Carboxylic acid

Structure and nomenclature of carboxylic acid

Structure of carboxylic acid

 Carboxylic acid is one of the class of organic compounds containing the carbonyl
functional group (C=O).
 A carboxyl group (COOH) is a functional group consisting of a carbonyl group (C=O)
with a hydroxyl group (O−H) attached to the same carbon atom.
 It is usually written as —COOH or —CO2 H.

A. Saturated monocarboxylic acids

The general formula for saturated monocarboxylic acids can be written as:

Where R is either hydrogen or an alkyl group for aliphatic carboxylic acids. When R is
phenyl (aryl) group, the structure represents aromatic carboxylic acids.

B. Di- and tricarboxylic acids

Carboxylic acids containing two carboxyl groups in their structure are called dicarboxylic
acids.
C. carboxylic acids that contain three carboxyl groups in their structure are called tricarboxylic
acids. Example: citric acid is a typical tricarboxylic acid.
Nomenclature of carboxylic acid
i. Common names carboxylic acids
A. Straight chain monocarboxylic acids
 A large number of carboxylic acids have widely used common names which
need to be learned.
 The common names of some basic carboxylic acids are derived from Latin
names that indicate the first original natural source of the carboxylic acid.

Note that the common name of carboxylic acids end with the suffix –ic acid.
 B. Branched chain and substituted carboxylic acids
 In common naming system, the branched chain and substituted acids are
named as derivatives of straight chain carboxylic acids.
 In this case, the position of the side chain or substituents is indicated by
Greek letters, α, β, γ, δ... for designating the 1st, 2nd, 3rd,… position of
carbon atoms as shown below:

Example

C. Dicarboxylic acids
 Dicarboxylic acids also possess common names which are based on their
sources.

D. Aromatic carboxylic acids

 Aromatic carboxylic acids are compounds which have a carboxyl group
directly attached to an aromatic ring.
 The common name of the simplest aromatic carboxylic acid is benzoic acid.

 In common naming system, the position of the substituent is indicated by the

prefixes ortho (o-), meta (m-), para (p-) as it is shown in the structure below
ii. IUPAC names of carboxylic acids
A. Straight chain monocarboxylic acid
 In IPUAC system, monocarboxylic acids are named by replacing the terminal
“−e” of the corresponding alkane name with “−oic acid.”
 They are named as alkanoic acids.

B. Branched chain and substituted monocarboxylic acids CH2 CH2 CH2 O C OH

 The IUPAC name of a branched carboxylic acid is derived from that of the
longest carbon chain that contains the carboxyl group.
 The positions of the substitutes are indicated by Arabic numerals as 1, 2, 3.
The numbering of the chain starts from the carboxyl carbon and it is always
assigned C-1 position.
Note that C-2 position in the IUPAC system corresponds to the α-position in
the common naming system.

C. Dicarboxylic acids
In the IUPAC system, dicarboxylic acids are named as alkanedioic acids.
 These names are obtained by replacing the suffix ‘‘–e’’ in the name of
corresponding alkane by ‘‘–dioic acid’’.
HOOC–CH2–CH2–COOH
Butanedioic acid
D. Aromatic carboxylic acids
o IUPAC name of the simplest aromatic carboxylic acid is benzenecarboxylic acids.

o Substituted aromatic acids with one carboxyl group are named as derivatives of
benzenecarboxylic acids.
o The position of substituents is indicated using the Arabic numerals 2,3, etc
according to their position on the benzene ring relative to the carboxyl group.
o The carbon on which the carboxyl group is attached is by convention C-1.

Physical properties of carboxylic acid

1. State;- The lower aliphatic acids containing up to 9 carbon atoms are liquids, whereas
the higher members are colourless waxy solids. Benzoic acid and most of its derivatives
are also colourless solids.
2. Odor;- The odors of the lower aliphatic acids progress from a sharp, irritating odor of
methanoic acid and ethanoic acids to the distinctly unpleasant odor of the butanoic,
pentanoic and hexanoic acids.
3. Melting and Boiling Points:- The melting points and boiling points of carboxylic acids
are higher than those of hydrocarbons and oxygen-containing organic compounds of
comparable size and shape and indicate strong intermolecular attractive forces.
Example

4. Solubility:- In aqueous solution intermolecular association between carboxylic acid

molecules is replaced by hydrogen bonding to water. The solubility properties of
 carboxylic acids are similar to those of alcohols. Carboxylic acids of four carbon atoms
or fewer are miscible with water in all proportions.

