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CHEMICAL BONDS
2.1
2.3
The Li ion is smaller than the Rb ion (58 vs 149 pm). Because the
lattice energy is related to the coulombic attraction between the ions, it
will be inversely proportional to the distance between the ions (see
Equation 2). Hence the larger rubidium ion will have the lower lattice
energy for a given anion.
2.5
(a)5;
(b)4;(c)7;(d)3
2.7
10
2
5
10
2
(a)[Ar];(b)[Ar]3d 4s ; (c)[Kr]4d ; (d)[Ar]3d 4s
2.9
14
10
2
14
10
(a)[Ar]3d10; (b)[Xe]4 f 5d 6s ; (c)[Ar]3d10; (d)[Xe]4 f 5d
2.11
10
2
(a)[Kr ]4d 5s ; same; In+ and Sn2+ lose 5p valence electrons.
(b)none
10
(c) [Kr] 4d ; Pd
2.13
2.15
2.17
(a)4s;(b)3p;(c)3p;(d)4s
SM-73
2.19
2.21
(a)3;(b)6;(c)6;(d)2
2.23
10
2
10
(a)[Kr ]4d 5s ; no unpaired electrons;(b)[Kr] 4d ; no unpaired
14
4
electrons; (c) [Xe]4 f 5d ; four unpaired electrons;(d)[Kr]; no
(a)3p;(b)5s;(c)5p;(d)4d
2.27
2.29
2.31
2.33
Cl
(a)
Cl
(b)
Cl
Cl
Cl
Cl
(c)
SM-74
(d)
2.35
H
(a) H
Br
(b)
H
H
(c)
2.37
O
(a)
(b)
H
(c)
2.39
SM-75
2.41
H
(a)
H N H
K
(b) K
K
Cl
3_
(c) Na
Cl O
2.43
H
H
C
H
H
C
C
C
C
C
C
C
C
C
C
C
Cl
N
C
C
2.47
(a)
+1
-1
(d) C
-1
(b)
-2
(e)
-1
SM-76
-1
+1
(c) C
H
C
Cl
O
C
C
2.45
C
C
H
C
C
C
C
C
H
C
C
C
C
H
2.49
2.51
1-
H
-1
..
.. 0
-1
..
.. +1
S
..
O
..
O
..
lower energy
-1
-1
..
..
O
..
-1
+2
H
O
..
10
O
..
..
..
O
..
lower energy
2.53
..
..
O
..
1-
..
..
-1
+1
..
..
(b)
..
O
..
-1
..
..
-1
..
..
O
..
..
..
..
..
O
..
..
..
O
..
..
(a)
1-
(a)In the first structure, the formal charges at Xe and F are 0, whereas, in
the second structure, Xe is 1, one F is 0, and the other F is +1. The first
structure is favored on the basis of formal charges.(b)In the first
structure, all of the atoms have formal charges of 0, whereas, in the second
SM-77
structure, one O atom has a formal charge of +1 and the other O has a
formal charge of 1. The first structure is thus preferred.
2.55
(a) The sulfite ion has one Lewis structure that obeys the octet rule:
-2
O
and three with an expanded octet:
-2
-2
-2
Notice that, unlike the sulfite ion, which has three resonance forms, the
presence of the hydrogen ion restricts the electrons to the oxygen atom to
which it is attached. Because H is electropositive, its placement near an
oxygen atom makes it less likely for that oxygen atom to donate a lone
pair to an adjacent atom.
SM-78
(c) The perchlorate ion has one Lewis structure that obeys the octet rule:
..
..
..
..
Cl
..
O
..
..
..
O
..
..
..
O
..
The formal charge at Cl can be reduced to 0 by including three doublebond contributions, thereby giving rise to four resonance forms.
..
..
..
O
..
..
O
..
..
Cl O
..
..
..
..
..
..
Cl
O
..
..
..
..
..
..
O
..
..
Cl
O
..
O
..
..
..
..
..
O
..
O
..
..
Cl
O
..
..
..
..
..
For the nitrite ion, there are two resonance forms, both of which obey the
octet rule:
O
2.57
Radicals are species with an unpaired electron, therefore only (b) and (c)
are radicals since they have an odd number of electrons while (a) and (d)
have an even number of electrons allowing Lewis structures to be drawn
with all electrons paired.
SM-79
2.59
(a)
Cl
(b)
Cl
Cl
O
(c)
Cl
Radicals are species with an unpaired electron, therefore (a) and (c) are
radicals.
