You are on page 1of 178

LECTURE 1: Fundamentals on

Atomic Structure
Prof. Jet G. Guerrero, R.Ch, M.Sc.

Inorganic Chemistry
If organic chemistry is considered to be the
chemistry of carbon, then inorganic chemistry
is the chemistry of all elements except carbon.
Inorganic chemistry is not simply the study of
elements and compounds; it is also the study of
physical principles.

Fundamental Particles of an Atom


Atom
smallest unit quantity of an element that is
capable of existence
composed of the proton, electron and
neutron.

The Nuclide
atomic number, Z
number of protons in the nucleus

mass number, A
number of protons and neutrons in the nucleus

A Z = # of neutrons

Isotopes
Nuclides of the same element
Same number of protons and electrons; but
Different number of neutrons
Different mass numbers.

e.g.

Allotropes
Allotropy is the property of some chemical
elements to exist in two or more
different molecular forms.
e.g.
diamond, graphite, and buckminsterfullerene (C 60)
S6, S8, and polycatenasulfur (Sx)

Atomic Weight or Average Mass, Ar


atomic weights [AR] are calculated from the
summation of measured values of atomic mass
(for each nuclide) multiplied by its isotopic
composition.

Atomic Weight or Average Mass, Ar


Example:

Drill #1: Ar
1. Calculate the value of Ar for naturally occurring
Cu if the distribution of isotopes is 69.2% 63Cu
and 30.8% 65Cu; accurate masses are 62.93 and
64.93.
2. What is the ratio of 63Cu:65Cu?

Drill #1: Ar

63Cu:65Cu is 2.25:1.

Mass Spectroscopy
Capable of separating and detecting individual
ions even those that only differ by a single
atomic mass unit.
Molecules containing different isotopes and has
difference in molecular form can be
distinguished.

Mass Spectroscopy
Separates isotopes
MS plots A/e not AR or atomic weight

Separates allotropes
MS plots M/e not MR or average molar mass

Review on Atomic Theory


Electron wave-particle duality
Classical quantum theories: particle
Results obtained by classical quantum theory may
also be obtained from wave mechanics.
More practical to treat the electron as a particle.

Review on Atomic Theory


Classical quantum theory
Low temperature = low energy = infrared
Increase in temperature = radiation becomes
dull red -> bright red -> white
Why?
1901: energy could be absorbed or emitted only in
quanta of magnitude E related to the frequency
of the radiation, (Planck)

intensity/wavelength/temperature
relationship

where ,
Plancks constant, h = 6.626 x 10-34 J.s
= frequency ( in Hz or s-1)
c = 2.998 x 10 10 cm/s
= wavelength

Rutherford-Bohr model of the Atom


Return to lower energy
state -> spectral lines.
1885: Balmer showed the
energies of visible light
emitted by the H atom.

where RH is Rydberg constant for


hydrogen (1.097 x 105 cm-1)
and n is an integer greater than 2.

Balmer and Lyman Series

Other series of spectral lines: Paschen, Brackett and Pfund (infrared)

Series of Spectral Lines

Lyman series, n = 1
Balmer series, n = 2
Paschen, Brackett and Pfund series, n = 3, 4 and
5 respectively.

Bohrs postulate for an electron in an atom


1.1 Stationary states
circular orbits with constant E

1.2 Electron has angular momentum,


where n = principal quantum number
m = mass of electron
v = velocity of electron
r = radius of the orbit
h = Plancks constant

Bohrs postulate for an electron in an atom


2. Energy is absorbed or emitted only when an
electron moves from one stationary state to
another.

Bohrs theory of the atomic spectrum of


hydrogen
Applying these to the H atom, the radius of H is

Bohr radius, a0 = 52.93pm

Ionization Energy (IE)


Energy required to remove an electron from a
gaseous atom or ion. It is ALWAYS a POSITIVE
VALUE!
Sample:
from nlow = 1 to nhigh =
where,

Plugging in all the values we obtain,


for H or H-like atoms.

