Carboxylic Acids: Some Important Acids and Their Structural Formula's

Carboxylic acids
Some important acids and their structural formula’s.

Preparation
Physical Properties
As we would from their structure, carboxylic acid molecules are polar, and like alcohol
molecules, can form hydrogen bonds with each other and with other kinds of molecules. The
aliphatic acids therefore show very much the same solubility behavior as the alcohols. The first
four are miscible with water, the five carbon acid is partly soluble, and the higher acids are
virtually insoluble. Water solubility undoubtedly arises from hydrogen bonding between the
carboxylic acid and water. The simplest aromatic acid, benzoic acid, contains too many carbon
atoms to show appreciable solubility in water.
Carboxylic acids are soluble in less polar solvents like ether, alcohol, benzene, etc.
Carboxylic acids are even higher boiling than alcohols. For example, propionic acid (b.p.141°C)
boils more than 20°C higher than the alcohol of comparable molecular weight, n-butyl alcohol
(b.p. 118°C). These very high boiling points are due to the fact that a pair of carboxylic acid
molecules are held together not by one but by two hydrogen bonds.
Acidic strength of carboxylic acid
HCOOH is more acidic than benzoic acid due to +M effect of ring while inorganic acids like
HCl, HI, HBr and HClO4 are strong acids than organic acids due to complete ionisation of these
acids. Benzene sulphonic acid is highly acidic than carboxylic acid due to more number of
intermediate resonanting structure of benzene sulphonate ion than acetate ion.
Acidic nature depends upon stability of anion
if G is electron withdrawing group it gives strength to acids while releasing nature of G

decreases acidic nature. For example :
CCl3COOH > HCOOH > CH3COOH
Due to +R effect or +I effect acidic nature decreases while – R and – I effect increases acidic
power. Benzoic acid is weaker than formic acid due to +R effect of phenyl group in benzoic acid,
but C6H5CH2COOH is stronger than CH3COOH because here phenyl group give – I effect
Some important acidic strength order are given below :
(i) FCH2COOH > ClCH2COOH > BrCH2COOH > ICH2COOH > CH3COOH
(ii) CCl3COOH > Cl2CHCOOH > ClCH2COOH > HCOOH > CH3COOH
(iii) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH > ClCH2CH2CH2COOH >

CH3CH2CH2COOH
(iv) CH3COOH > CH3CH2COOH > (CH3)2CHCOOH > (CH3)3CCOOH
(v) NO2CH2COOH > NCCH2COOH > ClCH2COOH > CH3COOH
(vi) OHCH2COOH > ClCH2COOH > CH3COOH
Maleic acid is stronger than fumaric acid due to stable intermediate by intramolecular H-
Bonding. Ka1 for maleic acid is higher than fumaric acid but Ka2 is Low because second proton
is busy in hydrogen bonding. Here we create a great concept that hydrogen decreases acidic
nature but when number of proton are two or more than two it may be increases acidic nature by
intermediate stabilization.
(xi) (COOH)2 > HCOOH > CH3COOH
(xii) (COOH)2 > CH2(COOH)2 > (CH2)2(COOH)2

Chemical properties
Conversion to functional derivatives

(iv) Fisher – speir method or Esterification :
When carboxylic acid reacts with alcohol in the presence of acidic medium, they form esters
with fruity smell. In this reaction, alcohol acts as a nucleophile and attack at electrophilic site of
carboxylic acids.
Mechanism of reaction
It is evident from the above mechanism that this reaction involves cleavage of O – H bond of
alcohol and not the C – O bond. It has been further established by isotope tracer technique.

Hunsdicker Reaction :

Effect of heat
When acid undergo heating process they follow ‘Leblanc’ stability rule, for example when single
carbon contains two carboxylic group on heating forms mono carboxylic acid with evolution of
CO2 gas.
A hydroxy acid is both alcohol and acid. In those cases where a five or six membered ring can be
formed, intramolecular esterification occurs. Thus readily eliminate water to
form a cyclic ester known as lactone. The ring readily opens up on treatment with a base to give
the salt of the acid.
Arndt eistert reaction
The reaction consists in increasing the length of the carbon chain by introducing one methylene
group in carboxylic acids.
The reaction contains the following phases in its mechanism.

Substitution of Hydrocarbon part:
(i) Hell – Volhard – Zelinsky reaction
When carboxylic acid with a-hydrogen atom, reacts with halogen in the presence of phosphorous
to form a-haloacids. These derivatives are easily converted into hydroxy acid and aminoacids by
subsequent treatment with alkali and ammonia.
(ii) Ring substitution in aromatic acids:

Aromatic carboxylic acids undergo electrophilic substitution reactions in which
carboxyl group is deactivating and meta directing group. Aromatic carboxylic acids
however do not undergo Friedel – Crafts reaction.
Decarboxylation
(i) Kolbe’s electrolysis
When sodium or potassium salt of acids undergo electrolysis to form alkanes by ionic cum free
radical mechanism.
(ii) Decarboxylation by sodalime
Sodalime is a mixture of sodium hydroxide and CaO (CaO is porous in nature absorb CO2 gas
due to basic nature) when it reacts with carboxylic acid, forms alkanes with less number of
carbon atom, this reaction follows carbanian active mechanism for example
Mechanism of reaction
Some Commercially important carboxylic acids
(1) HCOOH (Formic acid) (2) (COOH)2 Oxallic acid
Formic acid (systematically called methanoic acid) is the simplest carboxylic acid. Its formula is HCO 2H. It
is an important intermediate in chemical synthesis and occurs naturally, most famously in the venom of
bee and ant stings.
(3) CH3COOH (Acetic acid)
Acetic acid, also known as ethanoic acid, is an organic chemical compound best recognized for giving
vinegar its sour taste and pungent smell. Pure water-free acetic acid (glacial acetic acid) is a colorless
hygroscopic liquid and freezes below 16.7°C (62°F) to a colourless crystalline solid. Acetic acid is
corrosive, and its vapour is irritating to eyes and nose, although it is a weak acid based on its ability to
dissociate in aqueous solutions.

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Carboxylic acids

Some important acids and their structural formula’s.

Acidic strength of carboxylic acid

Acidic nature depends upon stability of anion

if G is electron withdrawing group it gives strength to acids while releasing nature of G

CCl3COOH > HCOOH > CH3COOH

Some important acidic strength order are given below :

(iii) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH > ClCH2CH2CH2COOH >

(iv) CH3COOH > CH3CH2COOH > (CH3)2CHCOOH > (CH3)3CCOOH

(v) NO2CH2COOH > NCCH2COOH > ClCH2COOH > CH3COOH

(vi) OHCH2COOH > ClCH2COOH > CH3COOH

(xi) (COOH)2 > HCOOH > CH3COOH

(xii) (COOH)2 > CH2(COOH)2 > (CH2)2(COOH)2

Conversion to functional derivatives

The reaction contains the following phases in its mechanism.

(i) Hell – Volhard – Zelinsky reaction

(ii) Ring substitution in aromatic acids:

(ii) Decarboxylation by sodalime

(3) CH3COOH (Acetic acid)

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