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AND THEIR MECHANISMS: ACIDS AND BASES

SOLUTIONS TO PROBLEMS

F
3.1 (a) CH3

CH3

B F

F
Cl

Cl
+

(b) CH3

Cl

Al

CH3

Cl

Al Cl

Cl

Cl

Cl
F

F
(c) CH3

CH3

CH3

F
3.2 (a) Lewis base

(d) Lewis base

(b) Lewis acid

(e) Lewis acid

(c) Lewis base

(f) Lewis base

H
3.3 CH3

CH3
Lewis base

3.4 (a) K a =

B F

CH3

CH3

CH3

Lewis acid

[H3 O+ ][HCO2 ]
= 1.77 104
[HCO2 H]

Let x = [H3 O+ ] = [HCO2 ] at equilibrium

then, 0.1 x = [HCO2 H] at equilibrium
but, since the K a is very small, x will be very small and 0.1 x ' 0.1
35

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AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

Therefore,
(x)(x)
= 1.77 104
0.1
x 2 = 1.77 105
x = 0.0042 = [H3 O+ ] = [HCO2 ]

(b) % Ionized =
=

[H3 O+ ]
100
0.1

or

[HCO2 ]
100
0.1

.0042
100 = 4.2%
0.1

3.5 (a) pK a = log 107 = (7) = 7

(b) pK a = log 5.0 = 0.669
(c) Since the acid with a K a = 5 has a larger K a , it is the stronger acid.
3.6 When H3 O+ acts as an acid in aqueous solution, the equation is
H3 O+ + H2 O H2 O + H3 O+
and K a is
[H2 O][H3 O+ ]
= [H2 O]
[H3 O+ ]
The molar concentration of H2 O in pure H2 O, that is [H2 O] = 55.5; therefore, K a = 55.5
Ka =

The pK a is
pK a = log 55.5 = 1.74

H
3.7

(a)

(c)

(d)

HO
(b)

O
3.8 The pK a of the methylaminium ion is equal to 10.6 (Section 3.6C). Since the pK a of the
anilinium ion is equal to 4.6, the anilinium ion is a stronger acid than the methylaminium
ion, and aniline (C6 H5 NH2 ) is a weaker base than methylamine (CH3 NH2 ).
3.9

NH2

Na+

C
O

NH3

O
3.10 R

R
OH

Na+

C
O

+
HO

OH

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ACIDS AND BASES

37

3.11 (a) Negative. Because the atoms are constrained to one molecule in the product, they have
to become more ordered.
(b) Approximately zero.
(c) Positive. Because the atoms are in two separate product molecules, they become more
disordered.
3.12 (a) If K eq = 1
then,
log K eq = 0 =
1G = 0

1G
2.303RT

(b) If K eq = 10
then,
1G
2.303RT
1G = (2.303)(0.008314 kJ mol1 K1 )(298 K) = 5.71 kJ mol1

log K eq = 1 =

(c) 1G = 1H T 1S
1G = 1H = 5.71 kJ mol1 if 1S = 0
3.13 Structures A and B make equal contributions to the overall hybrid. This means that the
carbon-oxygen bonds should be the same length and that the oxygens should bear equal
negative charges.

O
CH3

CH3

C
O
A

O
B

O
CH3

O
hybrid

3.14 (a) CHCl2 CO2 H would be the stronger acid because the electron-withdrawing inductive
effect of two chlorine atoms would make its hydroxyl proton more positive. The electronwithdrawing effect of the two chlorine atoms would also stabilize the dichloroacetate ion
more effectively by dispersing its negative charge more extensively.
(b) CCl3 CO2 H would be the stronger acid for reasons similar to those given in (a), except
here there are three versus two electron-withdrawing chlorine atoms involved.
(c) CH2 FCO2 H would be the stronger acid because the electron-withdrawing effect of a
fluorine atom is greater than that of a bromine atom (fluorine is more electronegative).
(d) CH2 FCO2 H is the stronger acid because the fluorine atom is nearer the carboxyl group
and is, therefore, better able to exert its electron-withdrawing inductive effect. (Remember:
Inductive effects weaken steadily as the distance between the substituent and the acidic
group increases.)
3.15 All compounds containing oxygen and most compounds containing nitrogen will have an
unshared electron pair on their oxygen or nitrogen atom. These compounds can, therefore,
act as bases and accept a proton from concentrated sulfuric acid. When they accept a proton,
these compounds become either oxonium ions or ammonium ions, and having become ionic,
they are soluble in the polar medium of sulfuric acid. The only nitrogen compounds that do

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AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

not have an electron pair on their nitrogen atom are quaternary ammonium compounds, and
these, already being ionic, also dissolve in the polar medium of concentrated sulfuric acid.

