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BONDING AND MOLECULAR STRUCTURES

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 electrons 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 carbon, nitrogen, oxygen, and uorine 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 IV A and has four valence electrons; uorine, in group VII A, 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 rst show a hydrogens electron as x, carbons electrons as os, and uorines 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 Cl

or

Cl

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O
1.1 (a) H

(d) H

(g) H

P O O

O H

O (b) F F H (c) H C H F (f ) H (e) H O H B H

O
1.2 (a) O

(h) H

C O O H

(i) H

(c)

C C N O (e) H O O

(b) H

N H

(d) H

S O O

(f ) H

H
1.3 (a) H
C

H C+ H O

H C (c) H O

H N H
+

(e) H

C H

(b) H

O H

(d) H

C H

(f ) H H

O C H

H H

O
1.4 (a) H

O H C O

C O

(b) and (c). Since the two resonance structures are equivalent, each should make an equal contribution to the overall hybrid. The CO 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.

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1.5 (a) CH3CH

CH

CH

OH

CH3CH CH3CH
+

CH CH

CH CH

OH OH

+ CH3CH (b) CH2 CH CH

+

CH

+ CH

+ OH
+

CH + CH2

CH2 +

CH2 +

CH CH CH2

CH CH

CH CH

CH2 CH2
+

CH2 CH CH CH

(c)
+ +

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

+ +

CH2

CH

Br

CH

+ Br CH2+
+

CH2

CH2

CH2

+ + O (f )

CH2 +

O C CH3 CH2 O C CH3 CH3 + + S CH2 S

+

C CH2 CH2

CH3

(g) CH3

CH2+ CH3

CH2

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(h) CH3

O CH3 O

2+

O CH3 N O (minor)

N O O

CH3
+

N O

1.6 (a) CH2 N(CH3)2 because all atoms have a complete octet (rule 6b), and there are more covalent bonds (rule 6a). O

(b) CH3 (c) NH2

C C

OH because it has no charge separation (rule 6c). N because it has no charge separation (rule 6c).

1.7 (a) In its ground state, the valence electrons of carbon might be disposed as shown in the following gure. The electronic conguration of a ground state carbon atom. The p orbitals are designated 2 px , 2 p y , and 2 pz to indicate their respective orientations along the x, y, and z axes. The 2s 2py assignment of the unpaired electrons to the 2 p y and 2 px orbitals is arbitrary. They could also have been placed in the 2 px C 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 Hunds rule.) (Section 1.10.) The formation of the covalent bonds of methane from individual 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:

C + 2 H H

C H

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(b) An excited-state carbon atom might combine with four hydrogen atoms as shown in the gure 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 mol1 . 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 hydrogensthose overlapping their 1s orbitals with the three p orbitalswould, 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 connes 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:

C + 4 H H H C H H

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

(b) CH3 C H C

CH3 and H

CH3 C H C

H CH3

(c) Cis-trans isomers are not possible.

(d) CH3CH2 C H C

Cl and H

CH3CH2 C H C

H Cl

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1.9 (a)

H H H B H

There are four bonding pairs. The geometry is tetrahedral.

(b)

Be

There are two bonding pairs about the central atom. The geometry is linear.

(c)

H H H N H

There are four bonding pairs. The geometry is tetrahedral.

(d)

H H

There are two bonding pairs and two nonbonding pairs. The geometry is angular.

(e)

H B H H

There are three bonding pairs. The geometry is trigonal planar.

(f)

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

(g)

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

(h)

Cl

C Cl

Cl

There are three bonding pairs and one nonbonding pair around the central atom. The geometry is trigonal pyramidal.

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F
1.10 (a)

120 F C C 120 F 180 C C CH3 linear (c) H 180 C N linear , trigonal planar at each carbon atom.

F (b) CH3 H
1.11 H

H O C H CH3

H C H H

C H

1.12 (a)

CH CH3 CH3 CH2

CH3

(b) CH3 CH3 (c) CH3

CH CH2 H C CH2 CH2 CH2 C

CH2 OH CH3 CH2 CH2 CH3 CH2 CH OH CH2 CH3 CH3

(d) CH 3 (e) CH3

(f ) CH2

C CH2 O CH3

(g) H3C

C CH2 Cl

CH2 CH2 CH3 CH CH2 CH3

CH3

(h) H3C

CH

Cl

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1.13 (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
1.14 (a) H

Cl C H

H C H O

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

O C

H C H H (c)

H H

C C C
H H H

H H

C C

C H

C C

H H

H H H (b) H H

C C C
H H H C C C H H

C C

Cl
1.15 (a)

C H H Cl

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

Cl or H C H Cl H and others H (d) H H H C C H Cl and others and so on H

(b) Cl

C H Cl

(c) Br

C H

Exercises 1.16 (a) Na+ has the electronic conguration, 1s 2 2s 2 2 p 6 , of Ne. (b) Cl has the electronic conguration, 1s 2 2s 2 2 p 6 3s 2 3 p 6 , of Ar.

