = 1- p so
p=M 251
E19.17(a) The kinetic chain length varies with concentration as
v = k,[MJ[Ir 1n [19.57]
so the ratio of kinetic chain lengths under different concentrations is
l/2= _l x (- 1 )1/2= lo.1251

v2 = [MJ2 x
V1 [M] 1 (fil
[1] J 2 4.2 3.6
E19.18(a) Number of photons absorbed= rf 1 x number of molecules that react [19.59a]. Therefore,
3 23
(2.28xl0- mol / 2)x(6.022x10 einstein - 1) 1 1s l
numb er ab sorb ed = . x 10
33
2.1 x 10 2 mol einstein- 1
E19.19(a) For a source of power output P at wavelength /..,, the number of photons (n,t) generated in a time tis
the energy output divided by the energy per mole of photons
Pt PJ.t (100 W)x(45 min)x(60 s min- 1)x(490xl0-9 m)

n;. = - - = - - =
hvNA hcN A (6.626xl0-34 J s)x(2.998xl08 m s- 1)x(6.022xl0 23 mor 1)
= 1.11 mo! = 1.11 einstein
If 40% of the incident photon flux is transmitted, then 60% is absorbed. Therefore,
</J =molecules decomposed= 0.344 mo! = lo. 52 1

photons absorbed 0. 60 x 1.11 einstein
E19.20(a) The Stem-Volmer equation (eqn. 19.66) relates the ratio of fluorescence quantum yields in the
absence and presence of quenching.
<Pr,o = 1+ r 0 kQ[Q] = -Z-

l f,0
<Pr
The last equality reflects the fact that fluorescence intensities are proportional to quantum yields.
Solve this equation for [Q]:
[Q] = U r,o I Ir) - 1 = 2 _1 3

Tok Q (6.0xlO 9 s)x(3.0 x 10s dmJ moi-1 s-1 ) = lo.56 mo! dm- 1
E19.21 (a) The efficiency of resonance energy transfer is given by [19.67].
'llr =l-_fr_=0.10
<Ao
Forster theory relates this quantity to the distance R between donor-acceptor pairs by
'llr = Ro 6Ro+R'
6
[19.68]
where R0 is an empirical parameter listed in Table 19.6. Solving for the distance yields
116 116
1 1
R=Ro ( - -1) =(4.9nm)x( - --1) =f7.lnmf
TJr 0.10 l
P19.1 A simple but practical approach is to make an initial guess at the order by observing whether the
half-life of the reaction appears to depend on concentration. If it does not, the reaction is first-order;
if it does, refer to Table 19.3 for an expression for the half-life of a reaction of the type A~ P for
orders other than 1:
2•-I l
t - - oc [A] 1-•
112 - (n-l)k,[A]~-1 o
Examination of the data shows that the first half-life is roughly 45 minutes and the second is about
double the first. (Compare the 0-50 minute data to the 50-150 minute data.) That is, the half-life
starting from half of the initial concentration is about twice the initial half-life, suggesting that the
half-life is inversely proportional to initial concentration:
!112 oc [A]o- 1 = [A]o 1-n with n = 2
Confirm this suggestion by plotting l/[A] against time. A second-order reaction will obey
1 1
- = k , t + - [19.13b]
[A] [A] 0
We draw up the following table (A= NILiCNO).
t/min 0 20.0 50.0 65.0 150
m(urea)/g 0 7.0 12.1 13.8 17.7
m(A)/g 22.9 15.9 10.8 9.1 5.2
[A]/(mol dm- 3) 0.381 0.265 0.180 0.152 0.0866
[Ar 1t(dm 3 mor 1) 2.62 3.78 5.56 6.60 11.5
12 ~--~--
11
IO I
~ 9
1....
~ s I
~: I
~ 5
4
3
2 ~--------------~
0 20 40 60 80 100 120 140 160
//min Figure 19.2
The data are plotted in Figure 19.2 and fit closely to a straight line. Hence, the reaction is indeed
lsecond-orded. The rate constant is the slope: /k, = 0.0594 dm 3 mol- 1min- 1/. To find [A] at 300 min,
use eqn. 19.13(c):
3
[A]= [A] 0 = 0.38lmoldm- = 0 _048 9 moldm-3
1+ k/[A]0 1+ (0.0594)x(300)x(0.381)
The mass of NH 4 CNO left after 300 minutes is
m = (0.0489moldm-3)x(l.00dm 3 )x(60.06gmor 1) = )2.94 g/
P19.3 Use the procedure adopted in the solutions to problems 19.1 and 19.2: Is the half-life (or any other
similarly defined "fractional life") constant, or does it vary over the course of the reaction? The data
are not quite so clear-cut. The half-life appears to be approximately constant at about 10 minutes: in
the interval 0-10 the initial concentration drops by just over half, while in the interval 2-12 the
concentration drops by slightly less than half. Another measure would compare the fractional
consumption in two equal time intervals. The fractional consumption in the 0-2 interval is about
1/6, while that in the 10-12 interval is about 1/10-suggesting that the fractional consumption is not
constant over the time the reaction was monitored. We draw up the following table (A= nitrile) to
examine both first-order and second-order plots. The former is a plot of 1n[ [A]o
[A]) against time
(eqn. 19.lOb); the latter is a plot of 1/[AJ against time.
t/(10 3 s) 0 2.00 4.00 6.00 8.00 10.00 12.00

[A] I (mol dm- 3) 1.50 1.26 1.07 0.92 0.81 0.72 0.65
[A]
1.00 0.840 0.713 0.613 0.540 0.480 0.433
[A Jo
1n[ [A] ) 0 -0.174 -0.338 -0.489 -0.616 -0.734 -0.836

[A Jo
l/[A] 0.667 0.794 0.935 1.09 1.23 1.39 1.54
First-Order Plot
0
- 0. l
--0.2
~
--0.3
<
;::;:
- 0.4
--0.5
:::.
:s --0 .6
- 0. 7
--0.8
-0.9
-I
0 2 4 6 8 10 12
t I {10 3 s) Figure 19.3(a)
The first-order plot (Figure 19.3a) is not bad: the correlation coefficient is 0.991. The corresponding
first-order rate constant is kr =-slope= f7.ox10-5 s- 11.
Second-Order Plot
J.6
J. 5
1.4
1.3
l.2
<
.... I.I
""" l
0.9
0.8
0.7
0.6
0 2 4 6 8 JO 12
t I {103 s) Figure 19.3(b)
The second-order plot (Figure 19.3b) looks even better: the correlation coefficient is 0.999. The
corresponding second-order rate constant is kr =slope= f7.3x10- 5 dm 3 mo1- 1 s- 11.
COMMENT. Based on the given data, the reaction appears to be closer to second-order than to first-
order. (The reaction order need not be an integer.) This conclusion is a tenuous one, though, based on
the assumption that the data contain little experimental error. The best course of action for an
investigator seeking to establish the reaction order would be further experimentation, following the
reaction over a wider range of concentrations.
P19.5 Since both reactions are first-order,
- d[A] =ki(A]+k2[A]=(k1 +k2)[A]

dt
so [A]=[A] 0 e -<k, +k,)t [19.10bwithk,=k1 +k2]
We are interested in the yield of ketene, CH2CO; call it K:
Integrating yields
The percent yield is the amount of K produced compared to complete conversion; since the
stoichiometry of reaction (2) is one-to-one, we can write
% yield= [K] x100% =_3_(I-e -r1, +11>1)xIOO%

[A] 0 k, + k2
which has its maximum value when the reaction reaches completion.
4 65
max%yield=____!2_xl00%= · s-' xl00%=l55.4%I
k, +k2 (3.74+4.65) s- 1
COMMENT. If we are interested in yield of the desired product (ketene) compared to the products of
side reactions (products of reaction 1), it makes sense to define the conversion ratio, the ratio of desired
product formed to starting material reacted, namely,
[K]
[Al0 - [Al
which works out in this case to be independent of time.
[K] = _!5:.___
[Al 0 - [Al k 1 + k 2
If a substance reacts by parallel processes of the same order, then the ratio of the amounts of products
will be constant and independent of the extent of the reaction, no matter what the order.
Question. Can you demonstrate the truth of the statement made in the comment?
P19.7 The stoichiometry of the reaction relates product and reaction concentrations as follows:
[A]= [A] 0 -2[B]
When the reaction goes to completion, [B] = [A]o/2; hence [A]o = 0.624 mo! dm- 3. We can therefore
tabulate [A], and examine its half-life. We see that the half-life of A from its initial concentration is
approximately 20 min, and that its half-life from the concentration at 20 min is also 20 min. This indicates a
first-order reaction. We confirm this conclusion by plotting the data accordingly (in Figure 19.4), using
In [A]o = k t [19.lOb]
[A] A
which follows from
d[A) = - kA[A]
dt
ti min 0 10 20 30 40 00
3
[B] / (moldm- ) 0 0.089 0.153 0.200 0.230 0.312
3
[A] / (moldm- ) 0.624 0.446 0.318 0.224 0.164 0
[A]o
In- 0 0.34 0.67 1.02 1.34
[A]
0 - - - - - - - - - · - · - · - - - - - · ----···--·····--------·--
-0.2
-0.4
~
-0.6
~ -0.8
~
- I
-1.2
-1 .4 ~------------------~
0 10 20 30 40
Time/min Figure 19.4
The points lie on a straight line, which confirms lfirst-orded kinetics. Since the slope of the line is
-3.4x10-2 min- 1, we conclude that kA = 3.4x10-2 min- 1. To express the rate law in the form v =
.k,[A], we note that
1
V=-1
- d[A] =-(l)x(-k
2 A [A])=- kA[A]
2 dt 2
and hence k, = tkA= li.1x10-2 min- 1 I.

P19.9 If the reaction is first-order, the concentrations obey
1n( [A[A])=
Jo
-k,t [19.lOb]
and, since pressures and concentrations of gases are proportional, the pressures should obey
In Po =kt
r
p
and ~In Po should be a constant. We test this by drawing up the following table.
t p
p 0 /Torr 200 200 400 400 600 600

t Is 100 200 100 200 100 200
p I Torr 186 173 373 347 559 520
104 (-1-) In Po 7.3 7.3 7.0 7.1 7.1 7.2

t Is p
The values in the last row of the table are virtually constant, so (in the pressure range spanned by
the data) the reaction has lfrrst-order kinetic~ with k, = 17.2xl 0-4 s- 'I.
P19.11 Using spreadsheet software to evaluate eqn. 19.27(b), one can draw up a plot like that in
Figure 19.5. The curves in this plot represent the concentration of the intermediate [I] as a function
of time. They are labeled with the ratio k.fkb, where kb = 1 s- 1 for all curves and ka varies. The
thickest curve, labeled 10, corresponds to k. = 10 s- 1, as specified in part (a) of the problem. As the
ratio k.fkb gets smaller (or, as the problem puts it, the ratio ktlka gets larger), the concentration
profile for I becomes lower, broader, and flatter; that is, [I] becomes more nearly constant over a
longer period of time. This is the nature of the lsteady-state approximatio~, which becomes more
and more valid as consumption of the intermediate becomes fast compared with its formation.
0.6
'I'
E
"'0
E 0.4
0.2
2 3 4 5
tis Figure 19.S
P19.13 (a) First, find an expression for the relaxation time, using Example 19.4 as a model.
d[A] = -2k [A] 2 + 2k'[A ]

dt a a 2
Rewrite the expression in terms of a difference from equilibrium values, [A]= [A]eq + x.
d[A] = d([A]eq + x) = dx = -2k ([A] + x) 2 + 2k' ([A ] -.Lx)

2
dt dt dt 3
eq
3
eq 2
2 2
dx =-2k.[A]eq -4k,[A]eqx-2k.x +2kJA 2 ]eq -k:x
dt
Neglect powers of x greater than x 1, and use the fact that at equilibrium the forward and reverse
rates are equal,
to obtain
To get the desired expression, square the reciprocal relaxation time,
introduce [AJtot = [A]eq + 2[A2]eq into the middle term,

and use the equilibrium condition again to see that the remaining equilibrium concentrations cancel
each other.
COMMENT. Introducing [A],0 , into just one term of eqn. (i) above is a permissible step but not a very
systematic one. It is worth trying because of the resemblance between eqn. (i) and the desired
expression: We would be finished if we could get [A],0 , into the middle term and somehow get the first
term to disappear! A more systematic but messier approach would be to express [A]"" in terms of the
desired [A],0 , by using the equilibrium condition and [A],°' = [A]"" + 2[A,]"": Solve both of those equations
for [A,]"", set the two resulting expressions equal to each other, solve for [A]"" in terms of the desired
[AJ.o,, and substitute that expression for [A]"" everywhere in eqn. (i).
l
(b) Plot 2 vs. [A]iot
r
The resulting curve should be a straight line whose y-intercept is (k.') 2 and whose slope is 8k.k.' .
(c) Draw up the following table.
[A],0 , I (mol dm-3) 0.500 0.352 0.251 0.151 0.101

Tins 2.3 2.7 3.3 4.0 5.3
1/(r/ns) 2 0.189 0.137 0.092 0.062 0.036
The plot is shown in Figure 19.6.
0.2 ·--,--....-·*---·- ---

0.18
y =0.379 x + 0.0003 A
0. 16
R' - 0.996
/ I
/v
0. 14
N 0. 12
/
~ 0.l
/"' I
"" 0.08 /'
0.06
/
0.04
/
0.02
/
0
I/
0 0. 1 0.2 0.3 0.4 0.5
[A J.0 , I (moVdm3) Figure 19.6
The y-intercept is 0.0003 ns-2 and the slope is 0.38 ns- 2 dm3 mor 1, so
k: = {3x10-4 x(lo-9 sr2}112 = (3xl0 14 s-2)1 12 = li.7xl0 7 s- 1I