3.16 (a) CH3O

H
Stronger base
(from NaH)

NH2
Stronger base
(from NaNH2)

Stronger acid
pKa = 16
(b) CH3CH2O

Stronger acid
pKa = 16
(c) H

H
Stronger acid
pK a = 38

methanol

CH3O
Weaker
base

ethanol

CH3CH2O
Weaker
base

hexane

CH2CH3

NH2

H2
Weaker acid
pKa = 35

NH3
Weaker acid
pKa = 38

CH3CH3

Weaker
base

Stronger base
(from CH3CH2Li)

Weaker acid
pKa = 50

H
(d) H

H
Stronger acid
pK a = 9.2
(from NH4Cl)

(e) H

liq. NH3

NH2

NH3

Stronger base
(from NaNH2)

Weaker
base

H2O

OC(CH3)3

Stronger base
[from (CH3)3CONa]

Stronger acid
pK a = 15.7

NH3
Weaker acid
pKa = 38

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+ HOC(CH3)3

Weaker
base

Weaker acid
pKa = 18

(f) No appreciable acid-base reaction would occur because HO is not a strong enough base
to remove a proton from (CH3 )3 COH.
3.17 (a) HC

(b) HC

CH

hexane

NaH

CNa

D2O

(c) CH3CH2Li

D2O

(d) CH3CH2OH

(e) CH3CH2ONa
(f ) CH3CH2CH2Li

HC
hexane

NaH

hexane

T2O

+
+

HC

D2O

hexane

CNa

H2

CD

NaOD

CH3CH2D

LiOD

CH3CH2ONa

H2

CH3CH2OT

NaOT

CH3CH2CH2D

LiOD

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ACIDS AND BASES

39

Problems
Brnsted-Lowry Acids and Bases
3.18 (a) NH2 (the amide ion)

(b) H
(c) H

3.19

(d) H

(the hydroxide ion)

(e) CH3O

(the ethynide ion)

(the methoxide ion)

(f ) H2O (water)

(the hydride ion)

NH2 > H > H

3.20 (a) H2 SO4

> CH3O

> H2O

(d) NH3

(b) H3 O+

(e) CH3 CH3

(c) CH3 NH3 +

(f) CH3 CO2 H

3.21 H2 SO4 > H3 O+ > CH3 CO2 H > CH3 NH3 + > NH3 > CH3 CH3

Lewis Acids and Bases

Cl
3.22 (a) CH3CH2

Cl

AlCl3

Lewis
base

CH3CH2

Cl

Al Cl

Lewis
acid

Cl
F

(b) CH3

OH +

Lewis
base

BF3

CH3

Lewis
acid

C+

B F
F

CH3
+

H2O

CH3
Lewis
acid

CH3
(c) CH3

Lewis
base

CH3

OH2

CH3

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AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

Curved-Arrow Notation
3.23 (a) CH3

OH

CH3

Cl

H
H
(b) CH3

NH2 +

CH3

Cl

H
H

H
(c)

C
H

3.24 (a)

(b)

(c)

H
+

O BF3

O
+ BF3

+
O BF3

+ BF3

H + H

(d)

H Cl

H + CH3CH2CH2CH2

O H

Cl

Li

CH3CH2

O
(b) C6H5

+H

+ H

O
O

Li+ + CH3CH2CH2CH3

O
3.25 (a) CH3CH2

C6H5

(c) No appreciable acid-base reaction takes place because CH3CH2ONa is too weak a
base to remove a proton from ethyne.
(d) H

(e) CH3

CH2

CH2CH3
(from
LiCH2CH3)
+

hexane

CH2CH3

hexane

CH3

CH2

+ CH3CH3

+ CH3CH3

(from
LiCH2CH3)

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ACIDS AND BASES

41

Acid-Base Strength and Equilibrium

3.26 Because the proton attached to the highly electronegative oxygen atom of CH3 OH is much
more acidic than the protons attached to the much less electronegative carbon atom.