24

de Broglies Wave-Particle duality


all moving particles have wave properties
i.e. electrons

where h = Plancks constant


m = mass of the particle
v = velocity of the particle
= wavelength of the particle

Heisenbergs uncertainty principle


The electron is wave-like.
It is impossible to know exactly both the
momentum and position of the electron at
the same instant in time.
Instead, use the probability of finding the
electron in a given volume of space.

The Schrdinger equation


can be solved exactly only for a species
containing a nucleus and only one electron
e.g.
, i.e. a hydrogen-like system
describes the wave properties of an electron in
terms of mass, total energy and potential energy.
where H = Hamiltonian Operator
= Wave function given by
E = Energy of electron

The Schrdinger equation


Better written in spherical coordinates
Separate variables
the wave function can be factored into a radial
component and two angular components.

Wave function describes the electron behavior


in space called atomic orbitals.

The quantum numbers n, l, m


Symbo
l

Name

Values

Principal

1, 2, 3,

Role
from R(r)

Determines the major part


of energy

Angular
Momentum

0, 1, 2, ,
(n-1)

from
A (, )

Describes angular
dependence and
contributes to the energy
(shape)

ml

Magnetic

0,1, 2,

from
A (, )

Describes orientation in
space (direction)

ms

Spin

(1/2)

Describes orientation of the


electron spin in space

The radial part of the wavefunction, R(r)


Describes the electron density at different
distances from the nucleus.
It is determined by the quantum numbers n and
l, the principal and angular momentum quantum
numbers.

where

Hydrogen-like Atom Wave Functions (Radial


Part)

Radial parts of wavefunctions


s atomic orbitals have a finite value of R(r)
for all orbitals other than s, R = 0 at the nucleus
for the 1s orbital, R(r) is always positive

R(r) for 1s and 2s


Radial Node = n l - 1

Radial parts of wavefunctions


for the first orbital of other types (i.e. 2p, 3d, 4f),
R(r) is positive everywhere except at the origin
for the second orbital of a given type (i.e. 2s, 3p,
4d, 5f ), R(r) may be positive or negative but the
wavefunction has only one sign change (radial
node)

R(r) for 2p, 3p, 4p and 3d

Radial Distribution Function


It is the physical representation of an atomic
orbital
It is ALWAYS POSITIVE
Depicts probability density
It is given by,

Radial Probability Distribution for


1s, 2s, and 3s

Radial Probability Distribution for


2p, 3p, 4p, and 4d

Angular Parts of the Wavefunction


The angular functions, and , describe the shape
of the orbitals and orientation in space.
It is independent of the principal number, n; but are
determined by the quantum numbers l and ml.
It is independent of angles for s orbitals
Angular nodes signifies the changes in phase or sign;
it is equal to l.

Hydrogen-like Atom Wave Functions


(Angular Part)

A(, )

A2(, )
Determines the shape of an atomic orbital.
It is ALWAYS POSITIVE.
Signs (+ or -) were assigned for lobes for
convenience.
Important in orbital interactions during bonding.

A2(, )

A2(, )

Contour Plots
contour lines indicate lines along which the
function is constant
1s:

Contour Plots:
2pz

2 lobes.
The probability to find the electron at a certain position is highest
in these lobes.
2 colors = 2 different signs. Changes in the sign of a wave function
are very important, because they are related to the energy of the
wave function

Contour Plots:
3dxy

4 lobes.
Opposite lobes have the same sign, neighboring lobes
have opposite sign.
The isosurfaces on which a wave function is zero, are
called nodal planes . In general the energy increases
when the number of nodal planes increases.
There are two nodal planes. One is the xz- and the
other the yz-plane.

Contour Plots: 3dz2

The upper and lower lobe resemble the lobes of a p function, except both lobes
have the same sign. The middle lobe is a torus with an opposite sign to that of
the upper and lower lobe. The nodal planes for 3dz2 are two cones.

The spin quantum number and the


magnetic spin quantum number
spin quantum number, s
determines the magnitude of the spin angular
momentum of an electron and has a value of

magnetic spin quantum number, ms


determines the direction
has a value of + or -

Spin-orbit coupling
L = Orbital angular momentum =
with 2l +1 possible vector directions
S = Spin angular momentum =
J = Total angular momentum =
with 2j+1 possible vector orientations
J is inner quantum number with values l+s and
l-s.