9 2 3
k = 0.38x(l0- sf dm mol-I =l2.7x109 dm3 moi-1 s-1 1
a 8x (I.7 x l0 7 s-t)
3 1 1 9
and K=k.l dm moi- s- =2.7xl0 =II.6x1021
1 7
k: 1s- l.7xl0
COMMENT. The data define a good straight line, as the correlation coefficient R2 = 0.996 shows. The
straight line appears to go through the origin , but the best-fit equation gives a small non-zero y-
intercept. Inspection of the plot shows that several of the data points lie about as far from the fit line as
the y-intercept does from zero. This suggests that the y-intercept has a fairly high relative uncertainty
and so do the rate constants.
P19.15 (a) The fluorescence intensity is proportional to the concentration of fluorescing species, so
Ir - [S] =
I0 - [S]o
e -11r, [19.62) so 1n(Ir)
Io
= _!._
'ro
A plot of ln(fr/10) against t should be linear with a slope equal to -lit() (i.e., io = -1/slope) and an
intercept equal to zero. See Figure 19.7. The plot is linear, with slope -0.150 ns- 1, so
'f0 = -1/ (-0.145 ns- 1 ) = /6.9 ns/
-0.5
- I
c
-!:::'
..:; -1.5
:s
-2
- 2.5
0 5 10 15 20
Time Ins Figure 19.7
Alternatively, average the experimental values of ~ln(!J_J

t 1
and check that the standard deviation is
0
a small fraction of the average (it is). The average equals -1/tQ (i.e., io = - 1/average).
(b) The quantum yield for fluorescence is related to the rate constants for the various decay
mechanisms of the excited state by
kf
<A= [19.64]=kr'fo [19.63)
kr + krsc + krc
so kr =<A I -r0 = 0.70 I (6.9 ns) =lo.IO 1 ns- 1 I
P19.17 Proceed as in Problem 19.15. In the absence of a quencher, a plot of ln ft/10 against t should be
linear with a slope equal to -l/'t0 . The plot is in fact linear with a best-fit slope of -1.004 µs -' . (See
Figure 19.8)
-1
'f0 = = 9.96 µs
-1.004 µs-'
0 - ---------··-------------··---·····--···---··----·--··-----.--------------.···--·-·-·--·1
--0.5
No
'6 -1
-:::. With
::::: quencher
.e -1.5
-2
I
-2.5 ~--------------~
0 10 15 20
Time I µs Figure 19.8
In the presence of a quencher, a graph of ln fr/10 against t is still linear but has a slope equal to
-1/'t. This plot is found to be linear with a regression slope equal to -1.788 µs -'.
-1
-r= =5.59µs
-1.788 µs-'
The rate constant for quenching (i.e., for energy transfer to the quencher) can be obtained from
1 1
-=-+k0 [Q] [Example19.8]
'f 'fo
Thus k =T- I - T0
-I
= RT( T - I - - 1)
T0
Q [N2l PN,
_ (0.08206dm 3 atmK- 1mol- 1)(300K)(O.l788-0.1004)x(10-6 sr1
9.74xl0-4 atm
= ll.98xl0 9 dm 3 mol- 1 s- 1 I
P19.19 The rate of change of [A] is
d[A] = -k, [A]"

dt
Hence, f[ AJ d(A] = -k, dt = -kJ

J[AJo [A]" o
f
Therefore, kt- -
r - n-1( 1 ) (1
x - -1- - -
[Ar- [A]~-i
1)
At t = t 112 , [A] = [A]o/2
1 ) ( 2 n- l
k,t112 = ( n -1 x [A ]~-1 - [A ]~-1
1 J= (-;=IlJ x ( [A1]~-1 J
2 n-l -
2 n- I
and t112 =I k, (n - l)[A]~-'
-1 I [as m
. eqn. 19.15]
Now let t 113 be the time at which [A] = [A]o/3. Substitute these expressions into the integrated rate
law:
1 ) 1 (3n-l
k,t113 = ( n -1 x [A ]~-1 - [A ]~-1 =
J (3"-
-;=I-lJ ( 1 J
1
x [A ]~-1
3n- I -1
and
1113 =ik,(n-l)[A]~ I
P19.21 v = d[P] =k [A][B]

dt r
Let the initial concentrations be [A] 0 = A0 , [B] 0 = B0 , and [P] 0 = 0. Then when P is formed in
concentration x, the concentration of A changes to Ao - 2x and that of B changes to Bo - 3x. Therefore,
d[P] = dx
= k, (Ao_ 2x)(B0 -3x) with x = 0 att = 0
dt dt
lx dx
i t
o '
kdt=
o (Ao-2x)x(B0 -3x)
Apply partial fractions decomposition to the integrand on the right.
f' kdt=
Jo ' Jo
r( 6
2B0 -3Ao
1
Jx( 3(Ao-2x) 1
2(B0 -3x)
Jdx
=((2B ~ 3Ao) )x( f x-(1~2)Ao f x-(~3)B0

1
]
0
kt= -1
' ( (2Bo -3Ao)
x J [~x--!Ao
1. ~x- 1. B ) ]
2 'A
-'() ) -
- ±Bo
3 0
P19.23 The rate equations are
d[A] =-k [A]+k'[B]

di a a
d~~] = k, [A]-k:[B]-kb[B]+kaC]
d[C] = k [B]-k'[C]
dt b b
These equations are a set of coupled differential equations. Although it is not immediately apparent,
they have a closed-form general solution; however, we are looking for the particular circumstances
under which the mechanism reduces to the second form given. Since the reaction involves an
intermediate, let us explore the result of applying the steady-state approximation to it. Then
d[B] = k. [A]-kJB]-kb[B]+kaC] "'0

dt
and [B]"' k. [A]+kaC]

k: +kb
d[A] kk k'k'
Therefore, - - =--,-•-b-[A]+-,-•-b-[C] .
dt k. +kb k. +kb
This rate expression may be compared to that given in the text [Section 19.4) for a first-order
reaction approaching equilibrium.
k
A~C
t-y-'-
r
Here k = k, kb and k' = k:k~

r k: +kb r k: +kb
k' k -(k;+k,)t )
The solutions are [A]= '+ ;e x[A] 0 [19.19]
[ k,+k,
and [CJ =[AJo- [A]
Thus, the conditions under which the first mechanism given reduces to the second are the conditions
under which the steady-state approximation holds, namely, when B can be treated as a lsteady-stat~
~ntermediat~.
P19.25 Let the forward rates be written as
and the reverse rates as
The net rates are then

But [AJ = [Alo and [DJ= 0, so the steady-state equations for the net rates of the individual
steps are
k1[AJ 0 -k;[BJ = k2 [BJ-k;[C] = k3 [C]
From the second of these equations we find
[CJ= k2 [BJ
k; +k3
After inserting this expression for [C] into the first of the steady-state equations, we obtain
[BJ= k,[AJ +k;[C] k1[AJ 0 +k;( ki(BJ

l0
1+k -- k'2+k3
J
k 2 k'1+k2
which yields, on isolating [BJ,
kl
[AJ x
[BJ= o k' +k - ( k;+k,
k,k;
I 2
Thus, at the steady state,
R, =R, =R, =[AV;x[I k1 J k1k2k3[AJ 0

k'I + k2 -( k~,k;
+k
) - k:k; + k:k3 + k2k3
2 3
COMMENT. At steady state, not only are the net rates of reactions 1, 2, and 3 steady but so are the
concentrations [BJ and [CJ. That is,
-d[BJ = k1[AJ 0 -(k1I +k2 )[BJ+ k'JC]"" 0

dt
and d[C]=k2 [BJ-(k;+k3 )[C]z0

dt
In fact, another approach to solving the problem is to solve these equations for [BJ and [C].
P19.27 The number-average molar mass of the polymer is the average chain length times the molar mass of
the monomer.
(M) = (N)M1= M 1 [19.49aJ

1-p
The probability PN that a polymer consists of N monomers is equal to the probability that it has
N - 1 reacted end groups and one unreacted end group. The former probability is pN-I; the latter
1 - p. Therefore, the total probability of finding an N-mer is
PN = PN-l(l - p)
We need this probability to get at (u 2

), again using number averaging:
(u2) = M12 (N2) = M1 2LN2PN = M12(l- P)LN2p N-1

N N
= M 2 (1- ) ~ ~" N = M 2 (1- ) ~ ~ (1- )-1 = M/ (1 + p)

I p dppdp";:p I p dppdp p (1-p)2
Thus, (u2t-(u)N2 =M12 [ (l-p)2

1+ p 1 J_
pM12
(1-pf)- (1-pf
The time dependence is obtained from

k,t[A] 0
p= [19.48)
1+k,t[A] 0
1
and (N)=-=l+k/[A]0 [19.49a and 19.49b]
1-p
1/2
Hence, _!!__ = /
1-p
12
(1 +k/[A] 0 ) ={k,t[A]0 (1 +k/[A] 0 )f 2
and
P19.29 In termination by disproportionation, the chain carriers do not combine. The average number of
monomers in a polymer molecule equals the average number in a chain carrier when it terminates,
namely, the kinetic chain length, v.
(N) = v = lkJMJ[Ir 1' 2 I

COMMENT. Contrast this result to the reasoning before eqn. 19.58, in which the average number is the
sum of the average numbers of a pair of combining radicals.
P19.31 The rates of the individual steps are
A-7B d[B] =I
dt a
d[B] = -k [B]2
df r
In the photostationary state, I. - k,[B]2 = 0 . Hence,
[B] = (
t- )
1/ 2
This concentration can differ significantly from an equilibrium distribution because changing the
illumination may change the rate of the forward reaction without affecting the reverse reaction.
Contrast this situation to the corresponding equilibrium expression, in which [B]eq depends on a
ratio of rate constants for the forward and reverse reactions. In the equilibrium case, the rates of
forward and reverse reactions cannot be changed independently.
P19.33 A simple but practical approach is to make an initial guess at the order by observing whether the
half-life of the reaction appears to depend on concentration. If it does not, the reaction is first-order;
if it does, it may be second-order. Examination of the data shows that the half-life is roughly 90
minutes, but it is not exactly constant. (Compare the 60-150-minute data to the 150-240-minute
data; in both intervals the concentration drops by roughly half. Then examine the 30-120-minute
interval, where the concentration drops by less than half.) If the reaction is first-order, it will obey
~ ~) = -k,t [19.lOb]
If it is second-order, it will obey
1 1
- = k,t+- [19.13b]
C c0
See whether a first-order plot of In c versus time or a second-order plot of lie versus time has a
substantially better fit. We draw up the following table.
t I min 30 60 120 150 240 360 480

c I (ng cm-3) 699 622 413 292 152 60 24
(ng cm-3) I c 0.00143 0.00161 0.00242 0.00342 0.00658 0.0167 0.0412
In {c/(ng_ cm-3)} 6.550 6.433 6.023 5.677 5.024 4.094 3.178
7 ~·~~~~~~~~~~~~~~~~~~~~~~~
0.05
: : : :
.. lY.,,,.::0,0.0.765,,; ..t: 6.S:i~ !R2 = 0.8403:

6.5 •
~2 ~r:9.9.84
0.04
....... ........... .:
6
7 5.5 ~ 0.03
E
u
00 5
"e
<.)
c 00
'6 . ..
5 O.D2
.5 4.5 ~·
•
4 O.Dl ~ .......... .
3.5 •
3 O+---~«-+---~--~---~-----<
0 100 200 300 400 500 0 200 300 400 500

t/min tlmin
(a) (b)
Figure 19.9
The data are plotted in parts (a) and (b), of Figure 19.9. The first-order plot fits closely to a straight
line with just a hint of curvature near the outset. The second-order plot, conversely, is strongly
curved throughout. Hence, the reaction is lfirst-orded. The rate constant is the slope of the first-order
plot: k, = ~l00765 min- 11= ~.459 h- 11. The half-life is (eqn. 19.11)
ln2 ln2 ~ .
t 112 =- = -1 = Ll.:a.hJ = 191 mml
k, 0.459 h
COMMENT. As noted in the problem , the drug concentration is a result of absorption and elimination of
the drug, two processes with distinct rates. Elimination is characteristically slower, so the later data
points reflect elimination only because absorption is effectively complete by then. The earlier data
points, by contrast, reflect both absorption and elimination. It is therefore not surprising that the early
points do not adhere so closely to the line so well defined by the later data.
P19.35 The initial rate is
v0 = (3.6xl0 6 dm9 mol-3 s- 1 )x(5xl0-5 mol dm-3 )2 x(I0- 5·6 mo! dm-3 )2
=l6xl0- 14 moldm-3 s- 1 1
The half-life for a second-order reaction is
tl / 2 1
= kerr [HSO-] [19.13b]
3 0
where kerr is the rate constant in the expression
d[Hso; ] = 2v = kerr [Hso; ]2

dt
Comparison to the given rate law and rate constant shows
kerr = 2k,[H+]2 = 2(3.6xl06 dm9 mol-3 s-1)x(10-56 mol dm-3)2

= 4.5xl0-5 dm 3 mol- 1 s-1
P19.37 The rate of reaction is the rate at which ozone absorbs photons times the quantum yield. The rate at
which ozone absorbs photons is the rate at which photons impinge on the ozone times the fraction
of photons absorbed. That fraction is 1 - T, where T is the transmittance. T is related to the
absorbance A by
A = -log T = t:cl so 1 - T = 1 - 10-a-i
and 1-T = 1-10-{(260dm 3 1 1 9 3 5
mol- cm- )x(8x!0- moldm- )x(I0 cm) = 0.38
If we let F stand for the flux of photons (the rate at which photons impinge on our sample of ozone),
then the rate of reaction is
(lxl0 14 cm-2 s-1)x(1000cm 3 dm-3)

v=¢(1-T)F=(0.94)x(0.38)x ( _) (
6.022x10 23 mol 1 x 10 5 cm
)
= ls.9xl0- 13 moldm-3s- 1 I
20 Molecular reaction
dynamics
020.1 The parameter A is called the pre-exponential factor or the frequency factor. The parameter E. is
called the activation energy. Collectively, the two quantities are called the Arrhenius parameters.
Plots of In lcr versus 1/T (called Arrhenius plots) yield a straight line for many reactions over
temperature ranges of interest. In such plots the intercept of the line at 1/T = 0 (at infinite
temperature) is In A and the slope is -E.fR. For some reactions over some temperature ranges,
though, the plot is not linear, and we describe the temperature dependence as non-Arrhenius.
However, it is still possible to define an activation energy as
E = RT 2
•
(dlnk,)
dT
(20.2]
This definition reduces to the earlier one (as the slope of a straight line) for a temperature-
independent activation energy. The latter definition is more general, however, because it allows Ea
to be obtained from the instantaneous slope of an Arrhenius plot even if it is not a straight line (i.e.,
the tangent of the curve at the temperature of interest). Non-Arrhenius behavior is sometimes a sign
that quantum mechanical tunneling is playing a significant role in the reaction.
020.3 Collision theory expresses a rate of reaction as a fraction of the rate of collision, on the assumption
that reaction happens only between colliding molecules, and then only if the collision has enough
energy and the proper orientation. So the rate of reaction is directly proportional to the rate of
collision, and the expression of this rate comes directly from kinetic-molecular theory. The fraction
of collisions energetic enough for reaction also comes from kinetic-molecular theory via the
Boltzmann distribution of energy.
020.5 In collision theory, the steric factor or P-factor is introduced as the probability that a collision
energetic enough to lead to reaction actually does lead to reaction. This probability can be
interpreted in various ways, such as the probability of proper orientation of colliding reactants. In
the RRK model, the P-factor is the probability that sufficient energy is concentrated in a particular
mode of motion that leads to reaction; thus, the complexity of a reacting molecule affects the steric
P-factor. The RRK expression for the P factor is
~·J-
1
P=(l- [20.19a]
where E' is the energy needed to break the bond-critical for reaction, E is the energy available
within the molecule for distribution over various modes of motion, ands is the number of modes.
020.7 The Eyring equation (eqn. 20.40) results from activated complex theory, which is an attempt to
account for the rate constants of bimolecular reactions of the form A+B ~ c• ~ P in terms of
the formation of an activated complex. In the formulation of the theory, it is assumed that the
activated complex and the reactants are in equilibrium, and the concentration of activated
MOLECULAR REACTION DYNAMICS 493
complex is calculated in terms of an equilibrium constant, which in turn is calculated from the
partition functions of the reactants and a postulated form of the activated complex. It is further
supposed that one normal mode of the activated complex, the one corresponding to displacement
along the reaction coordinate, has a very low force constant. Displacement along this mode leads
to products, provided that the complex enters a certain configuration of its atoms, known as the
transition state. The derivation of the equilibrium constant from the partition functions leads to
eqn. 20.39 and in tum to eqn. 20.40, the Eyring equation. See Section 20.6 for a more extensive
discussion.
020.9 An expression of the rate constant for electron transfer is given by eqn. 20.58:
k =CH (r) 2e- 1!.' G1Rr

et DA
This rate constant depends on the distance between donor and acceptor (r) through the function
, which is given by eqn. 20.57; ket decays exponentially with increasing r. The parameter f3
2
HoA(r)
in eqns. 20.57 and 20.61 determines how strongly ket depends on distance. This parameter changes
with the transfer medium. The standard Gibbs energy of the electron-transfer process (il,G 0 ) affects
the rate through the activation Gibbs energy and a quantity called the reorganization energy (A), as
shown in eqn. 20.59. In systems where the reorganization energy is constant, the dependence of ln
ket on ilrG 0 is given by eqn. 20.62; it is an inverted parabola in which the maximum rate occurs
when il,G 0 = A. A more thorough discussion can be found in Section 20.8.
020.11 The saddle point on the potential energy surface corresponds to the transition state of a reaction.
The saddle-point energy is the minimum energy required for reaction; it is the minimum energy for
a path on the potential energy surface that leads from reactants to products. Because many paths on
the surface between reactants and products do not pass through the saddle point, they necessarily
pass through points of greater energy, so the activation energy can be greater than the saddle-point
energy. Thus, the saddle-point energy is a lower limit to the activation energy.
020.13 Attractive and repulsive potential-energy surfaces are discussed in Section 20.ll(b). An attractive
surface is one whose saddle point is closer to reactants than to products so that the transition state
occurs early in the reaction. On such a surface, trajectories in which excess energy is translational
tend to end in products, whereas trajectories in which the reactant is vibrationally excited tend not
to cross the saddle point and end in products. Conversely, on a repulsive surface, the oscillatory
motion of a trajectory that has excess vibrational energy in the reactant enhances the likelihood that
the trajectory will end in products rather than simply reflect back to reactants.
E E
E20.1 (a) Ink (T) = InA- - • In k,(T2 ) =In A- R; [20. la]
r I RT
I 2
Subtract these two expressions and solve for E.:
R ln(~(i.) J (8.3145JK-' mor') x 1J 2.67xlo-:)

