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CHAPTER 3

THE CHEMICAL BOND


3.4

3.6

The triple bond is composed of a sigma ( and two pi ( bonds. The bond is a result of the head-on overlap of 2px
orbitals. The two pi bonds formed by the overlap of the 2py and 2pz orbitals on the carbon atom with their counterparts on
the nitrogen atom. The two lone pairs of electrons remain in the 2s orbitals of each atom.

3.7

The bonding orbitals, depicted below, are due to the overlap of the p-orbitals. The lone pairs of electrons remain in the 2s
orbitals on each atoms (not shown in the illustration below).

3.14

(a) The two silicon atoms are the same. The bond is covalent.
(b) The electronegativity difference between Cl and Si is 3.0 1.8 1.2. The bond is polar covalent.
(c) The electronegativity difference between F and Ca is 4.0 1.0 3.0. The bond is ionic.
(d) The electronegativity difference between N and H is 3.0 2.1 0.9. The bond is polar covalent.

3.16

Pauling related the difference in electronegativities (A B) to the difference in bond energy of the heternuclear molecule
and the bond energies of the two homonuclear molecules ().
D0 (AB)

1
D (AA)+D0 (BB)
2 0

A B 0.102
We can use the two equations above to solve for the bond dissociation energy of the heteronuclear molecule.
D0 (AB)

A
1
1
D0 (AA)+D0 (BB) D0 (AA)+D0 (BB) A

2
2
0.102

Using the bond dissociation energies from Table 3.3 and the electronegativities from Figure 3.10, we get the following:

CHAPTER 3: THE CHEMICAL BOND

1
D0
2

D0

A A

2.8 2.1

0.102

1

2
0.102

D0

241

1-1
kJ mol

358.0 kJ mol-1 is close to the value of 363.6 kJ mol-1 given in Table 3.3.
3.20

By Hess's law, the overall enthalpy (energy) change in a reaction is equal to the sum of the enthalpy (energy) changes for
the individual steps. The reactions shown in the problem are just the sums of the ionization energy of the alkali metal and
the electron affinity of the halogen.
(a) Taking data from the referenced figures we have:

Li(g) Li (g) e

I(g) e I (g)

H 520 kJ mol-1
H 295 kJ mol-1

Li(g) I(g) Li (g) I (g)

H 225 kJ mol-1

Parts (b) and (c) are solved in an analogous manner.

(b) Na(g) F(g) Na (g) F (g)

(c) K(g) Cl(g) K (g) Cl (g)

H 163 kJ mol-1
H 71 kJ mol-1

3.22
(a)

(b)

H
(d)

(e)

(c)

Si

Si

O
C

(f)

Cl
3.24

Strategy: We follow the procedure for drawing Lewis structures outlined in Section 3.4 of the text.
Solution:
(a)
Step 1: It is obvious that the skeletal structure is: O

O
2

Step 2: The outer-shell electron configuration of O is 2s 2p . Also, we must add the negative charges to the number of
valence electrons, Thus, there are
(2 6) 2 14 valence electrons
Step 3: We draw a single covalent bond between each O, and then attempt to complete the octets for the O atoms.

Because this structure satisfies the octet rule for both oxygen atoms, step 4 outlined in the text is not required.

Check: As a final check, we verify that there are 14 valence electrons in the Lewis structure of O 2 .
Follow the same procedure as part (a) for parts (b), (c), and (d). The appropriate Lewis structures are:

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CHAPTER 3: THE CHEMICAL BOND

H
(b)

(c)

(d)

H
3.26

Strategy: We follow the procedure for drawing Lewis structures outlined in Section 3.4 of the text. After we complete the
Lewis structure, we draw the resonance structures.

Solution: Following the procedure in Section 3.4 of the text, we come up with the following Lewis structure for ClO3 .

Cl

We can draw two more equivalent Lewis structures with the double bond between Cl and a different oxygen atom.
The resonance structures with formal charges are as follows:

O
O

3.28

Cl

Cl

Three reasonable resonance structures for OCN are:

Three reasonable resonance structures with the formal charges indicated are

3.31

3.30

The structures of the most important resonance forms are:

H
3.29

Cl

Reasonable resonance structures are:

O
H

(a)

O
O

O
(b)

O
O

O
O

O
O

There are two more equivalent resonance structures to the first structure above.

O
(c)

H O

H O

O
O

2+

H O

O
(d)

3.34

CHAPTER 3: THE CHEMICAL BOND

S+ O

243

There are two more equivalent resonance structures to the first structure.
The molecular orbital electron configuration and bond order of each species is shown below.
H2

H2

H2

1s

1s

1s

1s

bond order 1

3.36

1s

1s

bond order

1
2

bond order 0

The internuclear distance in the 1 ion should be greater than that in the neutral hydrogen molecule. The distance in the
2 ion will be very large because there is no bond (bond order zero).
The electron configurations are listed. Refer to Table 3.4 of the text for the molecular orbital diagram.
Li2:

( )2 ( 1s )2 ( 2s )2
1s

bond order 1

Li2 :

( )2 ( 1s )2 ( 2s )1
1s

bond order

Li2 :

( )2 ( 1s)2 ( 2s )2 (
)1
2s
1s

1
2
1
bond order
2

Order of increasing stability: Li2 Li2 < Li2


In reality, Li2 is more stable than Li2 because there is less electrostatic repulsion in Li2 .

