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1 THE BASICS: BONDING AND

MOLECULAR STRUCTURE

SOLUTIONS TO PROBLEMS

Another Approach to Writing Lewis Structures

When we write Lewis structures using this method, we assemble the molecule
or ion from the constituent atoms showing only the valence electrons (i.e., the elec-
trons of the outermost shell). By having the atoms share electrons, we try to give
each atom the electronic structure of a noble gas. For example, we give hydrogen
atoms two electrons because this gives them the structure of helium. We give car-
bon, nitrogen, oxygen, and fluorine atoms eight electrons because this gives them
the electronic structure of neon. The number of valence electrons of an atom can
be obtained from the periodic table because it is equal to the group number of the
atom. Carbon, for example, is in Group IVA and has four valence electrons; fluo-
rine, in Group VIIA, has seven; hydrogen, in Group 1A, has one. As an illustration,
let us write the Lewis structure for CH3 F. In the example below, we will at first
show a hydrogen’s electron as x, carbon’s electrons as o’s, and fluorine’s electrons as
dots.

Example A

3 H , C , and F are assembled as

H H
H C F or H C F
H H
If the structure is an ion, we add or subtract electrons to give it the proper charge. As
an example, consider the chlorate ion, ClO3 − .

Example B

Cl , and O and an extra electron × are assembled as

− −
Ο Ο
Ο Cl Ο or Ο Cl Ο

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2 THE BASICS: BONDING AND MOLECULAR STRUCTURE

14
1.1 N, 7 protons and 7 neutrons; 15 N, 7 protons and 8 neutrons

1.2 (a) one (b) seven (c) four (d) three (e) eight (f ) five

1.3 (a) covalent (b) ionic (c) covalent (d) covalent

••
••

1.4 − O P O −

O −

••
••
O
•• •• •• •• •• ••
1.5 (a) H F
••
•
• (d) H O
••
N O (g) H O
••
P O
••
H
•
•

•
• O
••
H

•
••

•
O
O
•• •• •• C ••
(b) •• F
••
F
••
•
• (e) H O S O H (h) H O
••
O
••
H

H –
H
••
(c) H C F
••
•
• (f ) H B H

H H

O
H
C
− − −
1.6 (a) H C O (c) C N (e) H O O

H
O
− −
(b) H N (d) H C (f ) H C C
−
H O

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 3

−
H H O H

1.7 (a) H C C+ (d) H C H (g) H C C N

H H H H
H H H
+ + +
(b) H O H (e) H C N H (h) H C N N

H H H H
+
O H O H

(c) C (f ) H C H
H O −
H

O O −

1.8 (a) H C H C
O − O

(b) and (c). Since the two resonance structures are equivalent, each should make an equal
contribution to the overall hybrid. The C—O bonds should therefore be of equal length (they
should be of bond order 1.5), and each oxygen atom should bear a 0.5 negative charge.

−
O Ο
1.9 (a)
C C
H H H + H
O −
H O
−
H C C C
(b) C H
H H
H
H
H H
(c) H +
C
N
H C
+
N
H H
H
H H
−
(d) − C C N C C N
H H

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4 THE BASICS: BONDING AND MOLECULAR STRUCTURE

+ +
1.10 (a) CH3CH CH CH OH CH3CH CH CH OH
+
CH3CH CH CH OH
δ+ δ+ δ+
CH3CH CH CH OH
+
(b) CH2 CH CH CH CH2 CH2 CH CH CH CH2
+
+
CH2 CH CH CH CH2
δ+ δ+ δ+
CH2 CH CH CH CH2
+

(c)
+ +
δ+

δ+ δ+

− +
(d) CH2 CH Br CH2 CH Br
δ− δ+
CH2 CH Br
+
CH2+ CH2+ CH2 CH2 CH2
(e)
+ +
δ+ δ+
CH2

δ+ δ+

−
O O

− C C
(f ) H2C CH3 H2C CH3
O δ−

δ− C
H2C CH3
+
(g) CH3 S CH2+ CH3 S CH2

δ+ δ+
CH3 S CH2

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 5

O − O −
O
+ + 2+
(h) CH3 N CH3 N CH3 N
O − O O −
(minor)
δ−
O
+
CH3 N
−
+
Oδ
1.11 (a) CH2 N(CH3)2 because all atoms have a complete octet (rule 3), and there are more
covalent bonds (rule 1).
••
••