2.61
(a)
Cl
Cl
Cl
Cl
(b)
lone pairs
Cl
Cl
Cl
(c)
Cl
lone pairs
I
Cl
I has 5 bonding pairs and 1
Cl
(d)
Cl
Cl
lone pair
Cl
Cl
SM-80
2.63
(a)
(b)
S
F
Xe
F
F
12 electrons
10 electrons
(c)
Te
As
F
Cl
Cl
(d)
Cl
12 electrons
Cl
10 electrons
2.65
(a)
(b)
O
F
Xe
(c)
F
F
F
Xe
F
2 lone pairs
Xe
F
2 lone pairs
F
1 lone pair
2.67
2.69
2.71
SM-81
Rb < Sr2 < Be 2 ; smaller, more highly charged cations have greater
polarizing power. The ionic radii are 149 pm, 116 pm, 27 pm, respectively.
2.75
O 2 < N 3 < Cl < Br ; the polarizability increases as the ion gets larger
and less electronegative. The ionic radii for these species are 140 pm, 171
pm, 181 pm, 196 pm, respectively.
2.77
SM-82
2.81
SM-83
2.83
+1
-1
+1
N
+1
-1
+1
+1
-1
+1
2.85
(a)
-2
-2
-1
-1
C
O
C
O
C
O
0
-2
O
C
-2
(b)
-1
Br
(c)
-1
-1
-2
2.87
(a)
O
CH3
O
CH3
SM-84
(b)
H
H
H
C
CH3
(c)
CH3
2.89
CH3
CH3
P and S are larger atoms that are less able to form multiple bonds to
themselves, unlike the small N and O atoms. All bonds in P4 and S8 are
single bonds, whereas N 2 has a triple bond and O 2 a double bond.
2.91
(a)
SM-85
(b)
N
N
N
N
SM-86
2.93
(a) In H2O2, hydrogen peroxide, the oxidation number of oxygen is -1; the
oxygen in water has an oxidation number of -2. Since oxygen is gaining
electrons on going from H2O2 to H2O it is undergoing reduction.
Ascorbic acid (C6H8O6), on the other hand is undergoing oxidation: the
oxidation number of carbon changes from +2/3 to +1 on conversion from
ascorbic acid to C6H8O6 which means it is losing elecctrons.
(b) The Lewis structures for hydrogen peroxide and water, respectively,
are
Note that all atom have formal charges of zero, suggesting that there is no
driving force for this conversion based solely on formal charges; however,
since we know that hydrogen peroxide does react to form water in the
lung, and that this conversion is borne by the change in oxidation states,
oxidation numbers are far more useful in determining whether a material
has been oxidized or reduced.
2.95
(a)
MI
Li
NaI
KI
RbI
CsI
d(MI), pm
274
294
329
345
361
(1 d*/d)/d
3.19 10-3
3.00 10-3
2.72 10-3
2.61 10-3
2.51 10-3
A high correlation (R2 = 0.9731) exists between lattice energy and d(MI).
A better fit (R2 = 0.9847) is obtained between lattice energy and
(1 d*/d)/d.
(b) Using the equation L.E. = 218331(1 d*/d)/d) + 54.887 and the Ag-I
distance (309 pm), the estimated AgI lattice energy is 683 kJmol-1.
(c) There is not close agreement between the estimated (683 kJmol-1) and
experimental (886 kJmol-1) lattice energies. A possible explanation is that
SM-87
the Ag+ ion is more polarizable than the alkali metal cations of similar size
and therefore the bonding in AgI is more covalent.
2.97
(a)
2_
O
H
H
O
(b) All the atoms have formal charge 0 except the two oxygen atoms,
which are -1. The negative charge is most likely to be concentrated at the
oxygen atoms.
(c) The protons will bond to the oxygen atoms. Oxygen atoms are the
most negative sites in the molecule and act as Lewis bases due to their
lone pairs of electrons. The resulting compound is named hydroquinone.
O H
H
H
O H
SM-88
2.99
Number of
Z
26
52
16
39
30
Configuration
[Ar]3d6
[Kr] 4d105s25p56s1
[Ne]3s23p6
[Kr]4d1
[Ar] 3d84s2
unpaired e
4
2
0
1
2
Element
Fe
Te
S
Y
Zn
Charge
2+
222+
2+
Energy state
ground
excited
ground
ground
excited
2.101
(a)
H
H
C
(c)
-1
+1
(b)
-1
+1
+1
-1
H
C
H
(d)
+1
-1
-1
+1
SM-89
2.103
H
R'
R'
R'
2.105 (a) I: Tl2O3; II: Tl2O; (b) 3+; 1+; (c) [Xe]4f145d10; [Xe] 4f145d106s2; (d)
Because compound II has a lower melting point, it is probably more
covalent which is consistent with the fact that the 3+ ion is more
polarizing.
