Carboxylic acids and Their derivatives 1351

4. (d) Amide group represent by the formula CONH 2 27. (c) Phthalic acid is the isomer of 1, 4 benzene dicarboxylic acid
because both have the same molecular formula but differ in
5. (a) Cl  CH 2  CH 2  COOH their structure.
3 2 1
3 chloro propanoic acid COOH
COOH ONa
7. (d) Soaps are sodium salt of fatty acids e.g.- C17 H 35 COONa ONa
Sodium Steariate acid.
COOH
8. (c) R  CONH 2 (RCO )2 NH Phthalic acidONa COOH
Primary amide Secondary amide 28. (d) Esters are RCOOR’ , where OR’ =1, alkoxyONagroup
4 benzene and R =acid
dicarboxylic H or
alkyl or aryl group.
CHOHCOOH 29. (a) Soaps are the sodium or potassium salts of higher fatty acids.
9. (c) | is known as tartaric acid and its potassium
CHOHCOOH 33. (d) Vinegar is the diluted solution of acetic acid (CH 3 COOH ). It
salt is known as Tartaremetic.
is formed by the fermentation of ethyl alcohol in the presence
O O of enzyme acetobacter.
|| |
11. (a) RC OH  R  C  O        H COOH COOH
OCOCH
It represent the acidic nature. 34. (c) 3

O O
|| || Aspirin Benzoic acid
12. (c) CH 3  C  CH 2  C  O  C 2 H 5 ⇌
Acetoacetic ester OH COOH
( keto form)
ON NO
2
2
OH
OH O
| ||
CH 3  C  CH  C  O  C2 H 5
(enolic form)
NO 2
Salicylic acid
 H 2O Picric acid
13. (d) 2 RCOOH 
 (RCO )2 O 35. (a) Acetic acid is the chief constituent of vinegar and hence its
Acid anhydride
name (Latin : acetum = vinegar).
OH 36. (b) Phenol was discovered by Runge in the middle oil fraction of
| coal-tar distillation and named it ‘carbolic acid’ (carbo-coil,
14. (d) HOOC  CH 2  C  CH 2  COOH oleum = oil) or phenol containing 5% water in liquid at room
|
COOH temperature and it is termed as carbolic acid.
37. (a) Any electron withdrawing substituent (having-I-effect) stabilises
It is citric acid consist three carboxylic group. the anion by dispersing the negative charge and therefore,
16. (c) Wax are long chain ester. increases the acidity. Chlorine is an electron withdrawing
17. (d) Glycine do not have the chiral carbon so it is not optically group.
active acid. 38 (d) The order of reactivity of acid derivatives towards different
reactions decreases in the order,
H
| RCOCl  (RCO)2 O  RCOOR  RCONH 2
H 2 N  C  COOH
| In other words, the reactivity decreases as the basicity of the
H leaving group increases i.e.,
(Glycine)

18. (d) Except phenyl acetic acid all rest acid are fatty acid. Cl   RCOO   RO   NH 2
19. (c) Vinegar contain 8-10% acetic acid.
20. (b,d) General formula of monocarboxylic acid is Cn H 2n 1COOH Preparation of Carboxylic Acids and Their
or Cn H 2nO2 . Derivatives
21. (a) Formula of Acetamide is CH 3 CONH 2 which consist single
1. (d) CH 3 CH 2 NO 2  H 2 O  
H 2 SO 4
oxygen atom.
CH 3 COOH  NH 2 OH
22. (a) Urea behaves as a monoacidic base and react with nitric acid
and form sparingly soluble nitrate. 2. (a) HCOOH  PCl5  HCOCl  POCl3  HCl
Formic acid Formyl chloride
23. (c) Fats and oil jointly known as lipid which are the ester of
glycerol with high fatty acid. 4. (c) 2CH 3 CHO 
 CH 3 CH 2 OH
Al(OC 2 H 5 )3

