Covalent Compounds: Bonding Theories and Molecular Structure

Covalent Compounds:
8 Bonding Theories and

Molecular Structure
8.1 Number of Number of

Bonded Atoms Lone Pairs Shape
(a) O3 2 1 bent
(b) H3O+ 3 1 trigonal pyramidal
(c) XeF2 2 3 linear
(d) PF6S 6 0 octahedral
(e) XeOF4 5 1 square pyramidal
(f) AlH4S 4 0 tetrahedral
(g) BF4S 4 0 tetrahedral
(h) SiCl4 4 0 tetrahedral
(i) ICl4S 4 2 square planar
(j) AlCl3 3 0 trigonal planar
8.2 (a) 4 charge clouds, tetrahedral charge cloud arrangement, tetrahedral molecular
geometry
(b) 5 charge clouds, trigonal bipyramidal charge cloud arrangement, seesaw molecular
geometry.
8.3
8.4 H The bond angle around every carbon is 120o (trigonal planar).
Benzene is a planar hexagon.
H C H
C C
C C
H C H
H
8.5 CH2Cl2; The C is sp3 hybridized. The C–H bonds are formed by the overlap of one singly
occupied sp3 orbital on C with a singly occupied H 1s orbital. The C–Cl bonds are formed
by the overlap of one singly occupied sp3 orbital on C with a singly occupied Cl 2p
orbital.
Copyright © 2016 Pearson Education, Ltd. 183

Chapter 8 S Covalent Compounds: Bonding Theories and Molecular Structure
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8.6 H H H Each C is sp3 hybridized. The C–C bonds are formed by the
overlap of one singly occupied sp3 hybrid orbital from each C. The
H C C C H
C–H bonds are formed by the overlap of one singly occupied sp3
H H H orbital on C with a singly occupied H 1s orbital.
8.7
The carbon in formaldehyde is sp2 hybridized.
8.8 H The two Cs with four single bonds are sp3 hybridized. The
O C with a double bond is sp2 hybridized. The C–C bonds are
H
formed by the overlap of one singly occupied sp3 or sp2
H C C C O H
hybrid orbital from each C. The C–H bonds are formed by
H H the overlap of one singly occupied sp3 orbital on C with a
O
singly occupied H 1s orbital.
8.9
In CO2 the carbon is sp hybridized.
8.10
In HCN the carbon is sp hybridized.
8.11 (a)
SF6 has polar covalent bonds but the molecule is symmetrical (octahedral). The individual
bond polarities cancel, and the molecule has no dipole moment.
184 Copyright © 2016 Pearson Education, Ltd.

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(b)
The C–F bonds in CH2CF2 are polar covalent bonds, and the molecule is polar.
(c)
SO3 has polar covalent bonds but the molecule is symmetrical (trigonal planar). The
individual bond polarities cancel, and the molecule has no dipole moment.
(d)
The Br–F bonds in BrF3 are polar covalent bonds, and the molecule is polar.
8.12 (a) CF4 (b) CH2F2 (c) CHF3 (d) CH3F
1D
8.13 µ = Q x r = (1.60 x 10S19 C)(92 x 10S12 m) = 4.41 D
3.336 x 10S30 C @ m
1.83 D
% ionic character for HF = x 100% = 41%
4.41 D
HF has more ionic character than HCl. HCl has only 18% ionic character.
8.14 HBr is predicted to have greater percent ionic character than HI because the difference in
electronegativity between hydrogen and bromine (0.7) is greater than between hydrogen
and iodine (0.4).
1D
HBr, µ = Q x r = (1.60 x 10S19 C)(142 x 10S12 m) = 6.81 D
3.336 x 10S30 C @ m
0.82 D
% ionic character for HF = x 100% = 12%
6.81 D
1D
HI, µ = Q x r = (1.60 x 10S19 C)(161 x 10S12 m) = 7.72 D
3.336 x 10S30 C @ m
0.38 D
% ionic character for HF = x 100% = 4.9%
7.72 D
The calculation of percent ionic character supports the prediction.
8.15 (b) and (c) are correct depictions of hydrogen bonding. (a) and (d) are incorrect because
hydrogen is covalently bonded to C, which is not one of the highly electronegative
elements F, O, or N.