O
(b) CH3 C because it has no charge separation (rule 2).
O H
(c) NH2 C N because it has no charge separation (rule 2).
1.12 (a) In its ground state, the valence electrons of carbon might be disposed as shown in the
following figure.
The electronic configuration of a ground state carbon atom:
The p orbitals are designated 2 px , 2 p y , and 2 pz to indicate
2s their respective orientations along the x, y, and z axes. The
2py assignment of the unpaired electrons to the 2 p y and 2 px or-
C bitals is arbitrary. They could also have been placed in the 2 px
2px and 2 pz or 2 p y and 2 pz orbitals. (To have placed them both
2pz in the same orbital would not have been correct, however, for
this would have violated Hund’s rule.) (Section 1.10A)
The formation of the covalent bonds of methane from indi-
vidual atoms requires that the carbon atom overlap its orbitals containing single electrons
with 1s orbitals of hydrogen atoms (which also contain a single electron). If a ground
state carbon atom were to combine with hydrogen atoms in this way, the result would
be that depicted below. Only two carbon-hydrogen bonds would be formed, and these
would be at right angles to each other.
The hypothetical formation of CH2 from a carbon atom in its ground state:

+ 2
H H

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6 THE BASICS: BONDING AND MOLECULAR STRUCTURE

(b) An excited-state carbon atom might combine with four hydrogen atoms as shown in the
figure above.
The promotion of an electron from the 2s orbital to the 2 pz orbital requires energy.
The amount of energy required has been determined and is equal to 400 kJ mol−1 . This
expenditure of energy can be rationalized by arguing that the energy released when two
additional covalent bonds form would more than compensate for that required to excite
the electron. No doubt this is true, but it solves only one problem. The problems that
cannot be solved by using an excited-state carbon as a basis for a model of methane
are the problems of the carbon-hydrogen bond angles and the apparent equivalence of
all four carbon-hydrogen bonds. Three of the hydrogens—those overlapping their 1s
orbitals with the three p orbitals—would, in this model, be at angles of 90◦ with respect
to each other; the fourth hydrogen, the one overlapping its 1s orbital with the 2s orbital
of carbon, would be at some other angle, probably as far from the other bonds as the
confines of the molecule would allow. Basing our model of methane on this excited
state of carbon gives us a carbon that is tetravalent but one that is not tetrahedral, and
it predicts a structure for methane in which one carbon-hydrogen bond differs from the
other three.
The hypothetical formation of CH4 from an excited-state carbon atom:

+ 4
H
H

H
C

H
H

1.13 (a) Cis-trans isomers are not possible.

(b) CH3 CH3 CH3 H

C C and C C
H H H CH3

(c) Cis-trans isomers are not possible.

(d) CH3CH2 Cl CH3CH2 H

C C and C C
H H H Cl

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 7

1.14 sp 3

1.15 sp 3

1.16 sp 2

1.17 sp

1.18 (a) −
H

B There are four bonding pairs.

H H The geometry is tetrahedral.
H

(b) F Be F There are two bonding pairs about

the central atom. The geometry is linear.

(c) +
H
There are four bonding pairs.
N
H H The geometry is tetrahedral.
H

(d)
There are two bonding pairs and two
S
H nonbonding pairs. The geometry is angular.
H

(e) H
There are three bonding pairs. The geometry
B is trigonal planar.
H H

(f) F
There are four bonding pairs around the central
C
F F atom. The geometry is tetrahedral.
F

(g) F
There are four bonding pairs around the central atom.
Si
F F The geometry is tetrahedral.
F

(h) −

There are three bonding pairs and one nonbonding pair

Cl C
around the central atom. The geometry is trigonal pyramidal.
Cl Cl

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8 THE BASICS: BONDING AND MOLECULAR STRUCTURE

F 120° F
1.19 (a) C C 120° trigonal planar at each carbon atom
F F
180° 180°
(b) CH3 C C CH3 linear (c) H C N linear

H H H

1.20 H C O C C H

H H H
CH3
1.21 CH3CHCHCHCH3 or (CH3)2CHCH(CH3)CH(CH3)2

CH3 CH3

CH3
1.22 (a) CH CH3 =
CH3 CH2

CH3
(b) CH CH2 =
CH3 ΟΗ
CH2 OH

CH3 H
(c) C C CH3 =
CH3 CH2

CH2 CH2
(d) CH CH2 CH3 =
3

CH2 CH2
(e) CH3 CH CH3 =
ΟΗ
OH
CH2 CH3
(f ) CH2 C =
CH2 CH3

O
Ο
(g) C CH2 CH3 =
CH3 CH2 CH2

Cl CH3
Cl
(h) CH CH =
CH3 CH2 CH3

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 9

1.23 (a) and (d) are constitutional isomers with the molecular formula C5 H12 .
(b) and (e) are constitutional isomers with the molecular formula C5 H12 O.
(c) and (f) are constitutional isomers with the molecular formula C6 H12 .

