CARBOXYLIC ACIDS

MONO CARBOXYLIC ACIDS

SYNOPSIS S NO STRUCTURE NAME
1 CH3COOH Acetic acid
Introduction and Nomenclature
 
 Organic compounds containing carboxyl 2. C6 H5 C H  C H  COOH Cinnamic acid
  C O O H  group are called carboxylic acids.  
3 CH3 C H  C HCOOH Crotonic acids
 The general formula of carboxylic acids is
4 CH 2  CHCOOH Acrylic acid
Cn H 2 nO2 .Higher member of carboxylicacids   Amino
5 H2 N  CH2 COOH
 C12  C18  are known as fatty acids. Acetic acid
6 CH 3CH  OH  COOH Lactic acid
 These may be aliphatic, alicyclic or aromatic.
Phenylacetic
These may be further divided into saturated 7 C6 H5CH 2COOH
acid
Unsaturated and substituted.
eg: hydroxy, amino and halo substituted Note:Carboxylic acid in which carboxylic group is
carboxylic acids. attached to a cyclic compound can be named as:
 The aliphatic mono carboxylic acids are known Cycloalkanecarboxylic acid: Cycloalkenecarboxylic
acid or cycloalkynecarboxylic acid .
as fatty acids, as many of these acids (especially
the higher members) found in fats in the form COOH Carboxylic acid
of their glyceryl esters.
 Trivial names or common names of lower
members were derived from their source of Cycloalkane
occurence. 
Cyclohexane carboxylic acid
N A M E S O F S A T U R A T E D A L IP H A T IC M O N O OH
C A R B O X Y L IC A C I D
S
ST R U C T U R E
CO M M O N I UPA C 2
NO N AM E NAME COOH
1 H C O OH F o r m ic ac id
M e th a n o i c 1
a c id
2 C H 3C O O H A c e tic a ci d E t h a n o i c a ci d 3
Br
P r o p io n ic
3 C H 3C H 2C O O H P r o p a n o i c a ci d
a ci d 3-Bromo-2-hydroxycyclopropane
4
CH 3  C H 2  2 C OO H n – B u ty r ic
B u ta n o i c aci d carboxylic acid
a ci d

5
CH 3 CH 2 3 CO O H n – v a le r ic
P e n t an o ic aci d
a ci d
S.No Structure Name
6
CH 3  C H 2  4 C OO H C a p r o ic ac id H e x an o ic ac id
COOH Cyclohexane
CH  C H 2  6 C OO H 1
7 3
C ap r y li c a ci d O c ta n o i c a ci d carboxylic acid
8
CH 3 CH 2 8 CO O H C a p r i c a ci d D e ca n o i c a ci d
2 COOH Benzoic acid
9
CH 3  C H 2 1 0 C O O H L a u r ic a ci d
D o d e c an o i c
a c id

10
CH 3  C H 2 1 2 C O O H M y r i st ic ac id
T e tr a d e ca n o ic
a c id
3 OH Salicylic acid
11
CH 3  C H 2 1 4 C O O H P al m i t ic aci d
H e x a d e ca n o ic
a c id

CH  C H 2 1 6 C O O H O ct ad ec an o i c COOH
3
12 St e ar i c a ci d
a c id
COOH COOH
COOH 4 NH2 Anthranilic
acid
COOH
COOH COOH COOH
Phthalic acid Isophthalic acid Terephthalic acid
 Sol. The compound is carboxylic acid. The aldehyde
S.NO Structure Name group and the hydroxyl group are treated as
COOH substituents. The compound is heptenoic acid
1 derivative. The name is
Oxalic acid
COOH
  E   4  hydroxy- 7 - formyl - 5 - heptenoic acid

2 COOH
Malonic W.E-2:
acid OH
COOH

3 CH2COOH COOH
Succinic a) b)
O COOH
acid
CH2COOH
Sol. a) 2 - hydroxy - 4 carboxyclohexanone
4 CH2COOH b) Cyclopropanecarboxylic acid
Glutaric
acd Nomenclature of Esters
 Esters are named in the following way:
CH2COOH i) The first word of the name is the stem name of
the alkyl group attached to oxygen.
5 CH2CH2COOH
Adipic acid ii) The second word of name is the name of the
parent acid with the suffix - ic acid replaced by
- ate.
6 HO – CH – COOH iii) This nomenclature applies for both common and
Malic acid IUPAC names of esters.

O
7 (OH)CHCOOH
Tartaric acid R – C – O – R'
(OH)CHCOOH
CH–COOH
O
8 Maleic (cis) 
and fumaric H  C  O  CH 3
Methyl methanoate
CH–COOH (trans) acid Alkyl
9 CH2COOH Alkanoate
Citric acid
O

CH 3  CH 2  C  O  CH 2  CH 3
CH2COOH Ethyl propanoate

W.E-1:Provide IUPAC name for the compound

given below:
CHO H
O
C=C
H CH – CH2 – CH2 – C – OH Note-1: Cyclic esters are called lactones. The
IUPAC system names of these compounds as
OH oxacylolkanone.
 O  (A) Primary Amides: Primary amides are
named by using the acid name, replacing oic
acid with amide. Thus, the general name is
O O alkanamide, alkenamide and alkynamide.
O O
2-Oxycyclopentanone 2-Oxacyclohexanone 
 OH

CH 3  C  OH 
 CH 3  C  NH 2
 NH 2
Nomenclature of Anhydrides Ethanoic acid Ethanamide

i) Symmetrical anhydrides are named by using the O

acid name and replacing acid with anhydride.
CH3 – CH – CH2 – COOH
O O
 
CH 3  C  O  C  CH 3 CH3 CH3
Ethanoic anhydride 3 - Methylbutanoic acid 3 - Methylbutanamide

O O  (B) Secondary and Tertiary amides: In

 
CH 3  CH 2  C  O  C  CH 2  CH 3 these two amides, the names of the substituents
Propanoic anhydride are indicated first, followed by the name of the
ii) Mixed anhydrides are named by stating the amide. The name of each substituent is proceded
names of both acids in alphabetical order, by a capital N to indicate that the substituent is
followed by “anhydride” bonded to a nitrogen. Substituents present on
O O nitrogen are arranged alphabetically.
 