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8.16 Hydrogen bonds are shown as dashed lines.
Because of the three hydrogen bonds, DNA regions that are high in G–C pairs would
have the higher melting point.
8.17 (a) Both CH3F and HNO3 have net dipole moments and dipole–dipole forces.
(b) Only HNO3 can hydrogen bond.
(c) Ar has fewer electrons than Cl2 and CCl4, and has the smallest dispersion forces.
(d) CCl4 is larger than Ar and Cl2, has more electrons and the largest dispersion forces.
8.18 H2S dipole-dipole, dispersion

CH3OH hydrogen bonding, dipole-dipole, dispersion
C2H6 dispersion
Ar dispersion
Ar < C2H6 < H2S < CH3OH
8.19 For He2+ σ*1s 8

σ1s 89
number of number of
S
+ bonding electrons antibonding electrons 2 S 1
He2 Bond order = = = 1/2
2 2
+
He2 should be stable with a bond order of 1/2.

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8.20 The bond order in He22+ is 1, which is greater than the bond order of 1/2 in He2+; therefore
He22+ is predicted to have a stronger bond and be a more stable species
8.21 For B2
σ*2p
π*2p
σ2p
π2p 8 8
σ*2s 89
σ2s 89
number of number of
S
bonding electrons antibonding electrons 4 S 2
B2 Bond order = = = 1
2 2
B2 is paramagnetic because it has two unpaired electrons in the π2p molecular orbitals.
For C2
σ*2p
π*2p
σ2p
π2p 89 89
σ*2s 89
σ2s 89
6 S 2
C2 Bond order = = 2; C2 is diamagnetic because all electrons are paired.
2
8.22 The bond orders are: O22S = 1, O2S = 1.5, O2 = 2, O2+ = 2.5, O22+ = 3.
The order from weakest to strongest bond is: O22S < O2S < O2 < O2+ < O22+.
The order from shortest to longest bond is: O22+ < O2+ < O2 < O2S < O22S.
8.23
H H
C O C O
O O
8.24
8.25 (b), (c), and (e) are chiral.

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8.26 The mirror image of molecule (a) has the same shape as (a) and is identical to it in all
respects, so there is no handedness associated with it. The mirror image of molecule (b)
is different than (b) so there is a handedness to this molecule.
8.27 Only (a), lactic acid, is chiral.
8.28
(a) Cb is the chiral center. There are four different groups attached to it.
(b) 16 σ bonds and 2 π bonds.
(c) and (d) see figure
8.29 (a)
(b) Cc is the chiral center. There are four different groups attached to it.
(c) 32 σ bonds and 6 π bonds.
(d) see figure
(e) All three oxygens and Hc can participate in hydrogen bonding.
8.30 (a) Cc (b) Ca, sp3; Cb, sp2; Cc, sp3; Cd, sp2 (c) yes, because of the O.
Conceptual Problems
8.31 (a) square pyramidal (b) trigonal pyramidal

(c) square planar (d) trigonal planar
8.32 (a) trigonal bipyramidal (b) tetrahedral

(c) square pyramidal (4 ligands in the horizontal plane, including one hidden)
8.33 Molecular model (c) does not have a tetrahedral central atom. It is square planar.
8.34 (a) sp2 (b) sp (c) sp3

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8.35 The expected hybridizations of C and N in urea are sp2 and sp3, respectively. The
expected bond angles are (i) N–C–O and N–C–N, ~120o, and (ii) C–N–H and H–N–H,
~109o. Based on the molecular model, the C and N are both sp2 hybridized and all bond
angles are ~120o.
8.36 (a) C8H9NO2

(b), (c), and (d)
2
H H all C's in ring, sp , trigonal planar
C C H H H
3
O C C N C sp , tetrahedral
H C C C H
2
H H O sp , trigonal planar
8.37 (a) C13H10N2O4