H H H
H C
H Cl H H O H H
H C C C H
1.24 (a) H C C C C C C H (c) C C H
H H
H H H H H C C
H H
H O H
H C H
H C C
H
(b) H C C
H
C H
H H H
C
H H
C C
H H
H H

Cl
1.25 (a) (Note that the Cl atom and the three H atoms
C H
H may be written at any of the four positions.)
H

Cl Cl
(b) or and so on
C C
H H
Cl H
H Cl

Cl H
(c) and others (d) and others
C H H C Cl
Br C
H H
H H

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10 THE BASICS: BONDING AND MOLECULAR STRUCTURE

Problems

Electron Configuration

1.26 (a) no (b) yes (c) yes (d) no (e) yes (f ) yes (g) yes (h) yes

Lewis Structures

O
P
1.27 (a) O C O (b) H O S O H (c) Cl Cl
Cl
O
(d) H C N

1.28 CH3 O CH3 CH3 O H H3C H

Carbon FC = 0 Carbon FC = 0 Methyl Carbon FC = 0

Oxygen FC = 0 Oxygen FC = 0 Carbonyl Carbon FC = 0
Oxygen FC = 0

O O

H3C OH H3C OCH3

Methyl Carbon FC = 0 Methyl Carbon FC = 0

Carbonyl Carbon FC = 0 Carbonyl Carbon FC = 0
Carbonyl Oxygen FC = 0 Carbonyl Oxygen FC = 0
Hydroxyl Oxygen FC = 0 Alkoxy Oxygen FC = 0

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 11

Structural Formulas and Isomerism

HO CH3 OH O

1.29 (a) (b) CH3CH2CHCH2CH2COH

H3C

CH3

(c) (d) CH3CHCHCH3

CH3

1.30 (a) C8 H16 O (c) C6 H10 O

(b) C6 H12 O3 (d) C6 H14

1.31 (a) Different compounds, not isomeric (i) Different compounds, not isomeric
(b) Constitutional isomers (j) Same compound
(c) Same compound (k) Constitutional isomers
(d) Same compound (l) Different compounds, not isomeric
(e) Same compound (m) Same compound
(f) Constitutional isomers (n) Same compound
(g) Different compounds, not isomeric (o) Same compound
(h) Same compound (p) Constitutional isomers

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12 THE BASICS: BONDING AND MOLECULAR STRUCTURE

1.32 In each of the following structural formulas, place the appropriate number of lone pairs of
electrons on each heteroatom and indicate the charge on the heteroatom, if any.

O
(a) CH3 O H (b) (c) N

H H3C CH3

O CH3

(d) (e) H3C N CH3 Cl (f)

CH3 N
H

1.33 Write structural formulas for the constitutional isomers with the molecular formula C6 H14 .

hexane 2-methylpentane

3-methylpentane

2,2-dimethylbutane 2,3-dimethylbutane

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 13

H O H O −
+ +
1.34 H C N H C N
O − O
H H

H O C N H

H
H

H C O N O

H (Other structures are possible.)

Resonance Structures

−
1.35 (a) O Ο+
− −
Ο Ο Ο
+
(b) +

+ +
(c) NH2
NH2 NH2 +
− −
(d) +

Ο Ο −
Ο −

(e) + +
+
− − − −
(f ) Ο Ο Ο
+
− −
Ο Ο Ο
(g) Ο + Ο Ο+
− −
Ο Ο Ο
+
(h) Ν + Ν Ν

−
Ο Ο

1.36
+
H2N H2N

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14 THE BASICS: BONDING AND MOLECULAR STRUCTURE

1.37 Draw resonance structures for the benzyl cation, shown below, used curved arrows.

CH2 CH2 CH2

CH2 CH2

1.38 Which resonance structure shown below for acetone would contribute more to the overall
structure of acetone? Explain.

O O

H 3C CH3 H 3C CH3

The resonance structure on the left would be the major contributor. There are two contribut-
ing factors; first, the resonance structure on the left has one more formal bond, the C O,
compared to the one on the right. Second, in the resonance structure on the left there is no
formal charge separation as there is in the one on the right.

1.39 Indicate the number of bonds and lone pairs of electrons on each of the following atoms:
(a) A neutral carbon – four bonds and zero lone pairs
(b) A positively charged oxygen – three bonds and one lone pair
(c) A negatively charged nitrogen – two bonds and two lone pairs
(d) A positively charged carbon – three bonds and zero lone pairs

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 15

H
1.40 H C

(a) A −1 charge. (F = 4 − 6/2 − 2 = −1)

(b) A −1 charge. (It is called a methyl anion.)
(c) Trigonal pyramidal, that is

C−
H
H H

(d) sp 3

H
1.41 H C

(a) No formal charge. (F = 4 − 6/2 − 1 = 0)

(b) No charge.
(c) sp 2 , that is,

H
C H
H

1.42 (a) and (b)

+ +
O O
− −
O O O O

(c) Because the two resonance structures are equivalent, they should make equal contribu-
tions to the hybrid and, therefore, the bonds should be the same length.
(d) Yes. We consider the central atom to have two groups or units of bonding electrons and
one unshared pair.

