In aldehydes, the carbonyl group ( )C=O) is bonded to

carbon and hydrogen, while in the ketones, it is

bonded to two carbon atoms
Nature of Carbonyl Group
The carbon and oxygen of the carbonyl group are
Sp2 hybridised and the carbonyl double bond contains
one o-bond and one π-bond.

The electronegativity of oxygen is much higher than

that of the carbon, so there electron cloud is shifted
towards the oxygen. Therefore, C-O bond is polar in
nature.
Nomenclature
(i) Nomenclature of aldehydes In IUPAC system, the
suffix “e” of alkane is replaced by the suffIX “al”. e.g.,

(ii) Nomenclature of ketones In IUPAC system, the

suffix “e” of alkane is replaced by “one”. e.g.,
Preparation of Aldehydes and Ketones
(i) By oxidation of alcohols Aldehydes and ketones are
generally prepared by oxidation of primary and
secondary alcohols, respectively.

(ii) By dehydrogenation of alcohols In this method,

alcohol vapours are passed over heavy metal catalysts
(Ag or Cu). Primary and secondary alcohols give
aldehydes and ketones.

(iii) By ozonolysis of alkenes

(iv) By hydration of alkynes Acetylene on hydration
gives acetaldehyde and other alkynes on hydration
give ketones.

Preparation of Aldehydes
Preparation of Ketones
Physical Properties of Aldehydes and Ketones
1. Methanal (HCHO) is a gas at room temperature.
and its 40% aqueous solution is known as formalin. It
is a reducing agent in silvering of mirrors and
decolourising vat dyes.
2. Ethanal (CH3CHO) is a volatile liquid. Other
aldehydes and ketones are liquid or solid at room
temperature.
3. The boiling point of aldehydes and ketones are
higher than hydrocarbons and ethers of comparable
molecular mass due to high magnitude of dipole-dipole
interactions.
4. Aldehydes and ketones have lower boiling point
than those of alcohols of similar molecular masses due
to absence of intermolecular hydrogen bonding.
5. The lower members of aldehydes and ketones are
miscible with water due to the formation of hydrogen
bond with water. However, the solubility decreases
with increase in length of alkyl chain.
6. Acetophenone is a hypnotic (sleep producing drug)
so used as a medicine under the name hypnone.
Chemical Reactions of Aldehydes and Ketones
(ii) Addition of ammonia and its derivatives Reaction
with ammonia
Some N-substituted Derivatives of Aldehydes and
Ketones
(iii) Reduction Aldehydes and ketones are reduced to
primary and secondary alcohols respectively by
sodium borohydride (NaBH4) or lithium aluminium
hydride [LiAlH4].

(iv) Oxidation Aldehydes get easily oxidised to

carboxylic acids by HNO3, KMnO4, K2Cr2O7, etc., or
even by mild oxidising agent.
During oxidation of unsymmetrical ketones the point
of cleavage is such that keto group stays preferentially
with the smaller alkyl group popoff’s rule).

[Fehling solution is a mixture of Fehling solution A

and Fehling solution B in 1: 1 ratio. Fehling solution A
is aqueous copper sulphate and Fehling solution B is
alkaline sodium potassium tartrate which is also
called, Rochelle salt.]
(c) Benedict solution With it, aldehydes (except
benzaldehyde) also give red ppt. of CU2O.
(d) Schiff’s reagent It is an aqueous solution of
magenta or pink coloured rosaniline hydrochloride
which has been decolourised by passing SO2,
Aldehydes give pink colour with this reagent but
ketones do not.
Haloform reaction Aldehydes and ketones having at
east one methyl group [3-α hydrogen] linked to the
carbonyl carbon atom (methyl ketones) are oxidised
by sodium hypohalite to sodium salts of corresponding
carboxylic acids having one carbon atom less than that
of carbonyl compound. The methyl group is converted
to haloform.

Iodoform reaction with sodium hypoiodite is also used

for the detection of CH3 – group or CH3CH(OH)-
group by producing yellow solid CHI3.
(v) Aldol condensation
Its further condensation gives phorone,
This reaction is exhibited by those aldehydes and
ketones which have at least one a-hydrogen.
(vi) Cross aldol condensation Base catalysed crossed
aldol condensation between an aromatic aldehyde and
an aliphatic aldehyde or ketone is called Claisen-
Schmidt condensation or Claisen reaction.
The above reaction is called Benzoin condensation, not
the cross aldol condensation.
(vii) Cannizzaro reaction Aldehydes which do not have
any α – hydrogen atom, undergo self oxidation and
reduction (disproportionation) reaction on treatment
with concentrated alkali.

(viii) Electrophilic substitution reaction Aromatic

aldehydes and ketones undergo electrophilic
substitution. Carbonyl group shows + R effect,
therefore acts as a deactivating and meta directing
group.

(ix) Baeyer- ViLLiger oxidation With Caro’s acid

(H2SO5) or per benzoic acid (C6H5CO3H) or peracetic
acid (CH3CO3H) aliphatic ketones give ester.
(xi) Knoevenagel reaction It involves condensation
between active methylene group and ,carbonyl groups
in the presence of base.
Carboxylic Acids

Classification
Depending upon the number of -COOH groups, they
are classified as
(i) monocarboxylic acids; containing one -COOH
group
(ii) dicarboxylic acids: containing two -COOH groups.
Sources of carboxylic acids

Nomenclature
Their IUPAC names have been derived from the
corresponding alkanes by replacing the letter ‘li of the
alkane with ‘oic’ and adding suffix ‘acid’ at the end,
Thus, monocarboxylic acids are called alkanoic acids.