(b), (c), and (d)
H H H All carbons that have only single bonds are

O
H H sp3 hybridized and have tetrahedral
H C C C C
C C geometries. All carbons that have double
N C C O bonds are sp2 hybridized and have trigonal
C C planar geometries.
H C C H C N
H O O H
8.38 The electronegative O atoms are electron rich (red), while the rest of the molecule is
electron poor (blue).
8.39 net
H
H C O
H H
8.40 The N atom is electron rich (red) because of its high electronegativity. The C and H
atoms are electron poor (blue) because they are less electronegative.
8.41 (a) (i) is trans 1,2 dichloroethylene and (ii) is cis 1,2 dichloroethylene
(b) cis 1,2 dichloroethylene has a dipole moment of 2.39 D and trans 1,2
dichloroethylene has a dipole moment of 0.00 D.
(c) The polar molecule, cis 1,2 dichloroethylene, has the higher boiling point.

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Section Problems
The VSEPR Model (Section 8.1)
8.42 From data in Table 8.1:

(a) trigonal planar (b) T-shaped (c) linear (d) square planar
8.43 From data in Table 8.1: (a) linear (b) trigonal pyramidal (c) bent

(a) tetrahedral, 4 (b) octahedral, 6 (c) bent, 3 or 4
(d) linear, 2 or 5 (e) square pyramidal, 6 (f) trigonal pyramidal, 4

(a) seesaw, 5 (b) square planar, 6 (c) trigonal bipyramidal, 5
(d) T shaped, 5 (e) trigonal planar, 3 (f) linear, 2 or 5

(a) SnCl2 2 1 bent
(b) PCl3 3 1 trigonal pyramidal
(c) O3 2 1 bent
(d) SnH4 4 0 tetrahedral

(a) TeBr4 4 1 see saw
(b) COCl2 3 0 trigonal planar
(c) OsO4 4 0 tetrahedral
(d) SCl2 2 2 bent

(a) SbF5 5 0 trigonal bipyramidal
(b) N3− 2 0 linear
(c) SiF5S 5 0 trigonal bipyramidal
(d) CrO42S 4 0 tetrahedral

(a) CIF2S 2 3 linear
(b) CIF2+ 2 2 bent
(c) CIF4S 4 2 square planar

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(a) NO3S 3 0 trigonal planar
(b) BrO3S 3 1 trigonal pyramidal
(c) SeO32S 3 1 trigonal pyramidal
(d) ClO2S 2 2 bent
(a) XeF3+ 3 2 T shaped
(b) SF3+ 3 1 trigonal pyramidal
(c) AsCl4+ 4 0 tetrahedral
(d) ClO2+ 2 1 bent
8.52 (a) In NCl3 the nitrogen is bound to two chlorines and contains one lone pair of electrons.
NCl3 is trigonal pyramidal and the Cl–N–Cl bond angle is approximately 109E.
(b) In CH3+ the carbon is bound to two hydrogens and contains no lone pair of
electrons. The cation has a trigonal planar structure. The H–C–H bond angle is 120E.
(c) In KrF4 the krypton is bound to four fluorines and contains two lone pairs of
electrons. KrF4 is square planar, and the F–Kr–F bond angle is 90E.
(d) In NOCl the nitrogen is bound to one oxygen and one chlorine and contains one lone
pair of electrons. NOCl is bent, and the Cl–N–O bond angle is approximately 120E.
8.53 (a) In PCl6S the phosphorus is bound to six chlorines. There are no lone pairs of
electrons on the phosphorus. PCl6S is octahedral, and the Cl–P–Cl bond angle is 90o.
(b) In ICl2S the iodine is bound to two chlorines and contains three lone pairs of
electrons. ICl2S is linear, and the Cl–I–Cl bond angle is 180o.
(c) In OClF4− the chlorine is bound to four fluorines and one oxygen. There is one lone
pair of electrons on the chlorine. OClF4− is square pyramidal, and the O–Cl–F bond angle
is 90o.
(d) In BeF3− the beryllium is bound to three fluorines. There are no lone pairs of
electrons onthe beryllium. BeF3− is trigonal planar, and the F–Be–F bond angle is 120o.
8.54 H H – Ca – H ~ 120o Cb – Cc – N 180o