Ground State Configuration


Lowest energy or stable configuration
In multi electron atoms, orbitals of same n but
different l are no longer degenerate.
lower n+1 fills up first
when n+1 are same lower n fills first

Shielding Effect
An electron in a 2s or 2p atomic orbital experiences the
effective charge, Zeff, of a nucleus partly shielded by the
1s electrons.
2p orbital penetrates the 1s orbital less than a 2s orbital
does
2p electron is shielded more than a 2s electron.
occupation of the 2s atomic orbital gives a lower energy
system
E(2s) < E(2p).
E(3s)< E(3p) < E(3d)
E(4s) < E(4p) < E(4d) < E(4f)

The Aufbau Principle


Lowest E orbitals fills up first
relative energies (lowest energy first) of orbitals
in neutral atoms:
1s <2s<3s <3p < 4s < 3d < 4p <5s < 4d < 5p <6s <
5d 4f < 6p < 7s < 6d 5f

Paulis Exclusion Principle


No two electrons in the same atom may have the
same set of n, l, ml and ms quantum numbers
Each electron in an atom have unique set of four (4)
quantum numbers.

Each orbital can accommodate a maximum of


two electrons with different ms values (different
spins = spin-paired).

Hunds Rule of Maximum Multiplicity


Electrons must be placed in orbitals so as to
give the maximum total spin possible.

Multiplicity = n+1 = 2s+1

n is the number of unpaired electrons


s is the spin quantum number = 1/2

Hunds Rule of Maximum Multiplicity


Coulombic Energy of Repulsion, c
- Repulsion of two electrons that occupy the same part of
space around an atom.
- Positive in energy
- lowers IE.

Exchange Energy, e
- Arises from purely quantum mechanical consideration
- Depends on the number of possible exchanges between two
electrons with the same energy and spin.
- Negative in energy.

Hunds Rule of Maximum Multiplicity

First arrangement = higher IE = more stable

Drill!!
for p5

Drill!!
for p5
One configuration only.

Case of Cr (Z=24) and Cu (Z=29)


Cr [Ar] 4s1 3d5 instead of 4s2 3d4
Cu[Ar] 4s13d10 instead of 4s23d9
Arises from total energies arising from effective
nuclear charge and repulsive interactions
between e.
Traditionally explained as the special stability
of half-filled subshells
60

Coulombic Energy of Repulsion, c


- Repulsion of two electrons that occupy the same
part of space around an atom.
- Positive in energy
- lowers IE.

- Very important in that it can produce exceptions


in the trend for filling-up electrons:
1s <2s<3s <3p < 4s < 3d < 4p <5s < 4d < 5p <6s <
5d 4f < 6p < 7s < 6d 5f

- Example: Scandium

e-e repulsion: Scandium


What are the two possible electronic
configurations of Scandium (Sc)?

e-e repulsion: Scandium


What are the two possible electronic
configurations of Scandium (Sc)?
[Ar]4s23d1 OR [Ar]4s13d2
Which configuration is more stable?

e-e repulsion: Scandium


What are the two possible electronic
configurations of Scandium (Sc)?
[Ar]4s23d1 OR [Ar]4s13d2
Which configuration is more stable?
Higher IE.

e-e repulsion: Scandium


Experimental results showed that:

Removing from the 3d orbital makes it more


stable.
It is easier to ionize 4s than to ionize 3d.

e-e repulsion: Scandium


3d orbital is more stable than 4s.
Exciting the electron, the experimental energy
required to transfer the electron from the 3d to
the 4s is:

e-e repulsion: Scandium


If 3d is more stable then 4s (it is!), then why is
energy required to transfer an electron from the
3d to the 4s?

e-e repulsion: Scandium


If 3d is more stable then 4s (it is!), then why is
energy required to transfer an electron from the
3d to the 4s?
Answer: e-e repulsion.