E. = , ( ,) = ~\ 3 . 3 oxio- =II06kJmor'I
1 i J ~
308K - ~
1
( -I; - -Tz 323K
For A, we rearrange eqn. 20.l(b):

A= k, xeE, tRT = (3 .80 x 10-3 moldm-3 s-' ) x e106x10'1(s.J145xJos)
E20.2(a) Proceed as in Exercise 20.l(a):
_ R
ln(BJ;)
k,(T2))
=(8.3145JK-
I
mo 1 )x
- I ln3 =135kJmo1 1
I
E, - ( ) 1 _ 1
_l_ _ _l_ 297K - 322K
I; T2
E20.3(a) Let the steps be
A + B ~ I ( fast: k., k.') and l~P (kb)

Then the rate of reaction is
- = kb [I]
v= d[P]
dt
Applying the pre-equilibrium approximation yields
_I!L=K= k.
[A][B] k: so
k'a
k.kb[A][B] = k,(A][B] k - k.kb

and v= ·'
a
with ,-T a
Thus Ea= E.(a) + E.(b) - E.' (a) [20.4] = (25 + 10- 38) kJ mor 1 = t3 kJ mor 1/
COMMENT. Activation energies are rarely negative; however, some composite reactions are known to
have small, negative activation energies.
E20.4(a) The collision frequency is
z = O'Cre/JVA [20.9]
112
_ = (16kT) p
where crel ffm [20.10], O'= ml [20.7b] = 4trR. 2, and !NA = kT
112 12
l6kT)
Therefore, z = a!NA ( - - = 16 pR 2 ( __!!__ ) '
ffm mkT
= 16x(120xl03 Pa)x(190xl0- 12 m) 2
l/ 2
(
x 17.03 uxl.661xl0-27 kg u-~xl.381xl0-23 J K- x303 K J 1
= lu3xl010 s- 1 I
The collision density is
Z=z!NA [ 20.1 2a]=.:_(_.f!_)=l.13xl0

2 2 kT 2
10
s-
1
( 120xl0 Pa
3
l.38lxl0-23 JK- 1 x303K

J
= IL62xl0 35 s- 1 m-3 1
For the percentage increase at constant volume, note that :NA is constant at constant volume, so the
only constant-volume temperature dependence on z (and on Z) is in the speed factor.
so (oz )1
z oT v
=
2T
and
Therefore '5z = '5T "" '5T =-u K ) 10 = 0.017

z Z 2T 2 l 303 K
so both z and Z increase by about li.7 percenq.
E20.5(a) The fraction of collisions having at least E0 along the line of flight can be inferred by dividing out
of the collision-theory rate constant (eqn. 20.18) the factors that can be identified as belonging to
the steric factor or collision rate f = e -E. ' RT.
(a) (i)~=
3 1
20 x l0 Jmor = 69 so
RT (8.3145JK- 1 mor 1 )x(350K) .
(ii)~=
3 1
20 x 10 J mor = 2.67 so 1 = e-2·61 =~lo69I
RT (8.3145 JK- 1 mor 1 )x(900K)
(b) (i) ~ =
3 1
100 x I 0 J mor = 34 .4 so
RT (8.3145 J K- 1 mol- 1 ) x (350 K)
1
(ii)~=
3
100 x 10 J mor = l3.4 so f = e- 13 .4 = l1.57xl01
RT (8.3145 J K- 1 mol- 1) x (900 K)
. -E ! RT
E20.6(a) A straightforward approach would be to compute f =e • at the new temperature and compare
it to that at the old temperature. An approximate approach would be to note that f changes from
lo= e -E.'RT to exp ( -E. ). where xis the fractional increase in the temperature. If xis small,
RT(l+x)
the exponent changes from -E,IRT to approximately -E.( 1-x)/RT and f changes from Jo to
Thus the new fraction is the old one times a factor of fo-x. The increase in f expressed as a
percentage is
f - lo x 100% = 1o1o-x- lo x 100% = c1o-· -1) x 100%

lo lo
(a) (i) lo-x = (l.04 x 10- r = 1.22 and the percentage change is j22o/J
3 10 350
'
(ii) lo-x = (0.069f 10 900

' = 1.03 and the percentage change is~
(b) (i) 1o-x= (1.19 x 10- r 15 10 350

' = 2.7 and the percentage change is !11oo/d
(ii) lo-' = (1. 57 x I 0-(j f io

1900
= 1.16 and the percentage change is jl 6o/J
1/ 2
E20.7(a) k, = P<Y s;; NAe-E, IRT [20.18]

( )
We are not given a steric factor, so assume that P = 1.
23
k = 0.36x(l0-9 m) 2 x Sx(l.3Slxl0- JK- )x( 65 0K)
I Jl/2x(6.022xl0 23 mor 1)
r ( .1l'X(3.32xl0-27 kg)
-171xl0 J
3
J
xexp ( (8.3145 J K - mol- 1 )x(650 K)
1
= li.o3x10-5 m 3 mol- 1 s- 1 I= li.o3x10-2 dm 3 mol- 1 s- 1 I
COMMENT. Assuming that P = 1 is done because it is convenient in the absence of additional

information, not because it is likely to be accurate.
E20.8(a) The rate constant for a diffusion-controlled bimolecular reaction is

0
kd =4.1l'R DNA [20.22]
where D =DA+ D 8 = 2 x (6 x 10-9 m 2 s- 1) = 1.2 x 10- 8 m 2 s- 1

kd = 4.1l'X (0.5 x 10-9 m) x (1.2 x 10- 8 m2 s- 1) x (6.022x10 23 moi- 1)
kd = 14.5x10 7 m 3 mol- 1 s- 1 I=14.5x10 10 dm 3 moi- 1 s- I

1
E20.9(a) The rate constant for a diffusion-controlled bimolecular reaction is

1 1 3 1
k =&RT [ . ] = 8x(8.3145 J K - mol- )x(298 K) = 6.6lxl0 J mo1-
20 25
d 3'T/ 3'T/ 'T/
(a) For water, 'T/ = 1.00 x 10-3 kg m- 1 s- 1•
6 61 103 1
k = · x mol-i = 16.61x106 m 3 moi- 1 s- 1 I=16.61x10 9 dm 3 mol- 1 s- 1 I
ct 1.00x10-3 kg m- 1 s- 1
(b) Forpentane, 'T/=2.2x10-4kgm- 1 s- 1•
m~ 1 - _ = 13 .o x 10 1 m 3 moi- 1 s- 1 I=13.o x 10 10 dm 3 mo1- 1 s- 1 I

1 1
1
6 61 03 1
kd = · x:
2.2x 10 kg m s
E20.1 O(a) The rate constant for a diffusion-controlled bimolecular reaction is

1 1
k =&RT= 8x(8.3145 1 K- mor )x(320K)
ct 3T] 3x(0.89xl0-3 kgm- 1 s- 1 )
= ls.Oxl0 6 m 3 mol- 1 s- 1 I= ls.Oxl0 9 dm 3 mol- 1 s- 1 I
Since this reaction is elementary bimolecular, it is second-order; hence,

!112 = 1 [Table 19.3, with k, = 2kd because 2 atoms are consumed]
2kAAJ0
so t112 = 1 = /4.2 x 10-s s/
2x(8.0x10 9 dm 3 mor 1 s- 1) x (1.5 x 10-3mol dm -3)
E20.11 (a) The steric factor, P, is

.
P =!!___[Section 20.3(c)]
<Y
The mean collision cross-section is <Y= mf with d = (dA + d8 )12.
Get the diameters from the collision cross-sections:

and da = ( <Js/1f) 112
{(0.95 nm 2)1' 2 +(0.65 nm 2 ) 112 } 2

so
4
=J0.79 nm 2J
9.2x10-22 m 2
Therefore, P =
0.79 x (lo-9 m) 2
_
= lu6xl0 3 I.
E20.12(a) Since the reaction is diffusion-controlled, the rate-limiting step is bimolecular and therefore second-
order; hence,
d[P] = k [A][B]
dt d
1 1
k = 2 x (8.3145 JK- mol- )x(313K) x (655 +l 820)x(-l-+_l_)
d 3x(2.93 x 10-3 kgm- 1s-1) 655 1820
6 3 1 1 9 3 1
= 3.04 x l0 m mor s- = 3.04xl0 dm mo1- s- 1
Therefore, the initial rate is
d[P] = (3 .04xl09 dm 3mor 1s- 1)x(0.170mol dm-3)x(0.350mol dm-3)

dt
= ll.8lxl08 mol dm-3s- 1I
9 3
COMMENT. If the approximation of eqn. 20.25 is used, kd = 2.37 x 10 dm mol-' s-' . In this case the
approximation results in a difference of about 25% compared to the expression used above.
E20.13(a) The enthalpy of activation for a bimolecular solution reaction is [Section 20.7(a)]
t:..*H=E. -RT= (8681 K-303 K) x 8.3145 J mor 1 K- 1 =~69 .7 kJ mor 1J
k: )x(;~ ) [20.46] = ~:~

2
k, = Bea'siRe -a'HIRT , B =(
= Bea's1Re -E, 1Rr e = Ae-E, tRr
Therefore, A = e B e a'SIR' implying that /::,.as= R (In ;-1)

(l.38l x l0-23 JK- 1)x(8.3145JK- 1 mor')x(303K) 2
B = - - - - - - - - -34- - -5 - - - - - -
6.626 x 10- J s x l 0 Pa
= 1.59 x 10 m mor 1s- 1 = 1.59 x 1014dm 3 mor 1s- 1
11 3
and hence 1::,.:t S = R[1n ( 2.05x1013 dm3 mol-1 s-1) -1]

l.59xl014 dm 3 mor' s- 1
= 8.3145 J K- 1 mor' x(-3.05) =J-25 J K- 1 mo1- 1J.

E20.14(a) The enthalpy of activation for a bimolecular solution reaction is [Section 20.7a]
t).*H = E. - RT= 8.3145 J K- 1 mo1- 1 x (9134 K - 303 K) = ~ 73.4 kJ mor'I

The entropy of activation is [Exercise 20.13a]
t).*S=R( ln~-1)
kRT 2
with B= -f7- = 1.59 x 10 14 dm 3 mor 1 s- 1[Exercise 20.13a]
hp
14
Therefore, t).*S=8.3145JK- I mor'x ln 7.78xl014 ) -1 =+4.9JK- I mor' .
[ ( l.59xl0
l
Hence, t).*G=t).*H- rn*S= {73.4-(303) x (4.9 x 10- 3) } kJ mor 1 =~71.9 kJ mor'I.
E20.15(a) Use eqn. 20.47(a) to relate a bimolecular gas-phase rate constant to activation energy and entropy:
k, =e2Bet.*s1Re-E, IRT
23 1 2 1 1
where B = (kT)x(RT) [2 0.4 6] = (1.38lxl0- J K - )x(338 K) x(8.3145 J mo1- K- )
h pf7 34 5
(6.626xl0- J s)x(l0 Pa)
= 1.98xl011 m 3 mol- 1 s- 1
Solve for the entropy of activation:
t).*S=R(ln~ - 2)+i
The derivations in Section 20.7(a) are based on a k, that contains concentration units, whereas the
rate constant given here has pressure units. Sok, is not the given rate constant, but
kr =7 .84 x 10-3 kPa- 1 s-' x RT
lcr = 7.84 x 10- 3 x (10 3 Par' s- 1 x 8.3145 J K- 1 mo1- 1 x 338 K = 0.0220 m 3 moi- 1 s- 1
3 1
Hence t).* S = 8.3145 J K -1 mol-1 x(ln 0.0220 m3 mol-1 s-1 2)+ 58.6xl0 J moi-
11 3
l.98xl0 m mo1- s-1 1
338 K
= l-91 J K- 1 mo1- 1I
E20.16(a) For a bimolecular gas-phase reaction,
t).* S = R(ln k, -2)+ E. [Exercise 20.15(a)] = R(ln A -~-2)+ E. = R(ln A -2)

B T · B RT T B
kRT 2
where B =-ff- [Exercise 20.13(a)]
hp
For two structureless particles, the rate constant is

1/2
k, =NACJ.
(
~: ) e-Mo lRT [20.42]
The activation energy is [20.2]
E = RT 2 dlnk, = RT 2 _j__(lnN <7* +.!.ln~+_!_lnT- Mo J

a dT dT A 2 :reµ 2 RT
=RT2(_l_+ M 0 J=M0 +RT

2T RT 2 2 '
so the pre-factor is
Hence,
2 6
t,,.*S=R lnN <7* 8kT 112 +.!.-lnkRT -2 } =R { ln<Y• p h ( _!_ J112 -~ }
{ A
( :reµ 2 p6 h (kT) 312 :reµ 2
J
For identical particles,

µ = rn/2 = (65 u)(l.661 x 10- 27 kg u- 1)/2 = 5.4 x 10- 26 kg
and hence,
t,,.* S = 8.3145 J K - 1 moi- 1

9 2 5 34 112
ln 0.35x(l0- m) xl0 Pax6.626xl0- J s ( 8 J 3}
x{ (1.38lxl0- 23 J K - 1x300 K) 312 :rrx5.4xl0- 26 kg -2
= l-74 J K - 1 mo1- 1I
E20.17(a) At low pressure, the reaction can be assumed to be bimolecular (see Chapter 19.7).
(a) /',,. *S = R ( ln ~ - 2J [Exercise 20.16(a)]
23 1
( )] l.38lxl0- JK- x8.3145JK- 1 mol- 1x(298K) 2
2
kRT [E .
where B = - - xerc1se 2013 . a = --------:-:- ----,-------
hp6 6.626xl0-34 J sxl0 5 Pa
= l.54x10 11 m 3 mol- 1 s- 1 = l.54xl0 14 dm 3 moi- 1 s- 1
Hence, t,,.*S=8.3145 JK-1 mo1-1x(ln 4.6xl012 dm3 mol-1 s-1 2J

l.54xl0 14 dm 3 moi- 1 s- 1
= l-46 J K - 1 mo1- 1I
(b) The enthalpy of activation for a bimolecular gas-phase reaction is [Section 20.7(a)]
t,,.*H = E. - 2RT= 10.0 kJ mo1- 1 - 2 x 8.3145 J mor' K- ' x 298 K = f+5.0 kJ mol 'I.
(c) The Gibbs energy of activation at 298 K is
t,,.*G = t,,.*H - n *s = 5.0 kJ mor' - (298 K) x (-46x10- 3 kJ K- 1 mor')
t,,.*G = ~18 .7 kJ mor'I
E20.18(a) Use eqn. 20.51 to examine the effect of ionic strength on a rate constant:
log le,= log le, 0 + 2AlzAz8 j/112

