~rtYDES, KETONEs

cARBOXYLIC ACIDS

~~~j p~~r oup, )C=O : The functional group , _ .

~!
,,'fbC
corbonY wining carbonyl group are aldehydes keto ,......C-.o 1s catted c..r1.._
ds con d
1, . • nes carbox . ... uunyt grou
-,o\lfl 1 e of these compoun s are given below: ' Y11c acids and th . CD
j
cotll~ foflilU a . p. 0 rgunic
cir denvativcs. The
gefle O
)>
J!. H j
--
R--'-'- R -I{
A}dehyde K
etone
R
-OH Vl
n
be }I or any alkyl, (where R and R'. may be Carboxylic acid
(wltere "o rnaYara}kyl group) same or d:"
u,erent alky!, (where R rna be
Y H or any alkyl
ar)'l or aryl or aralky! group)

n
ary1or aralkyt group) '
arboxylic Acids:
ti·ves 0 f C
perif8 ? ?
R_c-
X R-C- 0-C- R'
Acid anhydride
R-c-o -R•
Ester R
j -NH
o:
MY
11talide
(where R and R' may be Acid amide 2
2·
n
(where Rand R' may be
)(:; J{alogen same or different groups) same or different groups) (where R may be H
2 or any group)
b O atom of the carbonyl group is sp hybridised. The structu f
The car o
Fig. 8.1. re o carbonyl group is shown in m
1J
•~m im~ 1t
-i
l/)
0

-==-
C o 0
120
I
,w·~,,,:,esu 1t
120°

Fig. 8.1 Structure o f ~ Grolip (2~0) , j

The ){ 8- bond is polar due to higher electronegativity of oxygen atom as compared to carbon.
2. Common and JU PAC Names of Some Aldehydes and Ketones:
Table 8.1: Commo n and IUPAC Names of Some Aldehydes and Kctones
Common Name
Structur al Formula IUPACName
Formaldehyde
HCHO Methanal
Aceta1dehyde
CH3-CHO Ethanal

Aldehydes, Ketones and Carboxylic

 a

I- a-Methylbutyraldehyde
CH3 -CH2 -CH-CHO
I
2-MelhylbutanaJ

C.. CH3

LU CH 3

u lsobutyraldebyde I 2-MethylpropanaJ
CH3-CH-CHO
Valeraldebyde CH3-CH2- CH2-CH2-CHO Pentanal

2 Acrolein CH2=CH-CHO
a
Prop-2-enal

CH3-CH-CHO
a-Methoxypropionaldehyde I 2-MethoxypropanaJ
OCH3

H3VH O 3-Methylcyclohexanecart,ai
y-Methylcyclohexane dchy<fc

Phthaldehyde
©= CHO
CHO
------
Benzene-I, 2-dicarbaldehyde

m-Bromobenzaldehyde
o/CHO or
-------
3-Bromobenzenecarbaldehyde

3-Bromobenzaldehyde

----
Br

----
Crotonaldehyde CH3-CH=CH- CHO But-2-enal

~=ClrC HO
Cinnamaldehyde 3-Phenyl prop-2-enal

Acetone

Diisopropyl ketone
CH3COCH3
CH3 0
I II
CH3
I
Propanone

2, 4-Dimethylpentan-3-one
----
CH:,-CH- C-CH-CH3

CH3
-
Mesityl oxide I 4-Methylpent-3-en-2-one
CH3-C = CH-COCH3
-
0
a-Methylcyclohexanone 2-Methylcyclohexanone
CXCH3

0
60 ~o II
@-c-eH 2-CH3
Cyclohexanecarbaldehyde N02 I-Phenyl propanone
4-Nitrobenzenecarbaldehyde
or 4-Nitrobenzaldehyde

3-0xopentanal 3-Methylcyclopentanone

idea Chemistry-XII
 ~H2-CH-CH2--CHO CHr--C-CH2-C-CH3
oJ-IC I II 11
CHO O o
PrOpane • l.2,J-tticarbaldehyde Pcntanc· 2,4 • dionc

cpara
tion of Aldehydes l O • _,. 1• .. 1--J>
3, P(a)
r BY oxidation
-
of primary alcohols
- JY- , . ...J .. I ..-:,
A
-OH + [O] K2Cr201/H2S04
R-CH2 orKMno4 R-CHO + H2O
1° Alcohol . , Aldehyde
W .,td Odd}.l t '-"I (distilled out as soon
c_:;:;.C
/p&'lrH 2Cl2 ()------ as formed) r, 0 -c) '(J../JC..
R-CH2-0H '--7'= • R-CH0-- - .'---(1,v\

z
1• Alcohol Aldehyde

CH3-CH=CH--CH2-0H PCC/CH2Cl2 CH3--CH=CH-CHO

But-2-cn-l-ol But-2-cn-1-al
(b) BY debydrogenatio~f Drimary alcohols
R--CHO + H2 m
-c
R-CH2-0H 573 K
1• Alcohol Aldehyde

(c) From hydrocarbons

(i) By ozonolysis of alkenes
-f
J\:
R-CH=CH-R' + 0 3 --+ R---Cfl \ /tHR'
I :: I
H20,Zn
-ZnO
R-CHO + R'-CHO

o+:--:o

(ii) By hydration of alkynes

H2S04/HgS04 Rearrangement
CH== CH +H2O CH3-CHO
333K Acetaldehyde
Acetylene
Unstable
(d) From acyl chloride
0 0
II II
R-C-Cl + H2 _ _Pd·BaS04
_ _..;..____ R-C-H + HCI
( Rosenmund reduction)
Aldehyde

0 0
II Pd· BaS04 II
CH -C-Cl + H2 _ _ _....;...__ CH3-C-H + HCI
3
Acetyl chloride Acetaldehyde

(e) From nitriles and esters

SnC1 2 + 2HCI - SnC14 + 2 [H]

R-CH = NH.HCI
__+_H.:c..20__ R-CHO
R-C == N + HCI + 2 [H] - - NH4CI Aldehyde
This reaction is called Stephen reaction
I. AIH(i - Bu}z
R-CN R-CHO
2.Hz0 Aldehyde
I. AIH(i- Bu}z
CH 3-CH = CH-CH2-CH2-CN CH3-CH = CH-CH2-CH2-CHO
2.Hz0 Hex-4-en-1-al
Hex-4-enenitrile

0 0
II I.DIBAL·H
II
CH3-(CH 2) 9 -C-0-CH2-CH3 CH3(CH2)g-C-H
2.Hz0 Undecanal
Ethyl undecanoate

Aldehydes, Ketones and Carboxylic

4• Preparation of Benzaldehydc
(a) By oxidation of toluene
/0Cr(OH)Cl2
@0Cr(OH)Cl2 ~o
~l

Chromium complex Benzaldehyde

Toluene

This reaction is called Etard reaction.