+ 2− + 2− +
− −
1.43 N N N N N N N N N
A B C
Structures A and C are equivalent and, therefore, make equal contributions to the hybrid.
The bonds of the hybrid, therefore, have the same length.

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16 THE BASICS: BONDING AND MOLECULAR STRUCTURE

1.44 (a) ΟΗ OH O O

O
OH
OH

(b) (CH3)2NH CH3CH2NH2

(c) (CH3)3N CH3CH2NHCH3 CH3CH2CH2NH2 CH3CHCH3

NH2

(d)

1.45 (a) constitutional isomers (b) the same

(c) resonance forms (d) constitutional isomers
(e) resonance forms (f) the same

Challenge Problems
+
1.46 (a) O N O

(b) Linear
(c) Carbon dioxide

Br
1.47 Set A: Br Br Br
Br
Br Br
Br

Set B: H2N H2N OH OH NH2

OH NH2 O

OH N O O
N N N
O
H H H

H
O OH H OH
O O
Set C: H
C
a b
H
O
c O
[and unstable enol forms of a, b, and c]

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 17

+ N
Set D: NH3 +
H H

− −
Set E: − (i.e., CH3CH2CH2 and CH3CHCH3)
−

1.48 (a) Dimethyl ether Dimethylacetylene cis-1,2-Dichloro-1,2-difluoroethene

O Cl Cl
CH3 C C CH3
CH3 CH3 C C
F F
Cl Cl
(b) O
F F

H H Cl Cl
H O H Cl Cl
C C H C C C C H C C or C C
(c) H H F F
H H H H F F

1.49 The large lobes centered above and below the boron atom represent the 2 p orbital that was
not involved in hybridization to form the three 2sp 2 hybrid orbitals needed for the three
boron-fluorine covalent bonds. This orbital is not a pure 2 p atomic orbital, since it is not an
isolated atomic p orbital but rather part of a molecular orbital. Some of the other lobes in
this molecular orbital can be seen near each fluorine atom.

−
1.50 The two resonance forms for this anion are CH2 CH O and CH2 CH O − .
The MEP indicates that the resonance contributor where the negative charge on the anion
is on the oxygen is more important, which is what we would predict based on the fact that
oxygen is more electronegative than carbon.
δ− δ−
Resonance hybrid, CH2 CH O

QUIZ
1.1 Which of the following is a valid Lewis dot formula for the nitrite ion (NO−
2 )?

− − −
(a) O N O (b) O N O (c) O N O (d) Two of
these
(e) None of the above

1.2 What is the hybridization state of the boron atom in BF3 ?

(a) s (b) p (c) sp (d) sp 2 (e) sp 3
F H

1.3 BF3 reacts with NH3 to produce a compound, F B N H . The hybridization state
of B is
F H
(a) s (b) p (c) sp (d) sp 2 (e) sp 3

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18 THE BASICS: BONDING AND MOLECULAR STRUCTURE

1.4 The formal charge on N in the compound given in Problem 1.3 is

(a) −2 (b) −1 (c) 0 (d) +1 (e) +2

1.5 The correct bond-line formula of the compound whose condensed formula is
CH3 CHClCH2 CH(CH3 )CH(CH3 )2 is

Cl Cl Cl

(a) (b) (c)

Cl Cl
(d) (e)

1.6 Write another resonance structure for the acetate ion.

−
Ο

O
Acetate ion

1.7 In the boxes below write condensed structural formulas for constitutional isomers of
CH3 (CH2 )3 CH3 .

1.8 Write a three-dimensional formula for a constitutional isomer of compound A given below.
Complete the partial structure shown.

H H
H H
C Cl C

C H H C
H3C H3C
H
A
Constitutional isomer of A

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THE BASICS: BONDING AND MOLECULAR STRUCTURE 19

1.9 Consider the molecule (CH3 )3 B and give the following:

(a) Hybridization state of boron

(b) Hybridization state of carbon atoms

(c) Formal charge on boron

(d) Orientation of groups around boron

(e) Dipole moment of (CH3)3B

1.10 Give the formal charge on oxygen in each compound.

(a) CH3 O CH3

(c) −
CH3 O

O
(b)

1.11 Write another resonance structure in which all of the atoms have a formal charge of zero.

− H
O +
N
H H

1.12 Indicate the direction of the net dipole moment of the following molecule.
H3C Cl
C
H3C F

1.13 Write bond-line formulas for all compounds with the formula C3 H6 O.

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