26. (b) Urea is the diamide of carbonic acid. CH 3 COOH  CH 3 COOC 2 H 5  H 2 O
Ethylacetate
O O
||
H O
||
5. (c) CH 3 CHO  CH 3 COOH
K 2 Cr2 O7
HO  C  OH  2 NH 3 
2
 H 2 N  C  NH 2 H 2 SO 4
carbonic acid Urea
6. (a) C 2 H 5 OH  CH 3 COOH
Acetobacter

So two mole of NH 3 required that why it is the diamide of

carbonic acid. 7. (a) 
CO  NaOH  HCOONa
 1352 Carboxylic acids and Their derivatives
2
OH It is called esterification reaction.
9. (a) CH  CH   CH 3  CH
1 % Hg
OH
H 2 SO 4
Unstable 26. (d) 2 NH 4 Cl  KCNO  NH 2  CO  NH 2  KCl
Ammonium Potassium Urea
 CH 3 CHO   CH 3 COOH [O ] chloride Cyanate

acetic acid
28. (b) RCOOH  C 2 H 5 OH  RCOOC 2 H 5  H 2 O
dry
10. (b) Reimer-Tiemann reaction involves a carbene intermediate. HCl

Cl Cl Cl
 | |  29. (a) CO 2  C 3 H 7 MgBr 
 Hydrolysis

: O H   H  C  Cl  H 2 O  : C  Cl : Cl   : C : Cl
 | | (a carbene)
Cl Cl C3 H 7 COOH  Mg Br
..
Butanoic acid
OH
O O :O : –

H CHCl 2
O
||
O
||
– : CCl2 – ONa + 2OH– 31. (c) CH 3  COO Na  CH 3  CO  Cl  CH 3  C  O  C  CH 3  NaCl
CCl
.. 2 Acetic anhydride

.. H 32. (a) CH 3  CO  NH 2    CH 3 COOH  NH 3

Hydrolysis
:O : – | Acetamide H 2O Acetic acid
C=O
+ 2Cl + H O –
O  OMgI 
2
||  | 
CH 3 Cl  CH 3 CN  CH 3 COOH (b) CH 3 MgI  Cl  C  OC2 H 5  Cl C  OC2 H 5 
KCN H 2O
11. (d) 33.
 KCl
Ethyl chloroform ate  | 
 
 
 CH 3 COONH 4 
NH 3
CH 3 CONH 2  CH 3 
O
12. (a) CH 3 CN   CH 3 COOH  NH 3
H 2O ||
Br
 CH 3  C  OC2 H 5  Mg
Ethyl acetate
I
13. (b) C6 H 5 CH 2OH  [O]   C6 H 5 COOH  H 2O
KMnO 4

34. (c) CH 3 COONa  CH 3 COCl  NaCl  CH 3 COOCOCH 3

CH Cl2 COOH Sodium
acetate
Acetyl chloride Acetic anhydride

o
14. (d)  [O]  
K 2 Cr2 O7
 HCl 35. (a) CH 3 COONH 4  CH 3 COOH  
110 C
H 2 SO 4 Ammonium acetate

CH 3 CONH 2  H 2 O
CH 3 CH 3 OH
15. (a) C  O  
NaCN
C Acetamide
CH 3 ( HCl ) CH 3 CN
( A) O
||
H 3O
CH 3 OH 36. (b) 2 RCHO   CH 3  C  O  CH 2  CH 3
Al(OC 2 H5 )3
 C
 CH 3 COOH
(B)
37. (b) R COOAg  R  I  R COO R  Ag I
ester
CH 3 COOH CH 3  CO
16. (c)  P2 O5  O  H 2O 38. (c) When Cl 2 or Br2 is react with carboxylic acid in the
CH 3 COOH CH 3  CO
presence of red phosphorus then -hydrogen of carboxylic acid
COOH Glycerol,110 C is replaced by Cl 2 or Br2
17. (c) |  HCOOH  CO 2
C OOH Decarboxylation
Br2
CH 3 COOH   CH 2 BrCOOH
18. (a) CH 3 COOH  CHCl 3  No reaction Aceticacid   bromo acetic acid
This reaction is known as Hell Volhard Zelinsky reaction.
CH 3
COOH 39. (b) Tertiary alcohol are not oxidised easily but on drastic
19. (c)  
V2 O5
conditions, these oxidise to give first ketone and then acid by
Oxidation
CH COOH losing one carbon at each step
o- xylene 3

