Carboxylic Acids

What Are Carboxylic Acids?

• The functional group of a carboxylic acid is
a carboxyl group, which can be represented
in any one of three ways:
 How Do We Name Carboxylic Acids?
A. IUPAC Names
• Drop the final -e from the name of the parent
alkane and replace it by -oic acid.
• Number the chain beginning with the carbon
of the carboxyl group.
• When a carboxylic acid also contains an -OH
(hydroxyl) group, we indicate its presence by
adding the prefix hydroxy-.
• When it contains a primary (1°) amine, we
indicate the presence of the -NH2 group by
amino-.
• To name dicarboxylic acids, we add the suffix -
dioic acid to the name of the parent alkane that
contains both carboxyl groups. The numbers of
the carboxyl carbons are not indicated because
they can be only at the ends of the parent chain.
Formic acid was first obtained in 1670 from the
destructive distillation of ants, whose Latin genus is
Formica. It is one of the components of the venom
injected by stinging ants.
B. Common Names
• Lists of several unbranched aliphatic carboxylic acids found
in the biological world and the common name.
• The unbranched carboxylic acids
having between 12 and 20 carbon atoms
are known as fatty acids.
• Those with 16, 18, and 20 carbon atoms
are particularly abundant in animal fats
and vegetable oils, and the phospholipid
components of biological membranes.
• When common names are used, the Greek
letters alpha (α), beta (ß), gamma (γ), and
so forth are often added as a prefix to locate
substituents.
Example: IUPAC Names of Carboxylic Acids

• Write the IUPAC name for each carboxylic acid:

Example. IUPAC Names of Carboxylic
Acids
• Write the IUPAC name for each carboxylic acid:

2-ethylpentanoic acid 4-Hydroxybenzoic acid

trans-3-Phenyl-2-propenoic acid (cinnamic acid)

What Are the Physical Properties
of Carboxylic Acids?
• A major feature of carboxylic acids is the
polarity of the carboxyl group.
• This group contains three polar covalent
bonds: C=O, C-O, and O-H. The polarity of
these bonds determines the major physical
properties of carboxylic acids.
• Carboxylic acids have significantly higher
boiling points than other types of organic
compounds of comparable molecular weight
• Carboxylic acids, aldehydes, and ketones
of comparable molecular weight.
Polarity of a carboxyl group.
Boiling Points and Solubilities in Water of Two Groups of
Compounds of Comparable Molecular Weight.
What Are Soaps and Detergents?
A. Fatty Acids
• long, unbranched chain carboxylic acids,
most commonly consisting of 12 to 20
carbons.
• derived from the hydrolysis of animal fats,
vegetable oils, and the phospholipids of
biological membranes.
The Most Abundant Fatty Acids in Animal Fats,
Vegetable Oils, and Biological Membranes.
Characteristics of the most abundant fatty acids
in higher plants and animals:
1. Nearly all fatty acids have an even number of
carbon atoms, most between 12 and 20, in an
unbranched chain.
2. The three most abundant fatty acids in nature are
palmitic acid (16:0), stearic acid (18:0), and oleic
acid (18:1).
3. In most unsaturated fatty acids, the cis isomer
predominates; the trans isomer is rare.
4. Unsaturated fatty acids have lower melting
points than their saturated counterparts. The
greater the degree of unsaturation, the lower the
melting point.
Fatty acids can be divided into two groups:
saturated and unsaturated.

• Saturated fatty acids have only carbon–carbon

single bonds in their hydrocarbon chains.

• Unsaturated fatty acids have at least one C=C

double bond in the chain.
• Saturated fatty acids are solids at room
temperature because the regular nature of their
hydrocarbon chains allows their molecules to pack
together in close parallel alignment.
• All common cis unsaturated fatty acids are liquids at room
temperature because the cis double bonds interrupt the
regular packing of the chains and the London dispersion
forces act over only shorter segments of the chains so
that less energy is required to melt them.
Trans Fatty Acids: What Are They and
How Do You Avoid Them?
Structure and Preparation of Soaps

Saponification
• (Latin: saponem, “soap”).
• The hydrolysis of an ester in aqueous NaOH or
KOH to an alcohol and the sodium or potassium
salt of a carboxylic acid.
A. Soap micelles
B. How Soap Cleans
• Soap owes its remarkable cleansing properties
to its ability to act as an emulsifying agent.
• Thus, in water, soap molecules spontaneously
cluster into micelles.

A spherical arrangement of molecules in an

aqueous solution such that their
hydrophobic (water-hating) parts are
shielded from the aqueous environment and
their hydrophilic (water-loving) parts are on
the surface of the sphere and in contact
with the aqueous environment.
• Soaps, however, have their disadvantages,
foremost among which is the fact that they form
water-insoluble salts when used in water containing
Ca(II), Mg(II), or Fe(III) ions (hard water).

These water-insoluble salts like calcium, magnesium, and iron

salts of fatty acids create problems, including rings around the
bathtub, films that spoil the luster of hair, and grayness and
roughness that build up on textiles after repeated washings.
C. Synthetic Detergents
• contains sulfonate (-SO3-) group instead of a
carboxylate (-COO-) group.
• calcium, magnesium, and iron salts of
alkylsulfonic acids (R-SO3H) are much more
soluble in water than comparable salts of
fatty acids.
• linear alkylbenzenesulfonates (LAS)
- most widely used synthetic detergents
-4-dodecylbenzenesulfonate
• To prepare this type of detergent, a linear
alkylbenzene is treated with sulfuric acid to form
an alkylbenzenesulfonic acid, followed by the
neutralization of the sulfonic acid with sodium
hydroxide.
• Among the most common additives to detergent
preparations are foam stabilizers, bleaches, and
optical brighteners.