Hence, log k, 0 =log kr- 2AlzAzsll112 =log 12.2 - 2 x 0.509 x ll x (-1)1x(0.0525) 1n=0.85
and kr 0 =1'7.1 dm 6 mor2 min- 11
E20.19(a) The rate constant for electron transfer is
ket = C{H DA (r)} 2e-6*GiRT [20.58]
The reorganization energy, A, appears in two of these factors:
~ *G = (~,G f7.•+ ;l,) 2 ( 3 Jl/2

[20.59] and C = .!_ __!!___ [20.60]
h ;l,RT
(~J
1 2
' ~r (~J
1 2
So k = Ho/ ex ( -( Gf7 + A.)2 J = H 0 / ' ex (-(~,Gf7 +A)2 J

et h ;l,RT p 4;l,RT h ;l,kT p 4;l,kT
depending on whether the energies are expressed in molar units or molecular units. The only unknown
in this equation is A. Isolating A, analytically is not possible; however, one can solve for it numerically
using the root-finding command of a symbolic mathematics package, or graphically by plotting the
right-hand side versus the (constant) left-hand side and finding the value of A, at which the two lines
cross. Before we put in numbers, we must make sure to use compatible units. We recognize that
HoA(r) and ~,Gf7 are both given in molecular units, but that the former is really a wavenumber rather
than an energy. So we choose to express all energies in molecular units, namely, joules:
HoA(r) =hex 0.04 cm- 1 = (6.626 x 10-34 J s) x (2.998 x 10 10 cm s- 1) x (0.04 cm- 1)
HoA(r) = 8xl0-25 J
H DA 2 ( tr 3 Jl/2 _ (8x 10- 25 J) 2 ( tr 3 Jl /2 _ -s os - 1

34 23 8 10 1
-h- kT - 6.626xl0- J s 1.381xl0- J K - x298 K
1 - x s
~ r Gf} = -0.185eVx1.602x10- 19 J ev- 1 =-2.96x10-20 J
and 4kT= 4 x (1.381x10-23 J K- 1) x (298 K) = 1.65x10- 20 J
12 20
Thus 37.5 = 8xlQ-5 (_!_) ' exp(-(-2.96x10- J +;l,)2 J
A ;l,xl.65x10-20 J
where A,= kx 10- 21

~or~ kJ mo1- 1I
E20.20(a) For the same donor and acceptor at different distances, eqn. 20.61 applies:
In k01 = -/3r + constant

The slope of a plot of k01 versus r is -/3. The slope of a line defined by two points is
4 5
slope = ~y = In ket,2 - In ket,I = -/3 = 1n 4.51x10 - ln 2.02 x 10
& r2 -lj (1.23-1.11) nm
so /3=112 .5 nm- 1 1
P20.1 If the rate constant obeys the Arrhenius equation (eqn. 20. la), a plot of Ink, against l!T should yield
a straight line with slope -E.fR (eqn. 20.lb). Construct a table as follows.
K,I s 8/°C 103 K/T Ink,

2.46 x10-3 0 3.66 -6.01
0.0451 20 3.41 -3.10
0.576 40 3.19 --0.552
- ]
-2 '
-5
-6 1
In (k,/s- ) = -l1667 KJT + 36.702
0.0031 0.0032 0.0033 0.0034 0.0035 0.0036 0.0037

Kff Figure 20.1
The best-fit straight line fits the three data points very well:
ln (k/s- 1) = -1.17 x 104 KJT + 36.7
so E. = -(-1.17 x 104 K) x (8.3145 J mor' K- 1) = ~.70 x 104 J mor 1j = ~7.0 kJ mor 1i
P20.3 The relation between the equilibrium constant and the rate constants is obtained from
so K = kk; =exp ( !::i.~T

Hf7 J (
!::i. Sf} A) ( E' E )
exp ~ = A' exp •RT •
J(
Setting the temperature-dependent parts equal yields
!::i.,HB = E.-E: = [-4.2-(53.3)] kJ mor = -57.5 kJ mor 1 1
Setting the temperature-independent parts equal yields
so t:i.,SB = Rln( AA,)= (8.3145 J K- 1
l.4xl0
J
mol- 1) In ( l.OxlO:l = -41.1 J K-l mor 1
The thermodynamic quantities of the reaction are related to standard molar quantities, most of
which can be looked up in thermodynamic data tables.
!::i.,HB = !::i.rHB (C 2H 6 ) + !::i.rHB (Br)- !::i.rHB (C 2H 5)- !::i.rHB (HBr)
so . !::i.rHB (C 2H 5) = !::i.rHB (C 2 H 6 ) + !::i.rHB (Br)- !::i.rHB (HBr)- !::i.,HB
and !::i.rHB (C 2H 5) = [(-84.68) + 111 .88 - (-36.40) - (-57 .5)] kJ mor 1 = I+ 121.1 kJ mor 1 I
Similarly,
s: (C2H5) = [229.60+175.02-198.70-(-41.1)] J mor 1 K- 1 = 1247.0 J K- 1 mor 1 I

Finally, L\Ge (C2H 5) = {-32.82 + 82.396- (-53.45)} kJ mor 1- 11,Ge

= 103.03kJmol- 1 -11 r Ge
but 11Ge
r
=11 r H e -Tl1 r Se = -57.5kJmol- 1 -(298 K)x(-41.1 x 10-3 kJK- 1 mol- 1)
1
= -45 .3kJ mor
so 11fGe (C2H,) = [103.03-(-45.3)]kJ mor 1 = 1+148.3 kJ mor 1 I
P20.5 Draw up the following table as the basis of an Arrhenius plot.
TIK 600 700 800 1000

3
l0 K/T 1.67 1.43 1.25 1.00
k, I (cm 3 mor 1 s- 1) 4 .6 x 102 9.7 x 10
3
1.3 x 105 3. 1 x 106
In (k, I cm 3 mor' s- 1) 6.13 9. 18 11.8 14.9
30
... ·: . ... . ~ ..... ·: .................... .
I"'
I
0
.. ... . .... .
20 , ...... ····· sq ....

................................... .
··· ·· ··· ··· ·· ···· ······ ······ ··· ···
s ·· ··· ·-:···
.. ··· ·:·. ·· ····:-. ·· ·· ·:·. ···
. .
"'5
I Ii Jfu •
~ 10
..a
0
0 l.O 2.0
3
10 /(T/ K ) Figure 20.2
The least-squares intercept is at 28.3, which implies that

A I (cm3 mor 1 s- 1) = e28 ·3 = 2.0 x 10 12
l/ 2
8
But comparison of eqn. 20.18 to the Arrhenius equation tells us that A= NA P<J : : ( J
A ( )112
so P= NA <J 8:
The reduced mass is

µ = m(N02)/2 = 46 u x (l.661 x l0- 27 kg u- 1) I 2 = 3.8x 10-26 kg
so evaluating P in the center of the range of temperatures spanned by the data,
l/ 2
2.0xl0 12 x (lo-2 m) 3 mol- 1 s- 1 tr x 3.8x l0-26 kg
p
(6.022 x l0 23 mol- ) x 0.60 x (10- m) x 8x l.381 x l0-23 J K- 1 x 800 K
1 9 2 ( J
= l6.5 x 10-
3
I.
a ' = Pa= (6.5 x 10- 3) x (0.60 nm
2
) =l3.9x l0-3 nm1 =l3.9x l0-21 m~
P20.7 Draw up the following table for an Arrhenius plot.
81°C -24.82 -20.73 -17.02 -13.00 -8.95

TIK 248.33 252.42 256.13 260.15 264.20
103 K/T 4.027 3.962 3.904 3.844 3.785
104 kc I s- 1 1.22 2.31 4.39 8.50 14.3
ln (/(,/ s- 1) -9.01 -8.37 -7.73 -7.07 -6.55
-6 i - - - - -
-6.5 1
-7
~ -7.5
::s -8
.s
-8.5
-9 1. In (k/s- 1
) =- 10349/T + 32.659
-9.5 ~----------------
0.00375 0.0038 0.00385 0.0039 0.00395 0.004 0.00405

KIT Figure 20.3
A least-squares fit of the data yields the intercept +32.7 at l/T = 0, which implies that
Inc~,)= 32.7 and hence thatA = 1.53 x 10 14 s- 1• The slope is
-l.035x104 K = E.fR and hence IE.= 86.0 kJ mor 1I

In solution fi.*H =Ea - RT [Section 20.7(a)], so at -20°C,
fi.*H = 86.0 kJ mor 1 - (8.3145 J mor 1 K- 1) x (253 K) = ~83.9 kJ mor 1I
We assume that the reaction is first-order, for which, by analogy to Section 20.6(c),
K* = kT K* and k =k*K* =vxkT xK*

hv r hv
with fi.*G = -RTinK*
We can identify f;.*S by writing
kT t.'s!R -E /RT A -E /RT

k =-e e · e= e •
r h
and hence obtain
fi.*s =R[1nC:)-1J
34 14
= 8.3145 J K-' mol-' x[ln( (6.626xl0- J s)x (l.53x l0 s-' ) ) - l]
(l.38lxl0-23 J K-')x(253 K)
= 1+19.6JK-' mo1-' I.
Therefore, fi.*G = t-..*H- Tfi.*S= 83.9 kJ mor 1 - 253 K x 19.6 J K- 1 mor 1 = ~79.0 kJ mor11.
P20.9 Figure 20.4 shows that log kr is proportional to the ionic strength even when one of the reactants is a
neutral molecule.
- 0.155
~
-0.16
'=·5 log k, = 0.145 ll - 0.1815
lo -0.165
e
~.:::; - 0.17
OD
.52 -0.175
-0.18 ~·- - - ·
0 0.05 0.1 0.15 0.2

//(mot kg- 1) Figure 20.4
From the graph, the intercept at 1 = 0 is -0.182, so the limiting value of kr is
kr = l0-0.ts 2 = k}.658 dm 2 mol- 1 min- 'I

0
Compare the equation of the best-fit line to the logarithm of eqn. 20.49(b):
Y.e1 Y.r- rH 0
1ogk, = 1ogk, 0 -logKr = 1ogk, 0 -log = 1ogk, 0 + log--2- 2
Y;-rH,0 2 rel
Which implies that log Y;- rH,O, 0.1451.

rel
If the Debye-Htickel limiting law holds (an approximation at best), the activity coefficients of rand
the activated complex are equal, which would imply that logrH,o, = 0.1451.
P20.11 According to the Debye-Htickel limiting law, the logarithms of ionic activity coefficients, y, are
proportional to !1 12 (where 1 is ionic strength). Thus, a plot of log k, versus !1 12 should give a straight
line whose y-intercept is log k, 0 and whose slope is 2AzAz8 , where zA and z8 are charge numbers of
the component ions of the activated complex (eqn. 20.51). The extended Debye-Htickel law has log
]1 12 ) ( 11/ 2 )
rproportional to , so it requires plotting log kr versus , and it also has a slope
( l+B1 112 l+B1 112
of 2AzAz8 and a y-intercept of log k, 0 • The ionic strength in a 2: l electrolyte solution is three times
the molal concentration. The transformed data are in the following table and plots of log k, are in
Figure 20.5.
[Na2S04] I (mol kg- 1) 0.2 0.15 0.1 0.05 O.Q25 0.0125 0.005
k, I (dm 312 mor 112 s- 1) 0.462 0.430 0.390 0.321 0.283 0.252 0.224
1112 0.775 0.671 0.548 0.387 0.274 0.194 0.122
1112(1 +BJ'12) 0.436 0.401 0.354 0.279 0.215 0.162 0.109
/ogk, ~.335 ~.367 ~.409 ~.493 ~.548 ~.599 ~.650
-0.30
-0.40
• 11 12
_,,, J l/2
-0.50
..s""' 0 l + B/1 /2
-0.60
-0.70
0.0 0.2 0.4 0.6 0.8
12
1/ 2 11
l or 1+ B1 112 Figure 20.S
The line based on the limiting law appears curved. The zero-ionic-strength rate constant based on it is
k, 0 = 10-0'690 dm 312 mo1- 112 s- 1 = 0.204 dm 312 moi- 112 s- 1
The slope is positive, so the complex must overcome repulsive interactions. The product of charges,
however, works out to be 0.5, not easily interpretable in terms of charge numbers. The line based on
the extended law appears straighter and has a better correlation coefficient. The zero-ionic-strength
rate constant based on it is
k, 0 = 10-0·757 dm312 moi- 112 S- l = 0.175 dm 312 moi- 112 S- l
The product of charges works out to be 0.9, nearly 1, interpretable in terms of a complex of
~wo univalent ions of the same sig~.
P20.13 For a bimolecular gas-phase reaction,
ti*H = E. - 2RT [Section 20.7(a)]
so ti*H = 65.43 kJ moi- 1 - 2 x 8.3145 J mo1- 1 K- 1 x 300 K = ~60.44 kJ moi- 11
ti*H = ti*U + ti\pV)
so ti*U= ti*H-ti\pV) = ti*H-RTfivgas
ti*U = 60.44 kJ moi- 1 - (8.3145 J K- 1 mor 1) x (300 K) x (-1) = ~62.9 kJ mor'I
ti*S=R( ln~-2) [Exercise20.16(a)]
1
kRT 2 (1.381 x 10-23 JK - ) x (300K) 2 x (8.3145 J K- 1 mor 1)
where B - -- - --------------------
- hpe - (6.626 x l0-34 Js)x(10 5 Pa)
= 1.56x1011 m 3 moi- 1 s- 1 = 1.56 x 10 14 dm 3 mor 1 s- 1
so ti* S = (8.3145 J K-1 moi-1) x( ln 4.07x 10s dm3 mol-1s-1 2J

l.56 x l0 14 dm 3 moi- 1 s- 1
=l-181 JK- 1 mo1- 1I
ti*G = ti*H - Tti*S = 60.44 kJ mor 1 - (300 K) x (-181 J K- 1 mol- 1)
ti*G = ~ 114.7 kJ mor 1 i

P20.15 Estimate the bimolecular rate constant k, for the reaction
by using the approximate Marcus cross-relation:

1'r "' (kookAAK) 112
The standard cell potential for the reaction is
3
E f7 = E! (Ru(bpy)/+ )-E! (Fe(H 2 0) 6 +) = (1.26-0.77)V = 0.49 V
so the equilibrium constant is

1 1
K=ex (vFEf7 ) =ex ((1)(96485 Cmoi- s- )(0.49V) ) =l. 9 x l0 8
p RT p (8.3145 J K- 1 mor 1 )(298K)
The rate constant is approximately
k,"' {(4.0xl08 dm3 mor' s- 1)(4.2 dm 3 mor' s- 1)(1.9 x 108)} 112
k,"'~ .7 x 108 dm 3 moi- 1 s- 11
P20.17 We are to show that eqn. 20.29
[J]' = [J]e-k,r
is a solution of eqn. 20.28,
ap]' - D azpr -k [J]'

-at- dX2 r
provided that [J] is a solution of
d[J] = D a2[J]
dt dX 2
Evaluate the derivatives of [Jf:
2 2
d[J]' = ()[J] e-k,r _ k [J]e-k,r and d [J]' = d [J] e-k,t
df df r dX 2 dX2
Use the fact that [J] is a solution in the absence of reaction
2 2
Da [J]' =Da [J]e-k,r = d[J]e-k,r = d[J]' +k [J]e-k,r
dX 2 dX 2 dt dt r
which gives us back eqn. 20.28, as required.
P20.19 The standard molar partition function is defined in Section 17.3(a) as the molecular partition
function at standard pressure:
3
q::T = Vmf7 = RT = kT ( (T I KY (M / gmol- Y
12 1 12
J [Tablel3.l]
NA N A A 3 N A p f7 A 3 pf7 1749 pm
f7T
For T"'300 K , M"'50 g mol- 1, qm "'li.4x 10 1 I