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(c) F+ and (h) Br+ do not have the electronic conguration of a noble gas. (d) H has the electronic conguration, 1s 2 , of He. (e) Ca2+ has the electronic conguration, 1s 2 2s 2 2 p 6 3s 2 3 p 6 , of Ar. (f) S2 has the electronic conguration, 1s 2 2s 2 2 p 6 3s 2 3 p 6 , of Ar. (g) O2 has the electronic conguration, 1s 2 2s 2 2 p 6 , of Ne.

O
1.17 (a)

O Cl (b) Cl Cl Cl P Cl (c) Cl

Cl Cl P Cl (d) H O
+

Cl

N O

O
1.18 (a) CH3

O O

S O

(c)

S O O

O (b) CH3 S
+

CH3

(d) CH3

S O

1.19 (a) (CH3)2CHCH2OH

(c) HC C HC

CH2 CH2

O (b) (CH3)2CHCCH(CH3)2 (d) (CH3)2CHCH2CH2OH

1.20 (a) C4H10O

(c) C4H6 (d) C5H12O

(g) Different compounds, not isomeric (h) Same compound (i) Different compounds, not isomeric (j) Same compound (k) Constitutional isomers (l) Different compounds, not isomeric

(b) C7H14O

1.21 (a) Different compounds, not isomeric (b) Constitutional isomers (c) Same compound (d) Same compound (e) Same compound (f) Constitutional isomers

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(m) Same compound (n) Same compound

(o) Same compound (p) Constitutional isomers

1.22

(a)

(d)

(b)

(e)

or

(c)

(f )

H
1.23 (a)

C C C
N H H

H H H H H (c)

H C H H N C H H H

H C H H

H C H H

H H H

C C

O C C C C
H

H H H

C C C C C N

(d)

(b)
H

H H H

Problems

1.24

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H
1.25

O
+

H H C H
+

O N O

C H

N O

O H O C N H H H C H O N O (Other structures are possible.) H

1.26 (a) While the structures differ in the position of their electrons, they also differ in the positions of their nuclei and thus they are not resonance structures. (In cyanic acid the hydrogen nucleus is bonded to oxygen; in isocyanic acid it is bonded to nitrogen.) (b) The anion obtained from either acid is a resonance hybrid of the following structures: O

H
1.27

C H

(a) A +1 charge. (F = 4 6 /2 2 = +1) (b) A +1 charge. (It is called a methyl cation.) (c) Trigonal planar, that is,

H H
(d) sp 2

H
1.28

C H

(a) A 1 charge. (F = 4 6/2 2 = 1) (b) A 1 charge. (It is called a methyl anion.)

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(c) Trigonal pyramidal, that is

C H H
(d) sp 3

H
1.29

C H

(a) No formal charge. (F = 4 6/2 1 = 0) (b) No charge. (c) sp 2 , that is,

H C H H

Challenge Problems

1.30 (a) and (b)

O O

O O O

(c) Because the two resonance structures are equivalent, they should make equal contributions 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.

1.31

B A 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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1.32 (a)

OH

OH OH (b) (CH3)2NH CH3CH2NH2

(c) (CH3)3N

CH3CH2NHCH3

CH3CH2CH2NH2

CH3CHCH3 NH2

(d)

1.33 (a) constitutional isomers (c) resonance forms (e) resonance forms 1.34 (a)
+

(b) the same (d) constitutional isomers (f) the same

(b) Linear (c) Carbon dioxide

Br
1.35 Set A:

Br

Br Br

Br

Br

Br

Br

Set B:

H2N OH N H H

H2N

OH NH2 N O N H

OH O O O

NH2

OH

N H

Set C: a

O b

OH C H O c

OH H

[and unstable enol forms of a, b, and c]

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Set D:

NH3

N H
+

H
(i.e., CH3CH2CH2 and CH3CHCH3)

Set E:

1.36 (a) Dimethyl ether

Dimethylacetylene CH3 C C

cis-1,2-Dichloro-1,2-difluoroethene CH3 Cl C F Cl Cl F Cl or F F C C F Cl C F Cl

O CH3 CH3

(b)

O F H O C H H C H H H H H H C C C C H H H F Cl C C Cl

(c)

1.37 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-uorine 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 uorine atom. 1.38 The two resonance forms for this anion are CH2 CHO and CH2 CHO . 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.

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

(a)

(b) O

(c) O

N O

(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

(d) Two of these

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

H N H H . The hybridization state

B F

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 (a) (b)

Cl (c)

Cl

Cl (d) (e)

Cl

1.6 Write another resonance structure for the acetate ion.

O CH3 C

O Acetate ion

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

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

H C Cl C H H A H

C C CH3

H H

H3C

Constitutional isomer of A

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 O

CH3 (c) CH3

H C H O

(b) CH3

C CH3

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

C H

N H

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

C H3C F

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