Section Four Acids and Bases

Question 4.1
Rank the following species in terms of their basicity and explain your reasoning.

H
H C

H N

H O

Answer 4.1
Species in general do not like to bear a charge. Atoms with greater electronegativities (more affinity for
electron density) will bear a negative charge more readily than those atoms that are relatively
electropositive. Recall that basicity is a measure of affinity for a proton. The most basic of the above
species will be that which is least capable or least willing to bear a negative charge. That will the the
most electropositive (or least electronegative) of the atoms above: carbon. The methyl carbanion (one
of the most basic species known) shown on the left is approximately 20 orders of magnitude more basic
that the amide anion (center) which is about 22 orders of magnitude more basic that the hydroxide anion,
the weakest of these bases.
Question 4.2
Carboxylic acids and sulfonic acids are quite similar in many respects.

O
H3C S

O
OH

O
Methanesulfonic acid

C
H3C
OH
Acetic acid

Both are Brnsted acids. Methanesulfonic acid has a pKa of about -0.5 (Ka = 3). Acetic acid is a much
weaker acid with a pKa of 4.82 (Ka = 4.8 x 10-5). Explain why they have different acid strengths.
Answer 4.2
Both species have conjugate bases that are resonance-stabilized anions:

O
H3C S O
O

O
H3C S O
O

O
H3C S O
O

Methanesulfonate anion (the conjugate base of

methanesulfonic acid)

H3C

O
C

H3C

O
C

The acetate anion (the conjugate base of

acetic acid)

Remember: the more stable the base, then the stronger its conjugate acid. In this case, the
methanesulfonate anion is stabilized to a greater extent than the acetate anion. There are three resonance
structures, all of which have complete octets and all of which have the negative charge on an
electronegative oxygen atom. (In general, the more resonance structures, the more stable the species.)
The acetate anion has only two such resonance structures and is not stabilized to the same extent as a
result.
Question 4.3
The compound shown below is surprisingly acidic for an alcohol. Why?

OH
Squaric acid

OH

Answer 4.3
The conjugate base of Squaric acid (Squarate?) is resonance stabilized such that it very much resembles
a carboxylic acid in its behaviour. Squaric acid has a pKa of about 1.5 - pretty strong even for a
carboxylic acid. The anion has the following resonance structures:

OH

OH

Question 4.4
Give a mechanism for the following trivial Brnsted acid/base reaction using arrows to show the
electron flow. This particular mechanistic process is going to come in handy in the next question.

H3C

H
+ H2O

H3C

H3C

+ H 3O

H3C

Answer 4.4

H3C

OH2

H
O

H3C

+ H 3O

H3C

Question 4.5 (4 marks)

OH

OH

Phenol

Answer 4.5

H3C

p-Nitrophenol is 1000 times more acidic than

phenol.
a.) Write resonance structures that show
how the conjugate base is resonance stabilized.
b.) Indicate which resonance structure(s) is/are:
i.) most stable.
ii.) next most stable
iii.) which resonance structures are degenerate.

N
1

4
5
2
3
i) The most stable structure is 1, which has its special benzene ring intact.
ii.) Structures 2-4 all have the same number of bonds and charges, but no. 4 has the negative charge on
O, rather than C, O being more electronegative.
Question 4.6 (2 marks)
Which of the following molecules is more acidic? Explain your reasoning.

O
Ethanoic Acid
C
H
H3C
O

Ethanol

H3C

H2
C

O
+ H2O

H3C

+ H2O

H3C

H2
C

+ H3O

+ H3O

Answer 4.6
The conjugate base of ethanol has a negative charge localized on oxygen. The conjugate base of acetic
acid, however, can stablize the negative charge by delocalizing it over two O atoms:

O
H3C

H3C

H3C

C
O

Composite of
two resonance
structures.

Question 4.7 (3 marks)

Account for the trend in acidity presented in the following three compounds.

O
ClH2C
pKa

C
2.8

O
OH

H3C

O
OH

4.76

H3CH 2C

OH

4.87

Answer 4.8
Shown are the composites of the resonance structures of the conjugate bases of each acid. The first is
inductively stabilized by the Cl atom which, by virtue of its electronegativity, withdraws some of the
excess charge of the carboxylate through the -bonds. This stabilizes the conj. base rendering the conj.
acid more acidic. In the last case, the terminal methyl group has exactly the opposite effect. The
hydrogen atoms attached to the carbons are relatively electropositive and therefore push electron density
toward the carboxylate, destabilizing albeit slightly. This is also an inductive effect.

Cl

O
H2C

pKa

H3C

H3CH2C

2.8

4.76

C
O

4.87

Question 4.9 (3 marks)

Acetone is 30 orders of magnitude more acidic than propane. Indeed, its pKa is much closer to that of
ethanol (within two orders of magnitude). Explain why this is the case.