H
H – Ca – Cb ~ 120o Ca – Cb – H ~ 120o
C C C N
a b c Ca – Cb – Cc ~ 120o H – Cb – Cc ~ 120o
H
8.55 ~109o
H O H ~109o
H C S C H
H H
~109o

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8.56 F
F C F
F F
S
F F
F
The bond angles are 109.5o around carbon and 90o around S.
8.57 H F
H C O C F
H F
The geometry is tetrahedral around both carbons and bent around the oxygen.
8.58 All six carbons in cyclohexane are bonded to two other carbons and two hydrogens (i.e.,
four charge clouds). The geometry about each carbon is tetrahedral with a C–C–C bond
angle of approximately 109E. Because the geometry about each carbon is tetrahedral, the
cyclohexane ring cannot be flat.
8.59 All six carbon atoms are sp2 hybridized and the bond angles are ~120o. The geometry
about each carbon is trigonal planar.
Valence Bond Theory and Hybridization (Sections 8.2–8.4)
8.60 In a π bond, the shared electrons occupy a region above and below a line connecting the two
nuclei. A σ bond has its shared electrons located along the axis between the two nuclei.
8.61 Using the data here, the difference in energy between a carbon-carbon double bond and a
carbon-carbon single bond is (728 kJ/mol S 350 kJ/mol) = 378 kJ/mol. This represents
the energy of a π bond, which from this data would indicate that a π bond is stronger than
a σ bond. However, numerous other sources list the average carbon-carbon double bond
energy as ~615 kJ/mol, this would lead to a π bond energy of (615 kJ/mol S 350 kJ/mol)
= 265 kJ/mol. This data would indicate that a σ bond is stronger than a π bond.
8.62 See Table 8.2. (a) sp (b) sp2 (c) sp3
8.63 See Table 8.2. (a) tetrahedral (b) trigonal planar (c) linear
8.64 (a) sp3 (b) sp2 (c) sp2 (d) sp2
8.65 (a) sp3 (b) sp3 (c) sp2 (d) sp3

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8.66 O O H O
H O C C C c Cd O H
a b Carbons a, b, and d are sp2 hybridized and carbon c
H is sp3 hybridized.
The bond angles around carbons a, b, and d are ~120o. The bond angles around carbon c
are ~109o. The terminal H–O–C bond angles are ~109o.
8.67 (a) H H O
H N C C O H
H
(b) H–C–H, ~109o; O–C–O, ~120o; H–N–H, ~107o
(c) N, sp3; left C, sp3; right C, sp2
8.68
In Cl2CO the carbon is sp2 hybridized.
8.69
Dipole Moments and Intermolecular Forces (Sections 8.5 and 8.6)
8.70 The molecule needs to have one or more polar covalent bonds, and a molecular shape in
which the bond dipoles and lone pairs are asymmetrically arranged so that their polarities
don’t cancel.
8.71 Each molecule must have a hydrogen atom bonded to a very electronegative atom, and
an electron-rich region (often a lone pair on this electronegative atom).
8.72 (a) CHCl3 has a permanent dipole moment. Dipole-dipole intermolecular forces are
important. London dispersion forces are also present.
(b) CO2 has no dipole moment. London dispersion intermolecular forces are important.
(c) C2H5OH has a permanent dipole moment. Dipole-dipole intermolecular forces and
hydrogen bonding are important. London dispersion forces are also present.
(d) PF5 has no dipole moment. London dispersion intermolecular forces are important.

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8.73 (a) N2 has no dipole-dipole forces

(b) CH3NH2 has the largest hydrogen bond forces
(c) N2 has the largest dispersion forces
8.74 For CH3OH and CH4, dispersion forces are small. CH3OH can hydrogen bond; CH4
cannot. This accounts for the large difference in boiling points.
For 1-decanol and decane, dispersion forces are comparable and relatively large along the
C–H chain. 1-decanol can hydrogen bond; decane cannot. This accounts for the 57 oC
higher boiling point for 1-decanol.
8.75 (a) C8H18 has the larger dispersion forces because of its longer hydrocarbon chain.
(b) HI has the larger dispersion forces because of the larger, more polarizable iodine.
(c) H2Se has the larger dispersion forces because of the more polarizable and less
electronegative Se.
8.76 (a) (b)