NA
R . 1.0270 (T I K) 312
q (nonlmear) = - - x _ _ _ '" [Table 13.1]
<Y (ABC I cm-3 )
For T"" 300 K, A"" iJ "" C"" 2 cm- 1, a"" 2, q1\nonlinear)"" l2Qg
l 0 6950
(linear)= · x ~T 1K) [Table 13.1]
a (Blem- 1)
For T"" 300 K, iJ "" 1cm-1, a "" 1, /(linear) "" l20tj

Energies of most excited vibrational states in small molecules and of most excited electronic states
are high enough to make l ""
r/" ""[!].
k, = KkT K; [20.40]=(KkT)x(R~Jx[N;q~)e-M01 Rr[20.39]=Ae-£.IRr

h h p qA qB
If A and B are structureless molecules, then we use estimates from above to evaluate.
_f7 f7T R(linear)

isz._ = qc* q ""(2 312)x(l.4xl0 7)x(200) = 8xl09
NA NA
(The factor of 2312 comes from me= mA + m 8 ""2mA and l oc m
312
.)
1 1
RT= (8.3145 J K- moi- ) x (300 K) = _ x _2 m 3 mol_ 1
2 5 10
pf7 10 5 Pa
23 1
KkT"" kT = (l.38lxl0- JK- )x(300K) = .25 x 10 12 s-1
and 6
h h 6.626x10-34 J s
Strictly speaking, E. is not exactly the same as M 0 , but they are approximately equal--dose
enough for the purposes of estimating the order of magnitude of the pre-exponential factor. So once
we identify Ea"" M 0 , we identify the pre-exponential factor with everything other than the
exponential term. Therefore, the pre-exponential factor
A"" (6.25xl0
12 s- 1)x(2.5x10-2 m3 mor 1)x(8xl09)
(l.4xl0 7 ) 2
""6.3xl06 m3 moi- 1 s- 1 =l6.3xl0 9 dm 3 moi- 1 s- 11
According to collision theory [20.18],

l/ 2
8
A=Pa :: ( J NA
Take a "" 0.5 nm 2 = 5xl0- 19 m2 as a typical value for small molecules:
A= Px5x10-19 m2 x(8x(l.38lxl0-23 J K-1)x(300 K)J112 x6.022x l023 mor1

n-x(25 u)x(l.66lxl0-27 kg u- 1)
= 1.5xl08 m3 mor 1 s- 1xP.
The values are quite consistent, for they imply P"" 0.04, which is certainly a plausible value. If A
and B are non-linear triatomics, then
f7 f7
it,_"" (1.4x10 7) x (900) = 1.3x10 10 ""iL

NA NA
f7
Jsz__"" (2 312)x(l.4xl0 7)x(900) = 3.6xl0 10

NA
12 1 2 3 0
A"" (6.25 x l0 s- )x(2.5xl0- m mor')x(3.6xl0' )
and
(l.3xl010)2
""33 m 3 mor' s-' = 13.3x10 4 dm 3 mo!-' s- ' I
Comparison to the expression from collision theory implies IP= 2x10-1 I.
P20.21 The diffusion process described is unimolecular, hence first-order, and therefore analogous but not
identical to the second-order case of Section 20.6. We can write
[A*] = K*[A] [analogous to 20.32]
and - d[A] = k:t:[A:t:] = xv:t:[A:t:] ""v:t:[A:t:] = xv:t: K:t:[A] = k [A] [20.33- 20.35]
ili r
Thus, k, ""v:t: K:t: = v:t: ( :~ )x( ~:t: } - M. IRT
where q:i: and q are the (vibrational) partition functions at the top (missing one mode) and foot of
the well, respectively. Let they-direction be the direction of diffusion. Hence, for the activated atom
the vibrational mode in this direction is lost, and
q:t: = qx;v q, ;v for the activated atom, and
q = qx v qyv q, v for an atom at the bottom of a well
For classical vibration, q v "" k~ [Table 13.1] = kT.

hcv hv
3 3
H ence k =kT((kT
- / hv:l:)2J-MolRT
e = I-V- e - 6£0 /RTI ,,,, _ v_ e -E•IRT
' ' h (kT I hv) 3 (v:t:) 2 (v*) 2
(a) If v*= v, then k, ==ve-E,1Rr =10" s-'xe-6oooot(S.3I45x5oo) =5.4xl04 s-1
D = )} [18.59] == ..!. A-2k

2r 2 r
[r =__!_(period for vibration with enough energy)]
kr
=..!.x(316xl0- 12 m) 2 x5.4xl0 4 s- 1 =l2.7xl0- 15 m 2 s- 1!

2
(b) If v* = 112, then k r == 4ve- E, tRr = 2.2 x 105 s-'
D = 4 x (2.7 x 10- 15 m2 s- 1) = lux10- 14 m2 s- 1!
P20.23 The change in intensity of the beam, dl, is proportional to the number of scatterers per unit volume,
J{, the intensity of the beam, I, and the path length d.L. The constant of proportionality must be the
collision cross-section o; the "target area" of each scatterer. Thus, odL is the volume of scatterers to
be encountered within the beam, and
dl = -a<.Nld.L or d ln I= -CJ'.Nd.L
If the incident intensity (at L = 0) is I0 and the emergent intensity is I, we can write
I
ln- =-O':NL
Io
or II= Ioe-uJ<L I
P20.25 A+B~C* ~p
k, =(KkT)xK}[20.40]=(KkT)x(NA~TJ !~ ~ e-t.EolRT[20.39]
h h p qA qB
We assume that the only factor that changes between the atomic and molecular case is the ratio of
the partition functions. For collisions between atoms,
1029 -23
k (atoms) oc
26 26 = 10
' 10 xlO
For collisions between nonlinear molecules,
q: =(q: )3(q~ )3N-6(q:)"' (l01s)3 X (!) X (l026) = 3 X l03o "'q:

qi = (q~ )3(q~ )3(N+N'}-6(q~) "'(1015)3 X (1) X (1026) = 3 X 1030
k,(molecules) oc 3x1030 = 3x10-31

1x1061
10-23
Therefore, k,(atoms) I k (molecules)"'
r 3x10-31
= l3x10
1
I.
P20.27 For
the rate constant is
k, =Kk ,[20.55] =KKV*e- 6*GtRT[20.56]

0
2
(a) !J.*G - (!J.,Ge +A.) [20.59]
4A.
2
so !J.*G = (O+Aoo) =Ano !J.*G =AAA
DD 4Aoo 4 AA 4
/j. *G = (!J.,Ge + AnA )2 = (!J.,Ge)2 + 2!J.,Ge AoA +Ao/

and
DA 4AnA 4AnA
!J. Ge 1
(b) If l!J. r Gel= "DA
1
' then !J.*GDA "'-'-+-"t>_A
2 4
A. + 1
Assume ''DA
1
-- AA
2 ''Do -- 2(!J. *GAA + !J.*GDD )
(c) From the above expression based on eqns. 20.55 and 20.56, the rate constants for the self-
exchange reactions are
and
(d) Compare these results to the rate constant for the reaction of interest:
(e) Thusk = (k k )1 12 KDA e-6,Gt2Rr

r AA DD (K K )112
AA DD
The constants KoA and so on are equilibrium constants for diffusive pairing, i.e., for steps like eqn.
20.53(a). It is reasonable to expect that KoA = (KAAKoo)in, eliminating them from the expression.
Finally, the equilibrium constant for the overall reaction is
e - !'.,G1Rr = K
so the exponential term in our expression is its square root. Therefore
~r =(kAAkooK) 9
11
P20.29 (a) The rate constant of a diffusion-limited reaction is

1 1
k =8RT[ 0. S]=8x(8.3145JK- mol- )x(298K)
2 2
d 31'] 3x(l.06xl0-3 kgm- 1 s- 1)
= 16.23x106 m 3 moi- 1 s- 1 1=16.23x109 dm 3 mo1- 1s- 1 I
(b) The rate constant is related to the diffusion constants and reaction distance by
kd=4nR*DNA
1 1 3 3
R. = kd = (2.77xl09 dm 3 mo1- s- )x(lo- m 3 dm- )
so
4nDNA 4nx(lxl0-9 m 2 s- 1 )x(6.022xl0 23 mor 1 )
= l4x10- 10 ml= lo.4 nml
P20.31 For a series ofreactions with a fixed edge-to-edge distance and reorganization energy, the logarithm
of the rate constant depends quadratically on the reaction free-energy:
( .1 G(t ) 2 .1 G(t
Ink01 = - ' - - '- +constant [20.62 in molecular units]
4).kT 2kT
D.,G<t/ eV k01 I (10 6 s- 1 ) In (k0 /s- 1 )

-0.665 0.657 13.4
-0.705 1.52 14.2
-0.745 1.12 13.9
-0.975 8.99 16.0
-1.015 5.76 15.6
-1.055 10.1 16.1
Plot In ke1 versus .1, Gft (Figure 20.6).
17
16
---... ~
-
.............
• ......
\.,,,,.~ 15
~
.s
14
""' r--..
"""'-.
13
'""'. ""
-1.l - l.O -0.9 -0.8 -0.7 -0.6
11,d•1·ev Figure 20.6
The least-squares quadratic fit equation is

lnkeJs- 1= 3.23-21.1(~,GB /eV)-8.48(~ , GB /eV) 2 r 2 = 0.938
The coefficient of the quadratic term is
1 8.48
----
2
4AkT eV
(eV)2 (1.602 x 10-19 J ev-1 )(eV)2 = lus evl

so A-=----
4(8.48)kT 2(8.48)(1.381 x 10-23 J K- 1)(298 K)
P20.33 The theoretical treatment of Section 20.8 applies only at relatively high temperatures. At
temperatures above 130 K, the reaction in question is observed to follow a temperature dependence
consistent with eqn. 20.58, namely, increasing rate with increasing temperature. Below 130 K, the
temperature-dependent terms in eqn. 20.58 are replaced by Frank-Condon factors; that is,
temperature-dependent terms are replaced by temperature-independent wavefunction overlap
integrals.
P20.35 (a) The rate of reaction is

v = k,[CH 4 ][0H]
3
= (l.13xl0 9 dm 3 moi- 1 s- 1) x ex ( -l 4 .l x l0 J morl )
p (8.3145 J K- 1 mol- 1) x (263 K)
x (4.0xl0-8 mol dm-3 ) x (3.0 x 10- 15mol dm-3 ) = l2.1 x 10- 16 mol dm-3 s- 1I.
(b) The mass is the amount consumed (in moles) times the molar mass; the amount consumed is
the rate of consumption times the volume of the "reaction vessel" times the time.
m = MvVt =(0.01604 kg mor 1) x (2.l x l0-16 mol dm- 3

s- 1)
x(4xl0 21 dm 3 ) x (365x24x3600 s)
11
= 14.3 x 10 kg or 430 Tg l.
21 Catalysis
021.1 The Michaelis-Menten mechanism of enzyme activity models the enzyme with one active site,
weakly and reversibly, binding a substrate in homogeneous solution. It is a three-step mechanism. The
first and second steps are the reversible formation of the enzyme-substrate complex (ES). The third
step is the decay of the complex into the product. The steady-state approximation is applied to the
concentration of the intermediate (ES), and its use simplifies the derivation of the final rate expression.
However, the justification for the use of the approximation with this mechanism is suspect. Both rate
constants for the reversible step may not be as large (in comparison to the rate constant for the decay
to products) as they need to be for the approximation to be valid. The mechanism clearly indicates that
the simplest form of the rate law, v = vmax =kb [E] 0 , occurs when [S] 0 »KM" In addition, the general
form of the rate law does seem to match the principal experimental features of enzyme-catalyzed
reactions. It provides a mechanistic understanding of both the turnover number and catalytic
efficiency. The model may be expanded to include multisubstrate reactions and inhibition.
021.3 As temperature increases we expect the rate of an enzyme-catalyzed reaction to increase. However,
at a sufficiently high temperature, the enzyme denatures and a decrease in the reaction rate is
observed. Temperature-related denaturation is caused by the action of vigorous vibrational motion,
which destroys secondary and tertiary protein structure. Electrostatic, internal hydrogen bonding
and van der Waals interactions that hold the protein in its active, folded shape are broken with the
protein unfolding into a random coil. The active site and enzymatic activity are lost.
The rate of a particular enzyme-catalyzed reaction may also appear to decrease at high temperature
in the special case in which an alternative substrate reaction, which has a relatively slow rate at low
temperature, has the faster rate increase with increasing temperature. A temperature may be reached
at which the alternative reaction predominates.
021.5 Figure 21.1 is a sketch of the enzyme-catalyzed reaction rate against substrate concentration both
with and without product inhibition. Inhibition reduces the reaction rate and lowers the maximum
achievable reaction rate.
V IlllX I ------------ ------------- ----- - ---------------------------- ---- - - - ----- - - --
Reaction rate without inhibition
v
Reaction rate with product inhibition
[SJ Figure 21.1