O
H3C

CH3

Acetone

H3C

H2
C

CH3

Propane

Answer 4.9
We must look at the conjugate bases of these two species.

H2
C

H3C

O
CH2

H3C

O
CH2

H3C

CH2

The conjugate base of propane has a negative charge localized on a carbon atom. Carbon is not very
electronegative and hates to bear a negative charge. The conjugate base of acetone, in contrast, can
delocalize its charge over a C atom and an O atom. It is the second resonance structure that is the more
important contributor because it has the negative charge on an electronegative atom. So, two factors
influence the acidity of acetone - delocalization, and delocalization onto an electronegative element.
The pKa of acetone is close to that of ethanol because the second resonance structure shown for
acetone is, indeed, the conjugate base of an alcohol.
Question 4.10
Acetylacetone (below) is much more acidic (over 40 orders of magnitude more!) than most
hydrocarbons. When acetylacetone acts as an acid, it loses one of the two hydrogens shown in bold.
Draw the conjugate base of acetylacetone and explain, using resonance structures, why it is such a
strong C-H acid.

O
H3C

CH3
H H

pKa = 50

H3C

CH3
H H
pKa = 9.0

Answer 4.10
The conjugate base of acetylacetone has a negative charge that can be delocalized as shown by the
following three resonance structures, two of which have the negative charge on an O atom.

H3C

O
CH3

H3C

O
CH3

H3C

CH3
H

Delocalization helps stabilize the negative charge, but delocalization onto electronegative atoms helps
even more.
Question 4.11 (six marks)
a.) Give a mechanism for the forward reaction by adding reaction arrows to the scheme that show the
movement of electrons.

O
H

O
NH2

C H
H2
pKa = 19

CH2

NH3
pKa = 36

b.) Which side does this equilibrium favour: left or right?

c.) Acetaldehyde is unusually acidic for a C-H acid. In fact, the pKa of acetaldehyde is much closer to
that of ethanol, CH3CH2OH, (in which an O-H bond is broken, pKa = 17) than to the pKa of methane,
CH4, (in which a C-H bond is broken, pKa = 50). Look carefully at the conjugate base of acetaldehyde
and rationalize why acetaldehyde is more acidic than methane, and why its pKa is so close to that of
ethanol.
Answer 4.11
a)

O
H

C H
H2
pKa = 19

O
NH2
H

NH3
CH2

pKa = 36

b) Acid/base equilibria favour the side of the weakest acid. The right side in this case.
c) Vide supra.
Question 4.12
Shown below are pyridine, imidazole and their conjugate acids. The pKas of the conjugate acids are
given.
i) Imidazole protonates on only one of the two nitrogens as shown. Why that particular nitrogen?
ii) Imidazole is more basic than expected for this type of molecule, as comparison with pyridine shows.
Offer an explanation.

H
H

H+

pKa = 5.2

N
pKa = 7

Pyridine
H
Imidazole
Answer 4.12
i) The conjugate acid of imidazole is stabilized by resonance:

H
N

H+

H
N

H
N

N
H

Delocalization of the positive charge stabilizes the acid, making its conjugate base more basic than most
amines. This is only possible if protonation occurs on the sp2 hybridized N atom.
Question 4.13
i) Why are carboxylic acids more acidic than alcohols?
ii) Why is the alcohol shown below (pKa = 8) almost as acidic as a carboxylic acid?

H2
C
O
H3C
pKa = 17

C
O
H3C
pKa = 5

H3C
pKa = 8

Answer 4.13
i) The conjugate bases of ethanol and acetic acid respectively:

H2
C
H3C

O
O

H3C

C
O

H3C

The former involves a localized charge, the latter is stabilized by resonance, enhancing the acidity of its
conjugate acid.
ii) Three resonance structures can be drawn for the conjugate base of the alcohol given. Like the
carboxylate anion, in two structures the negative charge is found on O atoms (relatively electronegative).

O
C
H3C

O
O

C
H3C

H3C

C
O

Question 4.14 (five marks)

Rank the following molecules in order of decreasing acidity. Explain your reasoning.

ClH2C
1

C
H2

OH

H3C
2

CH
Cl

OH

ClH2C
3

C
H2

H2
C

OH

Answer 4.14
Molecules 1 and 2 have conjugate bases that are resonance stabilized whereas the conjugate base of 3 is
not. The conjugate base of 2 is also stabilized by the electron-withdrawing inductive effect of the
chlorine which helps reduce some of the negative charge. Molecule 1's conjugate base is also stabilized
in this way but the inductive effect is weaker since the Cl is further away.