3.27 CH3CH2

liq. NH3

CH3CH2

+H

3.28 (a) pK a = log 1.77 104 = 4 0.248 = 3.75

(b) K a = 1013
3.29 (a) HB is the stronger acid because it has the smaller pK a .
(b) Yes. Since A is the stronger base and HB is the stronger acid, the following acid-base
reaction will take place.

A + H B
Stronger
Stronger
base
acid
pKa =10

3.30 (a) C6H5

then

C6H5

(b) CH3

CH

H + NaNH2

B
A H +
Weaker
Weaker
acid
base
pKa = 20

ether

C6H5

Na+ + T2O

C6H5

H + NaH

CH3

CH

Na+ + NH3
T + NaOT

O Na+ + H2

CH3

CH3
then
CH3

CH

O Na+ + D2O

CH3

(c) CH3CH2CH2OH + NaH

then
CH3CH2CH2O Na+ + D2O

CH

D + NaOD

CH3

CH3

+
CH3CH2CH2O Na + H2

CH3CH2CH2OD + NaOD

3.31 (a) CH3 CH2 OH > CH3 CH2 NH2 > CH3 CH2 CH3
Oxygen is more electronegative than nitrogen, which is more electronegative than carbon.
The O-H bond is most polarized, the N-H bond is next, and the C-H bond is least polarized.
(b) CH3 CH2 O < CH3 CH2 NH < CH3 CH2 CH2
The weaker the acid, the stronger the conjugate base.

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AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

3.32 (a) CH3C

CH > CH3CH

CH2 > CH3CH2CH3

(b) CH3CHClCO2H > CH3CH2CO2H > CH3CH2CH2OH

+

(c) CH3CH2OH2 > CH3CH2OH > CH3OCH3

+
3.33 (a) CH3NH3 < CH3NH2 < CH3NH

(b) CH3O < CH3NH < CH3CH2

(c) CH3C

CH < CH3CH2CH2

C < CH3CH

General Problems
3.34 The acidic hydrogens must be attached to oxygen atoms. In H3 PO3 , one hydrogen is bonded
to a phosphorus atom:

O
H

O
3.35 (a) H

+
O

H
O

+
O

O
(c) H

CH3

CH3

CH3

+
O

CH3

CH3 + I

CH3
(e) H

O
H

O
O

(d) H

CH3

+
O

O
(b) H

CH2

C
CH3

CH3
Cl

CH2

+ Cl
CH3 + H

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ACIDS AND BASES

43

3.36 (a) Assume that the acidic and basic groups of glycine in its two forms have acidities and
basicities similar to those of acetic acid and methylamine. Then consider the equilibrium
between the two forms:

CH2

N
H
Stronger
base

CH2

H
Weaker
acid

Stronger
acid

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base

We see that the ionic form contains the groups that are the weaker acid and weaker base.
The equilibrium, therefore, will favor this form.
(b) The high melting point shows that the ionic structure better represents glycine.
3.37 (a) The second carboxyl group of malonic acid acts as an electron-withdrawing group
and stabilizes the conjugate base formed (i.e., HO2 CCH2 CO2 ) when malonic acid loses a
proton. [Any factor that stabilizes the conjugate base of an acid always increases the strength
of the acid (Section 3.11C).] An important factor here may be an entropy effect as explained
in Section 3.10.
(b) When O2 CCH2 CO2 H loses a proton, it forms a dianion, O2 CCH2 CO2 . This dianion
is destabilized by having two negative charges in close proximity.
3.38 HB is the stronger acid.
3.39

log Keq
pKa
pKa
pKa

H TS
6.3 kJ mol1 (298 K)(0.0084 kJ mol1K1)
3.8 kJ mol1
log Ka = pKa = G
2.303RT
G
=
2.303RT
3.8 kJ mol 1
=
(2.303)(0.008314 kJ mol1K1)(298 K)

=
=
=
=

= 0.66

3.40 The dianion is a hybrid of the following resonance structures:

O

If we mentally fashion a hybrid of these structures, we see that each carbon-carbon bond
is a single bond in three structures and a double bond in one. Each carbon-oxygen bond is
a double bond in two structures and a single bond in two structures. Therefore, we would
expect all of the carbon-carbon bonds to be equivalent and of the same length, and exactly
the same can be said for the carbon-oxygen bonds.

