Acids and Bases 2±1

C
Chhaapptteerr 22:: A
Acciiddss aanndd B
Baasseess

A
 A ccoom
mppaarriissoonn ooff B
Brrøønnsstteedd––LLoow
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wiiss aacciiddss aanndd bbaasseess

Type Definition Structural feature Examples

Brønsted–Lowry acid proton donor a proton HCl, H2SO4, H2O,
(2.1) CH3COOH, TsOH
–
Brønsted–Lowry base proton acceptor a lone pair or a
bond OH, –OCH3, H–, –NH2,
(2.1) CH2=CH2
Lewis acid (2.8) electron pair a proton, or an unfilled BF3, AlCl3, HCl,
acceptor valence shell, or a partial CH3COOH, H2O
(+) charge
–
Lewis base (2.8) electron pair a lone pair or a
bond OH, –OCH3, H–, –NH2,
donor CH2=CH2

A
 Acciidd––bbaassee rreeaaccttiioonnss
[1] A Brønsted–Lowry acid donates a proton to a Brønsted–Lowry base (2.2).
H
Example H O H + H N H H O + H N H

acid base conjugate base conjugate acid

proton donor proton acceptor

[2] A Lewis base donates an electron pair to a Lewis acid (2.8).

CH3 CH3
Example CH3 C + Br CH3 C Br
CH3 CH3
Lewis acid Lewis base
electrophile nucleophile

• Electron-rich species react with electron-poor ones.

• Nucleophiles react with electrophiles.

 IIm
 mppoorrttaanntt ffaaccttss
• Definition: pKa = log Ka. The lower the pKa, the stronger the acid (2.3).

NH3 versus H 2O
pKa = 38 pKa = 15.7
lower pKa = stronger acid
Chapter 2±2

• The stronger the acid, the weaker the conjugate base (2.3).

Increasing pKa
Increasing pKa of the conjugate acid
CH2 CH2 CH3COOH HCl
Cl CH3COO CH2 CH
pKa = 44 pKa = 4.8 pKa = –7
Increasing basicity
Increasing acidity

• In proton transfer reactions, equilibrium favors the weaker acid and weaker base (2.4).

H C C H + NH2 H C C + NH3

pKa = 25 pKa = 38
Equilibrium favors
stronger acid weaker acid
the products.
unequal equilibrium arrows

• An acid can be deprotonated by the conjugate base of any acid having a higher pKa (2.4).

Acid pKa Conjugate base

CH3COO–H 4.8 CH3COO—
CH3CH2O–H 16 CH3CH2O— These bases
HCCH 25 HCC— can deprotonate
—
H–H 35 H CH3COO–H.
higher pKa
than
CH3COO–H

 FFaaccttoorrss tthhaatt ddeetteerrm

 miinnee aacciiddiittyy ((22..55))

[1] Element effects (2.5A) The acidity of H
A increases both across a row and down a column
of the periodic table.

C H N H O H H F

Increasing electronegativity
Increasing acidity

H F H Cl H Br H I

Increasing size
Increasing acidity
 Acids and Bases 2±3

[2] Inductive effects (2.5B) The acidity of H
A increases with the presence of electron-
withdrawing groups in A.

CH3CH2OH CH3CH2O
weaker acid No additional electronegative
atoms stabilize the conjugate base.

–
F H

–
+
CF3CH2OH F C C O
stronger acid
F
– H
CF3 withdraws electron density,
stabilizing the conjugate base.

[3] Resonance effects (2.5C) The acidity of H
A increases when the conjugate base A:– is
resonance stabilized.

CH3CH2O H CH3CH2O
ethanol ethoxide
conjugate base
only one Lewis structure

O O O
CH3 C CH3 C CH3 C
OH O O
acetate
acetic acid conjugate base
more acidic
two resonance structures

[4] Hybridization effects The acidity of H
A increases as the percent s-character of
(2.5D) the A:– increases.

CH3CH3 CH2=CH2 H C C H
ethane ethylene acetylene

pKa = 50 pKa = 44 pKa = 25

Increasing acidity
Chapter 2±4

C
Chhaapptteerr 22:: A
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2.1 Brønsted–Lowry acids are proton donors and must contain a hydrogen atom.
Brønsted–Lowry bases are proton acceptors and must have an available electron pair (either a
lone pair or a
bond).
a. HBr NH3 CCl4
acid acid not an acid—no H

b. CH3CH3 (CH3)3CO H C C H
no lone pairs lone pairs
or
bonds on O
not a base base base—
bonds
O
c. CH3CH2OH CH3CH2CH2CH3 CH3 C
OCH3
not a base—no lone pairs
base—lone pairs on O or
bonds base—lone pairs on O's,
bond
acid—contains H atoms acid—contains H atoms acid—contains H atoms

2.2 A Brønsted–Lowry base accepts a proton to form the conjugate acid. A Brønsted–Lowry acid loses
a proton to form the conjugate base.

a. NH3 NH4+ b. HBr Br

Cl HCl HSO4 SO42–

(CH3)2C=O (CH3)2C=OH CH3OH CH3O

2.3 Use the definitions from Answer 2.2.

CH2 CH2 CH2 CH3 CH2 CH2 CH2 CH
ethylene accepts a proton loses a proton
conjugate acid conjugate base