CH 3  C  O  C  CH 2  CH 3 O
Ethanoic propanoic anhydride
CH3 – CH3 – C – NH
Nomenclature of Acid Chloride
 Acid chloride is named by using the acid name
N-Cyclohexylpropanamide
replacing ic acid with yl chloride, i.e,. alkanoyl
chloride : CH 3
O
 |
O O CH 3  CH 2  CH 2  C  N  CH 3
 
CH 3  C  Cl CH 3  CH 2  C  Cl N , N  di methylbutanamide
Ethanoyl chloride Propanoyl chloride
Note-1: Cyclic amides are called lactams. The
IUPAC system names of these compounds as
azacycloalkanone
O
O
3- Methyl pentanoyl chloride NH
 Nomenclature of Amides: Amides are NH
classified as primary, secondary or tertiary, 2-Azacyclobutanone 2-Azacyclohexanone
depending on the number of alkyl groups bonded
to the nitrogen atom. Primary amides have no
alkyl group bonded to nitrogen, secondary
COOH – CH – C – CH – C – COOH
amides have one and tertiary amides have two
alkyl groups.
O
R
O O R–C–N OH
 
R  C  NH 2 R  C  NHR R COCl – CH2 – CH – COCl
Primary amide Secondary amide
Tertiary amide 2-Hydroxybutanedinoyl chloride
 Isomerism: Carboxylic acids exhibits all From Gem Trihalides

types of structural isomerism except 
R  CX 3   R  COOH
i HOH / OH
metamerism.   ii  H 
 The following compounds are isomeric with 
C6 H 5  CCl3   C6 H 5  COOH
i NaOH / HOH
carboxylic acids.  ii  H 
(1) Esters (2)Hydroxy aldehydes 
H  CCl3 
i NaOH / HOH
 ii  H 
HCOOH
(3) Hydroxy ketones (4)Hydroxy oxiranes
Ex:- C H O  From Primary Alcohols: Primary alcohols
3 6 2
on oxidation give carboxylic acids as end
CH 3CH 2COOH , CH 3COOCH 3 , products.

CH 2  CH 2  CHO 
R  CH 2OH  4 i KMnO / O H / 
 R  COOH
HCOOC2 H 5 , | ,  ii  H 
OH
Ex :
O 2 2 7 
CH 3  CH 2  OH   CH 3CHO
4 K Cr O or KMnO
 H 2 SO4
CH 3  C H  CHO CH  C  C H 
O 
| , 3
|
2
OH
OH
Ethyl alcohol Acetaldehyde
2 7
    
K Cr O or KMnO
O O
2
 H 2 SO 4
4
CH 3 COOH
and Acetic acid

OH HO  From Aldehydes and Ketones: Carbonyl

Preparation of carboxylic acids compounds on oxidation give carboxylic acids.
 From Alkenes: Alkenes having atleast one R  CHO 
Feling's Solution or
Tollen's reagent,
 RCOOH
Or
hydrogen on vinylic carbon give carboxylic Θ
KMnO4 / O H / Δ
acids on oxidation.
O 
||
 i KMnO / O H / 
KMnO4 / OH  / 
CH 3  CH 2  CH 2  C  CH 3  4
i  H 

R  CH  CH  R      
 RCOOH  RCOOH
CH 3  CH 2  COOH  CH 3  COOH
 From Alkynes: Alkynes on ozonolysis and on
oxidation give carboxylic acids.  From methyl Ketones: Such compounds on

treatment with X 2 / O H give carboxylic acids.
O
 
 2
R  C  CH 3   RCOOH  CHX 3
i X /O H

 From Alkyl Benzene: Alkyl benzene on  ii  H 

oxidation gives carboxylic aicd.  From Nitriles: Nitriles on hydrolysis give

 i KMnO / OH 
carboxylic acids. The reaction is catalysed by
C6 H5  CH 2  R  4
ii  H O / H 
 C6 H5  COOH acids as well as by base. In this reation,
2

Ex: CN group converts into COOH group.


H3O / OH /  –
CH3 COOK COOH RCOO + NH4
R–CN 

H 3O 
H2O / H / 

KMnO4 . KOH

 RCOOH + NH3
 Carbonylation of Grignard Reagents and
Toluene Pot.Benzoate Benzoic acid Alkyl Lithium: Grignard reagents react with
COOK COOH carbon dioxide to yield magnesium
carboxylates. These, on acidification, produce
 carboxylic acids.

KMnO4 . KOH
 
H 3O
 O

O
   

RMgX  C  O 
 R  C  O M gX 
HOH / H
 R  COOH
 
Propylbenzene Benzoic acid
 O
 


O
 Physical properties: Aliphatic carboxylic
R  Li  O  C  O 
R  C OLi 
R  C OH HOH / H
acids upto nine carbon atoms are colourless
Br MgBr liquids at room temperature with unpleasant

dry
ether
 odour.

CO2  
dry ice
 The higher acids are wax like solids and
NO2 NO2
odourless due to their low volatility.
 Carboxylic acids have higher boiling liquids
O = C – OMgBr COOH
than aldehydes, ketones and even alcohols of
H O
comparable molecular masses, due to more

3

extensive association of carboxylic acid
NO2 NO2 molecules through intermolecular hydrogen
 From acylhalides and anhydrides: Acid bonding.
chlorides when hydrolysed with water give  Simple aliphatic carboxylic acids having upto
carboxylic acids or more readily hydrolysed with four carbon atoms are miscible in water due to
aqueous base to give carboxylic ions which on intermolecular hydrogen bonding with water.
acidification gives corresponding carboxylic  The solubility decreases with increasing number
acid. of carbon atoms. Higher carboxylic acids are
H2O
RCOOH + Cl
–
insoluble in water due to the increased
RCOCl –
OH / H2O H O
hydrophobic interaction of hydrocarbon part.
RCOO + Cl
– –

3
 RCOOH  Benzoic acid, the simplest aromatic carboxylic
H 2O 
Ex : CH 3COCl  CH 3COOH  Cl acid is nearly insoluble in cold water.
 Anhydrides on hydrolysis gives corresponding  Carboxylic acids are also soluble in less polar
acid organic solvents like benzene, ether, alcohol,
chloroform etc
 C6 H5CO 2 O 
H O
 2C6 H 5COOH2
Chemical properties
Ex : i)
Benzoic anhydride Benzoic acid Acidic nature and acidic strength:
C6 H 5COOCOCH 3 
H2O
 C6 H 5COOH  CH 3COOH Carboxylic acids dissociate in water to give
ii) Benzoic ethanoic Benzoicacid Ethanoicacid resonance stabilized carboxylate anions
anhydride
O O
 From esters +
O O

H2O + R – C – OH H3O + R – C  R – C  R–C

CH3CH2CH2COOC2H5 
 CH3CH2CH2COONa + C2H5OH

NaOH

Ethyl butanoate O O O
H3O+
CH3CH2CH2COOH O
Butanoic acid  ..
W.E-3:Complete the following. R  C O  H  H2O  R  C O : H3O
 ..
O O

i) CH 3  CH 2  C  CHBr2  i  NaOBr
 ii  H 

 RCOO    H 3O  
ii) C6 H 5  CH 3   A    B  H 2O / OH  Ka 
 RCOOH 
Cl2 / hv

O
Sol. i) CH  CH  C  CHBr 
 K a  Dissociation constant of acid
3 2 2
NaOBr

 Effect of substituents on the acidity of
 O
 
CH 3  CH 2  C  CBr3  
OH 
 carboxylic acids: Electron withdrawing
  groups increase the acidity of carboxylic acids
 
 by stabilising the carboxylate ion, the conjugate
CH 3  CH 2  COO   CHBr3 
H CH 3  CH 2  COOH