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AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

Challenge Problems
3.41 (a) A is CH3 CH2 S

B is CH3 OH

C is CH3 CH2 SCH2 CH2 O

D is CH3 CH2 SCH2 CH2 OH

E is OH

(b) CH3CH2

H + CH3

CH3CH2

S + CH2 CH2
O

CH3CH2

CH2CH2

+ H

CH3CH2

CH3CH2

CH3CH2

+ CH3

CH2CH2

H
S

CH2CH2

H + H

CH3(CH2)8O Li + + CH3(CH2)8 D

3.42 (a) CH3(CH2)8OD + CH3(CH2)8Li

Hexane could be used as solvent. Liquid ammonia and ethanol could not because
they would compete with CH3 (CH2 )8 OD and generate mostly non-deuterio-labelled
CH3 (CH2 )7 CH3 .
(b) NH2 + CH3C

CH

NH3 + CH3C

Hexane or liquid ammonia could be used; ethanol is too acidic and would lead to
CH3 CH2 O (ethoxide ion) instead of the desired alkynide ion.
+

NH3 + Cl

NH2

(c) HCl +

Hexane or ethanol could be used; liquid ammonia is too strong a base and would lead
to NH4 + instead of the desired anilinium ion.

3.43 (a,b)

O
CH3

C
H

N
CH3

C
H

CH3

N
CH3

The uncharged structure on the left is the more important resonance form.
(c) Since DMF does not bind with (solvate) anions, their electron density remains high and
their size small, both of which make nucleophiles more reactive.

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ACIDS AND BASES

3.44 (a)

45

O
+

(b)

O
(c)

NH2

CH3

H3C
O

+ NH3

C
H3C

CH2

H3C

CH2

+ D2O

+ OD

C
CH2D

H3C

3.45 The most acidic hydrogen atoms in formamide are bonded to the nitrogen atom. They
are acidic due to the electron-withdrawing effect of the carbonyl group and the fact that
the resulting conjugate base can be stabilized by resonance delocalization of the negative
charge into the carbonyl group. The electrostatic potential map shows deep blue color near
the hydrogen atoms bonded to the nitrogen atom, consistent with their relative acidity.

QUIZ
3.1 Which of the following is the strongest acid?
(a) CH3 CH2 CO2 H

(b) CH3 CH3

(c) CH3 CH2 OH

(d) CH2

CH2

3.2 Which of the following is the strongest base?

(a) CH3 ONa

(b) NaNH2

(c) CH3 CH2 Li

(d) NaOH

(e) CH3 CO2 Na

3.3 Dissolving NaNH2 in water will give:

(a) A solution containing solvated Na+ and NH2 ions.
(b) A solution containing solvated Na+ ions, OH ions, and NH3 .
(c) NH3 and metallic Na.
(d) Solvated Na+ ions and hydrogen gas.
(e) None of the above.

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AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

3.4 Which base is strong enough to convert (CH3 )3 COH into (CH3 )3 CONa in a reaction that
goes to completion?
(b) CH3 CH2 Na

(a) NaNH2

(c) NaOH

(d) CH3 CO2 Na

(e) More than one of the above.

3.5 Which would be the strongest acid?
(a) CH3 CH2 CH2 CO2 H

(b) CH3 CH2 CHFCO2 H

(d) CH2 FCH2 CH2 CO2 H

(e) CH3 CH2 CH2 CH2 OH

(c) CH3 CHFCH2 CO2 H

3.6 Which would be the weakest base?

(a) CH3 CO2 Na

(b) CF3 CO2 Na

(c) CHF2 CO2 Na

(d) CH2 FCO2 Na

3.7 What acid-base reaction (if any) would occur when NaF is dissolved in H2 SO4 ?
3.8 The pK a of CH3 NH3 + equals 10.6; the pK a of (CH3 )2 NH2 + equals 10.7. Which is the
stronger base, CH3 NH2 or (CH3 )2 NH?
3.9 Supply the missing reagents.

(a)
CH3CH2C

hexane

CH +

CH3CH2C

Li

+ CH3CH3

(b)

CH3CH2C

CD + LiOD

3.10 Supply the missing intermediates and reagents.

(a)
CH3Br

2 Li

LiBr

(b)

CH3
CH3CHCH2OT

(c)
+

LiOT

T2O

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