2.4 The Brùnsted±Lowry base accepts a proton to form the conjugate acid. The Brùnsted±Lowry acid
loses a proton to form the conjugate base. Use curved arrows to show the movement of electrons
(NOT protons). Re-draw the starting materials if necessary to clarify the electron movement.

a. H Cl + H2O Cl + H3O

acid base conjugate base conjugate acid

O O
b. C + OCH3 C + CH3OH
CH3 CH2 CH3 CH2
H
acid base conjugate base conjugate acid
 Acids and Bases 2±5

2.5 To draw the products:

[1] Find the acid and base.
[2] Transfer a proton from the acid to the base.
[3] Check that the charges on each side of the arrows are balanced.
O O
a. Cl3C C + O CH3 Cl3C C + HO CH3 (
)1 charge on each side
O H O

acid base

b. H C C H + H H C C + H2 (
)1 charge on each side

acid base

c. CH3 NH2 + H Cl CH3 NH3 + Cl net neutral on each side

base acid

d. CH3CH2 O H + H OSO3H CH3CH2 O H + OSO3H net neutral on each side

H
base acid

2.6 Draw the products in each reaction as in Answer 2.5.

HCl HCl
a. CH3OH CH3OH2 + Cl– c. (CH3)3N (CH3)3NH + Cl–

HCl HCl –
b. (CH3CH2)2O (CH3CH2)2OH + Cl– d. NH NH2 + Cl

2.7 The smaller the pKa, the stronger the acid. The larger Ka, the stronger the acid.

OH CH3
a. CH3CH2CH3 or CH3CH2OH b. or
pKa = 50 pKa = 16
Ka = 10–10 Ka = 10–41
smaller pKa
stronger acid
larger Ka
stronger acid

2.8 To convert from Ka to pKa, take (–) the log of the Ka; pKa = –log Ka.
To convert pKa to Ka, take the antilog of (–) the pKa.

a. Ka = 10–10 Ka = 10–21 Ka = 5.2 x 10–5 b. pKa = 7 pKa = 11 pKa = 3.2

pKa = 10 pKa = 21 pKa = 4.3 Ka = 10–7 Ka = 10–11 Ka = 6.3 x 10–4

Chapter 2±6

2.9 Since strong acids form weak conjugate bases, the basicity of conjugate bases increases with
increasing pKa of their acids. Find the pKa of each acid from Table 2.1 and then rank the acids in
order of increasing pKa. This will also be the order of increasing basicity of their conjugate
bases.

a. Increasing acidity Increasing acidity

b.
H2O, NH3, CH4 HCCH, CH2=CH2, CH4
pKa = 15.7 38 50 pKa = 25 44 50

OH,
NH
CH
CCH,
CH=CH
CH
conjugate bases: 2, 3 conjugate bases: 2, 3

Increasing basicity Increasing basicity

2.10 Use the definitions in Answer 2.9 to compare the acids. The smaller the pKa, the larger the Ka
and the stronger the acid. When a stronger acid dissolves in water, the equilibrium lies farther to
the right.
HCO2H (CH3)3CCO2H
formic acid pivalic acid
pKa = 3.8 pKa = 5.0
a. smaller pKa = larger Ka c. weaker acid = stronger conjugate base
b. smaller pKa = stronger acid
d. stronger acid = equilibrium farther to the right

2.11 To estimate the pKa of the indicated bond, find a similar bond in the pKa table (H bonded to the
same atom with the same hybridization).

H
a. N H b. O H c. BrCH2COO H

For NH3, pKa is 38. For CH3CH2OH, For CH3COOH, pKa is 4.8.
estimated pKa = 38 pKa is 16. estimated pKa = 5
estimated pKa = 16

2.12 Label the acid and the base and then transfer a proton from the acid to the base. To determine if
the reaction will proceed as written, compare the pKa of the acid on the left with the conjugate
acid on the right. The equilibrium always favors the formation of the weaker acid and the
weaker base.

a. CH2 CH2 + H CH2 CH + H2 Equilibrium favors

acid base conjugate base conjugate acid the starting materials.
pKa = 44 pKa = 35
weaker acid
b. CH4 + OH CH3 + H2O
Equilibrium favors
acid base conjugate base conjugate acid the starting materials.
pKa = 50 pKa = 15.7
weaker acid

c. CH3COOH + CH3CH2O CH3COO + CH3CH2OH Equilibrium favors

acid base conjugate base conjugate acid the products.
pKa = 4.8 pKa = 16
weaker acid
 Acids and Bases 2±7

d. Cl + CH3CH2OH HCl + CH3CH2O Equilibrium favors

the starting materials.
base acid conjugate acid conjugate base
pKa = 16 pKa =
7
weaker acid