..O F
..Xe F
net dipole moment = 0
Cl
.. Cl
net
F
.. F
(c) Cl (d) F
CH3 C H net net dipole moment = 0
B
H F F
8.77 (a) (b)

F N F net H3C N H
F net
H
(c) (d) Cl
F Xe F
net dipole moment = 0 Cl P Cl net dipole moment = 0
Cl
Cl
1D
8.78 µ = Q x r = (1.60 x 10S19 C)(113.2 x 10S12 m) = 5.43 D
3.336 x 10S30 C@ m
0.11 D x 100% = 2.03%
% ionic character for BrCl =
5.43 D
1D
8.79 µ = Q x r = (1.60 x 10S19 C)(121.3 x 10S12 m) = 5.82 D
3.336 x 10S30 C@ m
2.321 D x 100% = 39.9%
% ionic character for ClF =
5.82 D

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8.80 O F Be F
net
F F net dipole moment = 0
OF2 is bent and the individual bond dipole moments add to give the molecule a net dipole
moment.
BeF2 is linear and the individual bond dipole moments point in opposite directions to
cancel each other out. BeF2 has no net dipole moment.
8.81 Cl
Cl P Cl net
Cl Cl P Cl net dipole moment = 0
Cl
Cl
In both PCl3 and PCl5 the P–Cl bond is polar covalent. PCl3 is trigonal pyramidal and the
bond dipoles add to give the molecule a net dipole moment. PCl5 is trigonal bipyramidal
and the bond dipoles cancel. PCl5 has no dipole moment.
8.82 (a) 2 (b) 2

Br Br
Cl Pt Cl Cl Pt Br
Br Cl
8.83 SiF4 is tetrahedral and nonpolar. SF4 has one lone pair of electrons, adopts a see saw
geometry, and is polar.
8.84 H H
N H N H
H H
hydrogen bond
8.85 H
hydrogen bond
O
H CH2
O CH2
C
H2
8.86 Illustrations (ii) and (iii) depict the hydrogen bonding that occurs between methylamine
and water.
8.87 (a) No.

(b) Illustration (ii) depicts the hydrogen bonding that occurs between dimethyl ether and
water.

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Molecular Orbital Theory (Sections 8.7– 8.9)
8.88 Electrons in a bonding molecular orbital spend most of their time in the region between
the two nuclei, helping to bond the atoms together. Electrons in an antibonding
molecular orbital cannot occupy the central region between the nuclei and cannot
contribute to bonding.
8.89 The additive combination of two 2s orbitals is lower in energy than the two isolated 2s
orbitals and is called a bonding molecular orbital. The subtractive combination of two 2s
orbitals is higher in energy than the two isolated 2s orbitals and is called an antibonding
molecular orbital.
8.90 σ*2p
π*2p 8 8 8 89 8
π2p 89 89 89 89 89 89
σ2p 89 89 89
σ*2s 89 89 89
σ2s 89 89 89
O2+ O2 O2S
number of number of
–
bonding electrons antibonding electrons
Bond order =
2
F2
+
bond order = 10 S 7 = 1.5 F2 bond order = 10 S 8 = 1
2 2
F 2S bond order = 10 S 9 = 0.5
2
All are stable with bond orders between 0.5 and 1.5. F2+ and F2− have unpaired electrons.
8.91 σ*2p
π*2p 8
σ2p 8 89 89
π2p 89 89 89 89 89 89
σ*2s 89 89 89
σ2s 89 89 89
N2+ N2 N2S
number of number of
–
Bond order =
2
+ 7 S 2 8 S 2
N2 bond order = = 2.5 N2 bond order = = 3
2 2
S 8 S 3
N2 bond order = = 2.5
2
All are stable with bond orders of either 3 or 2.5. N2+ and N2S contain unpaired electrons.