CATALYSIS 513
021.7 AFM, atomic force microscopy, drags a sharp stylus attached to a cantilever across a surface and
monitors the deflection of a laser beam from the back of the cantilever. Tiny changes in
deflection indicate attraction to or repulsion from atoms on a sample surface. Since no current is
involved, both conductive and nonconductive surfaces may be viewed. Surface damage is
avoided by using a cantilever that has a very small spring constant. The method does not require
a vacuum, and it has been applied in a liquid environment. Biological polymers may be viewed
and nanometer resolutions have been achieved. However, an incorrect probe choice may cause
image artifacts and distortions. Thermal drift of adsorbates may result in image distortions during
relatively slow surface scans.
FIM, field-ionization microscopy, points a tip, with a point radius of about 50 nm, toward a
fluorescent screen in a chamber containing about 1 mTorr to 1 nTorr of either hydrogen or helium.
A positive 2- 20 kV potential applied to the tip causes the hydrogen or helium gas adsorbate
molecules to ionize and accelerate to the fluorescent screen. The image portrays the electrical
characteristics of the tip surface and surface diffusion characteristics of the adsorbate are deduced.
See the very interesting historical review of the technique in C&EN 83, no. 48 (November 28,
2005): 13-16.
LEED, low-energy electron diffraction, uses electrons with energies in the range 10-200 eV, which
ensures diffraction from atoms only on or near the sample surface. Diffraction intensities depend on
the vertical location of the atoms. The diffraction pattern is sharp if the surface is well-ordered for
long distances compared with the wavelength of the incident electrons. Diffuse patterns indicate a
poorly ordered surface or the presence of impurities. If the LEED pattern does not correspond to the
pattern expected by extrapolation of the bulk to the surface, then either a reconstruction of the
surface has occurred or there is order in the arrangement of an adsorbed layer. The interpretation of
LEED data can be very complicated.
SAM, scanning Auger electron microscopy uses a focused 1-5 ke V electron beam to probe
and map surface composition to a resolution of about 50 nm. The high-energy impact causes
the ejection of an electron from a low-lying orbital, and an upper electron falls into it. The
energy this releases may result either in the generation of X-ray fluorescence or in the
ejection of a second electron, the Auger effect. The emissions are used to identify chemical
constituents at interfaces and surfaces of conducting and semiconducting materials to a depth
of 1-5 nm .
SEM, scanning electron microscopy, uses magnetic fields to focus and scan a beam of electrons across
a sample surface. Scattered electrons from a small, irradiated area are detected and the electrical signal
is sent to a video screen. Resolution is typically between 1.5 and 3.0 nm. Nonconductive materials
require a thin conductive coating to prevent electrical charging of the sample.
STM, scanning tunneling microscopy, reveals atomic details of surface and adsorbate structure.
Surface chemical reactions can be viewed as they happen. The tip of the STM, which may end in a
single atom, can also be used to manipulate adsorbed atoms on a surface, making possible the
fabrication of complex and yet very tiny structures, such as nanometer-sized electronic devices. The
method is based on the quantum mechanical tunneling effect in the presence of a bias voltage
between the STM tip and sample surface. A piezoelectric scanner is used to position and move the
tip in very close proximity to the surface, and the electrical current of tunneling generates an image
of the surface topography with a resolution in the nanometer range. Images of surface electronic
states may be generated. A host of very interesting STM images can be viewed at
http://www.almaden.ibm.com/vis/stm/gallery.html.
021.9 In the Langmuir-Hinshelwood mechanism of surface-catalyzed reactions, the reaction takes place
by encounters between molecular fragments and atoms already adsorbed on the surface. We
therefore expect the rate law to be second-order in the extent of surface coverage:
Insertion of the appropriate isotherms for A and B then gives the reaction rate in terms of the partial
pressures of the reactants. For example, if A and B follow Langmuir isotherms (eqn. 21.11), and
adsorb without dissociation, then it follows that the rate law is
kKAKBpApB
v= 2
(l+KApA +KsPs)
The parameters K in the isotherms and the rate constant k are all temperature dependent, so the
overall temperature dependence of the rate may be strongly non-Arrhenius (in the sense that the
reaction rate is unlikely to be proportional to exp(- E. /RT) .
In the Eley-Rideal mechanism (ER mechanism) of a surface-catalyzed reaction, a gas phase
molecule collides with another molecule already adsorbed on the surface. The rate of formation of
product is expected to be proportional to the partial pressure, p 8 of the non-adsorbed gas B and the
extent of surface coverage, ()A , of the adsorbed gas A. It follows that the rate law should be
A+B~P V = kpA(}B
The rate constant, k, might be much larger than for the uncatalyzed gas-phase reaction because the
reaction on the surface has a low activation energy and the adsorption itself is often not activated.
If we know the adsorption isotherm for A, we can express the rate law in terms of its partial
pressure, p A . For example, if the adsorption of A follows a Langmuir isotherm in the pressure
range of interest, then the rate law would be
kKpApB
v=-~~
I+KpA
If A were a diatomic molecule that adsorbed as atoms, we would substitute the isotherm given in
eqn. 21.13 instead.
According to eqn. 21.33, when the partial pressure of A is high (in the sense KPA » 1 ), there is
almost complete surface coverage, and the rate is equal to kp 8 . Now the rate-determining step is the
collision of B with the adsorbed fragments. When the pressure of A is low (KpA « 1), perhaps
be~ause of its reaction, the rate is equal to kKpAp 8 • Now the extent of surface coverage is
important in the determination of the rate.
In the Mars van Krevelen mechanism of catalytic oxidation, for example in the partial oxidation of
propene to propenal, the first stage is the adsorption of the propene molecule with loss of a
hydrogen to form the allyl radical, CH 2 =CHCH 2 • An 0 atom in the surface can now transfer to
this radical, leading to the formation of acrolein (propenal, CH 2 =CH CHO ) and its desorption from
the surface. The H atom also escapes with a surface 0 atom and goes on to form H 2 0, which
leaves the surface. The surface is left with vacancies and metal ions in lower oxidation states. These
vacancies are attacked by 0 2 molecules in the overlying gas, which then chemisorb as o; ions
reforming the catalyst. This sequence of events involves great upheavals of the surface, and some
materials break up under the stress.
E21.1 (a) The fast, reversible step suggests the pre-equilibrium approximation:
[BW][A- ] [A- ] = K[AH][B]

K=--- and
[AH][B] [BH+]
Thus, the rate of product formation is
d[P] = kb[AH][A- ] =I kbK[AHf[B]

dt
[BW]
The application of the steady-state approximation to [A-] gives a similar but significantly different
result:
d[~- ] = k.[AH][B]-k:[A- ][BH+]-kb[A- ][AH] = 0

CATALYSIS 515
,,
Th ere1ore [A-] = -~----
k.[AH][B]
' k:[BW]+kb[AH]
and the rate of formation of product is
v
E21.2(a) Since v= max [21.4a], then
1+KM l [S] 0
Vmax = (1 +KM /[S] 0 ) V

= (1 +0.046 / 0.105)x(1.04 rnmol dm-3 s- 1 )
=Ii.so rnmol dm- 3

s- 1 I
E21.3(a) kcat = V max /[E]o [21.5]
=(0.425rnmoldm-3 s- 1 )! (3.60xl0--{j rnmoldm-3 )=11.18xl0 5 s- 1 1
'T/ = kcat / KM [21.6]

=(1.18xl0 5 s- 1 ) ! (0.015moldm-3 )=17.9xl06 dm 3 moi- 1 s- 1 1
Diffusion limits the catalytic efficiency, 'T/, to a maximum of about 108-109 dm 3 mo1- 1 s- 1. Since the
catalytic efficiency of this enzyme is significantly smaller than the maximum, the enzyme is not
"catalytically perfect."
E21.4(a) Eqn. 21.8 describes competitive inhibition as the case for which a= 1+[I] I K, and a'= 1. Thus,
V = _ _vm=ax"-----
1+ aKM /[S] 0
By setting the ratio v([I] = O)/v([I]) equal to 2 and solving for o., we can subsequently solve for the
inhibitor concentration that reduces the catalytic rate by 50%.
v([I] = 0) = I+aKM /[S] 0 =

2
v([I]) 1+KM/[S] 0
2(1+KM/[S] )-1
a = - - - -0- -
KM /[S]o
= 2(1+3.0 / 0.10)-1=2.03
3.0 / 0.10
[I] =(a - 1) K,
=l.03x(2.0xl0-5 moldm- 3 )=12.0xl0-5 moldm-3 1
E21.5(a) The collision frequency, Zw, of gas molecules with an ideally smooth surface area is given by eqn. 18.15.
p
Zw = 112
[18.15; m =M I NA]
(2nMkT I NA)
px{(kgm- 1 s-2 ) / Pa} x( l0-4 m 2 / cm 2 )
112
{ 2nx(I.381 x 10- 23 J K- 1 )x(298.15 K)x(kg mol- 1 ) I ( 6.022xl0 23 moi- 1 )} {M I (kg moi- 1 )r:
=4.825xl0 17 [ p / Pa 112
Jcm- 2 s- 1 at25°C
1
{ M ! (kg mol- )}
(a) Hydrogen (M= 0.002016 kg mor 1)

(i) p = 100 Pa, Zw = IL07 x 102 1 cm-2 d
(ii) p = 0.10 µTorr= 1.33 x 10- Pa, Zw = IL4 x 10 14 cm-2
5
d
(b) Propane (M = 0.04410 kg mor 1)
(i) p = 100 Pa, Zw = ~.30 x 1020 cm-2 s- 11
(ii) p = 0.10 µTorr= 1.33 x 10- 5 Pa, Zw = 13.1 x 10 13 cm- 2 s- 11
E21.6(a) A= trd 2 I 4 = tr(l.5 mm)2 I 4 = l.77 x l0-6 m 2
The collision frequency of the Ar gas molecules with surface area A equals ZwA .
p
ZwA = II? A [18.15; m =M I N A]
(2trMkT I NA)
2
p = (ZwA)x(2trMkT I NA )1' IA
= ( 4.5xl0 20
s- ) x { 2tr(39.95 x l0-3 kg mol- 1 ) x (1.38l x l0-23 J K- 1 )
1
x( 425 K) I ( 6.022xl0 23 mo1- 1 )x }1' 2 I (1.77xl0-6 m 2 )

= l.3xl0 4 Pa= lo.13 bar I
E21.7(a) The farther apart the atoms responsible for the pattern, the closer the spots appear in the pattern (see
Example 21.3). Doubling the vertical separation between atoms of the unreconstructed face, which
has LEED pattern (a), yields a reconstructed surface that gives LEED pattern (b) .
••• ••
••••
••• • ••
•••
••• ••••
••
••• ••••••
••• (a)
• •• (b)
E21.8(a) Let us assume that the nitrogen molecules are close-packed, as shown in Figure 21.2 as spheres, in
the monolayer. Then one molecule occupies the parallelogram area of 2.J3 r 2 where r is the radius
of the adsorbed molecule. Furthermore, let us assume that the collision cross-section of Table 18.1
(a = 0.43 nm 2 = 47rr2) gives a reasonable estimate of r: r = (a/47r) 112 • With these assumptions the
surface area occupied by one molecule is
Amolecule =2 .J3 (<J / 41r) = .J3 <J / 2tr

= .J3 (0.43 nm I 2tr = 0.12 nm
2
)
2
In this model, the surface area per gram of the catalyst equals AmoiecuI.N where N is the number of
adsorbed molecules. N can be calculated with the 0°C data, a temperature that is so high compared
to the boiling point of nitrogen that all molecule are liL:el. to
perfect gas.
pV (760 Torr) x (133 .3 Pa/Torr)x(3.86xl0-<> rn 1

N --- =l.0-txlO
- kT - (1.38l x l0· 23 J K - 1 ) x(273.1 5 K )
~o1ecu1eN=(0. 12 x l0- 18 m 2)x (1.04 x l0 20 )=112 m 2I
,.. r •
~60°
Figure 21.2
E21.9(a) B = .!:._ [21.9] = ~ = Kp [21.11]

V~ Vmon l+Kp
This rearranges to [Example 21.4]
p p 1
-=-+--
v Vmon KVmon
Solving for Vmon
V = p 2 - p, = (760 -145.4)Torr = 133 .6 cm3I

mon (p 2 I V2 - p, I v;) (760 /1 .443-145.4 I 0.286) Torr cm-3
E21.10(a) The enthalpy of adsorption is typical oflchemisorptionl (Table 21.2) for which To"' 10· 14 s [21.23]
because the adsorbate-substrate bond is stiff. The half-life for remaining on the surface is
E21.11(a)
which solves to
(m,p 2 1m2p,)-1 (m, l m2)x (p 2 / p 1 )-l 1

K= = x-
p2 - ( m, p 2 I m2) 1- ( m, I m2) p2
(0.44 / 0.19) x (3 .0 / 26.0)-1 1 -I
= x =0.19 kPa
1-(0.44 / 0.19) 3.0 kPa
Therefore,
(} = (0.19kPa-') x (26.0kPa) =I0. 83 1 [2 1.ll] and B = co.19) x(3.o) = lo. 361

1 2
(1)+(0.19 kPa-' ) x (26.0 kPa) (l)+(0.19)x(3.0)
E21.12(a) 8 = _!!l!_ [21.11], which implies thatp =

I+Kp
(~)_!_·
1-8 K
1
(a) p = (0.15 / 0.85) / 0.75 kPa- = lo.24 kPal
(b) p = (0.95 / 0.05) / 0.75kPa- 1 =125 kPal
E21.13(a) 8 = Kp [21.11], which implies thatK =

I+Kp 1-8
(~)x(_.!._)
p
Additionally, ln( ~: J = - ll~H ( ;i -; J [17.28] = lld;H ( ;i -; J [ll.dH = -lldesH].
Since f}i = Bi. Ki I K 1 = p 1I Pi and

1
ln.!!J...=L'ldesH(_!_ _ _!_J=( 10.2kJmor )x(-1_ _ _ 1_)=-0l 97
Pi R Ti I; 8.3145 J K- 1 mor 1 313 K 298 K .
which implies that pi= (12kPa)x(e 0· 191 )=115 kPal.
E21.14(a) 8= Kp [21.11], which implies that K =

I+Kp 1-8
(~)x(_.!._)
p
1
Additionally, ln (Ki J = - ll.dH (_!_ _ _!_J [17 .28] or ll.dH = -Rln(Ki Jx(_!_ _ _!_J-
K1 R Ti I; K1 Ti I;
Since B2 = Bi. Ki I K 1 = p 1I Pi and
ll 0dH =-Rln(l!J...Jx(; - ~ J-i

Pi i I -I
1
( 490 kPa ) x ( - 1 _ _
_1 1 )
=-(8.3145 J K- mo! )xln 3 .2 xl03 kPa 250 K 190 K
= 1-12.4 kJ mo! 1
I
E21.15(a) The desorption time for a given volume is proportional to the half-life of the absorbed species, and
consequently the ratio of desorption times at two different temperatures is given by
1(2) ! 1(1) = 111 i (2) 1111 i (1) = eE./Rr, I eE. /Rr, [2 1.231 = eE.(11r,-11r, )1R
Solving for the activation energy for desorption, Ed, gives
Ed =Rln{1(2) ! 1(l)}(11Ti -11I'if1

1
2 1 1
=(8.3145 JK- 1 mor 1 )x1n( ·0min)x(-- - -- ) -
27 min 1978 K 1856 K
=/651 kJmor 1 I
The desorption time, 1, for the same volume at temperature tis given by
1
1=1(l)eE.(itr-itr,)tR = (27 min)exp{( 65l x10 3 J mol- 1 )x(_!_--- ) 1(8.3145 J K- 1 mor 1 ) }
T 1856 K
1 1
={27min)expf78.J)x f - )}
/l (T 11000 K l.856)f
(a) At 298 K, t =I i.6 x 1097 mini, which is about forever.
(b) At 3000 K, t =I 2.8 x 10--Q mi~.
E21.16(a) The average time of molecular residence is proportional to the half-life of the absorbed species, and
consequently the ratio of average residence times at two different temperatures is given by
t(2) !t(I) = tl/2 (2) / tl/2 (!) = eE, / RT, / eE, / RT, [21.23) = eE,(l l T, -l l T,) I R
Solving for the activation energy for desorption, Ect, gives
Ed= Rln{t(2) ! t(1)}(11T2 -111;f'

1
1 1 3 9 1 1
= (8.3145 J K- mor )x1n( .4 s)x( - )-
0.36 s 2362 K 2548 K
1
=l61 l kJmor I
E21.17(a) At 400 K, '112 ='roe Ed /RT [21.23) = (0.10 ps)x eOJOl£, lkJ moi-•.
(a) Ed= 15 kJ mor 1

tu2 ( 400 K) = (0 .10 ps)xe 0301 xis = j9.I psj, t112 (1000 K) = (0.10 ps)xe 0120xis = j0.60 psj
(b) Ed = 150 kJ mor 1

[ATP]/(µmol dm- 3 ) 0.60 0.80 1.4 2.0 3.0
iv/(µmol dm-3 s- 1) 0.81 0.97 1.30 1.47 1.69
3
1/{[ATP]/(µmol dm- )} 1.67 1.25 0.714 0.500 0.333
1/( v/(µmol dm-3 s- 1)} 1.23 1.03 0.769 0.680 0.592
t112 ( 400 K) = (0.10 ps)xe 0301 xiso = j4. lxl0 6 sl, ! 112 (1000 K) = (0.10 ps) xe 012 oxiso = j6.6 µsj
kKp
E21.18(a) V =kB=-'- [21.28a)
' l+Kp
(a) On gold, B"" 1, and v = k,B ""constant, alzeroth-orderlreaction.