2.13 An acid can be deprotonated by the conjugate base of any acid with a higher pKa.

CH3COOH
pKa = 4.8 Acid pKa Conjugate base
Any base having a conjugate HCl –7 Cl
not strong enough
acid with a pKa higher than HCCH 25 HCC

strong enough
4.8 can deprotonate this acid. H2 35 H

HCCH Acid pKa Conjugate base

pKa = 25 H2 35 H

All of these acids have a higher pKa NH3 38
NH
2
than HCCH, and a conjugate CH2=CH2 44 CH2=CH

base that can deprotonate HCCH. CH4 50 CH3

2.14 An acid can be deprotonated by the conjugate base of any acid with a higher pKa.

CH3CN
pKa = 25 Base Conjugate acid pKa
Any base having a conjugate NaH H2 35
Na2CO3 HCO3– Only NaH and NaNH2
acid with a pKa higher than 10.2 are strong enough to
NaOH H2O 15.7
25 can deprotonate this acid. deprotonate acetonitrile.
NaNH2 NH3 38
NaHCO3 H2CO3 6.4

2.15 The acidity of H–Z increases across a row and down a column of the periodic table.

a. NH3, H2O b. HBr, HCl c. H2S, HBr

O is farther to the right in Br is farther down Br is farther across and down

the periodic table. the periodic table. the periodic table.
stronger acid stronger acid stronger acid

2.16 Compare the most acidic protons in each compound to determine the stronger acid.

a. CH3CH2CH2NH2 or (CH3)3N b. CH3CH2OCH3 or CH3CH2CH2OH

N–H bond C–H bond C–H bond O–H bond

N is farther to the right in O is farther to the right in
the periodic table. the periodic table.
stronger acid stronger acid
Chapter 2±8

2.17 Look at the element bonded to the acidic H and decide its acidity based on the periodic trends.
Farther right and down the periodic table is more acidic.

most acidic most acidic most acidic

a. CH3CH2CH2CH2OH b. HOCH2CH2CH2NH2 c. (CH3)2NCH2CH2CH2NH2

Molecule contains C–H Molecule contains C–H, Molecule contains C–H and N–H
and O–H bonds. N–H, and O–H bonds. bonds.
O is farther right; therefore, O is farthest right; therefore, N is farther right; therefore,
O–H hydrogen is the most acidic. O–H hydrogen is the most acidic. N–H hydrogen is the most acidic.

2.18 The acidity of HA increases across the periodic table. Pseudoephedrine contains C–H, N–H, and
O–H bonds. The O–H bond is most acidic.

H O H
N

pseudoephedrine

2.19 More electronegative atoms stabilize the conjugate base, making the acid stronger.
Compare the electron-withdrawing groups on the acids below to decide which is a stronger acid
(more electronegative groups = more acidic).

a. ClCH2COOH or FCH2COOH c. CH3COOH or O2NCH2COOH

more acidic more acidic
F is more electronegative than Cl, making the
NO2 is electron withdrawing, making the
O–H bond in the acid on the right more acidic.
O–H bond in the acid on the
right more acidic.
b. Cl2CHCH2OH or Cl2CHCH2CH2OH
Cl is closer Cl is farther from the
to the acidic O–H bond. O–H bond.
more acidic

2.20 More electronegative groups stabilize the conjugate base, making the acid stronger.

HOCH2CO2H CH3CO2H
an
-hydroxy acid acetic acid
The extra OH group contains an electronegative
O, which stabilizes the conjugate base.
stronger acid

2.21 The acidity of an acid increases when the conjugate base is resonance stabilized. Compare the
conjugate bases of acetone and propane to explain why acetone is more acidic.

O O O
base 2 resonance structures
C C C more stable conjugate base
CH3 CH3 CH3 CH2 CH3 CH2
Acetone is more acidic.
acetone One resonance structure places the (–) charge on the
pKa = 19.2 more electronegative O atom. This is especially good.
 Acids and Bases 2±9

base
CH3CH2CH3 CH3CH2CH2 only one Lewis structure
less stable conjugate base
propane
pKa = 50 (Any C–H bond in the starting
material can be removed.)

2.22 The acidity of an acid increases when the conjugate base is resonance stabilized. Acetonitrile
has a resonance-stabilized conjugate base, which accounts for its acidity.

H H H
base The negative charge is stabilized by
H C C N H C C N H C C N
delocalization on the C and N atoms.
H
acetonitrile
(one Lewis structure) Having the (–) charge on the electronegative N atom adds stability.

2.23 Increasing percent s-character makes an acid more acidic. Compare the percent s-character
of the carbon atoms in each of the C–H bonds in question. A stronger acid has a weaker
conjugate base.
H H
a. CH3CH2 C C H or CH3CH2CH2CH2–H b.
or H

sp hybridized C sp3 hybridized C sp2 hybridized C sp3 hybridized C

50% s-character 25% s-character
25% s-character 33% s-character
base more acidic base base more acidic
base

CH3CH2 C C or CH3CH2CH2CH2 H
or
stronger
conjugate base
stronger
conjugate base

2.24 To compare the acids, first look for element effects. Then identify electron-withdrawing
groups, resonance, or hybridization differences.