base through delocalisation of negative charge
ii) C6 H5  CH3 
Cl2 / hv
C6 H5  CCl3 
H2O / OH
C6 H5COO  CHCl3 by inductive effect (or) resonance effects.
 A
 Electron withdrawing group
O CH3CH2COOH
C stabilises carboxylate ion
O NO 2  CH 2 COOH  NC  CH 2 COOH 
Ex. F, Cl
 On the otherhand electron donating groups
decrease the acidity of carboxylic acids as they
destabilize the conjugate base  HCOOH  ClCH 2 CH 2 C6 H 4 COOH 
Electron donating group
O CH 3COOH  CH 3CH 2 COOH
C 
destabilises carboxylate ion
O
Ex. OCH3
 Increase in the number of Cl atoms at  -
position (-I effect) increases the acidic strength
and decreases pKa value
CCl3COOH > CHCl2COOH >
CH2ClCOOH > CH3COOH
 Increase in the distance of Cl atom from - COOH
group decreases the acidic strength
Cl Cl
| |
CH 3CH 2 C HCOOH  CH 3 C HCH 2COOH
 Increase in electronegativity of halogen 
increases the acidity
FCH 2COOH  ClCH 2COOH  BrCH 2COOH  ICH 2COOH 
 If the -COOH group is in bond with unsaturated
carbon acidic strength increases.
HC  C  COOH  C6 H 5COOH
CH 2  CH  COOH  CH 3COOH
 Electron withdrawing group on C6H5 of aromatic
carboxylic acid increases acidity where as 
electron donating groups decrease acidity
COOH COOH COOH
< <
OCH3 NO2
 Increasing order of acidic strength when the
carboxylic acid contains
Ph < I < Br < Cl < F < CN < NO2 < CF3
 decreasing order of acidic strength
CF3COOH > CCl3COOH > CHCl2 COOH>
BrCH2COOH > HCOOH > ClCH2COOH>
C6H5COOH>C6H5 -CH2COOH >
CF3COOH  CCl3COOH  CHCl2 COOH 
FCH 2 COOH  ClCH 2 COOH 
BrCH 2 COOH 
C6 H 5CH 2 COOH 
Ortho effect: Ortho substituents have an acid
strengthening effect and their effect is unusually
high. Thus ortho substituted Benzoic acids are
considerably stronger acids than benzoic acids
no matter whether the substituent is electron
releasing group or electron withdrawing group.
Ortho effect is believed to be due to the jont
application of inductive, steric and
intramolecular Hydrogen bonding wherever
applicable.
COOH COOH COOH COOH
NO2
< < <
NO2
NO2
Carboxylic acids are stronger in acidic character
than phenols and alcohols.
Unlike phenols carboxylic acids react with
weaker bases such as carbonates and
bicarbonates to liberate CO2
2RCOOH  Na2CO3 
 2RCOONa  H2O  CO2
2RCOOH  NaHCO3  RCOONa  H2O  CO2
Though the conjugate base of phenol, that is
phenoxide ion has resonance structures, they are
nonequivalent and negative charge is present on
carbon atom. More number of contributing
resonating structures towards acidic character
are present in carboxylate ion. So carboxylic
acids are more acidic than phenol.
Reactions due to - COOH Group:
Carboxylic acids give following reactions due
to the presence of carboxylic group:
(A) Reactions due to acidic hydrogen :
Acids react with bases to form salts. Salts of
carboxylic acids are important compounds for
the preparation of different organic compounds.
 Electrolysis (D) Schmidt reaction:Carboxylic acid on
R–R
NaOH
RCOO  Na 
treatment with hydrazoic aicd gives primary
NaOH Sodalime
R–H amine. This reaction is known as schmidt
O reaction or rearrangement. This reaction is very
 R – C – R
Ca(OH)2 Dry
(RCOO)2Ca
distillation useful for the conversion of COOH group to


O
PO
 NH 2 group.
ROOOH RCOO NH  R – C – NH2 
 
4
2 5  R – CN


X2(Cl2 or Br2) ROOH 

N3 H
Conc . H 2 SO4
R  NH 2  N 2  CO2
R–X
RCOO  Ag  I2/ CH 3  COOH 
N 3 H / Conc . H 2 SO4
 CH 3  NH 2
RCOOR 

C6 H 5  CH  CH  COOH  
O N3 H / conc.CH 2 SO4
R ' Li 
RCOO  Li     R – C – R
C6 H 5  CH  CH  NH 2
(B) Nucleophilic substitution reactions: (E) Borodine - Hunsdiecker reaction :
Carboxylic acids give the following nucleophilic Treatment of silver salt of acid with bromine in
substitution reaction in which - OH group is the presence of carbon tetrachloride to give an
replaced by nucleophiles, i.e., alkyl or aryl bromide is known as Hunsdiecker
O
reaction.
R – C – CL
SOCl2 Acid chloride RCOONa 
AgNO3
 RCOO  Ag 

O 
Br2 / CCl4
 R  Br  CO2  AgBr
R ' O H / H  

R – C – O – R + HOH  Silver salt of acid (excess) is treated with
O Ester

R – C – OH
O I 2 leading to the formation of ester. This reaction
|| 
O O
R  C O H is known as Simonini reaction.

R – C – O – C – R + HOH I2 / 
P2O5 /  Anhydride 2 RCOOAg   RCOOR  CO2  2 AgI

 O CH 3COOH 
AgNO3
 CH 3COO  Ag 
R ' N H 2
R – C – NH – R + HOH O
Amide 
I2 / 

 CH 3  C  OCH 3
 All carboxylic acids form acid chlorides except (F) Arndt - Eistert reaction: The reaction is
formic acid because formyl chloride is unstable.
a method for converting an acid RCOOH to a
O
   O
 homologous acid, R  CH 2  COOH , in which
  H  C  Cl  
H  C  OH   CO  HCl
  the wolff rearrangement is the key step. In this
 
Hence, HCOOH is used for the preparation of
reaction, R  CO  Cl from RCOOH is
mixture of CO and HCl which is used in converted to R  CH 2COOH by diazomethane
Gattermann - Koch aldehyde synthesis. via formation of   diazoketone.
(C) Reduction reaction: Carboxylic acids O O
undergo reduction with the following reagents: 
 i  SOCl2

R  C  OH   ii  CH 2 N 2  R  CH 2  C  OH
 ii  HOH / Ag 2O Carboxylic acid

H2 / Ni / 
O O
 
 i  SOCl2
O
LiAlH4 (or)
R  C  OH   ii  CH 2 N 2  R  CH 2  C  O  R '
R – C – OH  ii  R ' OH / Ag 2O Carboxylic acid

O O
 
 i  SOCl2
H2 / Ru (or) R  C  OH   ii  CH 2 N 2  R  CH 2  C  NH  R '
 ii  R ' NH 2 / Ag 2O
 Hell - Volhard - Zelinsky reaction : Acid derivatives: The main reaction of these
Carboxylic acids having at least one  - compounds is nucleophilic substitution reaction.
The order of reactivity for nucleopilic
hydrogen react with X 2  Cl2 or Br2  in the substitution is :
presence of phosphorus (or phosphorus halide) O