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8.92 σ*2p
π*2p
σ2p 8
π2p 89 89 89 89
σ*2s 89 89
σ2s 89 89
C2 C 2S
number of number of
–
Bond order =
2
6 S 2
(a) C2 bond order = = 2
2
(b) Add one electron because it will go into a bonding molecular orbital.
S 7 S 2
(c) C2 bond order = = 2.5
2
8.93 σ*2p
π*2p 8 8 8
π2p 89 89 89 89
σ2p 89 89
σ*2s 89 89
σ2s 89 89
O2 O2+
number of number of
–
Bond order =
2
8 S 4
(a) O2 bond order = = 2
2
(b) Remove one electron because it will come out of an anti bonding molecular orbital.
+ 8 S 3
(c) O2 bond order = = 2.5
2
8.94
σ*2p σ*2p 8 σ*2p σ*2p σ*2p
π*2p π*2p 89 89 π*2p 89 89 π*2p π*2p
89 σ2p σ2p 89 89 π2p 89 89 π2p σ2p
89 89 π2p 8 8 π2p 89 σ2p 89 σ2p 8 π2p
89 σ*2s 89 σ*2s 89 σ*2s 89 σ*2s 89 σ*2s
89 σ2s 89 σ2s 89 σ2s 89 σ2s 89 σ2s
(a) C22S (b) C22+ (c) F2S (d) Cl2 (e) Li2+
diamagnetic paramagnetic paramagnetic diamagnetic paramagnetic

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8.95
σ*2p σ*2p σ*2p σ*2p σ*2p
π*2p π*2p π*2p 8 8 π*2p 89 8 π*2p
89 89 π2p σ2p σ2p 89 89 π2p 89 89 π2p
89 σ2p 89 89 π2p 89 8 π2p 89 σ2p 89 σ2p
89 σ*2s 89 σ*2s 89 σ*2s 89 σ*2s 89 σ*2s
89 σ2s 89 σ2s 89 σ2s 89 σ2s 89 σ2s
(a) O22+ (b) N22+ (c) C2+ (d) F22+ (e) Cl2+
diamagnetic diamagnetic paramagnetic paramagnetic paramagnetic
8.96 p orbitals in allyl cation
H allyl cation showing only the σ bonds (each C is sp2 hybridized)
H C C C H
H H
delocalized MO model for π bonding in the allyl cation
8.97 p orbitals in NO2S
N NO2S showing only the σ bonds (N is sp2 hybridized)

O O
delocalized MO model for π bonding in NO2S

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Chapter Problems
8.98 Because chlorine is larger than fluorine, the charge separation is larger in CH3Cl compared
to CH3F, resulting in CH3Cl having a slightly larger dipole moment.
8.99 K2S, ionic (greater lattice energy than CsI because of higher ion charges and smaller ions)
Cl2, dispersion; I2, dispersion (larger and more polarizable than Cl2); NH3, H–
bonding, dipole-dipole; PH3, dipole-dipole; CsI, ionic
rank according to normal boiling points: Cl2 < I2 < PH3 < NH3 < CsI < K2S
8.100
(a) There are 34 σ bonds and 4 π bonds.

(b) and (c) Each C with four single bonds is sp3 hybridized with bond angles of 109.5o.
Each C with a double bond is sp2 hybridized with bond angles of 120o.
(d) The nitrogen is sp3 hybridized.
8.101
(a) There are 32 σ bonds and 6 π bonds.

(b) Each C with four single bonds is sp3 hybridized. Each C with a double bond is sp2
hybridized. Each C with a triple bond is sp hybridized.
(c) and (d) see figure

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8.102 Both the B and N are sp2 hybridized. All bond angles are ~120o. The overall geometry of
the molecule is planar.
8.103 The triply bonded carbon atoms are sp hybridized. The theoretical bond angle for C–C/C
is 180o. Benzyne is so reactive because the C–C/C bond angle is closer to 120o and is
very strained.
8.104 (a) H2C CH2 (b) H (c) O

O C
H Cl S Cl

(a) SbCl3 3 1 trigonal pyramidal (~107o)
AlCl3 3 0 planar (120o)
SbCl3 has the smaller Cl–X–Cl angles.
(b) SO42− 4 0 tetrahedral (~109.5o)
BO33− 3 0 planar (120o)
SO4 has the smaller O–X–O angles.
2−
(c) CCl3S 3 1 trigonal pyramidal (~107o)

