CHAPTER 2 CHEMICAL BONDS

2.1

The coulombic attraction is directly proportional to the charge on each ion (Equation 1) so the ions with the higher charges will give the greater coulombic attraction. The answer is therefore (b) Ga 3, O 2 . 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.

2.3

2.5

(a) 5;

(b) 4;

(c) 7;

(d) 3
5 (c) [Kr]4d ; 10 2 (d) [Ar]3d 4s

2.7

(a) [Ar];

10 2 (b) [Ar]3d 4s ;

2.9

(a) [Ar]3d ;

10

(b) [Xe]4 f 5d 6s ;

14

10

(c) [Ar]3d ;

10

(d) [Xe]4 f 5d

14

10

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

(a) Co ; (a) Co ;
3

(b) Fe ; (b) Fe ;
3

(c) Mo ; (c) Ru ;
3

2 (d) Nb

2.15

3 (d) Mo

2.17

(a) 4s;

(b) 3p;

(c) 3p;

(d) 4s

2.19

(a) 1; (e) +2

(b) 2 ;

(c) +1;

(d) +3 (+1 sometimes observed);

2.21

(a) 3;

(b) 6;

(c) 6;

(d) 2 (b) [Kr]4d10; no unpaired (d) [Kr]; no

2.23

(a) [Kr]4d105s2; no unpaired electrons;

electrons; (c) [Xe]4 f 145d 4; four unpaired electrons; unpaired electrons;

(e) [Ar]3d 8; two unpaired electrons

2.25

(a) 3p;

(b) 5s; (b) 1;

(c) 5p;

(d) 4d

2.27

(a) +7;

(c) [Ne] for +7, [Ar] for 1;

(d) electrons are lost

or added to give noble-gas configuration. (a) Mg3As2; (a) Bi 2O 3; (b) In2S3 ; (b) PbO2; (c) AlH 3; (c) Tl2 O 3 (d) H 2 Te; (e) BiF3

2.29

2.31 2.33

(a)

Cl Cl C Cl Cl

(b)

O Cl C Cl

(c)

(d)

F F N F

2.35

H
(a) H

B H H

(b)

Br

(c)

2.37

O (a) H C H (b) H

H C H H O C O H O H

(c)

N H

C H

2.39

The structure has a total of 32 electrons; of these, 21 are accounted for by the chlorines (3 Cls 7 valence electrons each); of the 11 electrons remaining, 6 come from the oxygen. This leaves 5 electrons unaccounted for; these must come from E. Therefore, E must be a member of the nitrogen family and since it is a third period element E must be phosphorous (P)

2.41

H
(a)

H N H H

Cl

K b K ) K

3_

( c )

Na

Cl O

2.43
H H C C H C H C C C C H H C C C C H H C C C H H H H C C C H

H C C C

H C C C C H

H C C C C H H H

H H C C H C H C C C

H C C C C H

H C C C C H H H H H C C

H C C C C H

H C C C C H

H C C C C H H H

2.45
Cl O N O O Cl N O

2.47
0 +1 + 0 0 -1 +1

(a)

(b)

(c) C

-1

-1

-2

-1

(d) C

(e)

2.49

2.51

H
-1

1-

..
(a) O ..

.. 0
S O

H
0 -1

10

O ..
0

..
O ..

.. +1
S
-1

..

..
-1

O ..

..

..

lower energy

.. ..
0

O ..

.. ..

O S

H
0

1-1

-1

(b)

.. O ..
-1

O S

..
+2

.. ..
+1

H
0

1-

.. ..

O ..

..
O ..
-1

..

..

O ..

..

..

O ..

lower energy

.. ..

O ..

.. ..

2.53

(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

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

S O

and three with an expanded octet:

-2 -2 -2

S O

S O

S O

The structures with expanded octets have lower formal charges. (b) There is one Lewis stucture that obeys the octet rule:
-

O H

S O

The formal charge at sulfur can be reduced to 0 by including one double bond contribution. This change gives rise to two expanded octet structures.
-

O H

S O

O H

S O

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.

(c) The perchlorate ion has one Lewis structure that obeys the octet rule:

..
O

.. ..

..
..
O .. 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 .. .. Cl O ..
O ..

.. O ..

..
Cl O .. O ..

..

.. ..

.. ..
O

..

.. ..

.. ..
..
O .. Cl O

..
O ..

..
O .. Cl O

..
O ..

..

.. ..

For the nitrite ion, there are two resonance forms, both of which obey the octet rule:
O N O O N 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.