O

O

to give  - halo acids. This reaction is known R  C  Cl  R  C  O  C  R 
as Hell - Volhard Zelinsky reaction (HVZ O

O

O

reaction) R  C  OR '  R  C  OH  R  C  NH 2
Br  Nucleophilic substitution reaction of acid and
| acid derivatives is called nucleophilic addition
 2
R  CH2  COOH 
ii HOH 
R  C H  COOH
i Br /Red P
 Halo acid elimination reaction or acyl substitution
reaction.
 If excess of X 2 is used in the reaction, the JEE ADVANCE
products obtained are  ,   dihalo acids or Acid Chloride:
 ,  ,   trihalo acids.  Preparation: It is prepared from carboxylic
Aromatic Carboxylic acids: First member acid.
of this class is benzoic acid. It gives two types
of reactions:
(1) Reactions due to COOH : These reactions are
O
identical to those of the aliphatic acids.
R – C – OH
(2) Reaction due to the benzene ring : It gives
electrophilic aromatic substitution reactions due
to the presence of benzene ring.
COOH (i) m-directing group and Chemical reactions: Acid chlorides give
(ii) Deactivating group the following chemical reactions:
(1) Nucleophilic substitution reactions:
 The nucleophilic substitution reactions are
given below in the table.

COOH
O
HOH / OH 
R – C – Cl

 O
||
Cl R ' C  O  Na 

m - chlorobenzoic acid Anhydride

O
COOH R ' O  Na  or 
COOH R – C – O – R
R ' OH / Base Ester

Fuming HNO3 O
R – C – NH 2
Amide
NO2
O O
m-Nitrobenzoic acid R – C – Cl R – C – NH – R

COOH
O
R–C–N
Fuming H2SO4
O
R – C – NH – NH 2
SO3H
O
m-Sulphobenzoic acid
R – C – CN
Acid cynide
(2) Reduction reaction:Reduction products of Curtius reaction: Acid chlorides give
acid chlorids with various reducing agents are primary amines when heated with sodium azide
given below in the followed by hydrolysis.
O O
 
R  C  Cl 
 R  C  N3
NaN 3

i 
O 
 ii  H 2O R  NH 2  CO2  N 2
R – C – Cl  This reaction is called Curtius rearrangement.
In this reaction, COCl group converts into
 NH 2 group.
O

C6 H 5COOH 
 C6 H 5  C  Cl
SOCl2

i NaN / 

 ii  H 2O  C6 H 5  NH 2
3

 Benzoylchloride is used as benzoyl lating agent

for alcohols and amines. It is less reactive than
acetyl chloride due to the  I effect of phenyl
group.
O O
C6H5 C Cl C Cl

W.E-4:Complete the following : Stronger bond Weaker bond

CH3  Benzoylation can be carried out in aqueous
(below 25C ) as well as in non - aqueous
medium. Benzoylation of amines in aqueous

CH 3COCl
AlCl3
  A medium is known as Schotten - Baumann
reaction.
Acid Anhydride: Nucleophilic substitution
 B  C
Zn Hg  reaction.

Conc. HCl
K2Cr2O7 / H
The nucleophilic substitution are given below
in the table.
Sol.
CH3 CH3


CH 3COCl
AlCl3
 O O
R–C–O–C–R

COCH3
(A)

CH3 COOH
Esters:
  Preparation :
Zn  Hg / HCl
  
K 2 Cr2 O7 / H


(1) From carboxylic acids and alcohols:
O O
 
a R  C  OH  H  O  R ' 

conc. H SO / 

2

4
C
R
  O  R ' HOH


O O
 
b R  C  OH  H  O  R ' 
 R  C O  R '
DCC
(2) From acid chlorides and alcohols: Acid  Product of the reaction is  - ketoester..
chloride reacts with alcohol to give ester: O O
 
O

O
 CH 3  C  OC2 H 5  H  CH 2  C  OC2 H 5
R  C  Cl  R ' OH 
 R  C  O  R ' HCl O

O

O

 CH 3  C  CH 2  COOC2 H 5  C2 H 5OH
C2 H 5ONa / C2 H 5OH

  keto ester
R  C Cl  R ' O Na 
 R  C OR ' NaCl
(3) From diazomethane and carboxylic acids:
Diazomethane gives methyl ester with LEVEL-I (C.W)
carboxylic acids.
O

O

NOMENCLATURE
R  C  O H  C  
H 2 N 2 / ether
 R  C  OCH 3 1. The acid present in red ants is
(4) From Tischenko reaction:In this reaction, 1) HCOOH H COOH
6 5
2 ) C

aldehydes convert into ester in the presence of OH

|
aluminium ethoxide. 3) CH3COOH 4) C H 3  C H  C O O H
O

R  CHO  RCHO 

 C H O
2 5 3 Al / 
 R  C O  CH2  R

2.   chlorobutyric acid is named in IUPAC
as
Chemical reactions: 1. 2-chlorobutanoic acid 2. 2-chlorobuteric acid
Nucleophilic substitution reactions: 3. 3-chlorobutanoic acid 4. 3-chlorobuteric acid
Hydrolysis: Esters undergo nucleophilic 3. A compound of general formula C nH2nO2
substitution reaction with water. This reaction could be
is known as hydrolysis which is catalysed by 1) an acid 2) a diketone
acid as well as base. 3) an ether 4) an aldehyde
(i) Catalysed by acid:
PREPARATION
O

H 4. CH3Cl  A;
KCN
R  C  O  R ' 
  RCOOH  R ' OH

A  H 3O 
This reaction is a reversible reaction.  B (Final product) In this reaction
(ii) Catalysed by base ‘B’ is
O

O

1) CH3COOC2H5 2) CH3COOH
R  C  O  R ' HOH 
NaOH

  
R
 C  O  Na   R ' OH 3) HCOOH 4) CH3CONH2
 Alkaline hydrolysis is known as saponification
CH 3 OH   CH 3 COOH. In this
(i ) X
which is irreversible reaction. This is because 5. ( ii ) Rh ; 

carboxylate ion is better stabilised by resonance reaction ‘X’ is

than carboxylic acid. 1) CO2 2) CO 3) MgO 4)C
 PROPERTIES
O O
  |
6. In vinegar the concentration of acetic acid is
R  C  O 
R C  O
Equivalent resonating structures nearly