R
CO H R C  OH  [O] R C  O  [O]  R.COOH
21. (a) Aerial oxidation
2

R R


CO H
2
40. (a) When succinic acid is heated it forms. Succinic anhydride
Naphthalene Phthalic acid
CH 2COOH  CH 2CO
22. (b) C 6 H 5 MgBr  
 C 6 H 5 COOH
(i) CO 2 | 
 O
(ii) H 3O (P ) CH 2COOH  H 2 O CH 2CO
Succinic acid Succinicanhydride
23. (b) Acetic acid freezes at 16.6C while water freezes at 0C . So
41. (d) Treatment of sodium salt of phenol with CO 2 under pressure
glacial acetic acid is obtained by crystallizing, separating and
melting acetic acid. bring about substitution of the carbonyl group COOH , for
the hydrogen of the ring. This is called as Kolbe’s reaction
25. (c) C 2 H 5 OH  CH 3 COOH   CH 3 COOC 2 H 5
Conc
H 2 SO 4 OH ONa OH
ONa COONa
ONa
 Carboxylic acids and Their derivatives 1353

 NaOH  CO
2
140 C (4 7 atm)

Phenol Sodium salt of phenol Sodium salicylate 3. (d)  

Zn Pdr

OH
ONa COOH
ONa 4. (b) 2CH 3 COOH   CH 3 COCH 3  CO 2  H 2 O
MnO


573 K


H
5. (d) Presence of –I effect chlorine atom increases the acidic nature
Salicylic acid by withdrawing electrons
Cl3 CCOOH  Cl 2 CHCOOH  Cl  CH 2  COOH  CH 3 COOH
42. (b) When an acyl halide is heated with acid salt, anhydrides are Trichloroacetic Dichloro acetic acid Monochloro acetic acid Aceticacid
formed acid (Most acidic) (Least acidic)


CH 3 COONa  CH 3 COCl  (CH 3 CO )2 O 8. (b) The reaction of acetamide with water is an example of
acetic anhydride hydrolysis.
9. (a) Methanoic acid resemble with aldehyde due to its structure. So
 NaCl O
||
43. (b) CO 2 adds to Grignard’s reagent to yield acids. it reduce fehling reagent. H  C  OH
Aldehydic group
CO 2   CH 3 COOMg I 
CH 3 Mg I
 CH 3 COOH
H . OH
O
OH ||
 Mg 11. (a) R  C  R    R  CH 2 OH  R OH
LiAlH4
I Two units of alcohols
44. (a) Amide, on treating with HNO 2 , give acids. OH
OCH 3

CH 3 CONH 2   CH 3 COOH  N 2  H 2 O

NaNO 2 / HCl
( HNO 2 )
acetic acid 12. (d)  HI  CH 3 I 
Methyl
45. (b) Aldehydes are easily oxidised to carboxylic acids on treatment Iodide
with common oxidising agents like nitric acid, potassium Anisol Phenol
permanganate and dichromate etc. 13. (b) CH 3 COOH  CH 3  Mg  X  CH 3  CH 3
CH 3
COOH 14. (b) Forms H-bonding by means two highly electronegative atoms
ONa present in it.
46. (d)  
KMnO 4 / K2Cr2O7 Br2 / KOH
15. (d) CH 3 CH 2 CONH 2     CH 3 CH 2 NH 2
Hofmann bromamide
Propionami de reaction Ethylamine
Toluene Benzoic acid
47. (c) This is an example of Perkin’s reaction.
16. (b) CH 3 COOCH 3   CH 3 COONa
NaOH
Therefore, (X) is Acetic anhydride. Methyl ethanoate CH 3 OH Sodium acetate
48. (a) OH OH
CH 3  CH 3   
Kolbe's electrolysis
 CO 2 ,  NaOH ,  H 2
CCl 4
NaOH (aq ), 60 C

CCl 3
17. (c) NH 4 CNO  NH 2  CO  NH 2
ONa OH Ammonium cyanate Urea


 
NaOH

H


NH 2  CO  NH 2  H  NH  CO  NH 2 
Urea  NH 3
H 2O
COONa COOH
salicylic acid
The above given reaction is known as Reimer- Tiemann NH 2  CO  NH  CO  NH 2
reaction. Biuret

49. (a) C 2 H 5 OH   CH 3 COOH .