PCl6S 6 0 octahedral (90o)
S
PCl6 has the smaller Cl–X–Cl angles.
8.106 (a) (1) (2) (3) 2

O C N O C N O C N
(b) Structure (1) makes the greatest contribution to the resonance hybrid because of the
S1 formal charge on the oxygen. Structure (3) makes the least contribution to the
resonance hybrid because of the +1 formal charge on the oxygen.
(c) and (d) OCNS is linear because the C has 2 charge clouds. It is sp hybridized in all
three resonance structures. It forms two π bonds.
8.107 H O
H C C H 21 σ bonds
C C O
5 π bonds
C C Each C with a double bond is sp2 hybridized.
H C O
The –CH3 carbon is sp3 hybridized.
H C
O CH3
8.108
H C N Xe F Both the carbon and nitrogen are sp hybridized.

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8.109 (a)
(b) There are 6 σ bonds and 3 π bonds.

(c) see figure
(d) The shortest bond is the C–N triple bond.
8.110 Every carbon is sp2 hybridized. There are 18 σ bonds and 5 π bonds.
8.111 H
H C O H
H
H C C H Each C with four single bonds is sp3 hybridized.
N
C N Each C with a double bond is sp2 hybridized.
H C
N C N C O
C
H H H
8.112 H
H O
H O
H C O Each C with four single bonds is sp3 hybridized.
O C C H Each C with a double bond is sp2 hybridized.
H C C
H H O C O
8.113 Li2 σ*2s

σ2s 89
σ*1s 89
σ1s 89
number of number of
S
bonding electrons antibonding electrons 4 S 2
Li2 Bond order = = = 1
2 2
The bond order for Li2 is 1, and the molecule is likely to be stable.
8.114 C22S σ*2p

π*2p
σ2p 89
π2p 89 89
σ*2s 89
σ2s 89

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number of number of
–
Bond order =
2
2S 8 S 2
C2 bond order = = 3 ; there is a triple bond between the two carbons.
2
8.115 (a) σ*3p

π*3p 8 8 89 89
π3p 89 89 89 89
σ3p 89 89
σ*3s 89 89
σ3s 89 89
S2 S22S
(b) S2 would be paramagnetic with two unpaired electrons in the π*3p MOs.
number of number of
–
(c) Bond order =
2
8 S 4
S2 bond order = = 2
2
2S 8 S 6
(d) S2 bond order = = 1
2
The two added electrons go into the antibonding π*3p MOs, the bond order drops from 2 to
1, and the bond length in S22S should be longer than the bond length in S2.
8.116 (a) CO σ*2p

π*2p
σ2p 89
π2p 89 89
σ*2s 89
σ2s 89
(b) All electrons are paired, CO is diamagnetic.
(c)
number of number of
–
Bond order =
2
8 S 2
CO bond order = = 3
2
The bond order here matches that predicted by the electron-dot structure ( C O ).
(d) O O
H C H C
O O

______________________________________________________________________________
8.117 (a) F
F S S F
F
The left S has 5 electron clouds (4 bonding, 1 lone pair). The geometry about this S is
seesaw. The right S has 4 electron clouds (2 bonding, 2 lone pairs). The geometry about
this S is bent.
(b) H O
H C C C C
H O
The left C has 4 electron clouds (4 bonding, 0 lone pairs). The geometry about this C is
tetrahedral. The right C has 3 electron clouds (3 bonding, 0 lone pairs). The geometry
about this C is trigonal planar. The central two C’s have 2 electron clouds (2 bonding, 0
lone pairs). The geometry about these two C’s is linear.
8.118
I I
I I
I
Multiconcept Problems
8.119 (a) 2
O O
O Cr O Cr O
O O
(b) Each Cr atom has 6 pairs of electrons around it. The likely geometry about each Cr
atom is tetrahedral because each Cr has 4 charge clouds.
8.120 (a) H Cl Cl Cl Cl H
C C C C C C
H Cl H H H Cl
polar polar nonpolar
(b) All three molecules are planar. The first two structures are polar because they both
have an unsymmetrical distribution of atoms about the center of the molecule (the middle
of the double bond), and bond polarities do not cancel. Structure 3 is nonpolar because the
H’s and Cl’s, respectively, are symmetrically distributed about the center of the molecule,
both being opposite each other. In this arrangement, bond polarities cancel.