/OCOCH3 CHO

~l
@OCOCH3
@ + 2CH3COOH

Toluene cu,J)o Benzylidene

diacetate
Benzaldehyde

CHri
0

(b) By side chain chlorination followed by hydrolysis

:,~o;
3 2

~ +;:, ~Cl
~o
Toluene Benzal chloride Benzaldehyde

(c) By Gatterman-Koch reaction

CO,HCI ~o
Anhyd. AICly'CuCI
Benzaldehyde

5. Preparation of Ketones
(a) By oxidation of secondary alcohols
R 7 2 4
+ [OJ K2Cr20 /H S0
R' orCr03
2°Alcohol

(b) By dehydrogenation of secondary alcohols

R R
"'-cH-OH Cu "'-c=0 + H2
R'/ • 573 K R'/
2°Alcohol Ketone

(c) From hydrocarbons

(i) By ozonolysis of alkenes

R, j \ / R H20,Zn
R
J
'-C:: C 2 "'-c=0
R/ I : : I "'-R
-ZnO R/
Q-,'........:...O Ketone
'' '

(ii) By hydration of alkynes

CH3--C= CH
Propyne
H2S04/HgS04 •
Marlcovnikov's
addition
OH
I
[CH3--C = CH
2
- l i
CH3-C---CH3
Acetone
Unstable

idea Chemistry-XII
 rom acyl chlorides
(ti) F
2R-MgX + Cd~l2 R2 Cd + 2MgXCI
0 0
II II
2R'-C- CI + R2Cd - 2R' -C-R + CdC1 2
Diallcyl Ketone
Acyl chloride
Cadmium

(e) From nitriles

6-
cH3-CH2-M gBr + CH3-C=N
-----__:/
Ethyl magnesium bromide Methyl cyanide

Ethyl methyl ketone

Preparation of Aromati c Ketones

6.
(a) By Friedel-Crafts acylation
0
II
0
II
@ +R-C- Cl
Anhyd. A1Ct3
R + HCI

0
II
C-CI

@+@ Anbyd. AIC1 3

+HCl
Benzyl chloride Benzophenone

(b) From nitriles

CH3--CH2-- C=N + C6H5MgBr

Ethyl cyanide Phenyl
Magnesium bromide

7. Physical Properti es of Aldehydes and Ketones

(a) Physical state: Most of the aldehydes (except formaldehyde which is a gas)
are liquids at room
temperature. The lower ketones are colourless liquids and have a pleasant smell. The higher members
are colourless solids. Aromatic ketones are usually solids with a pleasant smell.
bons
(b) Boiling points: Aldehydes and ketones have relativel hi h boilin oints as compared to hydrocar
aldehyde s and ketones contam po ar
of comparable molec.ul.aJ;.m~es. It is due to the reason that
ns between the opposite ends
carbonyl group and therefore, they have stronger dipole-dipole interactio
ofC=Od ipoles. tU~ >
alcohols.
These dipole-dipole interactions are however, weaker than intermolecular H-bonding in
than th~coh ols of
Consequently, boiling points of aldehydes and ketones are relatively lower
comparable molecular masses.

Aldehydes, Ketones and Carboxylic

 (c) Solubility: The lower members of aldeh des and ketones (up to four carbon atoms) are
~s due to their capability to form hydrogen bonds with water mol_ecules. The solubility 0 ~hibte in~
m water decreases with the increase in the size of alkyl group. It 1s because of the increase~CSe corri~·!t
of non-polar part in the molecule. However, higher homologues are soluble in organic In the oia~:"'~
6- SOivent\ 0-11~
·o·
• • R
R, o+ 6- o+ 5+/ '\ H,....Q=C"
6- o+/
'C=O·····H
R/ R
8. Chemical Properties
Aldehydes and ketones are highly reactive compounds. Both aldehydes and ketones unde
addition reactions. . rgo nucleop~I'
Explanation: The reactive nature of aldehydes and ketones ts because of the presence of
group. As the oxygen atom is more electronegative, therefore, it pulls the electron around i~P<>lar c<lrbo
partial negative charge (o-) whereas a partial positive charge (o+) is developed on the carb elf acquirion~I
+ .-. _ '- it_ o- on atom. &a
[)C=O.-- + )c-o] = /C-O
Resonating fonns
The positively charged carbon atom of carbonyl group is then readily attacked. by the nucleOphiijc ..
• ..
