Chapter 16 Carboxylic Acids and

Esters
16.1
Carboxylic Acids

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1
Carboxylic Acids

A carboxylic acid
 Contains a carboxyl group, which is a carbonyl group
(C=O) attached to a hydroxyl group (—OH).
 Has the carboxyl group on carbon 1.
carbonyl group
O

CH3 — C—OH hydroxyl group or CH3COOH
carboxyl group

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Models of Carboxylic Acids
 The three-dimensional models show the geometry
of atoms in carboxylic acid molecules.

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 IUPAC Names
The IUPAC names of carboxylic acids
 Replace the -e in the alkane name with -oic acid.
CH4 methane HCOOH methanoic acid
CH3—CH3 ethane CH3—COOH ethanoic acid
 Number substituents from the carboxyl carbon 1.
CH3 O
| ║
CH3—CH—CH2—C—OH
4 3 2 1

3-methylbutanoic acid
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Common Names

The common names of simple carboxylic acids

 Are formic acid (1C), acetic acid (2C), propionic acid
(3C), and butyric acid (4C).
HCOOH formic acid
CH3—COOH acetic acid
 Locate substituents using , , γ for the carbon
atoms adjacent to the carboxyl carbon.
CH3
γ | 
CH3—CH—CH2—COOH
3-methylbutanoic acid (-methylbutryic acid)
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Alpha Hydroxy Acids
Alpha hydroxy acids
(AHAs)
 Occur naturally in
fruit, milk, and
sugarcane.
 Are used in skin
care products.

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Names and Sources of Some
Carboxylic Acids
TABLE 16.1

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Common Carboxylic Acids

Methanoic acid (formic acid)

O
║
H─C─OH

ethanoic acid (acetic acid)

O
║
CH3─C─OH
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Aromatic Carboxylic Acids

Benzoic acid
 Is the aromatic carboxylic acid.
 Locates substituents by assigning 1 to the carbon
attached to the carboxyl group.
 Has common names that assign prefixes ortho,
meta, and para for 2 substituents.
ortho 1, 2 location
meta 1, 3 location
para 1, 4 location

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Aromatic Carboxylic Acids
O
O O

C OH C OH
C OH

Cl
NH2

benzoic acid 3-chlorobenzoic acid 4-aminobenzoic acid

m-chlorobenzoic acid p-aminobenzoic acid

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Learning Check

Give the IUPAC and common names:

A. CH3—COOH

CH3
|
B. CH3—CH—COOH

COOH
C.
Br

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Solution

A. CH3—COOH ethanoic acid (acetic acid)

CH3
|
B. CH3—CH—COOH 2-methylpropanoic acid
(-methylpropionic acid)
COOH
C. 2-bromobenzoic acid
Br (o-bromobenzoic acid)

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Learning Check
Give the IUPAC and common names for the following:
A. CH3─CH2─COOH
CH3
|
B. CH3─CH─CH2─COOH
C. O

C OH

Br
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Solution
A. CH3─CH2─COOH propanoic acid
(propionic acid)
CH3
|
B. CH3─CH─CH2─COOH 3-methylbutanoic acid
O (β-methylbutyric acid)

C. C OH 3-bromobenzoic acid
(m-bromobenzoic acid)

Br
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 Preparation of Carboxylic Acids
 Carboxylic acids can be prepared by oxidizing
primary alcohols or aldehydes.
 The oxidation of ethanol produces ethanoic acid
(acetic acid).

OH O O
| [O] || [O] ||
CH3—CH2 CH3—C—H CH3—C—OH

ethanol ethanal ethanoic acid

(ethyl alcohol) (acetaldehyde) (acetic acid)

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Learning Check
What alcohol could be used to prepare the following:

1. butanoic acid

2. propanoic acid

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Solution
What alcohol could be used to prepare the following:
[O] [O]
1. butanol butanal butanoic acid

[O] [O]
2. 1-propanol propanal propanoic acid

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Chapter 16 Carboxylic Acids and
Esters

16.2
Properties of Carboxylic Acids

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Polarity of Carboxylic Acids
Carboxylic acids
 Are strongly polar.
 Have two polar groups:
hydroxyl (−OH) and carbonyl (C=O).

δ-
O
║δ+ δ- δ+
CH3CO H

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Boiling Points of Carboxylic Acids

The boiling points of carboxylic acids

 Are higher than alcohols, ketones, and aldehydes of
similar mass.

 Are high because they form dimers in which

hydrogen bonds form between the polar groups in the
two carboxyl groups.

O H—O
|| |
CH3—C C—CH3
| ||
O—H O
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A dimer of acetic acid
Comparison of Boiling Points
Compound Molar Mass Boiling Point
O
║
CH3−CH2−C−H 58 49°C

CH3−CH2−CH2−OH 60 97°C

O
║
CH3−C−OH 60 118°C
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Solubility in Water
Carboxylic acids Water molecules
 Form hydrogen
bonds with many
water molecules.

 With 1-4 carbon

atoms are very
soluble in water.