1) 5% 2) 2% 3) 6-10% 4) 100%
O O 7. Which of the following has highest boiling
..
 | 
R  C  O  H 
 R  C  O H point?
..
Non  Equivalent resonating structures 1) C2 H 5OH 2) CH 3COOH
Claisen condensation: This reaction take 3) CH 3COCH 3 4) HCOOCH 3
place between two molecules of esters (same or
different). One ester should have at least one 8. The products formed when PCl5 reacts with
  hydrogen which behaves as a reagent. acetic acid are
 Reaction is catalysed by C2 H 5ONa in the 1) CH 3COCl , H 3 PO3 2) CH 3COCl , H 3 PO4
presence of C2 H 5OH as solvent. 3) CH 3COCl , HCl 4) CH3COCl, POCl3 , HCl
9. Which of the following reduces carboxylic LEVEL-I (C.W) - HINTS
acid directly to primary alcohols 1. Formica means red ant
1) LiAIH4 2) Na + C2H5OH
3) Lindlars Catalyst 4) H2 CH 3  CH  CH 2  COOH
10. Number of hydrogen bonds present between |
two acetic acid molecules when they are 2. Cl
existing as dimer
1) 1 2) 0 3) 3 4) 2 3. Cn H 2 n 1COOH or Cn H 2nOn
11. Which is false about acetic acid
CH3Cl+KCN  CH 3 CN 
Hydrolysis
1) it is a polar molecule 4. H   or OH 
2) it forms H bonds ( A)

3) it is stronger than mineral acids OH O

4) it has higher boiling point than corresponding | ||
alcohols. CH 3  C  NH   CH 3  C  NH 2 
H O
 CH 3 COOH  NH 3
2

(B)
12. In the following reaction, X and Y are
respectively :
CH3OH+CO   CH3COOH
Cobalt ( or )
5.
CH3COOH+NH3  X 
Rh , high pressure

 Y+H2O
6. 6 - 10% acetic acid is vinegar
1) CH3CONH2,CH4
2) CH3COONH4,CH3CONH2 7. The high boiling point of acetic acid in
3) CH3CONH2, CH3COOH comparision to alkanes, alkyl halides or alcohols
4) CH3NH2,CH3CONH2 of nearly same molecular masses is due to more
13. Assertion (A) : CH3CN on hydrolysis gives strong hydrogen bonds between acetic acid
Acetic Acid molecules.
Reason (R) : Cyanides on hydrolysis liberates 8. CH3COOH  PCl5  CH3COCl  POCl3  HCl
‘NH3’ gas
1. Both ‘A’ and ‘R’ ae true and ‘R’ is the
correct explanation of A 9. CH3COOH 
LiAlH 4
 C2H5OH
2. Both ‘A’ and ‘R’ are true and ‘R’ is not O H O
the correct explanation of A
10. H3C – C
3. ‘A’ is true but ‘R’ is false O
O H
4. ‘A’ is false but ‘R’ is true.
11. Acetic acid is less acidic than mineral acids.
14. Match the acids given in Column I with their
correct IUPAC names given in CH 3COOH  NH 3
Column I Column II 
12.  CH 3COO NH 4   CH 3 CO NH 2  H 2O
(Acids) (IUPAC names) (X ) (Y )

i) Phthalic acid a) Hexane-1, 6-dioic acid

13. CH3Cl+KCN  CH3 CN 
Hydrolysis
ii) Oxalic acid b) Benzene-1, 2-dicarboxylic H   or OH 
acid
iii) Succinic acid c) Pentane-1, 5-dioic acid
iv) Adipic acid d) Butane-1, 4-dioic acid NH 3  CH 3COOH
v) Glutaric acid e) Ethan-1, 2-doic acid
1) i - (b) ii - (e) iii- (d) iv - (a) v-(c)
2) i - (e) ii - (b) iii- (d) iv - (a) v-(c) LEVEL-I (H.W)
3) i - (b) ii - (d) iii- (e) iv - (a) v-(c)
4) i - (b) ii - (e) iii- (a) iv - (d) v-(c) NOMENCLATURE
1. In CH3COOH molecule, the C-C bond is
LEVEL-I (C.W) - KEY formed by
1) 1 2) 3 3) 1 4)2 5) 2 6)3 7)2 1) sp3 - sp3 overlap 2) sp2 - sp2 overlap
8)4 9)1 10) 4 11)3 12)2 13) 1 14) 1 3) sp3 - sp2 overlap 4) sp3 - sp overlap
 CH2COOH 8. Which of the following statements is/ are
correct?
1) the two carbon-oxygen bond lengths in
2. IUPAC name of molecular formic acid are different
2) the two carbon-oxygen bond lengths in
sodium formate are equal
1) Benzoic acid 3) partial resonance is there in formic acid
2) 2-phenyl ethanoic acid 4) all of the above
3) Benzene 1,2 carboxyllic acid 9. Which of the following will give readily a
4) 1-phenyl ethanoic acid hydrocarbon ?
 2) RCOO Ag 
I
3. Which of the following is a pair of functional 1) R  COONa electrolysis 2

 4) (CH3)2 CCl2  

isomers ? (2005E) I 2 / hv
3) CH3CH3  C H OH
2 5

1) CH3COCH3, CH3CHO 10. An organic compound reacts (i) with metallic

2) C2H5CO2H, CH3CO2CH3 sodium to liberate hydrogen and (ii) with
3) C2H5CO2H, CH3CO2C2H5 Na 2 CO 3 solution to liberate CO 2 . The
4) CH3CO2H, CH3CHO compound is
1) an alcohol 2) a carboxylic acid
PREPARATION 3) an ether 4) an ester
KMnO4 / KOH / H 3O
11. Acetic acid exists in a dimer state in benzene
4. Toluene   A. What is A? due to
1) Acetic acid 2) Benzene 1) condensation reaction
3) Benzoic acid 4) Benzaldehyde. 2) hydrogen bonding
5. Which of the following can’t form 3) presence of carbonyl group
CH3COOH from C2H5OH 4) presence of  - hydrogen
A) PCC B) PDC 12. Which hydrogen atom of acetic acid is
replaced by Cl2 in presence of Red P ?
C )

2
Cr2O7 / H+
K D) Micodermaaceti 1)  - hydrogen 2) carboxylic hydrogen
1) A and B only 2) C and D only 3) both 1 & 2 4) oxygen of carboxylic group
3) Only A 4) All A,B,C,D 13. The correct order of increasing acidic
strength is ____.
PROPERTIES 1) Phenol<Ethanol<Chloroacetic acid <
6. Lower carboxylic acids are souble in water Acetic acid
due to 2) Ethanol<Phenol<Chloroacetic acid< Acetic
1) Low molecular weight 2) Hydrogen bonding acid
3) Dissociation into ions 4) Easy hydrolysis 3) Ethanol<Phenol<Acetic acid <Chloroacetic
7. Which of the following graphs represents the acid
correct order of boiling points (B.P) of ethane 4) Chloroacetic acid<Acetic acid <
(1) ethyl alcohol (2) and acetic acid (3)? Phenol<Ethanol
14. Assertion (A): Compounds containing -
CHO group are easily oxidised to
corresponding carboxylic acids
Reason (R) : Carboxylic acids can be reduced
1) B.P 2)
B.P to alcohols by treatment with LiAlH 4
1 2 3 1 2 3 1) A and R both are correct and R is correct
explanation of A
2) A is correct statement but R is wrong
statement
3) A is wrong statement but R is correct
3) 4) statement
B.P
B.P
4) A and R both are correct statements but R is
1 2 3 1 2 3 not correct explanation of A
 LEVEL-I (H.W) - KEY
1)3 2) 2 3) 2 4) 3 5) 1 6) 2 7) 3
8) 4 9)1 10)2 11)2 12) 1 13) 3 14) 4

LEVEL-I (H.W) - HINTS

H O
H–C–C–O–H
1.
H 3 2
sp sp
2 1
CH2COOH

2. 2-phenyl ethanoic acid.