'1or m1t1ation ',onnatton •
• of an mterme di ate aruon which furth sPecies
of the reaction. This leads to the
of ion or other positively charged species to form the final product. 'l"L er Underg11o.
the attack (H+)
. . l b i ne nucleo ""3
. Philic
reactions may be catalysed by acids or bases. The reaction m genera, may e represented as·
- Nu Nu •
Nu
a,,,, H+
,,,1 Fast
'••. o+ a- Slow ,
/c
ff/I' Go Step 1 Step 2
b
Planar Tetrahedral intermediate Addition product

Relative Reactivity of Aldehydes and Ketones

In general, ketones are less reactive than aldehydes on account of the following facts:
Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to .
electronic reasons. Sterically, the presence of two relatively large substituents in ketones hinders th Slenc and
of nucleophile to carbonyl carbon than in aldehydes having only one such substituent. Elec::ach
aldehydes are more reactive than ketones because two alkyl groups reduce the electrophili . Cally,
carbonyl carbon more effectively than in forrner. city of the
H R R
""-c = o > '\.c = o > ""-c = o
H/ H/ R/
Formaldehyde Aldehyde

Some Important Nucleophilic Addition Reactions

(a) (1) Addition of hydrogen cyanide (HCN)

"! l
HCN + OH- :CN-+ H20

"~ t +
/,~
:CN- ;::::=::::
/c""-cN
/o-
Aldehyde Tetrahedral Cyanohydrin
or Ketone intennediate
OH
H3o+ I
-C-COOH
OH I
I a-Hydroxy acid
' -C-CN
I OH
Cyanohydrin LiAIH4 I
-C-CH2-N H2
I
~-amino alcohol

idea Chemistry-XII
 Pmcoa >
' lmsfcr
"-c /
/
0S0,Nn

"-oH
-
-
or BisuJphitr
Ketone addition compound
(~aJlinc)
This reaction is useful for separation and purification of aldehydes and ketones.
(iii) Addition of Grignard reagent _ . , . , ~ --:3 1f
-,-l•~
'- 6+ 6- 6- 6+ ' 6-6+
"-C=O + R-MgX 'C-OMgX Hf> "C-OH
/--- ,-· /1 /1
Aldehyde R R
or
Ketone Alcohol

(iv) Addition of alcohols

+R'-OH,
+R'-OH,
'- HClgas
'HClgas

Aldehyde Hemiacctal Acetal

Ketones do not react with monohydric alcohols but react with dihydric alcohols to give ketals.
R, CH2-0H
j "c=0 + I HCI gas
'dil. HCI
'-
R/ CH2-0H
Ketone Ethylene glycol Ethylene glycol
ketal
(b) Addition of ammonia and its derivatives Q.ffe 1
"--c=0
<idehyde
or
Ketone
+ H2-N-Z ~==
I"' l
/c"'-
/OH
NHZ

+NH3 " ' C-NH + H20

(fi>
(ammonia) / Irnine

+NHi-NHi - "'-c N--NH2 + H20

Hydrazine / Hydrazone

"-c=0 C6H5NH-NH2
(Phenylhydrazine)
"c-N-NHCJ!s + H20
/
Phenylhydrazone
~dehyde
or
Ketone 02N 0%N
NH2-HN¼No2_ • "'-c-N-NH O N02
(2, 4-Dinitrophenylhydrazme) /
2, 4-Dinitrophenylhydrazone

~+_NH_2::,..-0_H_ _~- "'-c N-OH + H20

> (Hydroxylami~) / Oxime O

H2N-HN~-NH2 - "'-c=N-NHJ-NH2
(Semicarbazide) / Semicarbazone

L..-_+_R_NH_2_ _~- "'-c N-R + tt2o

(Amine) '
Substituted imine
(Schiffs base)

Aldehydes, Ketones and Carboxylic

 \
I
.
(c) Reduction

J- (1) Reduction to alcohols: Aldehydes and ketones are reduced to primary and
sec0ndary atc<>ho
a. respectively, by LiA1H4 or NaBH4 or H2 in the presence of Ni or Pt.
R-CHO + 2[H] LiAJH•
-
R-CH2- 0H
or NaBH4 1° Alcohol
I\

LU ..

u
R -
R Ni or Pt

z
"'-e=o + H2 ~CH-O H
/· 2°Alcohol
R Ketone
(ii) Reduction to hydrocarbons
(Clemmensen reduction)
[H] Zn-Hg/cone. HCI
"'-e=o + 4
/ Aldehyde
or
Ketone
0
II CH2-CH3
C-CH3

@ +4[H]
Zn-Hg
HCI (cone.)
@ +H20

Acetophenone Ethyl benzene

(Wolff-Kishner reduction)
KOH
"C=O + NH2-NH2 "'-e= N-NH2 Ethylene glycol
/ -H20 /
Aldehyde
or
. , I Ketone
l '
.
•

(ti) Oxidation: Aldehydes are easily oxidised to carboxylic acids on treatment with common O ...
agents or mild oxidising agent like Tollens' reagent or Fehling's solution. XIdising

-COOH

Ketones undergo oxidation under vigorous conditions with cleavage of carbon-carbon bond.
0
,II, HNO
CH +C-1-CH + 3[0] cone. 3 HCOOH + CH3-COOH
3 3
! ! Methanoic Ethanoic acid
Acetone acid
C1---C2bond
cleavage
HCOOH + CHr-CHr-CHiCOOH
0 Methanoic acid Butanoic acid
} I 211 I 3 (Carbonyl group stays (Minor products)
CHrfCfC H2-CH2 -CH3 preferentially with the
smaller alkyl group)
Pentan-2-one C2---C3 bond
..__cle-av-ag-e_ __ . CHr:--COOH + CH3-CHrCOOH
Ethanoic acid Propanoic acid
(Major products)

As ketones are not oxidised by mild oxidising agents such as Tollens' reagent and Fehling's solution,
these reagents are used to distinguish aldehydes from ketones.
Electrophilic substitution reactions:
0 0
II II
As, -C-H or -C-R group are electron-withdrawing and, therefore they are deactivating aJMl
m-directing.