a. CH3CH2CH3 CH3CH2NH2 CH3CH2OH c. (CH3)3N CH3CH2NH2 CH3CH2OH

C is farthest left in intermediate O is farthest right in C is farthest left in intermediate O is farthest right in
the periodic table. acidity the periodic table. the periodic table. acidity the periodic table.
CH bond is OH bond is CH bond is OH bond is
least acidic. most acidic. least acidic. most acidic.

b. CH3CH2CH2OH CH3CH2COOH BrCH2COOH

OH group intermediate Br is electron withdrawing

least acidic acidity and the conjugate base
is resonance stabilized.
most acidic
Chapter 2±10

2.25 Look at the element bonded to the acidic H and decide its acidity based on the periodic trends.
Farther right and down the periodic table is more acidic.

most acidic
O
most acidic
OH

a. b. c.
COOH O N
H
O
OH most acidic
propranolol
THC ketoprofen
tetrahydrocannabinol The molecule contains C–H The molecule contains C–H,
The molecule contains C–H and O–H bonds. N–H, and O–H bonds.
and O–H bonds. O is farther right; therefore, O is farthest right; therefore,
O is farther right; therefore, O–H hydrogen is the most acidic. O–H hydrogen is the most
O–H hydrogen is the most acidic. acidic.

2.26 Draw the products of proton transfer from the acid to the base.

a. (CH3)2CHO
H + Na+ H (CH3)2CHO Na+ + H2

acid base conjugate base conjugate acid

b. (CH3)2CHO
H + H–OSO3H (CH3)2CHOH2 + HSO4–

base acid conjugate acid conjugate base

c. (CH3)2CHO
H + Li+ –N[CH(CH3)2]2 (CH3)2CHO Li+ + HN[CH(CH3)2]2

acid base conjugate base conjugate acid

(CH3)2CHOH2 + –OCOCH
d. (CH3)2CHO
H + H–OCOCH3 3
base acid conjugate acid conjugate base

2.27 To cross a cell membrane, amphetamine must be in its neutral (not ionic) form.

CH3 protonation CH3 deprotonation CH3

CH2 C H CH2 C H CH2 C H
NH2 by HCl in NH2 in the intestines NH2
the stomach
amphetamine H absorption here
in the neutral form

2.28 Lewis bases are electron pair donors: they contain a lone pair or a
bond.
a. NH3 b. CH3CH2CH3 c. H d. H C C H
yes - has no - no lone pair yes - has yes - has
lone pair or π bond lone pair 2 π bonds

2.29 Lewis acids are electron pair acceptors. Most Lewis acids contain a proton or an unfilled
valence shell of electrons.

a. BBr3 b. CH3CH2OH c. (CH3)3C+ d. Br

yes yes yes no
unfilled valence shell contains a proton unfilled valence shell no proton
on B on C no unfilled valence shell
 Acids and Bases 2±11

2.30 Label the Lewis acid and Lewis base and then draw the curved arrows.

new bond
F CH3
a. BF3 + CH3 O CH3 F B O b. (CH3)2CH + OH (CH3)2CHOH
F CH3
Lewis acid Lewis base Lewis acid Lewis base
unfilled valence shell lone pairs unfilled valence lone pairs
on B on O shell on C on O

2.31 A Lewis acid is also called an electrophile. When a Lewis base reacts with an electrophile other
than a proton, it is called a nucleophile. Label the electrophile and nucleophile in the starting
materials and then draw the products.
Cl
Br
Cl Al Cl
Br B Br O
O
a. CH3CH2 O CH2CH3 + BBr3 CH3CH2 O CH2CH3 b. C + AlCl3
CH3 CH3 C
Lewis base Lewis acid Lewis acid CH3 CH3
Lewis base electrophile
nucleophile electrophile nucleophile unfilled valence shell
lone pairs unfilled valence shell lone pairs
on O on B on Al
on O

2.32 Draw the product of each reaction by using an electron pair of the Lewis base to form a new
bond to the Lewis acid.

CH3
CH3 B CH3
a. CH3CH2 N CH2CH3 + B(CH3)3 CH3CH2 N CH2CH3
CH2CH3 CH2CH3
Lewis base Lewis acid
nucleophile electrophile
lone pair unfilled valence shell
on N on B
CH3
CH3 C CH3
b. CH3CH2 N CH2CH3 + +C(CH )
3 3 CH3CH2 N CH2CH3
CH2CH3 CH2CH3
Lewis base Lewis acid
nucleophile electrophile
lone pair unfilled valence shell
on N on C
Cl
Cl Al Cl
c. CH3CH2 N CH2CH3 + AlCl3 CH3CH2 N CH2CH3
CH2CH3 CH2CH3
Lewis base Lewis acid
nucleophile electrophile
lone pair unfilled valence shell
on N on Al
Chapter 2±12

2.33 Curved arrows begin at the Lewis base and point towards the Lewis acid.

new C–H bond

CH3 H H CH3
CH2 C + H2 O H C C + H2O
H H H
Lewis base Lewis acid
contains a
bond contains a proton

2.34 To draw the conjugate acid of a Brønsted–Lowry base, add a proton to the base.
H CH3CH2NH2CH3
H d. CH3CH2NHCH3
a. H2O H3O
H
H H CH3 O CH3
b. NH2 NH3 e. CH3OCH3