3. C 2 H 5 CO 2H, & CH 3 CO 2 CH 3 are a pair of

functional isomers
CH3 COOK COOK

4. a) KMnO4,KOH H3O
+

Toluene Benzoic acid

5. C2 H 5OH 
PCC or
PDC
 CH 3CHO
9. CH 3COONa  NaOH 
 Soda lim e   CH 4  Na2CO3
CaO

10. 2CH3COOH + 2Na  2CH3COONa + H2

O H O
11. H3C – C
O H O
12. CH3COOH   CH2ClCOOH
Re dP
Cl2

monochloro acetic acid

CH 2ClCOOH   CHCl2COOH
Re dP
Cl2

di-chloro acetic acid

CHCl2COOH   Cl3CCOOH
Re dP
Cl2

tri-chloro acetic acid

in the above reaction  -hydrogens are replaced
by chlorine
 CARBOXYLIC ACIDS 9. Which of the following is not a derivative of
carboxylic acids ?
LEVEL-II(C.W)
LEVEL-II (H.W) 1) anhydrides 2) esters 3) amines 4) amides
10. Which of the following reactions of acetic acid
involve C-OH bond ?
PROPERTIES I. Action with Na
1. The weaker acid among the following is II. Formation of acid chloride
1) CH 3COOH 2) ClCH 2COOH III. Action with NaHCO3
IV. Formation of an ester
3) Cl3CCOOH 4)  CH 3 2 CHCOOH 1. I, II 2. II, III 3. III, IV 4. II, IV
2. The correct order of decreasing acid strength LEVEL-II (C.W) - KEY
of trichloroacetic acid (A), trifluoro acetic acid 1) 4 2) 3 3) 3 4) 3 5) 1 6) 3 7) 1
(B), acetic acid (C) and formic acid (D) is
1) A  B  C  D 2) A  C  B  D 8) 3 9) 3 10) 4
3) B  A  D  C 4) B  D  C  A LEVEL-II (C.W) - HINTS
3. Which of the following has highest tendency 1. Due to + I effect of CH 3 groups
to ionise in aqueous solution?
2. Follow applications of inductive effect.
1) HCOOH 2) CH 3COOH The negative charge on carboxylate ion is
3) FCH 2COOH 4) BrCH 2COOH dispersed more due to - I.E. of F
( i ) KMnO / OH  F
4. Ethyl benzene  4
( ii ) H  / H 2O

X –
F C C O . The carboxylate ion thus
Predict X in above reaction
F O
1. C6 H 5CH 2COOH 2. C6 H 5CH 2CHO becomes more stable and acid becomes more
3. Benzoic acid 4. Benzaldehyde reactive
5. 
In the anion HCOO the two carbon-oxygen 1
bonds are found to be of equal length. What 7. CH 3COOH  Na CH 3COONa  H 2
2
is the reason for it ? 1 mole 1 mole 1/2 mole
1. The anion HCOO  has two equivalent 60g 23g 11.2 lit
resonating structures 0.1 mole 0.1 mole =?
2. The anion is obtained by removal of a proton = 6g 2.3 g 1.12 lit.
from the acid molecule
3. Electronic orbitals of carbon atom are
8. C2 H 5Cl 
AqKOH
C2 H 5OH
hybridised C2 H 5OH  CH 3COOH  CH 3COOC2 H 5  H 2O
4. The C=O bond is weaker than the C-O bond 9. Amines are not the derivatives of carboxylic
Y
6. X   Adipic acid; Here X and Y aree acids
respectively
1. Cyclohexene, Bayer’s reagent
2. Benzene, hot acidified KMnO4
PROPERTIES
3. Cyclohexene, hot acidified KMnO4
1. Which of the following orders is true
4. Cyclopentene, hot acidified KMnO4 regarding the acidic nature of COOH?
7. 2.3 gm Na is added to 6 gm of CH3COOH. 1) Formic acid > Acetic acid > Propanoic acid
The Volume of ‘H2’ gas liberated at S.T.P. 2) Formic acid > Acetic acid < Propanoic acid
1) 1.12 L 2) 2.24 L 3) 3.36 L 4) 4.48 L 3) Formic acid < Acetic acid < propanoic acid
8. C2H5Cl  aqKOH

A 4) Formic acid < Acetic acid >Propanoic acid
CH3COOH+A  B. IUPAC name of ‘B’ 2. Which of the following is the strongest acid
1) Ethyl propanoate 2) Ethyl acetate 1) HCOOH (pKa=3.77)
3) Ethyl ethanoate 4) Ethyl methanoate 2) C6H5COOH (pKa=4.22)
 3) CH3COOH (pKa=4.71) LEVEL-II (H.W) - HINTS
4) CH3CH2COOH (pKa=4.88) 1 Electron-releasing group weakens the acidic
3. In the manufacture of acetic acid from aerial nature of COOH
oxidation of acetaldehyde, the catalyst used 1
is 2. Acidic strength 
P ka
1) Acidified K2Cr2O7 2) (CH3COO)2 Mn
3) HgSO4 4) Ni 1
3. CH 3CHO  O2  CH 3COOH
4. Which of the following possess highest boiling 2
point 4 due to presence of more number of H-bonds
1) C2 H 5Cl 2) CH 3CHO 3) C2 H 5OH 4) CH 3COOH CH3
5. Which of the following will not undergo Hell CH3 C COOH
Volhard Zelinsky reaction 5. does not contain   H
1) CH 3COOH 2) CH 3CH 2COOH CH3
3) 2,2-dimethyl propionic acid 6. Methanoic acid (i.e. formic acid) reduces
4) 2-methyl propionic acid ammoniacal solution (Tollens reagent) while
6. Which of the following reagent/solution can ethanoic acid does not.
be used to distinguish between methanoic C2 H5OH  CH3COOH  CH3COOC2 H5  H2O
acid and ethanioc acid? 7. RCOOH 
NH 3
 RCOONH 4 
heat

 H 2O
1) Tollens reagent 2) FeCl3 solution
RCONH 2 
P2O5
 H 2O
 RCN
3) NaOH solution 4) Na2CO3 solution
7. The product ‘C’ in the following reaction is 8. CH 3CHClCOOH 
alcKOH
CH 2  CHCOOH
RCOOH  (A)  (B)  (C) PREVIOUS YEARS QUESTIONS
NH3 heat P2 O5 ,heat