Idea Chemistry-XII
I
 ~ltradon:

@
CHO CHO
+ HN03 (cone.) - ·H,so,
©-No1 + H 20
penzaldehYde m-Nitrobcn:zcne

0 0
II
~-CH3

@
C-CH 3
+ HN03 (cone.) """· H,SO,
@LN02 +H 20
Acetopbenone m-Nitroacetophenooc
AJdehydes and Ketones
vses of ft . nJ
9,
l •
4Q% aqueous so ution °
onnaldehyde is known as fonnalin and is used to preserve biologic
(i) A ·mens and to prepare bakelite.
spec• .
.. Acetaldehydes are used as a Starting material in the manufacture of acetic acid, ethyl acetnte,
(ii) . yl acetate, polymers and drugs.
v1n
.. ') Benzaldehyde is used in perfumery and in dye industries.
(Ill A etone and ethyl methyl ketone are common industrial solvents
(iV) C . •
boxylic Acid
10. car . .
·c compounds contammg carboxyl group -c,,... possess sufficient acidic character and are called
Qrgaill 'Vff
carboxylic acids. The carboxyl group is made up of carbonyl, )C=O and hydroxyl, -OH group. hence,
·ts name is carboxyl group (carb from carbonyl and oxyl from hydroxyl). Carboxylic acids may be aliphatic
~-COOR) or aromatic (Ar-C?OH) depending upon whether -COOH group is attached to aliphatic
aJkYI chain or aryl groups, respectively.
Aliphatic monocarboxylic acids are known as fatty acids because some of their high~r members (C 12--C1s)
like palmitic acid (C 15H31COOH) and stearic acid (C 17H35COOH) exist in natural fats as esters of glycerol
and are obtained by their hydrolysis.
Structure of Carboxyl Group
In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and are separated by about 120°. The
carboxylic carbon is less electrophilic than carbonyl carbon because of the possible resonance structure
shown below:

..- ..-
-C
92 ...._ _,.., -C
o·
+ /··.
-C'6,_H
/ ..
o:

..
"--0-H ~H

11. In IUPAC system, the name of carboxylic acid is derived by replacing terminal e of the alkane with oic
acid. For example,

I
0 COOH
3 2 I 4 311 2 I 21 3 4
CH3CH2COOH CH3 - C - CH2-COOH CH3-CH-CH2-COOH
Propanoic acid 3-0xobutanoic acid 2-Methylbutane-l, 4-dioic acid

Aldehydes, Ketones and Carboxylic

 ., .

Table 8.2: Common and IUPAC Names of Some Carboxy lic Acids
WPACName
-

------
Structura l Formula
, Common Name
0 Methanoic acid
Fonnic acid II

Acetic acid
H C
CH3-COOH
0-H

CH 3
Ethanoic acid

2-Methylpropanoic acid
------
----
---
Isobutyric acid I
CH3-CH -COOH
HOOC-C OOH
Ethanedioic acid
------
----
Oxalic acid
Propane- I, 3-dioic acid
HOOC-C H2-COOH

----
Malonic acid

---
Butane-I, 4-dioic acid
Succinic acid HOOC-( CH2)z-COOH
Pentane-1, 5-dioic acid

----
Glutaric acid HOOC-( CH2h-COOH
Hexane-I , 6-dioic acid
Adipic acid HOOC-( CH2) 4-COOH
OH 2-Hydroxy propanoic acid
Lactic acid I

-----
-----
CH3-CH -COOH
Prop-2-enoic acid
Acrylic acid CH2==CH-CO OH
But-2-enoic acid
Cr~tonic acid CH3-CH==C H-COOH

@°" Benzene carboxylic acid(Benzoic acid)

--
Benzoic acid

~,COO H 2-Phenylethanoic acid

-
Phenyl acetic acid

@= COOH Benzene- I, 2-dicarboxylic acid

Phthalic acid

CH2-CO OH
I
COOH

( wolJX, IA./i a..e)cl

- U dw vaf,\JeJ
r -
cH-eo oH /Jc.ic-l hftf1de -c..- X
bH2-eo oH - , Jc;{(_ ?.M-,;: ele -~- ~11.1, 0
\I
Propane - I, 2, 3 - tricarboxylic acid ••
• {
I-,(' r /') c. ·a.JJC1e -
l
O
11

J2. Methods of' Preparat ion of Carboxylic Acids

(a) By oxidation of p~ary alcoh~ and aldehydes:
, .1 r r,
' •l
I
- -- -f-C - O- G-
O 1'
1

(i) Alk. KMn0 4

R-CH2-0H R-COO H
(i1) H3 0+ Carboxylic acid
1° Alcohol
K2Cr201/H2S04
R-CHO + [0] or R-COO H
Aldehyde Cr03/H2S04 Carboxylic acid
(Jones reagent) - - .

(b) From alkyl cyanides and anuaes. •• -

H+ or OH-
w
0
II
L oII
H o - R-C-NH 2 - - - - R-C-- 0-H
R-C== N - - +
2 fl. Carboxylic acid
Alkyl cyanide Acid amide

~ i d e a Chemistry-XII
 0
H•orolf" II
CtlJ -C ::= N H20 CH3-C-NH
Acetonitrile 2 d CH3-COOH
Aaticllcid
front Grignard reagent
(c) 0
0
0
6-- M6+ -X + ~=O Dryether
__,,,, · II &- 6+ H30• II
R- ___g R-C-OMgX - - - R-C-OH
------------ - J(C,
Carboxylic acid

?ie__:583-MgBr
~6+ Dry ether
0
II 6- 6+ H30•
CH3-C-OMgBr --=--- CH~OOH
Acetic acid

(ti) By hydrolysis of acyl halides and acid anbydrides

!~ I:~ ~:~. :,~. RJ~H

Carboxylic acid

(C6 H5 CO)~O 2C6Hs-COOH

Benzoic anhydride Benzoic acid

CH3-C......_ __H___2o_,..