Multielectron System
Two effects are considered:
Electron-electron repulsion
Spin-pairing energy

Spin-pairing energy
refers to the energy associated with paired electrons sharing one
orbital and it's affect on the molecules surrounding it.
Two types:
Paramagnetic and diamagnetic

3 Factors that affect it:


the atom (electronic configuration and number of d electrons)
the Crystal Field Theory (field splitting of electrons)
the type of ligand field complex (tetrahedral or octahedral)

e-e repulsion
Results from the coulomb repulsion (c) of like
charges
For transition metal valence electrons (VE),
e-e repulsion >>>>>>> spin-pairing energy

Relative E of Atom with ambn


Assuming:
Interaction of core elements with VE is constant
Energy of the core is also constant..

The relative energy of atom A with valence


electronic configuration ambn is

72

Relative E of Atom with ambn

W = IE of a system containing only one VE


J = e-e repulsion

Relative E of Atom with ambn

Hence, for Sc (3d14s2)

Relative E of Atom with ambn

Hence, for Sc (3d14s2)

Relative E of Atom with ambn


Hence, for Sc (3d14s2)

Please do the same for:

Relative E of Atom with ambn

-W(d) and W(s) terms represent the binding


energy of the 3d1 and 4s1 electrons in Sc2+
J terms represent the e-e repulsion

Relative E of Atom with ambn


Going back to the experimental values:
The energy required to excite a 4s electron to 3d:

The energy required to ionize

a 4s electron
and
a 3d electron is:

Relative E of Atom with ambn


From literature values, the IE for Sc2+ are:

Since the core electrons 1s22s22p63s23p6 are


energy constant,
W(d) = 24.75 and W(s) = 21.60.

Relative E of Atom with ambn

Hence,

Relative E of Atom with ambn

Do the same for

Relative E of Atom with ambn

W(d) = 24.75 and W(s) = 21.60


Now solve for J(d,s), J(d.d), and J(s,s)..

Relative E of Atom with ambn

Relative E of Atom with ambn

J(d,d) > J(s,s)


3d electrons are less diffused than 4s
Greater e-e repulsion.

Relative E of Atom with ambn


The energy required to excite a 4s electron to 3d is
2.03eV.

W(d) & W(s) tend to favor 4s13d2 configuration.


However, this is overcome by the electron
repulsions (J).
Therefore, the preferred configuration is 3d14s2
because it has lower energy.

Relative E of Atom with ambn


Preferred configuration for Sc: 3d14s2
Why does 4s electrons ionize at lower E in
forming Sc+?

Relative E of Atom with ambn


Why does 4s electrons ionize at lower E in forming
Sc+?

W(s) < W(d). 4s ionizes first.


Reason: 4s has no nodes at the nucleus. 3d has two
containing the nucleus.
4s penetrates more.

Ionization Energy
1st IE is internal energy change, E, or potential
energy change, U at Zero K
E(g) -> E+(g) + e
2nd IE E+(g) -> E2(g) + e is also the 1st IE of ion E+
E(g) -> E2+(g) + 2e

Ionization Energy
IE = IE = IE1 + IE2
It is BEST used for H like atoms because e-e
repulsion and e pairing reduces IE and the
Energy, E, becomes no longer n dependent.

Slaters Rules
Electrons in groups higher than e considered
contributes NOTHING to S
For ns or np e considered
Other e in same group contribute 0.35 each
Each e in n-1 grpcontribute 0.85
Each e in n-2 group contribute 1.0

For nd or nf e considered
Other e in same group contribute 0.35 each
All other e below the group contribute 1.0 ea

Zeff and Slaters Rules


Ex. K, Z=19
1s22s22p63s23p64s1

1s22s22p63s23p63d1

Zeff = Z S

Zeff = Z S

= 19 [8(0.85) + 10 (1.00)
= 2.20
Based on Z* alone, MORE STABLE.

= 18 (1.00)
= 1.00

Ionization Energy
Z* or Zeff = Z S
S is screening or shielding constant

Ionization Energy

where n is the principal quantum # of the e being removed

Drill!!
Which electron will ionize first in Mn (Z=25),
4s2 or 3d5?