H H
c. HCO3 H2CO3 f. CH3COO CH3COOH

2.35 To draw the conjugate base of a Brønsted–Lowry acid, remove a proton from the acid.

H H
a. HCN CN d. HC CH HC C

H CO32 H CH3CH2COO
b. HCO3 e. CH3CH2COOH

H H
c. (CH3)2NH2 (CH3)2NH f. CH3SO3H CH3SO3

2.36 To draw the products of an acid–base reaction, transfer a proton from the acid (H2SO4 in this
case) to the base.

+
a. OH + H OSO3H O H + HSO4
H

+
b. NH2 + H OSO3H NH3 + HSO4

+ H OSO3H + + HSO4
c. OCH3 OCH3
H

+ H +
d. N CH3 + H OSO3H N HSO4
CH3

2.37 To draw the products of an acid–base reaction, transfer a proton from the acid to the base (–OH
in this case).

a. O H + K+ –OH O K+ + H2O
 Acids and Bases 2±13

O O
b. + K+ –OH + H2O
O H O K+

c. C C H + K+ –OH C C K+ + H2O

d. CH3 O H + K+ –OH CH3 O K+ + H2O

2.38 Label the Brønsted–Lowry acid and Brønsted–Lowry base in the starting materials and transfer
a proton from the acid to the base for the products.

a. CH3O H NH2 CH3O + NH3

acid base conjugate base conjugate acid

O O
b. CH3CH2 C + O CH3 CH3CH2 C + HO CH3
O H O
acid base conjugate acid
conjugate base
c.
CH3CH2 C C H + H CH3CH2 C C + H2
acid base conjugate base conjugate acid

d. (CH3CH2)3N + H Cl (CH3CH2)3NH + Cl
base acid conjugate acid conjugate base

e. CH3CH2 O H + H Br CH3CH2 O H + Br

base acid H
conjugate acid conjugate base

f. CH3C C + H OH CH3C CH + HO
base acid conjugate acid conjugate base

2.39 Label the acid and base in the starting materials and then draw the products of proton transfer
from acid to base.
O O
C H C
O O
a. + NH3 + NH4
acid base
O
O
b. F3C C + +
Na+ HCO3 F3C C H2CO3
acid O H base O Na

c. CH3 C C H + Na+ NH2 CH3 C C Na + NH3

acid base
Chapter 2±14

d. CH3CH2 O H + K+ OH CH3CH2 O K + H2O

acid base

O H
e. CH3 N H + CH3 S O H CH3 N H + CH3 SO3
CH3 O CH3
base acid
O O H
f. C H OSO3H C + HSO4
CH3 CH3 CH3 CH3
base acid

2.40 Label the acid and base in the starting materials and then draw the products of proton transfer
from acid to base.

a. CH2CH(CH3)NH2 + H Cl CH2CH(CH3)NH3 Cl

base acid

b. CH2CH(CH3)N H + Na+ H CH2CH(CH3)NH H2

H +
acid base Na

2.41 Draw the products of proton transfer from acid to base.

H CH H CH
3 3

COO–H COO– Na+

a. + Na+ OH + H2O
CH3O CH3O
acid base

H CH2CH2NHCH3 H CH2CH2NH2CH3

b. O CF3 + H–Cl O CF3 + Cl

base acid

2.42 Draw the products of proton transfer from acid to base.

CF3 CF3

CH2CH(CH3)NHCH2CH3 + H OCOCH3 CH2CH(CH3)NHCH2CH3 + OCOCH3

H
base acid

CH2C(CH3)2NH2 + H OCOCH3 CH2C(CH3)2NH3 + OCOCH3

base acid
 Acids and Bases 2±15

2.43 To convert pKa to Ka, take the antilog of (–) the pKa.

a. H2S b. ClCH2COOH c. HCN

pKa = 7.0 pKa = 2.8 pKa = 9.1
Ka = 10–7 Ka = 1.6 x 10–3 Ka = 7.9 x 10–10

2.44 To convert from Ka to pKa, take (–) the log of the Ka; pKa = –log Ka.

+ +
a. CH2NH3 b. NH3 c. CF3COOH

Ka = 4.7 x 10–10 Ka = 2.3 x 10–5 Ka = 5.9 x 10–1

pKa = 9.3 pKa = 4.6 pKa = 0.23

2.45 An acid can be deprotonated by the conjugate base of any acid with a higher pKa.
a. H2O Acid pKa Conjugate base
pKa = 15.7 CH3CH2OH 16 CH3CH2O

Any base with a conjugate HCCH 25 HCC
Strong
acid having a pKa higher than
15.7 can deprotonate it. H2 35 H
enough to
NH3 38
NH
2
deprotonate
H2O.
CH2=CH2 44 CH2=CH

CH4 50 CH3

c. CH4
b. NH3
Acid pKa Conjugate base pKa = 50
pKa = 38
44 CH2=CH
Strong enough to There is no base with a
Any base with a conjugate CH2=CH2
CH4 50 CH3
deprotonate NH3. conjugate acid having a pKa
acid having a pKa higher than
higher than 50 in the
38 can deprotonate it.
table.