0 C6",-COOH + CH3-COOH
HsC61/ Benzoic acid Ethanoic acid

Benzoic ethanoic anhydride

(e) By hydrolysis of esters

CH3-CH2-CHz-COOCHz-CH3
Ethyl butyrate - ...

l
CH3-CHz-CHz-COONa + CH~Hz-OH

H30•

CH3-CHz-CHz-COOH
Butanoic acid

Preparation of benzoic acid

@
(I) From alkyl benzene

2-CH2-CH3
~l

Toluene I-Phenyl propane

Benzoic acid

Aldehydes, Ketones and Carboxylic

 (ii) From oitriles and amides

N__H~2~_m_•_ . ~NH -2_H2=--~-1H-•........ @H

a. Phenyl cyanide
Benzamide Benzoic acid

LU
u
(iii) By hydrolysis of esters
COOH

@
COOCH2-CH3

z @
Ethyl benzoate
HO+
r--
Benzoic acid
+ C2H50H
Ethanol

u (iv) From Grignard reagent

u
0
II
C=O ~*
+ C6H5MgBr
CJ!s-COOH
Benzoic acid

13. Physical Properties of Carboxylic Acids

'a) Physical state: The first three aliphatic acids are colourle ss liquids with pungent smell. The nc~t •
" . h' h be colourless, od0 six
are oily liquids with an odour of rancid butter while the ig er mem rs are Urlcss,
• soI'd
waxy solids. Benzoic acid is a crystalline t •
intennolecular h dr
(b) Solubility: Carboxylic acid molecules are polar, like alcohols, and ca~ fonn
the CsH1!C OOH is partly soluble and th: hiogen
bonds. The first four acids are miscible with wat~r,
de of non-pol ar part in the moi:cr
acids are insoluble. It is because of the increase m the magmtu
ule.
Benzoic acid is practically insoluble in water.
, etc.
Carboxylic acids are soluble in less polar solvents like ether, benzene, alcohol
n bonding, carboxyliCactds .
(c) Boiling points: Because of their ability to fonn intennolecular hydroge 'd .
th b li s are stronger than thase
have high boiling points. The hydr_ogen bond~ fonne y e c~ oxy c ac1
db
~s. strongly polanse d due to the presence of electron.
in alcoho!s because 0-H b~nd 1~ COOH
than the 0--H .bond of alcohols . Therefore, the
withdrawmg carbonyl gr~up 1_n adJa~ent pos1t10n
membe rs are higher than alcohols of comparable
boiling points of carboxyhc acids particularly lower
molecular masses.

Intermolecular hydrogen bonding in carboxylic acids

14. Chemical Properties of Carboxylic Acids

Carboxylic acids are resonance hybrid of the following structures:
o:
.-.
9-2: / ••
R-C' (), • R-C" - +
0-H ~0--H .. Carboxylic acid
II

group have a reduced double

From these structures, it is clear that the carbonyl parts of the carboxyl
Also it is evident that the two
bond character. Thus, it does not give the reactions of the carbonyl group.
are less resonance stabilized.
contributing structures of carboxylic acid are not equivalent, therefore, they
e Il, this indicates its electron
Moreover, oxygen atom of -OH group has positive charge in structur
pulled towards oxygen
deficient nature. Hence, the shared pair of electrons of 0-H bond will be strongly
lic acids are characteristic of the
and this makes the 0-H bond quite polar. Thus, the reactions of carboxy
carboxyl group and alkyl group.

idea Chemistry-XII
 .----- f-l-o' eJ-, 'w),c_-/ o...,f . . .., (.;,) I -I / f

P.-cid -f- ~Me.. '_,, j

1 ~,,, ,,

r,.,,..u·a '1 .-, .

--~J/.J"',. .A.A.J ( { t
,,
Natu re
ff rl I I :) .J.. ( /'
_, • - 1
deli' . .
'd are quite strong acids because of the presence of polar 0-H group.• They wmse
}ic act s .
.
to give
carbO"y . and hence behave as acids.
gen ions
11ydf0 0 ..
:o
R-Cll-0-··H II .. _
.• R-C-o: + H+
Carboxylic acid Carbo ••
xylate ion

e acids behave as fairly strong adds: This can be explained as fio11ows..

bO%Yli .
csr xylic acids as well as carboxylat~ ion both are stabilised by resonance. However, carboxylate ion is
carbOstabiJised by resonance because its contributing structures are exactly identicaJ. On the other hand,
rnore ntributing stroctures of carboxylic acid involve charge separation. Since carboxylate ion is more
(he ;~sed by resonance than carboxylic acid, therefore, equilibrium lies very much in forward direction,
stabi_ 1 favour of ionised form. Hence, carboxylic acids behave as fairly strong acids.

;.e., in [ Rj~H • Jt~H ] = RJ~H

Carboxylic acid
Less stabilised

·o·
~llf;. -..:o:I .. l &-
0
Ii &-
[ R-C-0: R-C=Q = R-C=--0
Carboxylate ion
More stabilised

Acidity of carboxylic acids: Both carboxylic acid and carboxylate ion are resonance stabilised but
tabilisation is far greater for the carboxylate ion than for the acid. Thus, carboxylic acids get ionised due
: gain in the stability in ~oing from carboxylic acid to the more stable carboxylate ion. Any factor that
0
stabilises the carboxylate ion more would facilitate the release of protons and increase the acidity. Thus,
electron-withdrawing substituents (Cl, N02, CN, etc.) in a carboxylic acid would disperse the negative
charge of the coo-, stabilise it and thus enhance the acid strength. On the other hand, the presence of an
electron-donating substituent such as alkyl group, would intensify the negative charge on the coo- ion and
thus destabilise it, making the carboxylic acid less acidic.