• The most common bleach is sodium perborate

tetrahydrate, which decomposes at
temperatures higher than 50°C to give hydrogen
peroxide, the actual bleaching agent.
 What Are the Characteristic
Reactions of Carboxylic Acids?
A. Acidity
• Carboxylic acids are weak acids. Values of Ka
for most unsubstituted aliphatic and aromatic
carboxylic acids fall within the range of 10-4 to
10-5 (pKa 5 = 4.0 - 5.0). The value of Ka for
acetic acid, for example, is 1.74 X 10-5; its pKa is
4.76.
• Substituents of high electronegativity
(especially -OH, -Cl, and -NH3+) near the
carboxyl group increase the acidity of
carboxylic acids, often by several orders of
magnitude.

Electronegative atoms on the carbon adjacent to a carboxyl

group increase acidity because they pull electron density
away from the O-H bond, thereby facilitating ionization of
the carboxyl group and making it a stronger acid.
• If the pH of the solution is adjusted to 2.0 or lower by the addition of a
strong acid, the carboxylic acid then is present in the solution almost
entirely as RCOOH. If the pH of the solution is adjusted to 7.0 or higher,
the carboxylic acid is present almost entirely as its anion. Thus, even in a
neutral solution (pH 7.0), a carboxylic acid is present predominantly as its
anion.
B. Reaction with Bases
• All carboxylic acids, whether soluble or
insoluble in water, react with NaOH, KOH, and
other strong bases to form water-soluble salts.
• Sodium benzoate, a fungal growth
inhibitor, is often added to baked goods “to
retard spoilage.” Calcium propanoate is
used for the same purpose.
• Carboxylic acids also form water-soluble
salts with ammonia and amines.
• Carboxylic acids react with sodium bicarbonate
and sodium carbonate to form water-soluble
sodium salts and carbonic acid (a weaker acid).
Carbonic acid, in turn, decomposes to give water
and carbon dioxide, which evolves as a gas.

• Salts of carboxylic acids are named in the same

manner as the salts of inorganic acids: The cation
is named first and then the anion. The name of
the anion is derived from the name of the
carboxylic acid by dropping the suffix -ic acid and
adding the suffix –ate.
Example 10.2 Acidity of Carboxylic Acids
• Complete each acid–base reaction and
name the carboxylate salt formed.
Strategy and Solution
• Each carboxylic acid is converted to its sodium salt. In (b),
carbonic acid is formed and decomposes to carbon dioxide
and water.
Flowchart for the separation of benzoic acid, a water-insoluble
carboxylic acid, from benzyl alcohol, a nonacidic compound.
C. Reduction
• The most common reagent for the reduction of a
carboxylic acid to a 1° alcohol is the very
powerful reducing agent lithium aluminum
hydride, LiAlH4.
D. Fischer Esterification

Ester
• A compound in which the -OH of a carboxyl group,
RCOOH, is replaced by an alkoxy or aryloxy
group.

Fischer esterification
• The process of forming an ester by refluxing a
carboxylic acid and an alcohol in the presence of
an acid catalyst, commonly sulfuric acid.

German chemist Emil Fischer

• Treatment of a carboxylic acid with an alcohol in the
presence of an acid catalyst—most commonly,
concentrated sulfuric acid—gives an ester.
• In the case of Fischer esterification, the
intermediate loses a molecule of water to give
the ester.

• Acid-catalyzed esterification is reversible, and, at

equilibrium, the quantities of remaining
carboxylic acid and alcohol are generally
appreciable.
Example: Fischer Esterification
• Complete these Fischer esterification reactions
(assume an excess of the alcohol). The
stoichiometry of each reaction is indicated in the
problem.
Strategy and Solution
• Substitution of the -OR group of the alcohol for the -OH
group of the carboxylic acid gives an ester. Here are the
structural formulas and names for the ester produced in
each reaction.
• Complete these Fischer esterification reactions:
E. Decarboxylation
• the loss of CO2 from a carboxyl group.
• almost any carboxylic acid, when heated to a
very high temperature, undergoes thermal
decarboxylation.
• Carboxylic acids that have a carbonyl group β to
the carboxyl group undergo decarboxylation
quite readily on mild heating.

• For example, when 3-oxobutanoic acid (acetoacetic acid) is heated

moderately, it undergoes decarboxylation to give acetone and
carbon dioxide:
Mechanism: Decarboxylation of a 𝛃-ketocarboxylic Acid

Step 1: Redistribution of six electrons in a cyclic six-

membered transition state gives carbon dioxide
and an enol:
Step 2: Keto-enol tautomerism of the enol gives
the more stable keto form of the product:

• An important example of decarboxylation of a b-ketoacid

in the biological world occurs during the oxidation of
foodstuffs in the tricarboxylic acid (TCA) cycle.
• Oxalosuccinic acid, one of the intermediates in this
cycle, undergoes spontaneous decarboxylation to
produce α-ketoglutaric acid.
• Only one of the three carboxyl groups of
oxalosuccinic acid has a carbonyl group in the
position b to it, and this carboxyl group is lost as
CO2:
 END OF
CHAPTER