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Chem Class12 Chapter 8
Chem Class12 Chapter 8
CARBOXYLIC ACID
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INTRODUCTION
Aldehydes, ketones and carboxylic acids are widespread in plants and animal
kingdom. They play an important role in biochemical processes of life. This
chapter includes knowledge of carbonyl compounds i.e., the compounds
containing >C=O as functional group.
The common names of most aldehydes are derived from the common names of
the corresponding carboxylic acids by replacing the ending –ic of acid with
aldehyde. The location of the substituent in the carbon chain is indicated by Greek
letters α, β, γ, δ, etc. The α-carbon being the one directly linked to the aldehyde
group, β-carbon the next, and so on. For example
The common names of ketones are derived by naming two alkyl or aryl groups
bonded to the carbonyl group. The locations of substituents are indicated by
Greek letters, α α′, β β′ and so on beginning with the carbon atoms next to the
carbonyl group, indicated as αα′.
The IUPAC names of open chain aliphatic aldehydes and ketones are derived from
the names of the corresponding alkanes by replacing the ending –e with –al and –
one respectively.
Structure of Carbonyl Group
1. From alcohols
R-CH2(OH) ⟶ RCHO + H2
R-CH(OH)-R' ⟶ R-CO-R' + H2
2. From acid chlorides
4. Etard reaction
When benzene or its derivative is treated with carbon monoxide and hydrogen
chloride in the presence of anhydrous aluminium chloride or cuprous chloride, it
gives benzaldehyde or substituted benzaldehyde.
6. From carboxylic acids
7. From nitriles
Both aliphatic and aromatic ketones can be prepared by treating alkyl or aryl
nitrile with suitable Grignard reagent followed by acid hydrolysis.
Physical Properties
3. Boiling points: Boiling points of aldehydes and ketones are higher than those
of non-polar compounds i.e., hydrocarbons and weakly polar compounds, such as
ether, due to dipole-dipole interactions but lower than that of alcohols of
comparable molar masses, due to absence of intermolecular H-bondings.
Chemical Reactions
R-CHO ⟶ R-CH2-OH
>C=O ⟶ >CH-OH
The reduction can be done by many catalysts like zinc-amalgam, hydrazine and
potassium hydroxide, and hydriodic acid, and red phosphorus.
Aldehydes and ketones in the presence of dilute sodium hydroxide give aldols.
These reactions are given below:
Note: The reaction of aldehydes and ketones with alkalies is known as an aldol
condensation reaction. Aldehydes and ketones show so many chemical reactions
because they are very reactive.
Uses of Aldehydes and Ketones
Common names of carboxylic acids are based on their source of origin e.g.,
Formic acid (HCOOH) was first obtained from red ants (Latin Formica means ants)
similarly acetic acid (CH3COOH) is so named because it was obtained from vinegar
(Latin Acetum means vinegar) butyric acid (CH3CH2CH2COOH) from rancid butter
(Latin Butyrum means butter) etc. In common system position of substituents is
indicated by Greek letters α, β, γ, δ etc.
As per IUPAC system, the name of acid is derived by replacing suffix ‘e’ of alkane
by ‘oic acid’. Position of substituents is indicated by following rules:
Primary alcohols are easily oxidised to carboxylic acids with oxidants such as
KMnO4, in neutral, acidic or alkaline media or by CrO3 and K2Cr2O7 in acidic media.
CH3-CH2-OH ⟶ CH3COOH
Aldehydes can be oxidised to carboxylic acids even with mild oxidants while
ketones are oxidised with difficulty and usually mixture of acids is obtained.
CH3CHO ⟶ CH3COOH
CH3COCH3 ⟶ CH3COOH + CO2 + H2O
Nitriles are hydrolysed to amides and then to carboxylic acids in the presence of
H+ or OH- as catalyst. If conditions used are mild, then reaction can be stopped
even at amide.
Reaction of Grignard reagent with dry ice (i.e., solid CO2) in ethereal solution
followed by acidic hydrolysis produces carboxylic acid containing one more carbon
atom than Grignard reagent.
Acid chlorides and anhydrides are readily hydrolysed with aqueous base to form
carboxylate ions which form carboxylic acid on acidification.
Physical Properties
1. Physical State: First 3 members are colourless liquids with pungent smell, next
6 members are oily liquids with unpleasant odour. Higher acids are colourless
waxy solids. Benzoic acid and its homologues are colourless solids.
2. Solubility: Among aliphatic acids first four members are very soluble in water
and solubility decreases gradually with rise of molecular mass. All are soluble in
alcohol or ether. Benzoic acid is sparingly soluble in cold water but is soluble in
hot water, alcohol, ether.
3. Boiling Point: Due to the presence of H-bond, boiling points of carboxylic acids
are higher than corresponding aldehydes, ketones, ethers or even alcohols of
comparable molar masses.
Chemical Reactions
The reaction of carboxylic acids with metals like K, Na, Mg, and Ca results in the
formation of salts. A proton will be released from the carboxyl group of the
carboxylic acid where the metal substation will occur during the reaction phase.
H2 gas is produced as a result of the reaction.
The reaction of carboxylic acids with alkalis results in the formation of salts and
water.
Acid chlorides are formed when carboxylic acids react with thionyl chloride (SOCl2),
phosphorus pentachloride (PCl5), or phosphorus trichloride (PCl3).
When carboxylic acids and alcohols are heated in the presence of concentrated
sulphuric acid or dry hydrochloric acid, fruity esters are formed.
6. Formation of Amide
7. Decarboxylation
Decarboxylation reaction occurs when soda lime (NaOH + CaO) is distilled with
sodium salts of carboxylic acids, resulting in alkanes.
Acid anhydrides are formed when two molecules of carboxylic acid are heated
with a dehydrating agent such as phosphorus pentoxide.
Carboxylic acids shape -substituted carboxylic acids when they react with a
chlorine (Cl2) or bromine (Br2) molecule. In the presence of red phosphorus, the
reaction takes place. The H.V.Z. reaction, or Hell-Volhard Zelinsky reaction, is the
name given to this reaction.