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Boiling Points and Solubility

TABLE 16.2

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 Acidity of Carboxylic Acids
Carboxylic acids
 Are weak acids.
 Ionize in water to produce carboxylate ions
and hydronium ions.
O O
║ ║
CH3−C−OH + H2O CH3−C−O– + H3O+

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Acid Dissociation Constants

TABLE 16.3
Carboxylic acids
 Have small Ka values.
 Exist mostly as molecules
and a few ions in aqueous
solutions.

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Neutralization of Carboxylic Acids
Carboxylic acid salts
 Are a product of the neutralization of a carboxylic acid
with a strong base.
CH3—COOH + NaOH CH3—COO– Na+ + H2O
acetic acid sodium acetate
(carboxylic acid salt)
 Are used as preservatives and flavor enhancers.

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Learning Check

Write the equation for the reaction of propanoic acid with

A. water

B. KOH

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Solution
Write the equation for the reaction of propanoic acid with
A. water
CH3—CH2—COOH + H2O CH3—CH2—COO– + H3O+

B. KOH
CH3—CH2—COOH + KOH CH3—CH2—COO– K+ + H2O

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Chapter 16 Carboxylic Acids and
Esters
16.3 Esters
16.4 Naming Esters

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Esters
In an ester,
 The H in the carboxyl group is replaced
with an alkyl group.

O

CH3 — C—O—CH3
ester group

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Esterification

Esterification is
 The reaction of a carboxylic acid and alcohol in the
presence of an acid catalyst to produce an ester.
O
 H+
CH3—C—OH + H—O—CH2—CH3

O

CH3—C—O—CH2—CH3 + H2O
ethyl acetate (an ester)

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Learning Check
Write the equation for the reaction of propanoic acid
and methanol in the presence of an acid catalyst.

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Solution
Write the equation for the reaction of propanoic acid
and methanol in the presence of an acid catalyst.
O
 H+
CH3—CH2—C—OH + H—O—CH3
propanoic acid methanol
O

CH3—CH2—C—O—CH3 + H2O

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Naming Esters
The name of an ester contains the names of
 The alkyl group from the alcohol.
 The carbon chain from the acid with –ate ending.
from alcohol from acid
O
methyl 
CH3— O—C —CH3
ethanoate (acetate)
IUPAC: methyl ethanoate
common: methyl acetate

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Ester Products
Aspirin O
 Is used to relieve pain and C OH
reduce inflammation. O
 Is an ester of salicylic acid
O C CH3
and acetic acid.

Oil of wintergreen
O
 Is used to soothe sore
muscles. C O CH3
 Is an ester of salicylic acid
and methanol. OH

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Esters in Plants
TABLE 16.4
Esters give
flowers and
fruits their
pleasant
fragrances and
flavors.

36
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Learning Check

Give the IUPAC and common names of the following

compound, which is responsible for the flavor and odor
of pears.

O

CH3—C—O—CH2—CH2—CH3

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Solution
Give the IUPAC and common names of the following
compound, which is responsible for the flavor and odor
of pears.
from 1-propanol
O

CH3—C—O—CH2—CH2—CH3

Propyl ethanoate (IUPAC)

Propyl acetate (common)

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Learning Check

Name the following esters:

O
║
A. CH3—CH2—CH2—C—O—CH3

O

B. CH3—CH2 —C—O—CH2—CH3

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Solution

A. Methyl butanoate (methyl butyrate)

B. Ethyl propanoate (methyl propionate)

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Learning Check

Write the structure of the following esters:

A. Ethyl pentanoate

B. Propyl butyrate

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Solution

A. Ethyl pentanoate
O
║
CH3—CH2—CH2—CH2—C—O—CH2—CH3

B. Propyl butyrate
O
║
CH3—CH2—CH2—C—O—CH2—CH2—CH3

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Chapter 16 Carboxylic Acids and
Esters
16.5
Properties of Esters

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Acid Hydrolysis of Esters

In acid hydrolysis
 An ester reacts with water to produce a carboxylic
acid and an alcohol.
 An acid catalyst is required.
O
 H+
H—C—O—CH2—CH3 + H2O

O

H—C—OH + H—O—CH2—CH3

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Base Hydrolysis (Saponification)
Base hydrolysis (also called saponification)
 Is the reaction of an ester with a strong base.
 Produces the salt of the carboxylic acid and an
alcohol.
O
||
CH3—C—O—CH2—CH3 + NaOH
O

CH3—C—O– Na+ + HO—CH2—CH3
salt of carboxylic acid alcohol

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“Soaps”
The base hydrolysis of long chain fatty acids
produces acid salts called “soaps”.

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Cleaning Action of Soap
A soap
 Contains a nonpolar
end that dissolves in
nonpolar fats and
oils, and a polar end
that dissolves in
water.
 Forms groups of
soap molecules
called micelles that
dissolve in water
and are washed
away.
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Learning Check

Write the organic products when methyl acetate reacts

with
A. Water and an acid catalyst

B. KOH

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Solution
Write the organic products when methyl acetate reacts
with:
A. Water and an acid catalyst
O

CH3—C—OH + HO—CH3

B. KOH
O

CH3—C—O– K+ + HO—CH3

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