3.37

See Table 3.4 of the text. Removing an electron from B2 (bond order 1) gives B2 , which has a bond order of (1/2).

Therefore, B2 has a weaker and longer bond than B2.

3.38

The energy level diagrams are shown below.


C2

C2

2p

x
2p , 2p
z
y

2p

2s

1s

1s

.
.

2p , 2p
y

2s

x
2p , 2p
z
y

2p

2p , 2p

2p

2s

1s

1s

2s

3.40

The bond order of the carbide ion is 3 and that of C 2 is only 2. With what homonuclear diatomic molecule is the carbide
ion isoelectronic?

In forming the N2 from N2, an electron is removed from the sigma bonding molecular orbital. Consequently, the bond

order decreases to 2.5 from 3.0. In forming the O2 ion from O2, an electron is removed from the pi antibonding molecular
orbital. Consequently, the bond order increases to 2.5 from 2.0.

3.41

We refer to Table 3.4 of the text.


O2 has a bond order of 2 and is paramagnetic (two unpaired electrons).

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CHAPTER 3: THE CHEMICAL BOND

O2 has a bond order of 2.5 and is paramagnetic (one unpaired electron).

O2 has a bond order of 1.5 and is paramagnetic (one unpaired electron).


O2

has a bond order of 1 and is diamagnetic.

Based on molecular orbital theory, the stability of these molecules increases as follows:
O2

< O2 < O2 < O2

3.42

From Table 3.4 of the text, we see that the bond order of F2 is 1.5 compared to 1 for F2. Therefore, F2 should be more
stable than F2 (stronger bond) and should also have a shorter bond length.

3.43

As discussed in the text (see Table 3.4), the single bond in B2 is a pi bond (the electrons are in a pi bonding molecular
orbital) and the double bond in C2 is made up of two pi bonds (the electrons are in the pi bonding molecular orbitals).
The resonance structures are:

3.46

Which is the most plausible structure based on a formal charge argument?


3.52

The rest of the molecule (in this problem, unidentified) would be attached at the end of the free bond.

(a)

3.59

O
O

(b)

(a) This is a very good resonance form; there are no formal charges and each atom satisfies the octet rule.
(b) This is a poor choice for several reasons. All of the atoms have non-zero formal charges and carbon has
electrons. Only elements in the third period and lower can have more than eight electrons.
(c) This is a poor choice because the oxygen have non-zero formal charges.

ten

(d) This is a mediocre choice because of the large formal charge and lack of an octet on carbon.
3.83

3.85

. Therefore, it only has a bond order of


Referring to Table 3.4, we see that F2 has an electron in
(compared with a
2
2px
bond order of one for F2).

We start by filling in the molecular orbitals and calculating the bond orders. Because NO + has the largest bond order it
should have the largest bond dissociation energy and the shortest bond length. NO has the smallest bond order of the three
and hence should have the smallest bond dissociation energy and the longest bond length.

NO+

NO

NO

2p x

2p y , 2p z

2px

2p y , 2p z

2s

2s

Bond order:

3.0

2.5

2.0

CHAPTER 3: THE CHEMICAL BOND

245

3.88

BN-

CO-

OF+

2p x

2p y , 2p z

2p x

2p y , 2pz

2s

2s

bond order =

3.96

BN-: bond order =

1
7 2 2.5
2

CO-: bond order =

1
8 3 2.5
2

OF+-: bond order =

1
8 4 2
2

In each case, we examine the molecular orbital that is occupied by the valence electrons of the molecule to see if it is a
bonding or antibonding molecular orbital. If the electron is in a bonding molecular orbital, it is more stable than an
electron in an atomic orbital (1s or 2p atomic orbital) and thus will have a higher ionization energy compared to the lone
atom. On the other hand, if the electron is in an antibonding molecular orbital, it is less stable than an electron in an
atomic orbital (1s or 2p atomic orbital) and thus will have a lower ionization energy compared to the lone atom. Refer to
Table 3.4 of the text.
(a) H2

3.98

number of electrons
1 number of electrons

2 in bonding MOs
in antibonding MOs

(b) N2

(c) O

(d) F

(a) From Table 3.4 of the text:


__________
or
2p y
2pz

First excited state: N 2

__________ 2p

Ground state: N2

(b) The bond order for N2 is 3. The bond order for N 2 is (5 1) 2. N 2 should have a longer bond length
(c) N 2 is diamagnetic. Electrons do not change their spins during transitions.
(d) E

hc

(6.63 1034 J s)(3.00 108 m s-1 )


4.23 1019 J
470 109 m

than N2.