2.46 An acid can be deprotonated by the conjugate base of any acid with a higher pKa.

Base Conjugate acid pKa

CH3CH2CH2C
CH H2 O H3O+ –1.7
pKa = 25 NaOH H2O 15.7
Any base having a conjugate NaNH2 NH3 38
NH3 NH4+ Only NaNH2, NaH, and
acid with a pKa higher than 9.4
NaH H2 CH3Li are strong enough
25 can deprotonate this acid. 35 to deprotonate the acid.
CH3Li CH4 50

–
2.47 OH can deprotonate any acid with a pKa < 15.7.
a. HCOOH b. H2S c. CH3 d. CH3NH2

pKa = 3.8 pKa = 7.0 pKa = 41 pKa = 40

stronger acid stronger acid weaker acid weaker acid
deprotonated deprotonated

These acids are too weak to be

deprotonated by
OH.
Chapter 2±16

2.48 Draw the products and then compare the pKa of the acid on the left and the conjugate acid on the
right. The equilibrium lies towards the side having the acid with a higher pKa (weaker
acid).
O O
CF3 C + OCH2CH3 products favored
a. CF3 C + HOCH2CH3
O H O pKa = 16
pKa = 0.2

O O
b. CH3CH2 C + Na+ Cl CH3CH2 C + HCl starting material favored
O H O Na+ pKa = –7
pKa = ~5
+
c. (CH3)3COH + H
OSO3H (CH3)3COH2 + HSO4 products favored

pKa = –9 pKa = ~ –3

O H O Na+
d. + Na+ HCO + H2CO3
3 starting material favored
pKa = 6.4
pKa = 10

e. H C C H + Li+ CH2CH3 H C C Li+ + CH3CH3

products favored
pKa = 25 pKa = 50

+
f. CH3NH2 + H
OSO3H CH3NH3 + HSO4 products favored

pKa = –9 pKa = 10.7

2.49 Compare element effects first and then resonance, hybridization, and electron-withdrawing
groups to determine the relative strengths of the acids.

a. Acidity increases across a row:
NH3 < H2O < HF
b. Acidity increases down a column:
HF < HCl < HBr
c. increasing acidity:
OH < H2O < H3O +
f. increasing acidity: H2O < H2S < HCl
Compare HCl and SH bonds first:
acidity increases across a row.
H–Cl is more acidic.
Compare OH and SH bonds:
acidity increases down a column.
SH is more acidic.
g. CH3CH2CH3, ClCH2CH2OH, CH3CH2OH

d. increasing acidity: NH3 < H2O < H2S only C–H bonds O–H bond and O–H bond
Compare NH and OH bonds first: weakest acid electron-withdrawing Cl
acidity increases across a row. strongest acid
OH is more acidic. increasing acidity: CH3CH2CH3 < CH3CH2OH < ClCH2CH2OH

Then compare OH and SH bonds: h. HC CCH2CH3 CH3CH2CH2CH3 CH3C CCH3

acidity increases down a column.
H H
SH is more acidic.
sp C–H all sp3 C–H sp2 C–H
e. Acidity increases across a row: strongest acid weakest acid
CH3CH3 < CH3NH2 < CH3OH
increasing acidity: CH3CH2CH2CH3 < CH3CH=CHCH3 < HC CCH2CH3
 Acids and Bases 2±17

2.50 The strongest acid has the weakest conjugate base.

a. Draw the conjugate acid. d. Draw the conjugate acid.

Increasing acidity of conjugate acids: Increasing acidity of conjugate acids:
CH3CH3 < CH3NH2 < CH3OH
increasing basicity: CH3O < CH3NH < CH3CH2 CH2CH3 < CH CH2 < C CH
b. Draw the conjugate acid.
Increasing acidity of conjugate acids: increasing basicity:
CH4 < H2O < HBr
C C < CH CH < CH2CH2
increasing basicity: Br < HO < CH3
c. Draw the conjugate acid.
Increasing acidity of conjugate acids:
CH3CH2OH < CH3COOH < ClCH2COOH
increasing basicity: ClCH2COO < CH3COO < CH3CH2O

2.51 More electronegative atoms stabilize the conjugate base by an electron-withdrawing

inductive effect, making the acid stronger. Thus, an O atom increases the acidity of an acid.

NH2 O NH2

pKa = 11.1 The O atom makes this cation the stronger acid.
pKa = 8.33

2.52 In both molecules the OH proton is the most acidic H. In addition, compare the percent s-
character of the carbon atoms in each molecule. Nearby C’s with a higher percent s-character can
help to stabilize the conjugate base.

HC CCO2H CH3CH2CO2H
pKa = 1.8 pKa = 4.9
The sp hybridized C's of the triple bond have a higher percent
s-character than an sp3 hybridized C, so they pull electron
density towards them, stabilizing the conjugate base.
stronger acid

2.53
CH3 O
CH3CH2CH2 H CH2 C C The negative charge on O
CH2 H CH3 CH2 H is good. This makes this
resonance structure
pKa = 50 pKa = 43 pKa = 19.2 especially good.
conjugate base:
CH3 CH3 O O
CH3CH2CH2 CH2 C CH2 C C C
CH2 CH2 CH3 CH2 CH3 CH2

one Lewis structure two resonance structures two resonance structures

weakest acid negative charge delocalized negative charge delocalized
on two carbons on one O and one C
strongest acid
Chapter 2±18

2.54 To draw the conjugate acid, look for the most basic site and protonate it. To draw the conjugate
base, look for the most acidic site and remove a proton.