Methods of Preparation of Monocarboxylic Acids

(i) From primary alcohols and aldehydes
(ii) From alkyl benzenes Alkyl benzene when treated
with strong oxidising agent like H2CrO4 (chromic
acid), acidic or alkaline KMnO4 gives benzoic acid.

(iii) From acid derivatives All acid derivatives like

amides (RCONH2), acid halides (RCOCl), esters
(RCOOR’), acid anhydrides (RCO-O-COR) on
hydrolysis give carboxylic acids. All acid derivatives
break from RCO+.

(iv) From nitriles and amides Nitriles are hydrolysed

to amides and then to acids in the presence of H+ or
OH– as catalyst. Mild reaction conditions are used to
stop the reaction at the amide stage.
(v) From Grignard reagents Grignard reagents react
with carbon dioxide (dry ice) to form salts of
carboxylic acids which in turn give corresponding
carboxylic acids after acidification with mineral acid

Physical Properties of Carboxylic Acids

1. Aliphatic carboxylic acids up to nine carbon atoms
are colourless liquids at room temperature with
unpleasant odours. The higher acids are wax like
solids.
2. The lower carboxylic acids are freely miscible with
water due to the presence of intermolecular hydrogen
bonding with H2O molecules. However, the solubility
in water decreases gradually due to increase in the size
of alkyl group.
3. Monocarboxylic acids have higher boiling points as
compared to the alcohols of comparable molecular
masses due to the presence of stronger intermolecular
hydrogen bonding as shown below.

4. Melting points of aliphatic monocarboxylic acids

shows alternation or oscillation effect, i.e., the m.p. of
an acid with even number of carbon atoms is higher
than the next lower and next higher homologue
containing odd number of carbon atoms. This is
because, in case of acids with even number of carbon
atoms, the terminal -CH3 and -COOH groups lie on
the opposite sides of the zig-zag chain. As a result, they
get closely packed in the crystal lattice.
5. Glacial acetic acid is completely pure acetic acid and
represents the solid state of acetic acid. Below 16.6°C
temperature pure acetic acid is converted into ice like
solid hence it is called glacial acetic acid.
Chemical Properties of Carboxylic Acids
Carboxylic acids do not give reactions of carbonyl
groups as it enters into resonance with lone pair of O
of -OH group.
(i) Acidity

Above reactions are used to detect the presence of

carboxyl group Ul an organic compound. ,
Carboxylic acids dissociate in water to give resonance
stabilised carboxylate anions and hydronium ion.

The strength of the acid is expressed in terms of the

dissociation constant (Ka), also called acidity constant.
A stronger acid has higher Ka but lesser pKavalue
(pKa == -log Ka).
The electron releasing substituents (+1 effect) decrease
the acidic strength of the carboxylic acids by
destabilising the carboxylate ion.

The electron withdrawing substituents (-1 effect) such

as halogen atoms (X), nitro (NO2) group increase the
acidic strength by decreasing the magnitude of the
negative charge on the carboxylate anion and thus
stabilising it. The release of H+ ion becomes easy.
Acidic strength order

This is because -1 effect decreases in the order : F > C1

> Br > I.
This is because – I effect decreases with distance.
Per acetic acid (CH3COOO-H) is a weaker acid than
acetic acid as acetate ion is stabilised by resonance.
Acidic strength of aromatic acids The parent member
of the family benzoic acid which is a weaker acid (Ka =
6.3 x 10-5) than acid (Ka = 17.7 x 10-5) but stronger
than acetic acid.
Some order of acidity are

(b) Similarly, Ka values of methyl substituted (toluic

acids) at 298 K are as follows:

From the Ka values, it is evident that with the

exception of o-isomer, both p and m-toluic acids are
weaker acids than benzoic acid whereas the three
isomeric nitro benzoic acids are stronger acids than
benzoic acid.
(ii) Reactions involving cleavage of C-O-H bond
(a) Formation of anhydride

Mechanism
(iii) Chemical reactions involving – COOH group

(iv) Substitution reactions in the hydrocarbon part α -

hydrogen atoms in carboxylic acids are acidic in
nature and can be easily replaced by halogen atoms in
HVZ reaction
The reaction is known as Hell-Volhard-Zelinsky
reaction.
(v) Arndt-Eistert reaction It is method of converting
lower carboxylic acids to their higher homologues

(vi) Reducing property Among carboxylic acids,

formic acid is the only acid that acts as reducing agent.
It reduces, acidified KMnO4 to MnSO4, HgCl2 to Hg,
Tollen’s reagent to silver mirror and Fehling’s
solution to red ppt. and itself gets oxidised to CO2 and
H2O.
HCOOH + HgCl2→ Hg + 2HCI + CO2
(vii) Electrophilic substitution reactions of aromatic
acids -COOH group shows -R effect, therefore, acts as
a deactivating and meta-directing group. Carboxylic
acids do not undergo Friedel-Craft’s reaction because
the carboxylic group IS deactivating and the catalyst
AlCl3 (anhy.) gets bonded to the carboxyl group.
Uses
1. Formic acid is used in leather tanning, textile dyeing
and finishing.
2. Acetic acid is used in the manufacture of rayon and
in plastics, in in rubber and silk industries, in cooking
and in vinegar (a 8-10% solution of acetic acid).
3. Benzoic acid and its salts are used as urinary
antiseptics.
4. Formic acid can act as a reducing agent.
Derivatives of Carboxylic acids
These are obtained when -OH group of carboxylic
acids is replaced by Cl, NH2, OR’ and OCOR and are
called respectively acid chloride, acid amide, ester and
acid anhydride.

Properties of Acid Derivatives

1. Chemical reactions of acid halides

2. Chemical reactions of acid amides

3. Chemical reactions of ester

4. Chemical reactions of anhydrides