2.59

The Lewis Structures are

(a)

Cl

(b)

Cl

Cl

O (c) O N O Cl

Radicals are species with an unpaired electron, therefore (a) and (c) are radicals. 2.61
+

(a)

Cl

Cl
-

I has 2 bonding pairs and 2 lone pairs I has 4 bonding pairs and 2 lone pairs

Cl

(b)

Cl

I Cl Cl
Cl
I has 3 bonding pairs and 2 lone pairs

(c)
Cl

I Cl
Cl
I has 5 bonding pairs and 1 lone pair

(d)

Cl Cl

I Cl

Cl

2.63

(a) F F

F S

(b) F F

F Xe F
10 electrons

F
12 electrons

(c) F F F
12 electrons

F As

F F

(d)

Cl Cl

Cl Te Cl

10 electrons

2.65
(a) F O Xe F F
2 lone pairs

(b) F Xe F F

(c) F F

O Xe

F F

2 lone pairs

1 lone pair

2.67

I (2.7) < Br (3.0) < Cl (3.2) < F (4.0)

2.69

In (1.8) < Sn (2.0) < Sb (2.1) < Se (2.6)

2.71

(a) The bond in HCl would be more ionic. The electronegativity difference is greater between H and Cl then between H and I, making the HCl bond more ionic. (b) The bonds in CF4 would be more ionic. The electronegativity difference is greater between C and F than between C and H, making the CF bonds more ionic.

(c) C and S have nearly identical electronegativities, so the CS bonds would be expected to be almost completely covalent, whereas the CO bonds would be more ionic.
Rb < Sr 2 < Be 2 ; smaller, more highly charged cations have greater

2.73

polarizing power. The ionic radii are 149 pm, 116 pm, 27 pm, respectively.
O 2 < N 3 < Cl < Br ; the polarizability increases as the ion gets larger

2.75

and less electronegative. The ionic radii for these species are 140 pm, 171 pm, 181 pm, 196 pm, respectively.
2

2.77

(a) CO 3

> CO 2 > CO

CO 3

will have the longest CO bond length. In CO there is a triple

bond and in CO 2 the CO bonds are double bonds. In carbonate, the bond is an average of three Lewis structures in which the bond is double in one form and single in two of the forms. We would thus expect the bond order to be approximately 1.3. Because the bond length is inversely related to the number of bonds between the atoms, we expect the bond length to be longest in carbonate. (b) SO 3
2

> SO 2 ~ SO 3

Similar arguments can be used for these molecules as in part (a). In SO 2 and SO 3 , the Lewis structures with the lowest formal charge at S have double bonds between S and each O. In the sulfite ion, however, there are three Lewis structures that have a zero formal charge at S. Each has one SO double bond and two SO single bonds. Because these SO bonds would have a substantial amount of single bond character, they would be expected to be longer than those in SO 2 or SO 3 . This is consistent with the experimental data that show the SO bond lengths in

SO 2 and SO 3 to be 143 pm, whereas those in SO 3 2 range from about 145

pm to 152 pm depending on the compound. (c) CH 3NH2 > CH 2NH > HCN The CN bond in HCN is a triple bond, in CH 2NH it is a double bond, and in CH 3NH2 it is a single bond. The CN bond in the last molecule would, therefore, be expected to be the longest.

2.79

(a) The covalent radius of N is 75 pm, so the NN single bond in hydrazine would be expected to be ca. 150 pm. The experimental value is 145 pm. (b) The CO bonds in carbon dioxide are double bonds. The

covalent radius for doubly bonded carbon is 67 pm and that of O is 60 pm. Thus we predict the CRO in CO 2 to be ca. 127 pm. The experimental bond length is 116.3 pm. (c) The CO bond is a double bond so it would be expected to be the same as in (b), 127 ppm. This is the experimentally found value. The CN bonds are single bonds and so one might expect the bond distance to be the sum of the single bond C radius and the single bond N radius (77 plus 75 pm) which is 152 pm. However, because the C atom is involved in a multiple bond, its radius is actually smaller. The sum of that radius (67 pm) and the N single bond radius gives 142 pm, which is close to the experimental value of 133 pm. (d) The

NN bond is a double bond so we expect the bond distance to be two times the double bond covalent radius of N, which is 2 (60 pm) or 120 pm. The experimental value is 123.0 pm.

2.81

(a) 77 pm + 72 pm = 149 pm

(b) 111 pm + 72 pm = 183 pm

(c) 141 pm + 72 pm = 213 pm. Bond distance increases with size going down Group 14/IV.