Drill!!
Which electron will ionize first in Mn (Z=25),
4s2 or 3d5?
ANSWER: 4s2

Drill!!
What is the 1st, 2nd, and 3rd ionization energy of
Ca (Z=20)?

Electron Affinity (EA)


Defined as the energy required to remove an electron from
a negative ion.
Energy change is exothermic.
ALWAYS POSITIVE.

where n is the principal quantum # of the e in focus

Electronegativity
Mulliken: M = (IE + EA)/2
Paulings relative scale sets 4.0 to F, which relates to bond enthalpies.
For atoms A and B,
96.5 kJ/mol (PA PB)2 = B(A-B) + (1/2)[B(A-A)+B(B-B)]
P= 1.35 M1/2 - 1.37
Allred and Rochow
-Relates to Z*/r2

Drill!!
For 1s2 2s2 2p6 3s2 3p6 4s2
Find: 1st IE, EA, electronegativity.

Drill!!
For 1s2 2s2 2p6 3s2 3p6 4s2
Find: 1st IE, EA, electronegativity.
1st IE = (13.6(2.85)2/16) = 6.9eV
EA = 6.044
Estimates off due to e-e repulsions and E not
only dependent on n in multielectron cases.

Drill!!
For 1s2 2s2 2p6 3s2 3p6 4s2
Find: 1st IE, EA, electronegativity.

M = (IE + EA)/2 = 6.472


P = 1.35 M1/2 - 1.37 = 2.06

Atomic Radius
Van der Waals radius
- the radius of an imaginary hard sphere which can
be used to model the atom for many purposes.

Covalent radius
- Dependent on valency and coordination number

Ionic radius
- Dependent on oxidation state

Stick to same source of radii and kind of radii

Polarizability,
Ability to distort a neighboring field.
High polarizability or softness if separation of frontier
orbitals is small.
Low polarizability or hardness, , if separation of frontier
orbitals is high.
Polarizability increases rapidly with an increase in atomic
size
Due to dispersion forces

Polarizability
Hard-Soft distinction
Reactions are more favorable for hard-hard and
soft-soft interactions

Polarizability
Hard acids and bases
Relatively small, compact and nonpolarizable
d electrons are NOT available for bonding
Hard acids are cations with large + charges (3+ or larger)

Soft acids
Larger and more massive the atom, the softer it is
Due to shielding
d electrons are readily available for bonding (+1
cations)

For bases: more electrons and larger size = softer

Polarizability
Soft-soft: HOMO and LUMO energies are much
closer
Hard-hard: stronger, depends on a larger range
of electrostatic force
Absolute hardness, = 1/2 (I-A)
where I = IE and A = EA, both in eV.

Softness , = -1

Spectral Terms:
total spin angular momentum (S)
(2S+1) is the multiplicity of the
S is the total spin quantum number.
2S+1

corresponds to a

singlet

doublet

triplet

quartet

Spectral Terms:
total orbital angular momentum (L)
L

corresponds to a

Spectral Terms:
total angular momentum (J)
J = L+S, , |L-S|
where S = total spin angular momentum
L = total orbital angular momentum
Based on LS or Russell-Saunders coupling

RussellSaunders Coupling
also known as the spin-orbit coupling and LS
coupling
in light atoms (generally Z < 30), electron
spins si interact among themselves so they combine to
form a total spin angular momentum S.
The same happens with orbital angular momenta li,
forming a total orbital angular momentum L.
S and L are to be added together and form a total
angular momentum J.
Spectral Term Symbol

LJ

2S+1

Determining Ground Spectral Term


(Lowest Energy)
1s22s22p1
Maximize multiplicity
S=1/2
2S+1 = 2(1/2)+1 = 2 (doublet)
2S+1 = 2

Determining Ground Spectral Term


(Lowest Energy)
1s22s22p1
Maximize L:
L = 1(1)+0(1)+0(-1) = 1
L=1 P term
P

Determining Ground Spectral Term


(Lowest Energy)
1s22s22p1
J = L+S, , |LS|
with S = 1/2 and L = 1,
2P
2
J = 3/2, 1/2
3/2 or P1/2
There are 2 values for J. Which one is for the
ground spectral term?
Hunds Rules.