The effect of some substituents is as follows:
(i) Effect of electron withdrawing substituents: The electron withdrawing substituents decrease the
electron density on the 0-H bond thus facilitating the release of W ions and also stabilise the
carboxylate anion by dispersal of negative charge. Thus, an electron-withdrawing group increases the
strength of the acid.
(ii) Effect of electron releasing substituents-alkyl groups: The presence of electron releasing substituent
intensifies the electron density in 0-H bond. As a result, it adversely affects the release of W ions
and thus decreases the acidic character.
(iii) Acidity decreases with larger alkyl groups as the +I effect of the alkyl group increase~ with size of
alkyl group. For example, Formic acid> Acetic acid> Propanoic acid.
(iv) Acidity increases with increasing number of electron-withdrawing substituents on the a-carbon. For
example, Acetic acid < Chloroacetic acid < Dichloroacetic acid (Cl2CH-COOH) < Trichloroacetic
acid (Cl3C-COOH).
(v) Acidity increases with increasing electronegativity of substituents. Thus,
lodoacetic acid (ICH2-COOH) < Bromoacetic acid (BrCH2-COOH) < Chloroacetic acid
(CICH2-COOH) < Fluoroacetic acid (FCH2-COOH).

Aldehydes, Ketones and Carboxylic

 (vi) Acidity declines with increasing distance between electron-withdrawing group and
C
2-Chlorobutanoic acid > 3-Chlorobutanoic acid > 4-Chlorobutanoic acid. OQI-{ &roup_
example,

a. (vii) Unsubstituted aromatic carboxylic acids are stronger acids than unsubstituted
ali h . or
.
acids. Benzoic acid is a stronger acid than acetic acid. Further, since fonnic acid d p atic carbo~ Ylic
• 'd Th
• a stronger ac1"d than benzmc ac1 . us, oes not contain
LU alkyl group, therefore, it 1s

u Fannie acid > Benzoic acid > Acetic acid ¾y

z
Effect of substituents on the acidic strength of benzoic acid.
(i) The electron-releasing groups such as, -CH3, -OH, -NH2, etc., tend to decrease
th .
of benzoic acid. The electron-withdrawing groups such as -Cl, -N02' etc ., tend to. e acid Stren
Rtli
strength of benzoic acid. increase the
(ii) Ortho isomer of benzoic acid is the strongest of all the isomers irrespective of the nature
of
This is called ortho effect. This effect may be due to a combination of steric and electroni~;SUbstitoenl
(iii) The acid-strengthening effect of electron-withdrawing group (e.g., -Cl, -NO
actors.
• •
• • n than at m-pos1tton.
pronounced at p-pos1tto
2, etc •) 1•s lllore
(iv) The acid-weakening effect of an electron-releasing substituent (e.g., -OH, -CH3
_
more pronounced at p-position than at m-position. ' NB2, etc.) is
15. Chemic~ Reactions
The reaction of carboxylic acids are classified as follows:
(a) Reactions involving cleavage of 0-H bond: Reaction with metals and alkalis.
-+
2R-COOH + 2Na - 2R-C00 Na + H2
Sodium carboxylate
-+
R-COOH + NaOH - R-COONa + H20
-+
R-COOH + NaHC03 - R-COONa + H20 + CO2 t

_;J) Reactions involving cleavage of C-OH bond

(i) Formation of anhydride

0
0 II
II R-C"
2R-C-O H / 0 + H20
R-C
II
0
Acid anhydride

0
0 II
II CH3-C"
2CH3-C -OH 0 + H20
Acetic acid CH3-C /
II
0
Acetic anhydride

(ii) Esterification: -

R-COOH 4 R' -OH

- R-COOR' + H20
'

CH3-COOCH2-CH3 + H20
Acetic acid Ethyl acetate

idea Chemistry-XII
 .th pCls, PCl3 and SOCl2
pons w•
,•') JleBc + l'Cls - RCOCI + POC1 3 + HCI
(iJJ _coo H Acyl chloride
R
+ pe1 3 - 3RCOCI + H3 P03
_co oH
3R H + SOCl2 RCOCI + S02 + HCI
R_coO
ith ammonia:
eactionW +
<M fl oH + NJI3 R-eoo-NH. __A _ R-CONH 2
-H20
R_..eo Acid amide

cooH
@ + NH3
Benzamide
ae,..,..oic acid

(nT"cooH + NH3
~co oH
P(halic acid
0
II
Strong heating
(n'(c-.....
~c Y"
II
0
Phthalimide

f involving -CO OH group

(c) Reac 100
(i) Reduction: fc,l
(,) LiAIH 4 /ethcr or B2H6 -,
R-CH 2--0H -
R-CO OH (ii) H30+ 1° Alcohol

(UJ oecarboxylation: ?: 1 ('"(' d °" N'--< -

- + NaOHa ndCaO
R-CO ONa A
Sodium carboxy latc

-+
COONa

© NaOH and CaO

I!
@ + Na2CO3

Sodium benzoate
Benzene

(iii) Halogenation:
(Hell-Volhard Zelins ky reaction)
X
,..,_, (i) XifRed P I
R-CH 2-COO H R-CH -COO H
a-Haloc arboxyl ic acid

acids undergo electrophilic substit ution reactions in

(d) Ring substitution reaction: Arom atic carboxylic
g group. They howev er do not undergo
which -COO H group acts as a deactivating and meta-directin
vating and the cataly st A1Cl 3 (Lewi s acid)
Friedel-Crafts reaction because the carboxyl group is deacti
gets bonded to the carbox yl group.

Aldehydes, Ketones and Carboxylic

 COOH

I- cone. HN03'conc. H2S04

@-N02
C..
(Nitration)
m-Nitrobenzoic acid

LJJ COOH

u
COOH

@ Br2/FeBr3
(Bromination) @-B,
2 Benzoic acid m-Bromobenzoic acid

COOH

(Sulphonation) ©-so3H
m-Sulphobenzoic acid

16. Uses of Carboxylic acids:

(i) Fonnic acid is used in rubber, textile, dyeing, leather and electroplating industry.