2.83
+1 -1 +1 -1 +1 +1

N
+1 +1

N
-1

2.85

(a)
0 -1

O
-1

-2

O C O C O O

-2

C O
0

C O
0

O C O C O O

-2

O C O C O O

-2

-1

0 -1 -1

-2

(b)
2.87
(a)

Br

(c)

O CH3 C O CH3

O C O

(b) H H C C CH3 O H H C C CH3 O

(c) O CH3 C H N CH3 O C H N

2.89

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 S 8 are single bonds, whereas N 2 has a triple bond and O 2 a double bond.

2.91

(a)

(b)

N N N N N N

+ suitable resonance form

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
0 0 0

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

Lattice Energy, kJmol-1 759 700 645 632 601

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 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)
O H H O H H 2_

(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 H H

2.99 Number of Z Configuration unpaired e 4 2 0 1 2 Element Fe Te S Y Zn Charge 2+ 222+ 2+ Energy state ground excited ground ground excited 26 [Ar]3d6 52 [Kr] 4d105s25p56s1 16 [Ne]3s23p6 39 [Kr]4d1 30 [Ar] 3d84s2

2.101
(a) H O N C O H O
+1 -1

O
+1

C
-1

(b)

H C H S O

H C H S
+1

O
-1

(c)

H C H N
+1

N
-1

(d) O

+1

-1

2.103
R H C H C H C H C R' C H H R C H C H C H C R' C H

R H C

H C

H C

H C

R' C H

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)
O ..

..

-1

Cl O ..
+1

..

O ..

..

-1

Cl O ..
+1

..
-1

O ..

..

O O

.. ..
..
-1

Cl O ..
+1

O ..

-1

O ..

-1

-1

O ..

..

-1

O O

.. ..
+1

.. .. .. ..
O

.. ..

.. ..

.. ..

Cl O ..

-1

O ..

..

..

..

-1

O ..

..

Cl O ..
+1

.. .. .. ..
O

.. ..
-1

.. ..

..
..
-1

O ..

..

..
Cl O ..
+1

.. ..

..

..

O ..

-1

.. ..
O

.. .. O Cl O .. .. O -1 ..
.. ..
O

.. .. O Cl O .. ..-1 O ..
.. ..
O

-1

.. .. O Cl O .. ..
O

..
..

.. ..

-1

.. .. O Cl O .. ..
O

.. ..

.. ..

.. ..

.. ..

..

O ..

..

-1

Cl O .. O

..

-1

.. ..
O

.. ..

.. ..-1
+3

.. .. .. ..

.. ..
O ..

-1

O ..

..

Cl O ..

..

.. ..

-1

-1

.. ..
+2

..

Cl O .. O ..
-1

-1

O ..

..

-1

Cl O ..
+2

.. -1
..

O ..

..

.. ..-1
..
+2

-1

Cl O .. O ..
-1

O ..

-1

-1

O ..

..

.. ..-1
..
+2

.. .. .. ..

.. ..

.. ..

.. ..

Cl O .. 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

(170 pm) 3 (140 pm) 147.5 pm, or just 3.5 pm longer than observed. 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 -1 +1

(a) C

(b) O

(c)

-1

+1

-1

+1

(d)

(e)

(f)

Ar

Of these, a, c, d, and e can all function as greenhouse gases

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

extremely reactive unless the total number of halogens is an even number. This can only be achieved if n is odd. Look at ICl2 vs. ICl3 as examples:

Cl

Cl

Cl

I Cl

Cl

2.115

(a) Compare the length of a S-S bond to that of a Cl-Cl bond. From Table 2.5, the Cl-Cl bond length is 199 pm; here the S-S bond length in S2F2 is reported to be 190 pm. From Table 2.5 it can be determined that, on average, an X-Y bond is approximately 20 pm longer that a X=Y bond; this suggests that the S-S bond (which is 9 pm shorter than a Cl-Cl single bond) has some double bond character. (b) and (c) The Lewis structures for the two possible S2F2 are:
+1 -1

S
favored

isomer 1

F F

+1

-1

F S F
favored

isomer 2

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

(a) The Lewis structures of NO and NO2 are:

N
-1

O
+1

(best possible structure)

+1 -1

(equivalent resonance structures)

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 0 +1 0 +1

(c)

N N
+1

O O
-1

O
(d)

N O
-1

N O
-1

O
0

(e) N2O5(g) + H2O(l) 2 HNO3(aq); Nitric acid is produced

(f)

4.05 g N 2O5

1 mol N 2O5 108.02 g N 2O5

2 mol HNO3 = 7.50 1 mol N 2O5

10-2 mol HNO3

Molarity =

7.50

10-2 mol HNO3 = 7.50 1.00 L

10-2 mol L-1 HNO3

(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.