Spectral Terms: Hunds Rules


Greater multiplicity (S) = Lower E
Look at 2S+1 term

For same S, maximum L has


lowest energy.
For same L
less than half filled = minimum J
more than half filled = maximum J

Determining Ground Spectral Term


(Lowest Energy)
1s22s22p1
J = L+S, , |LS|
with S = 1/2 and L = 1,
2P
2
J = 3/2, 1/2
3/2 or P1/2
Case: less than half-filled, therefore J E
The ground spectral term is then: 2P1/2

Drill!!
Determine the ground spectral term for:
1. Fluorine (Z=9)
2. Beryllium (Z=4)
3. Lithium (Z=3)

Drill!
Determine the ground spectral term for:
1. Fluorine (Z=9) 2P3/2 or 2P1/2
2. Beryllium (Z=4) 1S0
3. Lithium (Z=3) 2S1/2

Spectral Terms: Hole Formalism


If observed, fluorine (p5) has the same spectral
terms as the earlier example Boron (1s22s22p1).

Both have the same spectral terms: 2P3/2 or 2P1/2


because positrons and electrons only differ in charge.
J = L+S, , |LS|

Likewise, p2 and p4 also have the same term


symbols.

Spectral Terms: Hole Formalism

Spectral Terms
Consider C (Z=6): 1s22s22p2
Using the same methods,

L = 0, 1, 2 (S, P, D)
S = 0 (if spin-paired) or 1 (parallel spin)
2S+1 = 1 or 3, respectively.
It may seem that J = L+S, , |LS| = 0, 1, 2, 3.
But no. Because then there will be 2 electrons with
n=2, l=1, ml =1, , ms =+1/2. This CANNOT be.
violates Paulis principle.

Determining Spectral Terms


Microstates = all possible configurations of VE

where i = # of ml, ms combinations (s=2, p=6, d=10, f=14)


j= # of electrons involved

Drill!!
How many microstates do the following have:
1. d2
2. p6
3. f5

Drill!!
How many microstates do the following have:
1. d2 = 45
2. p6 =1
3. f5 =2002

127

p2 case (C, Z=6)


Possible configurations:
__ __
__
__
__ __

and

p2 case (array method)


ml

ms
1

-1

-1

-2

p2 case (array method)


from middle column
ml

ms
1

ml

-1

-1

ms
1

-1

-1

-1

-2

1 =1
s =-20, 2s+1
L = 2; L+SL-S = 2
1D2

p2 case (array method)


from middle column
ml

ms
1

ml

-1

-1

ml

ms
1

-11

-1

-1

-1

-2

-1

ms

-1

1 =1
s =-20, 2s+1
s = 0,-22S+10= 1
L = 2; L+SL-S = 2 L = 0 1S0
1D2

p2 case (array method)


ml

ms
1

-1

-1

-2

p2 case (array method)


the remaining rectangle:
ml

ms
1

-1

-1

-2

s = 1, 2s+1 = 3
L=1P
L-S..L+S = 0,1,2
3
P0, 3P1, 3P2

Spectral Terms: Hunds Rules


Greater multiplicity (S) = Lower E
Look at 2S+1 term

For same S, maximum L has


lowest energy.
For same L
less than half filled = minimum J
more than half filled = maximum J

p2 case (array method)


Spectral terms: 1D2, 1S0 , 3P0 , 3P1 , 3P2
Using Hunds Rules, the term symbols can be
arranged wrt their energies.
1. S : S E 3P < 1D2, 1S0

p2 case (array method)


Spectral terms: 1D2, 1S0 , 3P0 , 3P1 , 3P2
Using Hunds Rules, the term symbols can be
arranged wrt their energies.
1. S : S E 3P < 1D2, 1S0
2. L : L
E 3P< 1D2 < 1S0

p2 case (array method)


Spectral terms: 1D2, 1S0 , 3P0 , 3P1 , 3P2
Using Hunds Rules, the term symbols can be
arranged wrt their energies.
1. S : S E 3P < 1D2, 1S0
2. L : L
E 3P< 1D2 < 1S0
3. J: more than half filled: J E
less than half filled: J
E
3
P0< 3P1< 3P2 < 1D2 < 1S0

Drill!!!
Try to use the array method for the excited state
of Li: 1s1 2s1 2p1
Draw the rest of the possible configurations.
e.x.