(ii) Acetic acid is used as solvent and as vinegar in food industry.
(iii) Adipic acid is used in the manufacture of nylon-6, 6.
(iv) Sodium benzoate is used as preservative.
(v) Higher fatty acids are used for the manufacture of soaps and detergents.
(vi) Esters of benzoic acid are used in perfumery.
17. Some Important Name Reactions
(a) Rosenmund Reduction:
Acid chloride are converted to corresponding aldehydes by catalytic reduction. The reactionis. carnA.1
• f 'd hi 'd • th
out by passing H2 gas through a hot solution o act c on e m e presence of Pd depo . l,,\j

BaS04 (partially poisoned with sulphur or quinoline). Sited over

• 0 0
II Pd/BaS04 II
R-C-Cl + H2 - - - R-C-H + HCl
Acy! chloride Aldehyde
0 0
II Pd/BaS04
II
CH3-C-Cl + H2 CH3-C-H + HCI
Acetyl chloride Acctaldchyde

0 0
II II

~Cl+H2 Pd/BaS04 ~H
+ HCI
Benzoyl chloride Benzaldehyde

(b) Stephen reaction: Nitriles are reduced to corresponding imines with SnC12 in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde.
SnC1 2 + 2HC1 - SnC1 4 + 2 [H]

CH3-C = N + 2[H] + HCI - CH3-CH = NH.HCI CH3-CHO + NH40

Ethanenitrile Acetaldo,dme hydrochloride Acctaldchydc

C=N CH-NH.HCI CHO

@ + 2[H] + HCI 1111

@ H20 (boil)
1111 +HCI

Phenyl cyanide Benzaldox.ime Benzaldehyde

hydrochloride

idea Chemistry-XII
 reacdon: Chromyl chlorl<le oxidises toluene to chromium complex which on hydrolysis gives
) tts111aldehYde.
(C t,eflZ ...,0Cr(OH)Cl2

roiuene •
©0
'OCr(OH)Cl 2

. . .
~o
Bcnzaldehyde
.
an-Koch reaction. When benzene or Its denvattve is treated with carbon monoxide and
(ti) G~:. chloride in the presence of anhydrous AIC13 and CuCI, it gives benzaldehyde or substituted

z
hY aldehyde.
t,etlZ

CO,HCI
anhyd. AlCI/CuCJ
~o
n
Benzene Bcnzaldchyde
m
·ectei-Crafts reactions:
(e) F~edeJ-Crafts alkylation: Benzene and other aromatic compounds react with alkyl halides
in the -c
fl'l ce of anhydrous AICl3 to fonn
presen
alkyl benzenes. . --f
CH3

@ + CH -CI 3
anhyd. AICl3
@+HC I
Toluene
Benzene
CH3
CH3
@+ CH3 -CI
anhyd. AICl3
@i-CH, + ~3
o-Xylene
Toluene (Minor) CH3
p-Xylene
(Major)

Friedel-Crafts acylation: Benzene and other aromatic compounds react with acylchlorides or acid
anhydrides in the presence of anhyd. AIC13 to fonn aromatic ketone.

@ + CH -CO-Cl 3
anhyd. AICJ3
~OCH: HCI

Benzene Acetyl chloride Acetophenone

0
II
C
@ + (§TCOC I
anhyd. AICl3
@('@ + HCI
Benzoyl Diphenyl ketone
chloride

0
II
CH3-C.., anhyd. AICl3
@+ CH3-c....-0
+CH3-COOH

A
Acetic anhydride
Acetophenone

Aldehydes, Ketones and Carboxyli c

 (/) Oemmensen reduction: The carbonyl group of aldehyd~s an~ ketones is reduced to CH
2

I-- treatment with zinc amalgam and concentrated hydrochlonc acid. &roup 011

"\.C=O + 4[H] /"CH2 + H20

Cl..
Zn-Hg
HCl (cone.)
/
LU Zn-Hg
CH3-CH2-CH r-CH3 + H2o

u CH3-CHr--CHz-CHO + [HJ
Butyraldchyde
HCl (cone.) n-Butanc

2 Zn-Hg
HCI (cone.)

u Acetophcnonc
(g) Wolft'-Kishner reduction: The carbonyl gr~up o~ aldehyd:s and ket~nes is reduced to -CH

u
on treatment with hydrazine followed by heatmg with potassmm or sodium hydroxide in a high ~~up
1
solvent such as ethylene glycol. hng
"-e=o + NH:rNH2 "-e= N-NH2 KOH /"CH2 + N2
_H0 / Ethylene glycol,~
/ 2
Hydrazonc

CH3"- CH3" KOH

C=O C=NNH2 Ethylene glycol, CH3-CHr-CH3 + N
Propane 2
CH3/ CH3/
Acetone
(h) Aldol condensation: Two molecules of aldehydes or ketones containing at least one a.-h
ti' atom on treatment with dilute alkali undergo condensation to form ~-hydroxy aldehydes (~!?en
~-hydroxy ketones (Ketol). ) or

ff'\
OH

--
di!. NaOH, I
CH3-C-H + H-CHz-CHO CH3-CH-CH2 -CHO
3-Hydroxy butanal
Ethan~ (aldol)

CH3-CH=CH-CHO
But-2-enal

o, 0 OH 0
II \ II Ba(OH)i I II
CH3-C + H-CH2-C-CH 3 ' CH3-C-CHz- C-CH3
I
Acetone CH3
4-Hydroxy-4-methyl
-pentan-2-one
(Keto!)
0
II
CH3-C=CH-C -CH3
I
CH3
4-Methyl pent-3-en-2-one

(i) Cross aldol condensation: When aldol condensation is carried out between two different aldehydes
/ and/or ketones, it is called cross aldol condensation.