[O ]
19. (d) F  CH 2  COOH  Cl  CH 2  COOH 

Properties of carboxylic acids and Their Br  CH 2  COOH  CH 3 COOH

derivatives 20. (d) Formic acid resemble with aldehyde due to its structure so it
reduce Tollen’s reagent.
1. (c) BrCH 2 CH 2 COOH is least acidic or has less K a i.e., O
||
dissociation constant. It is (a) due to lesser –I effect of Br than H  C  OH
F and (b) Br atom further away form COOH group. Aldehydic group

2. (b) CH 3  CH  CH 2  O N  Br  22. (b) HCOOH    CO  H 2O

conc . H 2 SO 4
Propene
COOH COOH
O O
N–Bromosuccinimide
CH 2  CH  CH 2  23. (b) + conc. H 2 SO 4   H 2O
NH
| SO H
Br O
m  sulpho
3

allyl bromide benzoic acid

COOH COOH
OH

Salicylic acid Benzoic acid

 1354 Carboxylic acids and Their derivatives
24. (d) CHF2  COOH . Difluoroacetic acid is strongest because
presence of two F atoms increases its acidic nature. 52. (b) N-acetyl paraamino phenol
25. (c) CH 3 COOH does not give silver mirror test.
26. (c) 2CH 3 COOH  
MnO
 CH 3 COCH 3  CO 2  H 2 O
o
300 C Acetone 53. (b) Because it does not have -hydrogen atom.
27. (b) CH 3 COOH is slightly ionised than H 2 SO 4 . 54. (b) Molecular Mass increases due to dimer formation
28. (c) Presence of methyl group decreases the acidic character of O
||
acetic acid due to positive inductive effect ( I) . CH 3 COOH  CH 3  C  OH 
CH 3 CO
29. (c) O  2 NH 3  CH 3 CONH 2  CH 3 COONH 4 O H O
CH 3 CO Acetamide Ammonium acetate CH 3  C C  CH 3
O H O
CH COOH
3
Dimer is formed
30. (c) 
[O ]
 
SOCl 2
 SO 2 ,  HCl COOH COO –

(A)
55. (d)  H 2O   H 3 O  (dissociation)
.. 
COCl CO  N  N  N
..
 

NaN 3
In benzene solution
 NaCl
COOH
(B) Benzylazide
 C O H O C
.. (C) O H O
CO  N : N CO dimer(Association)

 
Heat
 
rearr.
57. (c) 2C 2 H 5 OH  2 Na  2C 2 H 5 ONa  H 2
2CH 3 COOH  2 Na  2CH 3 COONa  H 2
Benzyl nitrene Phenyl isocyanate (D)
59. (c) CH 3  CH 2  CCl 2  COOH ; ,-dichloro butanoic acid
32. (c) CH 3 COOH   CH 3 CH 2 OH
LiAlH4
is most acidic. Hence it will easily loose H  ions in solution.