1) RNH2 2) RCN 3) RNC 4) RCONH2 7. The major product obtained on interaction

8.  - chloropropanoic acid on treatment with of phenol with sodium hydroxide and carbon
alcoholic KOH followed by acidification dioxide is :
gives: 1) benzoic acid 2) salicylaldehyde
3) salicylic acid 4) phthalic acid
1) CH 3  CH  OH   COOH 2. Sodium ethoxide has reacted with ethanoyl
2) CH 2  CH  COOH chloride. The compound that is produced in
the above reaction is :
3) HO  CH 2  CH 2  COOH 1) 2-Butanone 2) Ethyl chloride
4) CH 3  CH 2  COOH 3) Ethyl ethanoate 4) Diethyl ether
3. The strongest acid amongst the following
9. Identify A and B in the following reaction,
compounds is :
CH 3CH 3  B
 CH 3COOH  A
 CH 3CH 2OH 1) HCOOH 2) CH3CH 2CH  Cl  CO2 H
A B
3) ClCH 2CH 2CH 2COOH 4) CH 3COOH
1) HI + Red P LiAlH 4
4. Compound (A), C8 H 9 Br, gives a white
2) Ni /  LiAlH 4
precipitate when warmed with alcoholic
3) LiAlH 4 HI  Re d P AgNO3 .
4) Pd  BaSO4 Zn  HCl Oxidation of (A) gives an acid (B), C H O . 8 6 4
(B) easily forms anhydride on heating.
LEVEL-II (H.W) - KEY Identify the compound (A).
1) 1 2) 1 3) 2 4) 4 5) 3 6) 1 7) 2
8) 2 9) 3
 CH2Br C2H5

1) 2)
Br 5.
CH3
CH2Br
CH2Br

3) 4) 1. Order of decreasing acidity of

CH3 (I) HCOOH (II) CH3COOH
CH3 (III) Cl2CHCOOH (IV) CF3COOH is
5. In the reaction, 1) IV > III > II > I 2) IV > III > I > II
LiAlH
3) III > IV > II > I 4) I > IV > II > III
CH 3COOH 
4
 A 
PCl5
 B 
Alc.KOH
 C, ,
2. The correct order of increasing acidic strength
the product C is: of the following acids is
1) Ethylene 2) Acetyl chloride
3) Acetaldehyde 4) Acetylene O O
Cl O
OH
OH Cl OH
PREVIOUS YEARS - KEY Cl
1) 3 2) 3 3) 2 4) 4 5) 1 I II III
1) I<II<III 2) I<III<II 3) III<II<I 4) II<III<I
PREVIOUS YEARS - HINTS 3. The relative order of rate of esterification of
OH ONa OH acids is
COONa
 
1)

NaOH CO2
6 atm ,1400 C

OH
2)
1.  COOH

H 3O
 3)
Salicylic Acid 4)
4. Among ethanol (I), Acetic acid (II), Phenol
(–) + (III) and Benzoic acid (IV), the correct order
C2H5 O Na+CH3–C–Cl CH3 –C–O–C2H5 Ethyl ethanoate
2. of increasing acid strength is
O O
1. I<II<III<IV 2. I<III<II<IV
3. Electron releasing groups (Alkyl groups) de
stabilizes conjugate base. 3. I<III<IV<II 4. III<IV<I<II
The +I effect of CH3 is less than - I effect of Cl 5. Which acid has lowest value of pK a ?
5
K a of HCOOH is 17.9  10 1. p - Methoxybenzoic acid
CH 3CH 2 C H  COOH 2. p - Chlorobenzoic acid
K a of | is 139  10 5 3. p - Aminobenzoic acid
Cl
4. p - Toluic acid
O LEVEL-III
CH2–Br COOH C 6. Which of following anion is a strongest base?
O 
 
 O
1. C6 H 5COO  2. HCOO 
4. CH3 COOH

(A) (B) C  O
3. CH 3COO  4. CH3 2 CHCOO
7. Which of the following compounds does not
 have a carboxyl group? 3) CH 3CHO, CCl3CHO
1) Methanoic acid 2) Ethanoic acid
4) CH 3COCH 3 , CCl3COCH 3
3) Picric acid 4) Benzoic acid 

8. The COOH group in benzene ring is 15. R  COCH 3 

X 2 / OH
 CHX 3  Carboxylate
H
1) ortho directing 2) para directing ion  carboxylic acid, In the above
3) ortho and para directing 4) meta directing sequence, the carboxylic acid obtained is
9. Which of the following reaction is not the 1) CH 3COOH 2) HCOOH
oxidation ?
3) RCOOH 4) RCH 2COOH
1) CH3 - CHO  CH3COOH
2) C2H5OH  CH3 - CHO LEVEL-III - KEY
3) C2H5OH  CH3 - COOH 1) 2 2) 3 3) 1 4) 2 5) 2 6) 4 7) 3 8) 4
4) CH3COOH  C2H5OH 9) 4 10) 2 11) 4 12)1 13) 4 14) 1 15) 3
O LEVEL-III - HINTS
10. Compound can be prepared 1. (IV) CF3COOH > (III) Cl2CHCOOH >
Ph  O  C  Ph (I) HCOOH > (II) CH3COOH
by the reaction of ________. O O
1) Phenol and benzoic acid in the presence of Cl O
2 OH >
NaOH OH >Cl OH
2) Phenol and benzoyl chloride in the Cl
presence of pyridine 3 The increasing number of R groups makes the
3) Phenol and benzoyl chloride in the esterification more difficult.
presence of ZnCl2 4. Conceptual
4) Phenol and benzaldehyde in the presence of 5. due to -I effect
palladium 6. Weak acid can give strong conjugate base
11. Acetic acid can be used 7. Picric acid is 2,4,6- trinitrophenol
1. For curing meat and fish 8. COOH is electron attracting group. It is
2. As vinegar in cooking
3. In the preparation of perfumes 4. All thus meta director.
12. Hydrolysis of an ester gives a carboxylic acid 9. CH3COOH 
LiAlH 4
 C2H5OH
which on Kolbe’s electrolysis yields ethane.
The ester is
1) methyl ethanoate 2) methyl methanoate
3) ethyl methanoate 4) methyl propanoate
13. Identify C in the following reaction: 1. Which of the following carboxylic acids
C2 H 2 
Chromic acid
 A 
NH 3
 B 
C undergoes decarboxylation easily?
 H 2O
1) C6 H 5  CO  CH 2COOH
1) CH 3CH 2 NH 2 2) CH 3CN
2) C6 H 5  CO  COOH
O
3) CH 3CH 2 NHCH 3 4)
CH 3  C  NH 2 3)