(b) On platinum, B ""Kp (as Kp « 1), so v = k,Kp and the reaction is Ifirst-order I.
P21.1 We draw up the table below, which includes data rows required for a Lineweaver-Burk plot (l/v
against l/[S] 0). The linear regression fit is summarized in Figure 21.3.
llvmax =intercept [21.4b]

Vmax = I/intercept= 1 I (0.433 µmol dm- 3 s- 1) = j2.3 l µmol dm-3 s- 11
kb= Vmax I [E]o [21.3b] = (2.31 µmol dm- 3 s- 1) I (0.020 µmol dm- 3) = !115 s- 11
1
kcal= kb [2u1=1115 s- 1
KM= Vmax x slope [21.4b] = (2.31 µmol dm- 3 s- 1)x(0.480 s) = lu 1 µmo! dm-~
TJ = kcai I KM [21.6] = (115 s- 1) I (l.l l µmol dm- 3) = /104 dm 3 µmor 1 s- 1/
l.4
"""' 1.2
I
y = 0.4796x + 0.433 l
2
'7
"' R = 0.9996
"O
s
0
s
~ 0.8
.:.
-. 0.6
......
0.4
0 0.5 l 1.5 2
l I {[ATP]/(µmol dm - 3 )) Figure 21.3
P21.3 (a) The dissociation equilibrium may be rearranged to give the following four relationships.
[E-] = KE,a[EH]/[H+] [EH; J = [EH][H+]/KEb
[ES-]= KEs,.[ESH]/[H+] [ESH 2 ] = [ESH][H+]/KEs,b
Mass balance provides an equation for [EH].
[E]0 = [E-] +[EH]+ [EH;]+ [ES-]+ [ESH]+ [ESH 2 ]

= KE,a[EH] +[EH]+ [EH][W] + KES,a[ESH] +[ESH]+ [ESH][W]
[H+] KEb, [H+] KESb,
[EJo -{1+ [H+] + KES,a}

[EH] = KES,b o:rJ
[ESH]
l+[W]+ KE,a
KE,b [H+]
- [EJo - c1 [ESH] [H+] KESa [H+] KEa
where c =1+--+--· andc =1+--+--·
Cz I KESb, [H+] 2 KEb, [H+]
The steady-state approximation provides an equation for [ESH].
d[ESH] = k. [EH][S]- kJESH]- kb [ESH] = 0
[ESH]= ~[EH][S] =KM -l[EH][S]

k. +kb
=KM _1[SJ { [E] 0 -;~[ESH]}
[ESH]= K~ [S][E] 0 I c2 =
1
[E] 0 /c1
l+K~ [S]c1 / c2
1
l+KM(c2 / c1) /[S]
The rate law becomes
kb[E]ofc1 = v:ax
v = d[P]/dt =kb[ESH] = 1+KM ( Cz I C1) /[SJ 1+ K~ /[SJ
where [H+] K } { [H+] KEs,a}

' - k [E] / 1+--+ E!,a = Vmax / l +-K + [W]
V max - b 0 { K ES,b [H ] ES,b
CATALYSIS 521
and
(b) KEsb =l.OxlO-{j KES,a = l.OxI0-8
Figure 21.4 shows a plot of v~ax against pH. The plot indicates a maximum value of v~ax at pH=
7.0 for this set of equilibrium and kinetic constants. A formula for the pH of the maximum can be
derived by finding the point at which dv~ = 0 . This gives
d[H ]
[H+]max = (KEs,a KEs,b)l/ 2 = J(i.ox10-s mo] dm-3 )(1.0xl0-6 mol dm-3 ) = l.Oxl0- 7 mol dm-3
which corresponds to IPH = 7.0I.
0.1
0.8
I
"'E"' I 0.6
~ """
~
';;,E 0
E
t 0.4
0.2
o'--~~--'-~~....C:~~---'~~~..__~~--==~~--'-~~--'
0 2 4 6 8 JO 12 14
pH Figure 21.4
(c) vmax = l.OxlO-{j mo] dm- 3 s- 1 KES,b = l.Oxl0--4 KESa = l.Ox10- 10
Figure 21.5 shows a plot of v~ax against pH. The plot once again indicates a maximum value of
v~ax at pH= 7.0 for this set of equilibrium and kinetic constants. However, the rate is high over a
much larger pH range than appeared in part (b). This reflects the behavior of the term
1+ [H+]/ KES,b + KEs,a I [H+] in the denominator of the v~ax expression. When KEs,b is relatively
large, large [H+] values (low pH) cause growth in the values of v~ax. However, when KEsa is
relatively small, very small [H+] values (high pH) cause a decline in the v~ax values. '
pH Figure 21.5
P21.5 Refer to Figure 21.6.
I
A
l~
8~
r~
c
[~
Figure 21.6
Evaluate the sum of ±1/r;, where r; is the distance from the ion i to the ion of interest, taking +llr
for ions of like charge and -1/r for ions of opposite charge. The array has been divided into five
zones. Zones B and D can be summed ~nalytically to give -ln 2 == -0.69. The summation over the
other zones, each of which gives the same result, is tedious because of the very slow convergence of
the sum. Unless you make a very clever choice of the sequence of ions (grouping them so that their
contributions almost cancel), you will find the following values for arrays of different sizes
!Ox 10 20 x 20 50 x 50 100x100 200x 200

0.259 0.273 0.283 0.286 0.289
The final figure is in good agreement with the analytical value, 0.289 259 7 ... .
(a) For a cation above a flat surface, the energy (relative to the energy at infinity and in multiples of
e 2 I 4JZ"Er0 where r0 is the lattice spacing (200 pm)) is
Zone C + D + E == 0.29 - 0.69 + 0.29 == lQ11], which implies an attractive state
(b) For a cation at the foot of a high cliff, the energy is
Zone A+ B + C + D + E == 3 x 0.29 + 2 x (-0.69) == t0.511, which is significantly more attractive
Hence, the latter is more likely the settling point (if potential energy considerations such as these are
dominant).
P21.7 Refer to Figure 21. 7.
ah
·~·~
a
a./ffli)
Figure 21.7
The (100) and (110) faces each expose two atoms, and the (111) face exposes four. The areas of the
faces of each cell are (a) (352 pm) 2 == 1.24x10- 15 cm 2 , (b) .Ji. x (352 pm) 2 == 1.75x10- 15 cm 2 , and
CATALYSIS 523
(c) J3 x(352 pm) 2 = 2.15 xl0- 15 cm 2 • The numbers of atoms exposed per square centimetre, the
surface number density, are therefore
2
(a) =II.61 x 10 15 cm-2 I
1.24x10- 15 cm 2
(b)
(c)
The collision frequency , Zw, of gas molecules with a surface is given by eqn. 18.15.
2 112
{2;rx(1.381 x l0-23 J K- 1 )x(298.15 K)x(kg mol- 1 ) ! (6.022xl0 23 mol- 1 )}1' {M ! (kg mo1- 1 )}
=4.825xl0 17 [ p / Pa 112
] cm-2 s- 1 at 25° C
1
{M ! (kg mol- )}
(a) Hydrogen (M = 0.002016 kg mor 1)

p
(i) = 100 Pa, Zw = 1.07 x 1021 cm-2 s- 1
(ii) p = 0.10 µTorr= 1.33 x 10- 5 Pa, Zw = 1.4 x 10 14 cm-2 s- 1
(b) Propane (M = 0.04410 kg mor 1)
(i) p = 100 Pa, Zw = 2.30 x 1020 cm-2 s- 1
(ii) p = 0.10 µTorr= 1.33 x 10- 5 Pa, Zw = 3.1 x 10 13 cm-2 s- 1
The frequency of collisions per surface atom, Z, is calculated by dividing Zw by the surface number
densities for the different planes. We can therefore draw up the following table.
Hydrogen Propane
1 1
Z /(atom- s- ) 100 Pa 1
10- Torr 100 Pa L0-7 Torr
(100) 6.6 x 105 8.7 x 10-2 1.4 x 10 5 1.9 x 10-2
(110) 9.4 x 105 1.2 x 10- 1 2.0 x 105 2.7 x L0-2
(111) 5.8 x 105 7.5 x 10-2 1.2 x 10 5 1.7 x 10-2
P21.9
v cz [21.15, BET isotherm, z =pp']
(1- z) {1- ( 1- c) z}
This rearranges to
z 1 (c-l)z
---=--+---
(1-z)V cVmon cVmon
A plot of the left-hand side, z/(l - z) V, against z should result in a straight line if the data obey the
BET isotherm. Should it be linear, a linear regression fit of the plot yields values for the intercept
and slope, which are related to c and Vmon by
11 cVmon =intercept and (c - 1)/ cVmon = slope
Solving for c and Vmon yields
c = 1 + slope/intercept and Vmon = l/(c x intercept)
We draw up the following tables.

(a) 0°C, p· = 429.6 kPa
--
p/kPa 14.0 37.6 65.6 79.2 82.7 100.7 106.4
103 z 32.6 87.5 152.7 184.4 192.4 234.3 247.7
103 z
3.03 7.11 12.1 14.1 15.4 17.7 20.0
(1-z)(V / cm 3 )
(b) 18°C, p· =819.7 kPa
p / kPa 5.3 8.4 14.4 29.2 62.l 74.0 80.1 102.0

3 124.4
10 z 6.5 10.2 17.6 35.6 75.8 90.3 97.8
3
10 z
0.70 1.06 1.74 3.27 6.35 7.58 8.08 10.l
(1-z)(V / cm 3)
The z/(1 - z)V against z points are plotted in Figure 21.8. It is apparent that the plots are linear, so we
conclude that the data fit the BET isotherm. The linear regression fits are summarized in the figure.
20 l (a) •, 12 (b)
1 y = 76.JP,+ 0.4638 )
R0 =0.9953 10
y = 79.527.Y+ 0.3036
R~ =0 . 9994
..
~
15
"'
88
0 .
·~
~ ~
.....
-:- 10 ~ ::. 6
::..
,-..
~: 1
"
%; 5 ~
0 0 J
0 0.1 0.2 0.3 0 0.05 0.1 0.15
z Figure 21.8
3 3
(a) Intercept= 0.4638 x 10- 3 cm- 3 and slope= 76.12 x 10- cm-
c = l +slope/intercept= 1 + 76.12/0.4638=11651
Vmon = l/(c x intercept)= 1/(165 x 0.4638 x 10- cm- )=113.l cm~
3 3
3 3
(b) Intercept= 0.3036 x 10-3 cm-3 and slope= 79.53 x 10- cm-
c = 1 +slope/intercept= 1 + 79.53/0.3036 = !2631
Vmon = 1/(c x intercept)= 1/(263 x 0.3036 x 10- cm- )=112.5 cm~
3 3
P21.11 () = c1p1 1c' [Freundlich isotherm, 21.19]
We adapt this isotherm to a liquid by noting that w. oc Band replacingp by [A], the concentration of the
acid. Then w. = c1[AJ1'c2 (with c 1, c2 modified constants), and hence log w. = logc1 +_!_xlog[A]. We
C2
draw up the following table.
[A]/(mol dm-3 ) 0.05 0.10 0.50 1.0 1.5

log([A]/mol dm-3 ) -1.30 -1.00 -0.30 -0.00 0.18
log(m. I g) -1.40 -1.22 -0.92 -0.80 -0.72
CATALYSIS 525
These points are plotted in Figure 21.9. They fall on a reasonably straight line with slope 0.42 and
intercept --0.80. Therefore, c 2 = l / 0.42 =I 2.41 and c 1 = I0.161. (The units of c 1 are bizarre: c 1=
0.1 6 g mol--o.42 dmi. 26 ) .
- 1.4
-0.6
0.5 0 --0.5 - 1.0 - 1.5
log([A]/(mol dm-3 )) Figure 21.9
P21.13 Taking the natural logarithm of the isotherm cads = Kc~1" gives
ln c ads = ln K + (ln C501)In
so a plot of ln cads versus ln c 501would have a slope of lln and a y-intercept of ln K . The
transformed data and plot are shown in Figure 21.10.
5
y = - 1.9838 + l.71,06x
R 2 = 0.98 1 .
4 ... ... .. ~ ......... .. ... ... ... -~.
~
<f 3 ·····:··················
..9
•
2.0 2.5 3.0 3.5 4.0
lncsol Figure 21.10
cso/(mg g-1) 8.26 15.65 25.43 31.74 40.00

c,ds/(mg g-1) 4.41 19.2 35.2 52.0 67.2
ln csol 2.11 2.75 3.24 3.46 3.69
ln cads 1.48 2.95 3.56 3.9 -Ul
K=e-1.9s3s mg g-1 =10.138mgg-1 I and n = l / l. 1 = lo.ssl

To express this information in terms of fractional O\'erage. the amount of adsorbate corresponding
to monolayer coverage must be known. This saturation poinL however. has no special significance
in the Freundlich isotherm (i.e. , it does not corre pond to any limiting case).
P21 .15 The Langmuir isotherm is
(} = .....!!E...._ = .!!:..... so n(l + Kp) = n_Kp and p = ..f!.._ _ _I _

l +Kp n_ n n_ Kn_
So a plot of pin against p should be a straight line with slope I I n_ and y-intercept I I Kn_ . The
transformed data and plot (Figure 21.11) follow.
p / kPa 31.00 38.22 53.03 76.38 101.97 130.47 165.06 182.41 205.75 219.91
n / (molkg- 1) 1.00 1.17 1.54 2.04 2.49 2.90 3.22 3.30 3.35 3.36
pln
31.00 32.67 34.44 37.44 40.95 44.99 51.26 55.28 61.42 65.45
kPamor 1 kg
70
y = 24.641 +'0.17313 :~
R 2 = 0.982 : . •
]i' 60
I
0
E
~ so (.:~ ,
. ....... ............. ;............. .
~
---
? •
~ 40
•.....-:
30
0 so 100 lSO 200 2SO 300
p/ kPa Figure 21.11
1
n_ = ______ ·-'· =15.78molkg- 1 I
They-intercept is
I I
b = - so K = -
Kn_ bn_ (24.641 kPa mol- 1 kg) x (5.78 mol kg- 1)
K = 7.02 x 10-3 kPa- 1 =11.02 Pa- 1 I
P21.17 (a) A+P ~ P+P autocatalytic step, v = k [Al [Pl
Let [Al=[Al 0 -xand [Pl=[Pl 0 +x.