CH 3 CH 2 OH 
 CHI 3 
 C 2 H 2
I2 / NaOH Ag
62. (c) CH 3 COOH   CH 3 CONH 2 
NH 3
CH 3  C  N
P2O5
2
34. (c) HCOOH  2Cu 
 Cu 2 O  H 2 O  CO 2
Fehling
Solution Red ppt
63. (b) CH 3 COOH 
 CH 3 CH 2 OH LiAlH4

64. (c) CH 3 CONH 2  NaOH  CH 3 COONa  NH 3

Boil
Whereas CH 3 COOH    No reaction
Fehling
Acetamide
Solution
65. (b) CH 2  CH  (CH 2 )5 COOH  
Peroxide

35. (d) HCOOH  NaHCO3  HCOONa  H 2O  CO 2 HBr

CH 2  (CH 2 )6  COOH
HCHO  NaHCO3  No reaction |
Br
O HO
37. (d) CH 3  C C  CH 3 . CHO
OH O CH 3

Due to H-bonding 69. (c)  

CrO 3
(Etard’s reaction)
38. (c) CH 3 COOH  NaHCO 3  CH 3 COONa  H 2 O  CO 2 (CH 3 CO )2 O

39. (c) Acetic acid forms dimer in benzene due to which molecular CHO COONa CH OH2

mass becomes doubles.

42. (b) CH 3 COOH    CH 2 Cl  COOH
I2 / Re d p 

NaOH
+
 / P2O5
44. (c) CH 3 COOH  (CH 3 CO )2 O O OMgBr
|| |
COOH 70. (a) CH 3 C  OCH 3  CH 3  C  OCH 3
PhMgBr
47. (c) |  KMnO4  H 2 SO 4  2CO 2  H 2 O |
COOH
Ph
 K 2 SO 4  MnSO 4 O OMgBr
|| |
 MgBr (OCH 3 )
49. (c) R  X   R  CN 
KCN
 R  COONa  NH 3
NaOH  CH 3  C  Ph  CH 3  C  Ph PhMgBr

H 2O |
Ph
50. (c) CH 3 CH 2 COOH   CH 3  CH  COOH
Cl 2 / Fe
OH
| |

Cl 
H
 CH 3 C  Ph
|
CH 2  CH  COOH  
Alcohol Ph
KOH 1,1 - diphenylethanol
OH

NH-COCH 3
 Carboxylic acids and Their derivatives 1355

72. (b) 2 NH 2 CONH 2  NH 2 CONHCONH 2  NH 3 106. (a) Due to intramolecular hydrogen bonding.
107. (c) CH 3  CH  COOH   CH 2  CH  COOH
H 2 SO 4
OH OCOCH 3
| Acrylic acid
COOH COOH OH
74. (b) 108. (d) Acetamide can behave as weak acid as well as base.
 22 
3 (CH CO ) O / H SO
4

CH 3  CO  NH 2  HCl  CH 3 CONH 3 Cl 
Salicylic acid Aspirin Acetamide hydrogen
chloride
75. (a) CH 3 COOH  PCl5  CH 3 COCl  POCl3  HCl 2CH 3 CONH 2  HgO  (CH 3 CONH )2 Hg  H 2 O
Acid Acid chloride Mercuricacetamide

77. (c) Alcohols react with acids to form esters which have fruity COOAg Br
smell. 109. (d) 
Br2
 CO 2  AgBr
NaOH
78. (a) Acidity decreases with the decrease in electronegativity of
halogen i.e., CHanhyd.
3 CO
110. (a) O  C 2 H 5 OC2 H 5
FCH 2 COOH  ClCH 2 COOH  BrCH 2 COOH CH 3AlCl
CO 3

2CH 3 COOC 2 H 5
NaOBr
CH 3 CONH 2   CH 3 NH 2
Ethyl acetate
79. (c) Hofmann bromamide reaction
COOH COOH
80. (d) Formic acid, HCOOH shows reducing property.
81. (a) HCOOH reduces ammoniacal silvernitrate solution, i.e., 111. (d)  
FeCl3
Cl 2
Tollen’s reagent but acetic acid does not.
Cl

85. (b) C6 H 5 COOC 2 H 5  NaOH  112. (b) Benzene sulphonyl chloride is called Hinsberg’s reagent.
Ethyl benzoate
114. (a) CHCOOH< ClCHCOOH< ClCHCOOH< ClCCOOH
3 2 2 2 3

C6 H 5 COONa  C 2 H 5 OH Increasing order of acidic nature.