Table show Physical constants of some carboxylic acids

Chemical properties of carboxylic acid

The carboxylic acids show reactions due to the alkyl or aryl group and the carboxyl group. The
carboxyl group is further considered to be made up of a carbonyl and a hydroxyl group. All these
groups modify the properties of each other due to their interaction. Some of the common
reactions of carboxylic acids are:

i. Reaction as an acid
In aqueous solution, the cleavage of O–H bond occurs leading to the formation of
carboxylate ion and hydronium ion. Carboxylic acids ionize partially and equilibrium
exists between the ionized and un-ionized forms.

Carboxylic acids are weak acids and dissociates slightly. The following are examples of
reactions of carboxylic acids as an acid.
a. Reaction with metals: Carboxylic acids react with active metals such as Na, K, Mg,
Ca, etc. to give metal carboxylate salts, RCO2 −M+, and hydrogen gas.
 The salts of carboxylic acids are named by writing the name of the metal first, followed
by the name of the acid replacing the ending -ic acid by -ate. For example, sodium reacts
with ethanoic acid to form sodium ethanoate and hydrogen.

b. Reaction with Bases: Carboxylic acids react with strong bases like sodium
hydroxide or potassium hydroxide to form the corresponding metal carboxylate salts
and water.

Reaction with a base is a simple neutralization reaction. Carboxylic acids react with
weak bases like carbonates or bicarbonates to form salt, water and carbon dioxide.

They also react with ammonia to form ammonium salts of carboxylic acids.

ii. Formation of Esters

One of the important reactions of carboxylic acids involves the replacement of –OH
group by an alkoxy group to form esters as products. In this reaction, carboxylic acids
are heated with alcohols in the presence of concentrated sulphuric acid. The reaction is
called esterification.

Preparation of carboxylic acid

 One of the important methods for preparation of carboxylic acids is oxidation.
 Many saturated monocarboxylic acids are obtained by the oxidation of the
corresponding primary alcohols, whereas aromatic acids are obtained from the
corresponding alkylbenzenes.
i. Oxidation of Primary Alcohols The primary alcohols are readily oxidized to the
corresponding carboxylic acids by their reaction with common oxidizing agents like
K2 Cr2 O7 or KMnO4 .
 For example, oxidation of ethanol yields acetic acid (ethanoic acid).

ii. Oxidation of Alkylbenzenes

 Aromatic compounds containing alkyl group as substituent undergo
oxidation to form aromatic acids.
 The reaction involves oxidation with KMnO4 or K2 CrO7 under vigorous
conditions. The alkyl group is oxidized to carboxyl group irrespective of its
size. For example, toluene and ethylbenzene, both give benzoic acid on
refluxing with KMnO4 in alkaline medium.

iii. Preparation of acetic acid (Ethanoic acid)

 Acetic acid is one of the important carboxylic acids which is used as food
preservative.
 It can be prepared in laboratory by the oxidation of ethanol with potassium
permanganate.
Fatty acid
Fatty acids are carboxylic acids with long hydrocarbon chains.
Most naturally occurring fatty acids contain an even number of carbon
atoms and are unbranched.
Fatty acids can be classified as saturated or unsaturated.
Double bonds in naturally occurring unsaturated fatty acids are never
conjugated.
 Some common naturally occurring fatty acids

The physical properties of a fatty acid depend on the length of the

hydrocarbon chain and the degree of unsaturation.
The melting points of saturated fatty acids increase with increasing
molecular weight because of increased van der Waals interactions between
the molecules.
The melting points of the unsaturated fatty acids decrease as the number of
double bonds increases.

Uses of carboxylic acid

 Acetic acid is used as a solvent and as a starting material in the preparation

of acetates, acetic anhydride, etc.
 It is also used to prepare the vinyl acetate polymer which is used in paints
and adhesives.
 Vinegar contains about 8-10% acetic acid which is used in many food
items.
 Perhaps one of the most important industrial applications of long chain
carboxylic acid is for making soaps, detergents, and shampoos.