14. CH 3CN  H 2O 
H
 A 
Excess Cl2
Re d P
 B . in the
above reaction A and B are respectively. 4)
1) CH 3COOH , CCl3COOH
2) CH 3CH 2OH , CH 3CH 2Cl 2. CH 3CH 2COOH 
Cl2
Fe
 X 
Alc
KOH
Y
 the compound Y is: L iA IH 4 the compound obtained will be
1) CH 3CH 2OH 2) CH 3CH 2CN 1) CH 2  CH  CH 2OH 2) CH 3  CH 2  CH 2OH
3) CH 2  CHCOOH 4) CH 2CHClCOOH 3) CH 3  CH 2  CHO 4) CH 3  CH 2  COOH
8. The correct order of increasing acid strength
3. Carboxylic acids react with diazomethane to
of the compounds.
yield :
1) Amines 2) Alcohols A) CH 3CO2 H B) Me OCH 2 CO2 H
3) Esters 4) Amides Me
4. Acetic acid on warming with hydrazoic acid C) CF3CO2 H D) CO2H
in presence of conc. H 2 SO4 gives: Me
1) D  A  B  C 2) A  D  B  C
1) CH 3CONH 2 2) CH 3 NH 2 3) B  D  A  C 4) D  A  C  B
3) CH 3COONH 4 4) CH 3CH 2 NH 2 9. Both the organic compounds A and B can
release hydrogen with Na. Only compound
CH2OH A can form a salt with NaOH, whereas B
cannot. When A reacts with B in presence of
5 
con.H2SO4, a pleasant smelling compound is
 
HBr
 A 
KCN
 B 
H3O

C formed. The pair of compounds A and B can
LEVEL-IV be respectively
In the above sequence of reactions, C is 1) C2H5OH and C2H2 2) CH3COOH and C2H2
COOH CH2COOH
3) CH3COOH and C2H5OH
4) C2H5OH and CH3COOH
1) 2)
10.
COOH CH2COOH In the above series of reaction ‘Z’ is
CHO CHO 1) CH3CN 2) CH3COOH
3) 4) 3) (CH3CO)2O 4) CH3-CH2-OH


11. 
CH3Cl
anhy . AlCl3
 A Cl2

Sunlight
 B 
NaCN
C 
H 2 OlH
D
CH=CH2
In the above sequence of reactions, D is
COOH CH2COOH
KMnO4  KOH
  A+B (non - aromatic)
6.
(styrene) 1) 2)

, In the above reaction, C is NC

CN
CH2COOH
3) 4)

1) HCOOH 2)
12. The order of rate of hydrolysis for the
following is
1) RCOX  RCONH 2  RCOOCOR  RCOOR
CH3
COOH
COOH
2) RCOX  RCOOCOR  RCOOR  RCONH 2
3) RCOOR  RCONH 2  RCOX  RCOOCOR
3) 4)
4) RCOOCOR  RCOOR  RCOX  RCONH 2
13. What are A, B, C in the following reactions ?
7. When CH2 CHCOOH is recduced with
 I.  CH 3CO  2 Ca 

A presence of phosphorus to give  - halo acids.
The reaction is known as Hell-
II. CH 3CO2 H  B
HI
Red P Volhard-Zelinsky reaction (HVZ reaction),
III. 2CH 3CO2 H 
P4O10
C R  CH2  COOH 
P / Br2

 R  CH (Br)COOH
A B C The HVZ reaction is limited to the formation
1. C2 H 6 CH 3COCH 3  CH 3CO 2 O of  - chloro and  - bromo acids and it is
sometimes backward to carry out. The
2.  CH 3CO 2 O C2 H 6 CH 3COCH 3
reagents ( X 2 and P) are noxious and the
3. CH 3COCH 3 C2 H 6  CH 3CO 2 O reaction time is often long and the conditions
4. CH 3COCH 3  CH 3CO 2 O C2 H 6
of reaction are harsh .
A. Which of the following carboxylic acids will not
COMPREHENSION - 1 give HVZ reaction ?
14 Dicarboxylic acids have two carboxylic groups, CH 3
e.g.
1) CH 3  COOH 2) |
HOOC-COOH,- oxalic acid CH 3  CH  COOH

HOOC-CH 2 -COOH,- Malonic acid CH 3

|
HOOC-(CH 2 )-COOH,- Succinic acid
CH 3  C  COOH
HOOC-(CH 2 )3 -COOH,- Glutaric acid 3) CH 3  CH 2  COOH 4) |
HOOC-(CH 2 )4 -COOH,- Adipic acid CH 3

Acidity of dicarboxylic acid depends upon the B. Whic of the following will be obtained when
stabillity of intermediate ion and upon the acetic acid is subjected to HVZ reaction ?
distance between two carboxylic groups. B r
Shorter the distance between two carboxylic |
groups, greater is the acidic character. B r  C  C O O H
1) BrCH 2COOH 2) |
Melting point of the acids depends on the
H
symmetry. Greater the symmetry, higher will
be the melting point. Dicarboxylic acids on Br
heating give monocarboxylic acid, alkanes, |
Br  C  COOH
cyclic ketones depending on the conditions. 3) 4) All of these
|
A. Which of the following is the most acidic? Br
1) Oxalic acid 2) Malonic acid
C. CH  COOH ( A) ( B ) (C )

Br2 / P NaCN HOH / H

3) Succinic acid 4) Adipic acid 3

B. Which of the following dicarboxylic acid is The product (C) will be :

used in the manufacture of nylon-6,6? COOH CH2 COOH
1) Succinic acid 2) Glutaric acid 1) CH2 2)
3) Adipic aicd 4) Oxalic acid COOH CH2 COOH
C. Sodium adipate on electrolysis gives :
1) but-2-ene 2) but-1-ene CH2 CO
3) cyclobutane 4) cyclobutene 3) O 4) CO
CH2 CO CH2–CH O
COMPREHENSION - 2
CO
15. Carboxylic acids having at least one
 - hydrogen react with Cl2 or Br2 in the LEVEL-IV - KEY
 1) 1 2) 3 3) 3 4) 2 5) 2 6) 3 7) 1 CH3 CH2Cl
8) 1 9) 3 10) 3 11) 2 12) 2 13) 3
CH3Cl Cl2
14) A-1;B-3;C-3 15) A-4, B-4, C-1 Sunlight
(A) (B)
CH3CN CH2COOH
LEVEL-IV - HINTS
11.
1.  -keto acids are readily decarboxylated. NaCN H3O+

CH3CH2COOH 
Cl2
CH3CHCl.COOH (C) (D)
2.

KOH alc
 HCl
CH2  CH .COOH KMnO4lH COOH (Adipic acid)
12.  COOH
3. RCOOH  CH 2 N 2  RCOOCH 3  N 2 ;
methyl esters are formed 14. A. due to +I effect
B. Nylon-6,6 is a polymer of adipic acid
4. CH3COOH  N3 H  CH3 NH2  N2  CO2 15. A. Absence of  - hydrogen atoms
CH2OH CH2Br CH2CN CH2COOH B. Presence of  - hydrogen atoms
HBr KCN H3O+
5
(A) (B) (C)

CH=CH2 COOK

KMnO4  KOH

(A)
H3O

6. COOH

7. LiAlH 4 can reduce COOH group and not the

c  c double bond.
CH 2  CH  COOH  CH  CH  CH OH
LiAIH 4

2 2

8. order of decreasing acid strength

CF3COOH  MeOCH 2COOH  CH 3COOH
( Me)2 CH .COOH Electron withdrawing
groups increase the acid strength and
electron donating groups decrease the acid
strength.
10. CH 3Cl  KCN   CH 3CN  
H 2O
 KCl

CH 3COOH 
P2O5
  CH 3CO 2 O