0 OH 0
a W II I I
H-C~H2 -C-H dil NaOH HO-CH2-CH 2-C-H + CH3-CH-CHrC-H
Fonnaldehyde Acetaldehyde (Cross aldol product) (Simple aldol product)

idea Chemistry-XII
 OH 0
I II
CH=CH-CHO
11}-l
0
C~-
~
+II-
-

H2
0
-~-H NaOH
~-CHzC-H ---H-20..,.
@
Etha.nal Cinnamaldehyde
oiaJdehYde
13e 0 0
"-@-
0 al~~a~H .. @-cH=CH- ~-@ + H20
Jn\.-CJ-10 + CH3-C
<.::::;.I Acetophenone Benzalace1ophenone
-A•dehyde -- - - - (I, 3-Diphenyl prop-2-en-l-one)
13eni<» (Major product)

reaction: Aldehydes which do not have an a-hydrogen, undergo self oxidation and
cainni_iis::isproportionation) reaction on treatment with concentrated alkali. In this reaction, one
0
U reductt00 f the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid saJt.
I JllO
1ecule o
cone. KOH CH3-0H + Hcoo-K+
zJICIIOd Methyl alcohol Potassium fonnate
forJJlaldehY e
-+
COONa

2(gJ
5:10
_cone. NaOH
- -
@zOH +
@
Benzyl alcohol Sodium benzoate
aenzaldehyde

CH3 CH3 CH3

I NaOH(50%) I I -+
CH3-C-CH2-0H + CH3-C-COONa
2CH3-1-CHO . I I
CH3 CH3 CH3
2,2 -Dimethylpropanol Sodium 2, 2- dimethylpropanoate
Z,2-Dimelhylpropanal

B U-Volbard-Zelinsky reaction: Carboxylic acids having an a-hydrogen are halogenated at

(k) th:ex-position on treatment with chlorine, or bromine in the presence of red phosphorus to give
a-halo carboxylic acids.
a
(i)X2/Red P
R-CH2-COOH R-CH-COOH (X = Cl, Br)
(ii) H20
I
X
a - Halocarboxylic acid
a
(1)Cl2/RedP CH3-CH-COOH
CH3-CH2-COOH
(ii) H2~ . f,-.'
Propanoic acid •• ...: --...... "\ Cl
2 - Chloropropanoic acid

18. Chemical Tests for Aldehydes and Ketones

(a) Test for carbonyl group (2, 4-Dinitrophenyl hydrazine test): Both aldehydes and ketones contain
carbonyl group. Hence, they react with 2, 4-dinitrophenyl hydrazine to form yellow, or orange
precipitate of 2, 4-dinitrophenyl hydrazone.

2, 4-Dinitrophenylhydrazine 2, 4-DNP-derivative
(Yellow, orange ppt.)

Aldehydes, Ketones and Carboxylic

 (b) (i) Tollens' test: When aldehyde s are heated with Tollens' reagent (ammoniacat s1.1ver • ,
. . . .
they form silver OllITOr on the mner side of the test tube,;._.Ketones do not respond nitrate ~,
I- solution),
test. !his

Q. R-CHO + 2[Ag(NH3ht + 3OH- - R-COO - + _2Ag_l + 2H 2 O + 4Nij ',·

LJJ {LA l)J L J - , ~ _-:, ({Stiver mtrroro 3 ,

Tollens' reagent
I
u
,,._..,- f
(ii) Febling's test: Aliphatic aldehydes when warmed with a few drops of Fehling's
soluti .
reddish brown precipitate of cuprous oxide. Ketones do not respond to thi~est. on &1vc a

2 R-CHO + 2Cu2+ +5OH- - R-COO - + Cu2O I + 3H2O

( Red brown PP'3
Fehling solution

u iii) Iodoform test: cetaldehyde, acetone or any ketone having at. least
d
.
one -CH
. 3 group Wh
• heated with alkaline solution of iodine form yellow coIoure prec1p1tate of 1odofonn.
en

U.
....... a.pµ i~ €Jv', 2NaOH + 12 - NaOI + Nal + H2O
+
R-COCH3 _+J_N_ao_I... R-COCl3
NaOH
R-COO-Na + CHI
-NaOH Iodoform
(Yellow ppt.)

(c) Tests for Carboxylic Acids

(1) Litmus test: Aqueous solutions of carboxylic acids tum blue litmus red. Phenols
also .
&Ive thi ,
s /
test. Alcohols do not respond to this test.
of .
(ii) Sodium bicarbonate test: When carboxylic acid is added to an aqueous solution 8
bicarbonate, brisk effervescence of CO2 is evolved. >'
odiUJn

RCOOH + NaHCO3 - RCOONa + H2 0 + CO2 t

Carboxylic acid Sodium
carboxylate

Phenols and alcohols do not give this test.

(iii) Ester formation test: On warming carboxylic acids with an alcohol (e.g., ethanol)
in presen
a small amount of sulphuric acid, a fruity smell of ester is obtained. ce of

RCOOH + R'OH RCOOR' + H2O

Carboxylic acid Alcohol Ester
(Fruity smell)

(ir) Distinction between formic acid and acetic acid.

Tollens' reagent test: Formic acid reduces Tollens' reagent to metallic silver but acetic acid does
not.
HCOOH + 2[Ag(NH3)zt + ·2OH- - 2Ag l + CO 2t + 2H2O + 4NH3
Formic acid ! ?'-:
-4'-~€£- --~
ff~ c:,de C l 4
HgCl2 test: Formic acid reduces HgCI2 to give white ppt. of Hg2CI2 while acetic acid does not
•

HCOOH + 2HgC12 - Hg 2Cl2 l + 2HCI + CO 2 t

Formic acid Mercuric Mercurous
chloride chloride
(white ppt.)

'. )(, r',1/ idea Chemistry-XII

...