Sod. benzoate Ethanol
COOH COOH COOH COOH
86. (b) CH 3  CHOH  COOH  [O]  KMnO 4
NO 2

Lacticacid 115. (d)

CH 3 CO  COOH  H 2 O
Pyruvic acid NO
NO
Electron withdrawing group, increases
2

the acidity of benzoic 2

87. (d) RCOOH 

 RCH 2 OH LiAlH4
acid, O-isomer will have higher acidity then corresponding m
CH 2 OH and p-isomer due to ortho effect.
116. (c) CH 3 COOC 2 H 5  NaCl(aq )  no reaction

90. (d) C6 H 5 COOCH 3 

 LiAlH4
 CH 3 OH (CH 3 COOC 2 H 5  NaCl (aq) )
H 3O
CH 3
CH 3

CO H
2
CO H 2

COOH
117. (c)  Br2 
 Fe
 HBr

92. (d)  NaOH  

CaO

Br
 COOH is meta directing group
OH

118. (d) R  COOR   R OH H R COO R   R OH
 Zn   ZnO The exchange of alcohol residue known as alcoholysis or trans
esterification
93. (c) 3CH 3 COOH  PCl3  H 3 PO3  3CH 3 COCl 119. (b) R COOH  PCl5  R COCl  POCl3  HCl  
KCN

94. (b) CH 3 COCl   CH 3 CH 2 OH  HCl

LiAlH4
R COCN  KCl   R CO COOH  2 NH 3
2 H 2O

98. (a) CH 3  CO  NH 2  CH 3  C  N  H 2 O

P2 O5
   R CH 2 COOH  H 2 O
Clemenson reduction
Zn  Hg / Conc . HCl
99. (a) In this reaction -H is replaced by chlorine.
120. (b) CH 3 COOH  Cl 2  CH 2 Cl COOH  HCl
100. (a) Urea are neutral in nature in aqueous solution.
CH 3 COOH  PCl5  CH 3 COCl  POCl3  HCl
102. (a) CH 3 COOH  4 H   CH 3 CH 2  OH
LiAlH4
CH 3 COOH  SOCl 2  CH 3 COCl  SO 2  HCl
COOH COOH COOH COOH
3CH 3 COOH  PCl3  3CH 3 COCl  H 3 PO3
NO 121. (a) C6 H 5 COOC 2 H 5  KOH (alc)  C6 H 5 COOK 
103. (a)
2

NO 2
C 2 H 5 OH  C6 H 5 COOH  KCl
HCl

NO 2
122. (c) R OH  PCl5  R  Cl  POCl3  HCl
COOH o R COOH  PCl5  R COCl  POCl3  HCl
105. (c) |  H 2 SO 4   CO  CO 2  H 2 O
95 C
COOH
 1356 Carboxylic acids and Their derivatives
123. (a) It is picric acid because it has three  NO 2 group are
arranged which are ortho and para position  
 
H CN
2
H O
124. (d) Benedict solution is readily reduced by aldehyde. It does not nucleophilic addition
oxidise anhydrides
2
125. (c) CH  CH  CH 3 COOH  

[ Hg ]
H
H 2 C  CH  OCOCH 3  
CH 3 COOH |
Vinyl acetate 135. (b) C 6 H 5 CHO  HCN  C 6 H 5  C  CN is optically active.
|
CH 3  CH (O  COCH 3 )2 OH
Ethylideneacetate
This reaction is an example of addition reaction. 137. (c) Claisen condensation
126. (a) When acetic acid is reacted with PCl5 the product formed step I CH 3 CO 2 C 2 H 5 2 5
 CH 3 COCH 2 COOC 2 H 5
NaOC H

are acetyl chloride, phosphoryl chloride and hydrochloric acid C 2 H 5 OH

(A)
CH 3 COOH  PCl5  CH 3 COCl  HCl  POCl3 heated in
Hydro 
Aceticacid Phosphorus
Penta chloride
Acetyl
Chloride Chloric
Phosphoryl
chloride step II presence of
acid
acid (H ) +