We substitute these definitions into the rate expression, simplify, and integrate.
v=- d[Al =k[Al[Pl

dt
- d([AJo-x) = k([Alo -x)([Plo +x)

dt
__ dx_ _ =kdt
([Al 0 -x)([Pl 0 +x)
1
- -[
[Al 0 +[Pl 0 [Al 0 -x
I + I
[Pl 0 +x
)dx = k dt
_I-
[Al 0 +[PJo
r[ I + l )
[Al 0 -x [Pl 0 +x
dx = k rdt
.Ii
[P-]
[Al +-
0
1
0
H[l~]~x )+m[[~;t )}=kt
and
[Pl =beat
[Al 0 +[Pl 0 -[Pl
[Pl= ([A lo+ [Pl 0 )beat -beat [Pl
(1 +beat )[Pl = [Pl 0 [1 +~;?:}eat= [Pl 0( 1+];) beat = [Pl 0 (b+ l)eat
[Pl eat
IP1=(b+l)~
(b) See Figure 21.12(a).
Autocatalytic Process
IO
b=O.l
-e;:~ 6
b=0.2
4
b= l.O
2
0
0 2 4 6 8 10
at Figure 21.12(a)
The growth to [P] reaches a maximum at very long times. As t-+oo, the exponential term in the
denominator of [Pl ! [Pl 0 =(b+l )eat ! (l+beat ) becomes so large that the denominator becomes
bea1• Thus, ([Pl ! [Plo)max = (b+l)eat ! (beat ) = (b+l) / b whereb = [Pl 0 / [Al 0 , and this maximum
occurs as t-+oo.
The autocatalytic curve [Pl I [P lo = ( b + 1) eat I (1+beat ) has a shape that is very similar to that of the
first-order process [Pl ! [Al 0 =1-e-"' . However, [P]max = [A] 0 at t-+00 for the first-order proc
whereas [P]max = (1 + l/b)[P] 0 for the autocatalytic mechanism. In a series of experimen -
[A] 0 and assorted [P]o, only the autocatalytic mechanism will show variation in [P] _ • -
difference is that the autocatalytic curve is initially concave up, which gives an OYerall - .........,...,...~
curve, whereas the first-order curve is concave down. See Figure 21.12(b).
First-Order Process
0.8
,...Q 0.6
;?
e;: 0.4
0.2
0
0 1 2 3 4 5
kt Figure 21.12(b)
(c) Let [P] be the concentration of P at which the reaction rate is a maximum and let tmax be the
v=
corresponding time.
v = k[A][P] = k([A] 0 -x)([P] 0 +x)

2
= k {[A ]0 [ P ]0 + ([A ]0 - [ P ]0 ) x - x }
dv = k([A] -[P] -2x)

dt 0 0
The reaction rate is a maximum when dv/dt = 0. This occurs when
x = [Pku -[P]o = [AJo-[P]o [PL= _ b+l

or
2 [Pf- 2b
Substitution into the final equation of part (a) gives
[PL= =b+l=(b+l) ea'=

[P ]0 2b
Solving for tmax.
1+ bea'= = 2bea'=
e a'~ = b-1
atmax = ln(b- 1) = -ln(b)
fmax = 1-±ln(b)I
(d) d[P] = k[Af [P]
dt
[A]= Ao-x, [P] =Po +x, _d[P_] = dx = k(Ao -x) 2 (Po +x)
dt dt
rx_ _dx,.---- - kt
1 (Ao-x) 2(Po +x) -
Solve the integral by partial fractions.
_____ = a +_f!_+_r_
(Ao-x)2(Po +x) (Ao-x)2 Ao-x Po +x
a(Po +x)+ fJCAo-x)(Po +x)+ rCAo-x) 2
(Ao - x) 2(Po+ x)
Poa + Ao-Po/J + Ag r = l}
a+(Ao-Po)/J-2Aor= o
-/J+r=O
CATALYSIS 529
This set of simultaneous equations solves to

1 a
a=-- /J=r=--
Av +Pa Av +Pa
Therefore,
kt~c, :,:] r[(A,~,)'+( A, :,J A, ~x +P, ~x l r

-(-1
Ao+Pa
){(-1
Ao-x
)-(_!_)+(-1
Av Ao+Pa
)[1n(_A___)+1n(Po+x)]}
Ao-x Po
-(-1
Ao+Pa
)[( Ao(Ao-x)
x )+(-1
Ao+Po
)in(Ao(Po+x))]
(Ao-x)Po
. x p
Therefore with y = - and p = _Q_,
Av Av
Ao(Ao+Po)kt= (_L)+(-
l-y l-p
1
)in[ (+y ))
p l-y
The maximum rate occurs at
dvrdt =O' VP = k[Af [P]
and hence at the solution of
2k(d[A])[A][P]+k[A] d[P] 2 =0
dt dt
k[A]([A]-2[p])vr = 0
The rate is a maximum when [A]= 2[P], which occurs at
Av - x = 2Pa + 2x, or t t
x = (Av - 2Pa); y = (1- 2 p)
Substituting this condition into the integrated rate law gives
Ao(Ao+Po)kfmax =(-l+1-)(~(1-2p)+ln-
p 2
1
2p
)
or l(Ao +I'o) ktmax 2
= t- p- ln 2pl
(e) d[P] =k[A][Pf
dt
-dx = k(Ao -x)(Po +x )2 [x = P-Pa]

dt
kt=
r dx
(Ao-x)(Pa +x)2
Integrate by partial fractions (as in part d).
kt{~~,:) r{(,, ~x)'+(A, ~,JP, ~x +A, ~xl} d<
~(A,~ l\){(~ -1\ ~x HA, ~P, )[ m(l\:.x )•lt~x )]}

~(A, ~P, )[( P, (:..Jl A, ~P,H~(:x2~)]
. x p
Therefore, with y = -[- -
and p = _Q_,
A o 1 4i
1
4i ( 4i +Po) kt = I( Y J + ( - ) in ( P + Y )
p(p+ y) 1+ p p(I-y)
The rate is maximum when
du p = 2k[ A )[P)(d[P)J+ k ( d[ A] J [PJ2

dt dt dt
= 2k[A][P]uP -k[P]2 Up= k[P](2[A)-[P])uP = 0
-that is, at [A]= Yi [P] .

On substitution of this condition into the integrated rate law, we find
2-p )+(-1
4i(4i+Po)ktmax = ( 2p(l+p) l+p
)1n~P
( 4i +Po ) ktmax =I 2 - p + ln ~
2
or
2p p
P21.19 Assuming a rapid pre-equilibrium of E, S, and ES for eqn. 21.1 implies that
k [ES)
K=k: =[E)[S) and [ES)=K[E)[S)
But the law of mass balance demands that [E) = [E] 0 -[ES), so [ES)= K ([E] 0 -[ES])[SJ, and
solving for [ES], we find that
[ES)=~
1+ _I
K[S) 0
where the free substrate concentration has been replaced by [S] 0 because the substrate is typically in
large excess relative to the enzyme. Now substitute the latter expression into the Michaelis-Menten
rate law [21.1).
kb [E)o
v =kb [ES)= l where vmax =kb [E) 0
l + --
K[S]o
v= vmaxl (rate law based on rapid pre-equilibrium approximation)

1+- -
K[S]o
CATALYSIS 531
v
v= ~ (rate law based on steady-state approximation)
KM
1+ [S]o
Inspection reveals that the two approximations are identical when KM= l!K, which implies that
( k: +kb) I k. = k: lk. or lk: »kb I
P21.21 (a) We add to the Michaelis-Menten mechanism [21.1] the inhibition by the substrate
SES~ES+S K 1 = [ES][S]/[SES]
where the inhibited enzyme, SES, forms when S binds to ES and thereby prevents the formation of
product. This inhibition might possibly occur when S is at a very high concentration. Enzyme mass
balance is written in terms of [ES], Ki. KM (= [E][S]/[ES]), and [SJ. (For practical purposes the free
substrate concentration is replaced by [S] 0 because the substrate is typically in large excess relative
to the enzyme.)
[E] 0 = [E] +[ES]+ [SES]
_KM [Es] [ ] [Es][s]

- [ ] + ES +
S K1
= [1 +KM
[S]
+ [s])[Es]
K1
Thus,
[ ES]- [E]o
-[1+ KM+ [s])
[s] K1
and the expression for the rate of product formation becomes
Vmax
v =kb [ ES ] = K [S]
l+_M_+ _ o
[s]o Kr
The denominator term [S]o/K1 reflects a reduced reaction rate caused by inhibition as the
concentration of S becomes very large.
(b) To examine the effect that substrate inhibition has on the double reciprocal, use the
Lineweaver-Burk plot of llv against l/[S] 0 to take the inverse of the above rate expression and
compare it to the uninhibited expression [21.4b]:
_!_ =-1-+( KM
v vmax
J-1-
vmax [S]o
[21.4b]
The inverse of the inhibited rate law is

The uninhibited and inhibited line shapes are sketched in Figure 21.13 .
Substrate inhibition at high concentration
;S
Without inhibition
lllS lo Figure 21.13
Comparing the two expressions, we see that the two curves match at high values of l/[S]o.
However, as the concentration of [S] 0 increases (1/[S] 0 decreases), the 1/v curve with inhibition
curves upward because the reaction rate is decreasing.
P21.23 For association:
dR
-=k0 na0 (R 0 q-R) [21.26]
dt
dR
----k
R.q - R - on a0 dt
J
Rf___!!!!:__= kon aodt = kon aot
0 Req -R o
-ln(Req - R) I~ = k00 a0 t
-ln
[R~eq-RJ= k 00 a0 t
_Req__
-R = e -kooao t
Req
R = Req{1-e-k.,,ao' }
IR= Req {1- e-k,t } where k, = k 00

a0I
For dissociation:
dR =-kotf R
dt
dR = -kotf dt
R
r
f
Rf dR = - kotfdt
R,. R o
CATALYSIS 533
P21.25 Equilibrium constants vary with temperature according to the van' t Hoff equation [17.28], which
can be written in the form
_K 2 =e- [~(.L
R
.L)]
T2-1i
K1
or
Kz =ex [ 160 x l03 Jmol-1 ( - l_ _ _

l_J]=I00247I
K1 p 8.3145JK- 1mol- 1 773K 673K .
As measured by the equilibrium constant of absorption, NO is less strongly absorbed by a factor of

0.0247 at 500°C than at 400°C.
P21.27 (a) q water = k(RH)""
With a power law regression analysis we find
lk = 0.22891, standard deviation= 0.0068
1n = 1.6182, standard deviation= 0.0093; ln=0.61801
R = 0.999508
A linear regres ion analy is may be performed by transforming the equation to the following form
by takin_ = "thm of the Freundlich type equation.
RH)
n
= o.0093; In= 0.61801
R =O
The two meth~ _- ~%1:.!-;e the oftware package for performing the power
onn for you. Both methods are actually
..::;:i::-=.::1D:c o~oo~ indicate that 99.95 % of the data variation
are independent and equivalent.

This assumption seems · es interact \"ery weakly.
However, water molecule..; t:::::r11::: - hydrogen bonding.
and multilayers can readi._
apparently cause adsorptio
the Freundlich-type isotherm 1oe::a:::es
(c) Yvoc = 1-qwater where Yvoc =qvoc I q VOC,RH =O
Yvoc = 1-k(RHY'"
1-rvoc = k(RH)1 1"
To determine the goodness-of-fit values for k and n, we perform a power law regression fit of
1- rvoc against RH . Results are
lk = 0.52271, standard deviation= 0.0719

..!. = 1.3749, standard deviation= 0.0601; In= 0.72731
n
R = 0.99620
Since 99.62% of the variation is explained by the regression, we conclude that the hypothesis that
rvoc = 1 - q water may be very useful. The values of R and n differ significantly from those of part
(a). It may be that water is adsorbing to some portions of the surface and VOC to others.
This solutions manual provides detailed solutions to the "a" exercises, and the
odd-numbered discussion questions and problems that feature in Quanta,
Matter, and Change by Peter Atkins, Julio de Paula, and Ronald Friedman.
Intended for students and instructors alike, the manual provides helpful
comments and friendly advice to aid understanding. The Student Solutions
Manual is an invaluable resource wherever Quanta, Matter, and Change is
used for teaching.
Charles Trapp is Professor of Chemistry,

University of Louisville, Louisville , Kentucky, USA
Marshall Cady is Professor of Chemistry,

Indiana University Southeast, New Albany, Indiana, USA
Carmen Giunta is Professor of Chemistry,

Le Moyne College, Syracuse, NY, USA
Also available:
Instructor's Solutions Manual to Accompany Quanta, Matter, and Change,

by Charles Trapp, Marshall Cady, and Carmen Giunta
1-4292-2374-X
Cover image: Peter Atkins
II ISBN 978-0-19-955907-7
Published. under license. in the Published in the rest of the world by

United States and Canada by
OXFORD
W.H. Freeman and Company UN I VERS I TY P R E SS
41 Madison Avenue. New York. NY 10010 . Great Clarendon Street. Oxford OX2 6DP
Houndmills. Basingstoke. RG21 6XS. England United Kingdom

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Atkins&#39; Physical Chemistry Solution Manual (7th Ed)

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Student Solutions Manual to Accompany

Charles Trapp, Marshall Cady, Carmen Giunta

Oxford University Press, Great Clarendon Street, Oxford,

Oxford is a registered trade mark of Oxford University Press

© C. A. Trapp, M. P. Cady, and C. Giunta, 2009

The moral rights of the author have been asserted.

All rights reserved. No part of this publication may be reproduced,

You must not circulate this book in any other binding or

Published in the United States and Canada by

ISBN-10: 1-4292-2375-8 ISBN-13: 978-1-4292-2375-1

British Library Cataloguing in Publication Data

Fundamentals 5 The chemical bond 102

PART1 Quantum theory 15 Answers to discussion questions 102

Solutions to theoretical problems 66

4 Atomic structure and atomic spectra 79

Answers to discussion questions 79 Answers to discussion questions 196

PART3 Molecular spectroscopy 225 15 The second law of thermodynamics 352

Answers to discussion questions 352

12 Magnetic resonance 271 17 Chemical equilibrium 411

Answers to discussion questions 271 Answers to discussion questions 411

PART4 Molecular PART5 Chemical dynamics 439

14 The first law of thermodynamics 314 19 Chemical kinetics 469

Answers to discussion questions 314 Answers to discussion quest1o~s 469

I;;;.· . , , ._ .·. ·-~.

20 Molecular reaction dynamics 492 21 Catalysis 512

Answers to discussion questions 492 Answers to discussion questions 512

F1 .2(a) Example Element Ground-state Electronic Configuration

(a) Group 2 Ca, calcium [Ar]4s2

F1 .3(a) (a) chemical formula and name: Mgeh, magnesium chloride

(b) chemical formula and name: FeO, iron(II) oxide

(c) chemical formula and name: Hg 2eh, mercury(!) chloride

F2.2(a) (a) Sulfite anion, S0 32- 2-

·a·. 0·. O". 0· .

(b) Xenon tetrafluoride, XeF4 ..

(c) White phosphorus, P4

Molecular shape: square planar with 90° bond angles

F2.5(a) (b) P - H Nonpolar or weakly polar. (c) 3+ 3-

F2.7(a) In the order of increasing dipole moment: C0 2 , N20 , SF4 , S0 2

F.3 Bulk matter

F3.2(a) (a) Mass is an extensive property.

F3.3(a) (a) n= ~ = 25.0 g( 1

(b) weight= F gravityonEanh = m g Eanh

= (180. g)x(9.81 m s-2 )x (~)

(b) 1.45 atm(l.01325 bar)= II.47 barl

F3.8(a) T I K =B I °C + 273.15 = 37.0 + 273.15 = 310.2 [P.2]

F3.10(a) 110 kPa x (7.0+273.15)K) = I105 kPa I

M = mRT = pRT where p is the mass density

(3.710 kg m-3 )(8.314 J K- 1 mor 1 )(773.15 K)

= l.8 x l0 6 Pa= li.8 MPal

F3.13(a) ~' = 1.0 mole and nH, = 2.0 mole

F.4 Thermodynamic properties

t:,,.U = Ct:,,.T [F.5] = nCmt:,,.T

= (0.483 mo!)( 26.44 J K- 1 mol- 1 )(10.0K)=1128 JI

H m-Um= RT= (8.3145 J moi- 1 K- 1)x(298K)=12.48 kJ mo1- 1I

F4.8(a) S Fe(3000 K ) > S Fe(300 K)

F.5 The relation between molecular and bulk properties

F5.3(a) lim(Hupper)=lim(e-w*r) [F.9]=e- =0

Vmean (T2) (T2/ M)l/2 =(T2J112

um= f NAkT = f RT [F.10] = +(8.3145 J mor 1 K-I )(298 K) = 3.72 kJ mor 1

um= f NAkT = f RT [F.10] = f(8.3145 J mol-I K- 1)(293 K) = 6.09 kJ mor 1

Um =%NAkT = 3RT [F.IO] = 3(8.3145 J mol- 1 K- 1)(293 K) = 7.31 kJ mol- 1

(a) Um =%RT for carbon dioxide

(b) Um = 3RT for methane

(a) v(l.O s)=(9.81 ms-2 )x(l.O s)=l9.81 ms- 1 1

Atkins' Physical Chemistry Solution Manual (7th Ed)

Atkins' Physical Chemistry Solution Manual (7th Ed)

(c) [x,p,] = x(~j)-(~j)x = i ~ -(~)- (~vgi = [!fil

(d) [.x2 ,ftx ]=x2(~j)-(~j)x2