NH3 OH NH2 OH NH2 O

conjugate acid A most acidic proton conjugate base

most basic site

2.55 Remove the most acidic proton to form the conjugate base. Protonate the most basic electron
pair to form the conjugate acid.
only O–H bond most basic electron pair N
most acidic proton O

OCH3
Increasing basicity:
COOH O
O N
O
ibuprofen cocaine
conjugate base: conjugate acid: H N O

OCH3
COO
O

2.56 A lower pKa means a stronger acid. The pKa is low for the C–H bond in CH3NO2 due to
resonance stabilization of the conjugate base.

H O H O H O H O
B
H C N H C N H C N H C N
H O O O O

The negative charge is delocalized on the

electronegative O atom. This stabilizes
the conjugate base.

2.57 Compare the isomers.

O
dimethyl ether CH3 CH3 CH3CH2OH ethanol

All H's are on C. One O–H bond

O–H bonds are more acidic
than C–H bonds.
more acidic
 Acids and Bases 2±19

2.58 Compare the Lewis structures of the conjugate bases when each H is removed. The more stable
base makes the proton more acidic.

H
B
N N N
H H H
O O O
O N O N O N
OH H OH H OH H
more acidic proton The negative charge on N is
H H
stabilized by resonance.
N N This conjugate base is more
H H
stable, so it is formed by
O O removal of the more acidic H.
O N O N
OH H OH
B
less acidic proton no resonance stabilization
formed from the weaker acid

2.59 Draw the conjugate base to determine the most acidic hydrogen.

O O O

O O O
H H H H

Resonance stabilization of the conjugate base resonance-stabilized conjugate base

makes this the most acidic proton.
In Appendix A, the closest compound for
comparison is CH3CO2CH2CH3 with a pKa of
24.5; therefore, the estimated pKa of ethyl
butanoate is 25.

2.60 Look at the element bonded to the acidic H and decide its acidity based on the periodic trends.
Farther right across a row and down a column of the periodic table is more acidic.

F most acidic
OH
H
a. b. O N
c.
CO2H O NH
O CH3O

most acidic O most acidic

The molecule contains C–H and O–H The molecule contains C–H and N–H The molecule contains C–H, N–H,
bonds. O is farther right in the bonds. N is farther right in the and O–H bonds. O is farthest right in
periodic table; therefore, the O–H periodic table; therefore, the N–H the periodic table; therefore, the O–H
hydrogen is the most acidic. hydrogen is the most acidic. hydrogen is the most acidic.
Chapter 2±20

2.61 Use element effects, inductive effects, and resonance to determine which protons are the most
acidic. The H’s of the CH3 group are least acidic since they are bonded to an sp3 hybridized C
and the conjugate base formed by their removal is not resonance stabilized.

O
lactic acid c>b>a
OH Both O–H protons [(b) and (c)] are more acidic than the C–H proton
H OH (a) by the element effect. The most acidic proton has added
c resonance stabilization when it is removed, making its conjugate
base the most stable.
a b
O O
resonance stabilization
conjugate base O O negative charge on O in both resonance structures
by loss of (c): This makes (c) most acidic.
H OH H OH

conjugate base OH no resonance stabilization, but

by loss of (b): H O negative charge on O, an electronegative atom

O O
This conjugate base has two
conjugate base OH OH resonance structures, but one
by loss of (a): places a negative charge on C.
OH OH

2.62 Lewis bases are electron pair donors: they contain a lone pair or a
bond. Brønsted–Lowry
bases are proton acceptors: to accept a proton they need a lone pair or a
bond. This means
Lewis bases are also Brønsted–Lowry bases.

O lone pairs on O
a. C both c. d.
H H

b. CH3 Cl lone pairs on Cl neither = no lone pairs
bonds

both or
bond both

2.63 A Lewis acid is an electron pair acceptor and usually contains a proton or an unfilled valence
shell of electrons. A Brønsted–Lowry acid is a proton donor and must contain a hydrogen
atom. All Brùnsted±Lowry acids are Lewis acids, though the reverse may not be true.

a. H3O+ b. Cl3C+ c. BCl3 d. BF4

both - Lewis acid - Lewis acid - neither -
contains a H unfilled valence unfilled valence no H or unfilled
shell on C shell on B valence shell
 Acids and Bases 2±21

2.64 Label the Lewis acid and Lewis base and then draw the products.

Cl O O
a. Cl + BCl3 Cl B Cl c. C + OH CH3 C Cl
CH3 Cl new bond
Lewis base Lewis acid Cl OH
Lewis base
new bond
Lewis acid

CH3 CH3 CH3 CH3

b. + H OSO3H + HSO4
C C C C H
CH3 CH3 CH3 CH3
Lewis acid
new bond
Lewis base

2.65 A Lewis acid is also called an electrophile. When a Lewis base reacts with an electrophile other
than a proton, it is called a nucleophile. Label the electrophile and nucleophile in the starting
materials and then draw the products.