O

O
127. (b) CH 3  C  O C 2 H 5  C 2 H 5 MgBr  CH 2  C CO
Ester CH 2
Step II :
O C2 H 5
 O H O O H O
 Mg (OC 2 H 5 ) Br
CH 3  C  O MgBr    CH 3  C  O || | ||
H
|| | ||
  CH 3  C  C  C  OC 2 H 5 
 CH 3  C  C  C
| heat
C2 H 5 C2 H 5 H
C2 H 5

 Mg (OH ) Br O
  CH 3  C  O Mg Br 
C 2 H 5 Mg Br
 O CH 2  C CO
 H .OH
 CH 2
C2 H 5 
C H 2  C C H  C
|  O
C2 H 5
H CH 2  C C O
 CH 2
H 3 C  C  OH 3° alcohol

C2 H 5
Zn  Hg /
NH 2 HOH OH  NH  138. (d) C H CONHCH   C H CH NHCH
128. (b) OC  O  C 3
6 5 3

HCl
6 5 2 3

NH 2 OH
Carbonic acid (unstable) This reaction is known as Clemmenson reduction.
CO + H O 1
139. (b) Ka  ; The value of K a is highest for HCOOH .
2 2

CN pK a
H HCN | H
129. (c) H 3 CC  CH 3  C  
H . OH
O OH 140. (c) X   C 2 H 6
NaOH / CaO

Acetaldehyde

COOH C 2 H 5 COOH   C 2 H 6

NaOH / CaO
CH 3 CH
OH propionic acid ethane
Lacticacid
141. (a) Glycine is a amphoteric acid as it contains both acidic as well
130. (a) Vinegar is 6 – 10% aqueous solution of acetic acid as basic groups.
131. (a) All esters are pleasant liquid having pleasant fruity smell. Many
of them are used in perfurmery, e.g. Benzyl acetate etc. 142. (a) Cinnamic acid reacts with bromine in carbon tetrachloride to
give dibromocinnamic acid.
132. (a) Lactic acid has one asymmetric (chiral) carbon atom, hence it
has (2  2) optical isomers. Br Br
| |
CH 3 CH 3
C6 H 5 CH  CHCOOH  Br2  C6 H 5 CH  CHCOOH CCl 4

dibromocin namic acid

 
C C 143. (a) OF all the acid derivatives, acid chlorides, i.e. CH 3 COCl is
OH HO H
H most reactive.
COOH COOH The order of reactivity of acid derivatives decreases in the
133. (a) 4-methyl benzene sulphonic acid is stronger than acetic acid following order,
thus it will release acetic acid from sodium acetate.
RCOCl  (RCO)2 O  RCOOR  RCONH 2 .
O

134. (a) CH 3 COOH   CH 3  C  Cl 
SOCl 2

Benzene 144. (c) Reaction can be explained as follows
Thionylchloride Anhy AlCl3
Friedel craft
acylation
O OH OH
||  
C  CH 3 NC  C  CH 3 HOOC  C  CH 3

(B) (C) (D)

 Carboxylic acids and Their derivatives 1357

O O O O
|| ||
CH3O– || |
(i) C C H  C  O  H  C  O
– ..
H CH 3 H CH 3 5. (a) Since a single alkyl halide is formed on treatment with HI, it
enolate ion must be a symmetrical ether i.e., ethoxyethane.
O O C 2 H 5 OC 2 H 5  2 HI  2C 2 H 5 I  H 2 O
|| + ||
(ii) C C 6. (b) CH 2  CH  COOH  
LiAlH4
.. –

H CH 2 CH 3 OCH 3 CH 2  CH  CH 2 OH  H 2 O
O O
|| || 7. (a) CH 3 COOH  PCl5  CH 3 COCl  

C6 H 6
 anh . AlCl3
C O C O
| || C2 H 5
H  OCH 3
CH 2  C  OCH 3  CH 2  C  CH 3
 H |
  ketoaldehyde
|
CH 3 CH 3 COC 6 H 5   CH 3  C (OH ) C6 H 5
C2 H 5 MgBr
Ether