______________________________________________________________________________
(c) 200 nm = 200 x 10S9 m

hc (6.626 x 10S34 J @ s) (3.00 x 108 m / s)
E = = (6.022 x 1023 / mol)
λ S9
200 x 10 m
5
E = 5.99 x 10 J/mol = 599 kJ/mol
(d)
C C
The π bond must be broken before rotation can occur.
8.121 (a) Each carbon is sp2 hybridized.

(b) and (c)
antibonding
antibonding
nonbonding 89 89
bonding 89 89
bonding 89
(d) The cyclooctatetraene dianion has only paired electrons and is diamagnetic.

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Covalent Compounds: Bonding Theories and Molecular Structure

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Covalent Compounds:

8 Bonding Theories and

8.1 Number of Number of

Copyright © 2016 Pearson Education, Ltd. 183

The carbon in formaldehyde is sp2 hybridized.

In CO2 the carbon is sp hybridized.

In HCN the carbon is sp hybridized.

184 Copyright © 2016 Pearson Education, Ltd.

8.12 (a) CF4 (b) CH2F2 (c) CHF3 (d) CH3F

Copyright © 2016 Pearson Education, Ltd. 185

8.16 Hydrogen bonds are shown as dashed lines.

8.18 H2S dipole-dipole, dispersion

8.19 For He2+ σ*1s 8

186 Copyright © 2016 Pearson Education, Ltd.

8.25 (b), (c), and (e) are chiral.

Copyright © 2016 Pearson Education, Ltd. 187

8.27 Only (a), lactic acid, is chiral.

8.31 (a) square pyramidal (b) trigonal pyramidal

8.32 (a) trigonal bipyramidal (b) tetrahedral

8.34 (a) sp2 (b) sp (c) sp3

188 Copyright © 2016 Pearson Education, Ltd.

8.36 (a) C8H9NO2

8.37 (a) C13H10N2O4

H H H All carbons that have only single bonds are

Copyright © 2016 Pearson Education, Ltd. 189

8.42 From data in Table 8.1:

8.44 From data in Table 8.1:

8.45 From data in Table 8.1:

8.46 Number of Number of

8.47 Number of Number of

8.48 Number of Number of

8.49 Number of Number of

190 Copyright © 2016 Pearson Education, Ltd.

8.50 Number of Number of

8.54 H H – Ca – H ~ 120o Cb – Cc – N 180o

Copyright © 2016 Pearson Education, Ltd. 191

Valence Bond Theory and Hybridization (Sections 8.2–8.4)

8.62 See Table 8.2. (a) sp (b) sp2 (c) sp3

8.64 (a) sp3 (b) sp2 (c) sp2 (d) sp2

8.65 (a) sp3 (b) sp3 (c) sp2 (d) sp3

192 Copyright © 2016 Pearson Education, Ltd.

In Cl2CO the carbon is sp2 hybridized.

Dipole Moments and Intermolecular Forces (Sections 8.5 and 8.6)

Copyright © 2016 Pearson Education, Ltd. 193

8.73 (a) N2 has no dipole-dipole forces

8.76 (a) (b)

8.77 (a) (b)

194 Copyright © 2016 Pearson Education, Ltd.

8.82 (a) 2 (b) 2

8.87 (a) No.

Copyright © 2016 Pearson Education, Ltd. 195

Molecular Orbital Theory (Sections 8.7– 8.9)

196 Copyright © 2016 Pearson Education, Ltd.

Copyright © 2016 Pearson Education, Ltd. 197

8.96 p orbitals in allyl cation

H allyl cation showing only the σ bonds (each C is sp2 hybridized)

delocalized MO model for π bonding in the allyl cation

8.97 p orbitals in NO2S