2.107 (a)
..
..
+1
..
..
..
..1
..1
Cl O
..
+2
..
..
..
..
+2
O
..
..
O
..
..
..
Cl O
..
..
..
..
..
SM-90
..
..
..
O
..
+3
O
..
..
..
+2
O
..
..
.. 1
Cl O
..
..
..
..
..
..
+2
O
..
..
O
..
..1
Cl O
..
..
1
..
..
..
..
..
O
..
..
..
..
Cl O
..
..
..
..
..
..
..
1
..
..
..
O
..
..
..
Cl O
..
..
..
O
.. Cl O
..
..
..
O
.. Cl O
..
..
..
1
..
..
..
..
..
..
O
..
+1
..
..
..
..
..
..
..
..
O
.. Cl O
..1
O
..
O
..
O
..
..
..
O
.. Cl O
..
O
.. 1
Cl O
..
..
..
..
+1
..
..
..
..
O
..
..
..
1
..
..
Cl O
..
..
Cl O
..
O
..
..
..
..
..
..
O
..
+1
..
..
..
..
Cl O
..
..
..
..
O
..
..
O
..
..
+1
..
..
O
..
..
+1
..
Cl O
..
..
O
..
..
..
..
Cl O
..
..
..
..
..
..
..
..
1
..
..
..
O
..
The four structures with three double bonds (third row) and the one with
four double bonds are the most plausible Lewis structures according to
formal charge arguments because these five structures minimize the
formal charges. (b) The structure with four double bonds fits these
observations best since its bond lengths would all be 140 pm, or only 4 pm
shorter than the observed length. However, the four structures with three
double bonds also fit because, if the double bonds are delocalized by
resonance, we can estimate the average bond length to be
1
4
(c) 7+; The structure with all single bonds fits this criterion best. (d)
Approaches (a) and (b) are consistent but approach (c) is not. This result
is reasonable because oxidation numbers are assigned by assuming ionic
bonding.
2.109 The alkyne group has the stiffer CH bond because a large force
constant, k, results in a higher-frequency absorption.
2.111 Look at the Lewis structures for the molecules:
-1
+1
(a) C
(d)
-1
+1
(b) O
(e)
(c)
-1
+1
-1
+1
(f)
Ar
2.113 Since the halogen all have an odd number of valence electrons (7),
interhalogen compounds of the type XXn will be radicals and therefore
SM-91
Cl
Cl
Cl
Cl
Cl
2.115
+1
-1
isomer 1
favored
+1
-1
F
S
isomer 2
favored
If resonance is occurring then one would expect that the S-S bond length
is indeed between a single and a double bond in length.
2.117
-1
+1
+1
-1
SM-92
From Table 2.4, the average bond dissociation energy of a N=O bond is
630 kJ mol-1, which is right in line with the Lewis structure of NO. The
bond dissociation energy of each NO bond in NO2 is 469 kJ mol-1, which
is about half-way between a N-O double and an N-O single bond,
suggesting that the resonance picture of NO2 is a reasonable one.
(b) An N-O single bond should have a bond length of 149 pm while an NO
double bond should have a bond length of 120 pm (values are obtained
by summing the respective covalent radii values from Figure 2.21). From
Table 2.5 the length of a N-O triple bond can be estimated to be between
105 and 110 pm. Since NO itself has a bond length of 115 pm, this
suggests that its actual bond order is somewhere between that of a double
and a triple bond.
0
+1
-1
(c)
(d)
+1
+1
-1
-1
(f)
4.05 g N 2 O5
Molarity =
1 mol N 2 O5
108.02 g N 2 O5
7.50
2 mol HNO3
= 7.50
1 mol N 2O5
(g) The oxidation number of nitrogen for the various nitrogen oxides are
as follows: NO: +2; NO2: +4; N2O3: +3; and N2O5: +5. An oxidizing
agent is a species that wants to gain electrons; based on oxidation
number, N2O5 should be the most potent oxidizing agent of the nitrogen
oxides, as it possesses the most positive oxidation number for N of the
group.
SM-93