Use the array method to find the spectral terms.

Drill!!!
Excited Li
1s1 2s1 2p1

Drill!!!

Spectral Terms: alternate method


p2 and p4

Drills.
Find the spectral terms for:
1. d2
2. f2
3. f3
4. d3 and d7

142

d2

143

f2

144

f3

Drills.
Find the spectral terms for:
1. d2
2. f2
3. f3
2
4. d3 and d7
H 2G 4F 2D 2P 4S

Photoelectron Spectroscopy
In a PES experiment, an atom or molecule is irradiated
with electromagnetic radiation of energy E, causing
electrons to be ejected from the system.
Each electron possesses a characteristic binding energy
and must absorb an amount of energy equal to, or in
excess of, this binding energy if it is to be ejected.
The energy of an ejected electron is that in excess of the
binding energy assuming that E is greater than the
binding energy.
Excess energy of electron = E (binding energy of
electron)

Photoelectron Spectroscopy
Since the excess energy can be measured and E is
known, the binding energy can be determined.
Koopmans theorem relates the binding energy of
the electron to the energy of the atomic or
molecular orbital in which it resides.
This relationship allows photoelectron
spectroscopy to be used to estimate the energies
of occupied orbitals, and, thus, obtain
information about the ordering of orbitals in a
particular atomic or molecular species.

X-ray Photoelectron Spectra

149

Valence Orbital Ionization Energy, VOIE


Ionization Energy required to remove e from average energy state.

We write: 2J+1= 15 (1 + 3 + 5 + 5 + 1)
E(C)average = (1/15)(E(3P0)) + (3/15)(E(3P1)) +
(5/15)(E(3P2)) +
(5/15)(E(1D2)) + (1/15)(E(1S0))
VOIE = IE - Eave

Nuclear Properties of Elements

Nuclear Binding Energy


mass of an atom of 1H = sum of mass of 1 proton
and mass of 1 electron
For other atoms, the atomic mass is less than the
sums of the masses of proton, electron and
neutron
The mass defect is a measure of the binding
energy of the protons and neutrons in the nucleus

the loss in mass and liberation of energy is


related by:

152

Average Binding Energy per Nucleon


E released per nucleon upon the formation of the
nucleus from its fundamental particles
The nucleus with the greatest binding energy is
most stable.

Nuclei with mass numbers ~60 have the highest


average binding energies per nucleon
these elements (e.g. Fe, Ni) that are believed to
constitute the bulk of the Earths core.

Average Binding Energy per Nucleon


Nuclei with mass numbers of 4, 12 and 16 have
relatively high binding energies per nucleon
Implies stability
Used as projectiles in the synthesis of the heaviest
nuclei (artificial isotopes and transuranium
elements)

A reaction involving nuclei will be exothermic if:


a heavy nucleus is divided into two nuclei of medium
mass (nuclear fission)
two light nuclei are combined to give one nucleus of
medium mass (nuclear fusion)

Radioactivity
A nuclide is radioactive if it decomposes to form
a different nuclide.
Types of emission:

-particle
Basically, an electron.
Energy: (0.03-5) x 10-13 J

Its emission causes increase in the atomic


number by one and leaves the mass number
unchanged.
Examples:

-particle
Energy: (6-16) x 10-13 J
Its emission lowers the atomic number by two
and the mass number by four.
Example:

-radiation
same range as -particle, but has greater
penetrating power
Very short wavelength very high energy
Energy: 1 mol 3.6 x 108kj/96.35 eV/kj= ca. in MeV

accompanies and -emission


the product of the loss of - or - particle is often
in an excited state
energy in the form of -radiation is emitted as the
transition from excited to ground state occur