BF3
a. CH3CH2OH + BF3 OH2
CH3CH2 O H + H2O
nucleophile electrophile d.
nucleophile
electrophile
AlCl3
b. CH3SCH3 + AlCl3
CH3 S CH3 Br
nucleophile electrophile e. Br Br + FeBr3 Br Br Fe Br
CH3 CH3 nucleophile electrophile Br
c. C O + BF3 C O BF3
CH3 CH3
nucleophile electrophile

2.66 Draw the product of each reaction.

CH2CH3 CH2CH3 CH2CH3 CH2CH3

a. CH3CH2 C + H2O CH3CH2 C OH2 d. CH3CH2 C + NH3 CH3CH2 C NH3
CH2CH3 CH2CH3 CH2CH3 CH2CH3

CH2CH3 CH3CH2 CH3 CH2CH3 CH3CH2 CH3

b. CH3CH2 C + CH3OH CH3CH2 C OH e. CH3CH2 C + (CH3)2NH CH3CH2 C NHCH3
CH2CH3 CH2CH3 CH2CH3 CH2CH3

CH2CH3 CH3CH2 CH3

c. CH3CH2 C + (CH3)2O CH3CH2 C O CH3
CH2CH3 CH2CH3

2.67
nucleophile
OH OH2 Br
proton transfer
a. H Br + Br + H2O

electrophile
Chapter 2±22

Br
b. H Br proton transfer + Br

electrophile
nucleophile

H H Br
c. + Br Br + Br proton transfer + HBr
H H H
nucleophile electrophile

2.68 Draw the products of each reaction. In part (a), –OH pulls off a proton and thus acts as a
Brùnsted–Lowry base. In part (b), –OH attacks a carbon and thus acts as a Lewis base.

+
a. CH2 C(CH3)2 H2O + CH2=C(CH3)2 b. OH + (CH3)3C+ (CH3)3COH
H
OH

2.69 Answer each question about esmolol.

most acidic
second most acidic
OH Esmolol contains C–H, N–H, and O–H bonds.
H
a. O N Since acidity increases across a row of the
periodic table, the OH bond is most acidic,
CH3O followed by the NH bond.

O esmolol

O H Na+ O
H H
b. O N Na+ H O N
+ H2
CH3O CH3O

O O

O H OH H H
H
c. O N H Cl O N
+ Cl–
CH3O CH3O

O O

OH
H
d, e, f. O N All sp2 C are indicated with an arrow.
* * The N is the only trigonal pyramidal atom.
* * *
CH3O The
+ C's are indicated with a (*).
* *
O
 Acids and Bases 2±23

2.70 Draw the product of protonation of either O or N and compare the conjugate acids. When
acetamide reacts with an acid, the O atom is protonated because it results in a resonance-
stabilized conjugate acid.
H H resonance stabilization of the + charge
O O
O is more readily protonated
protonate O C C because the product is
CH3 NH2 CH3 NH2
O resonance stabilized.
C
CH3 NH2 O
protonate N
C no other resonance structure
acetamide CH3 NH3

2.71
O O O O O O O O

HO OH HO O O O O O
pKa = 2.86 + pKa = 5.70

This group destabilizes the

O O second negative charge.

HO O
+
COO
now acts as an electron-donor group
+ stabilizes the (
) charge
which destabilizes the conjugate base,
of the conjugate base.
making removal of the second proton more
The nearby COOH group serves difficult and thus it is less acidic than CH3COOH.
as an electron-withdrawing group to
stabilize the negative charge. This
makes the first proton more acidic
than CH3COOH.

2.72 The COOH group of glycine gives up a proton to the basic NH2 group to form the zwitterion.

O O
proton transfer
a. acts as a base NH2CH2 C NH3CH2 C
OH acts as an acid O
glycine zwitterion form
b. O H Cl O
NH3CH2 C NH3CH2 C + Cl

O OH
most basic site

O Na+ O
OH
c. H NH2 CH2 C NH2CH2 C + Na+ + H2O
O O

most acidic site

Chapter 2±24

2.73 Use curved arrows to show how the reaction occurs.

O O O O
H
[1] H H

OH

O
O

[2]
+ OH

H O H H

Protonate the negative charge on this carbon to form the product.

2.74 Compare the OH bonds in Vitamin C and decide which one is the most acidic.

OH
HO O O
Vitamin C
This is the most acidic proton ascorbic acid
since the conjugate base is HO OH
most resonance stabilized.
loss of H+
OH OH OH
HO O O HO O O HO O O

O OH O OH O OH

Removal of either The most delocalized anion

of these H's does not with 3 resonance structures.
give a resonance-
stabilized anion.
OH OH OH
HO O O loss of H+ HO O O HO O O

HO OH HO O HO O
only 2 resonance structures

This proton is less acidic since its conjugate base is less

resonance stabilized.