Nuclear Transformations

The positron, the neutrino & the


antineutrino
Positron, +
Equal mass but opposite charge to an electron
loss of positron converts a proton into a neutron
Example:

Neutrino
Near zero mass; uncharged
Accompany the emission from the nucleus of a positron

Antineutrino
Near zero mass; uncharged
Accompany the emission from the nucleus of an electron
Variable energy

161

Nuclear Properties of
Elements

Drills!
Write the nuclear reactions.
1. Carbon-14 undergoes decay
2. Technietium-99m undergoes isomeric
transition, producing a gamma emission.
3. Carbon-11 decays by positron emission.
4. Radon-222 undergoes decay to form Polonium218.
5. Rubidium-81 undergoes decay by electron
capture.

Drills!
Write the nuclear reactions.
1. Carbon-14 undergoes decay
2. Technietium-99m undergoes isomeric
transition, producing a gamma emission.
3. Carbon-11 decays by positron emission.
4. Radon-222 undergoes decay to form Polonium218.
5. Rubidium-81 undergoes decay by electron
capture.

Kinetics of Radioactive Decay


Follows first order kinetics for any nuclide

Kinetics of Radioactive Decay


Half-Life, t1/2
period of time it takes for a substance undergoing
decay to decrease by half

where k is the rate constant.

166

Artificial Isotopes
Made by the bombarding the nuclei with highenergy neutrons or positively charged particles
The use of neutrons (uncharged)= more effective
No electrostatic repulsion by the nuclei.

Artificial Isotopes
Bombardment of nuclei with slow/thermal neutrons.
formed by fission of
and their kinetic energy is
reduced by elastic collisions with low atomic number
nuclei (e.g. ,
) during passage through graphite or
deuterium oxide (heavy water).
Energy: 0.05eV.
Example:

High-energy (or fast) neutrons are produced by


the nuclear fission of
(Energy: 1MeV)

169

Nuclear Fission
Branching chain reaction
If this involves a quantity of

larger than a

certain critical mass, a violent explosion occurs,


liberating enormous amounts of energy.
Principle behind fission-type nuclear bombs.

171

Balancing Nuclear Reactions

Drill!!

Drill!!

Ans.

175

Use of Radio-isotopes
Nuclear Medicine
used in some forms of tomography
for diagnosis, treatment, and research

Biochemistry and Genetics


label molecules and allow tracing chemical and physiological
processes occurring in living organisms

Agriculture
radiation is used to stop the sprouting of root crops after
harvesting, to kill parasites and pests, and to control the
ripening of stored fruit and vegetables

176

Use of Radio-isotopes
Food preservation
used to produce high-yield crops, disease and weather resistant
varieties of crops, to study how fertilizers and insecticides work, and
to improve the production and health of domestic animals

Mining Industry
examine welds, to detect leaks, to study the rate of wear, erosion and
corrosion of metals, and for on-stream analysis of a wide range of
minerals and fuels.

are also used to trace and analyze pollutants, to study the


movement of surface water, and to measure water runoffs from
rain and snow, as well as the flow rates of streams and rivers.

177

Radio-Isotopes for Tomography


Tumor
67Ga (, t1/2 = 78h, 300keV)

Brain, Kidney, and Bone


99Mo (t1/2 = 2d) -> - + 99Tc (, t1/2 = 6h, 140keV )

Heart
201Tl (, t1/2 = 73h, 78-80keV)

Thyroid
125I (, t1/2 = 13h, 159keV)

PET-scans (Positron Emission Tomography) requires short-lived isotopes


(i.e.: 68Ga, 68min; 11C, 20min; 18F, 110min; 67Cu, 9.7min; 82Rb, 76sec )

178

Radio-isotopes for Treatment


Cancer Treatment
Gamma radiation from 57Co (271 d, 122keV) and 60Co (,
, 5.27 y)

Brain Cancer Treatment


particles from Boron cluster for Boron neutron capture

Local Radiation Therapy with MAB attached isotopes


67Cu (, 62h); 90Y (, 64h); 186Re (, 89h); 188Re (, 17h),
212Bi (, , 1h)

You might also like