145. (a) CH 3 COOH  NaHCO 3  CH 3 COONa  CO 2  H 2 O 8. (d) Resonance stabilization of their conjugate base i.e., carboxylate
ion.
RCOOH P2O5 RCO 9. (a) R  CH 2 CH 2 OH   R  CH 2 CH 2  Br
PBr3
146. (d)  O  H 2O
RCOOH RCO 
  R  CH 2  CH 2  CN 
KCN

H 3O

P2 O 5 acts as a dehydrating agent.
R  CH 2  CH 2 COOH  NH 3
Uses of Carboxylic Acids and Their Derivatives 10. (d) CH 3 CH 2 COOH (aq)  NaHCO 3 (aq) 
Propionic acid sod. bicarbonat e

COOH COOH
OCOCH 3 CH 3 CH 2 COONa  CO 2  H 2 O
OH
3. (a)   
CH COCl COOH COCl
3

Aspirin
11. (c)
 SOCl 2   SO 2  HCl

Benzoic acid Benzoyl chloride

Critical Thinking Questions 12. (b) –COOH and –OH group form the hydrogen bond by which
they have high boiling point. –COOH group show strong
hydrogen bonding so it form dimer and have more boiling
point than –OH group. While –CHO group do not form
O – hydrogen bond. Thus the reactivity order are as 3 > 1 > 2.
:O OC H
1. (a) R CH 3 MgBr  2 5

13. (c) CaC 2 O 4 is a salt of oxalic acid which is more acidic than
OC2 H 5 R acetic acid, so it is insoluble in acetic acid.
CH 3
14. (d) –COOH and COCH 3 are meta directing group due to the
O
O
R C  C2 H 5 O  ||
presence of  C  , similarly CN is also meta directing due to
CH
the presence of multiple bond while NHCOCH 3 is
3

CH 3 MgX ortho/para directing group because of less electron density over

O
||
XMgO OH
CH HOH / H 
CH  C  group.


3 3

15. (c) Iodoform test is given by all the compounds having

R CH R CH CH 3  C  or CH 3  C  group.
3 3
|| |
CHOHCOOH CHOHCOOH OH
O
ONa ONa
2. (b) Rh  Al2O3
16. (c) C 2 H 5  C  CH 3  I 2  NaOH  C 2 H 5 CO 2 Na   CHI 3
+ 3H   2
 
O
CH 3 CO 
C 2 H 5 CO 2 Na  
H
 C 2 H 5 COOH  Na 
3. (d) C H So most acidic in nature.
CH 3 CO 17. (c) Formic acid can not be prepared by grignard’s reagent. Higher
OCCH acids are prepared by the reaction of CO 2 on grignard’s
3

reagent
4. (c) Anion HCOO has two resonating structure (identical).   
R Mg X  C O   R  C  O Mg X  
H . OH
O  ||
O
 1358 Carboxylic acids and Their derivatives
O 8. (e) The melting point of an aliphatic carboxylic acid containing an
 even number of carbon atoms is higher than the next lower
R  C  OH  Mg(OH )X and next higher homologue containing odd number of carbon
acid
atoms.
9. (e) Electron withdrawing groups increase the acidity of carboxylic
Assertion & Reason acids by stabilising the conjugate base through delocalisation of
the negative charge by inductive and resonance effects.
1. (a) Carboxylic acid exist as dimer due to the formation of 10. (a) The larger the electron withdrawing inductive effect the greater
hydrogen bonding. is the acidity.
11. (c) In aminoacetic acid, NH 2 group is electron repelling in
O H O
R C CR nature.
O H O 12. (b) Boiling points of carboxylic acids are higher due to their
H- bonding (dimer) tendency to associate and form dimers to a greater extent by
2. (c) Trichloro acetic acid is stronger than acetic acid because the
electron withdrawing group withdraw electrons from the hydrogen bonding.
carboxylate base and thus increasing the acid strength. 13. (a) Both formic acid and oxalic acid behave as reducing agent and
decolourise acidified KMnO4 solution.
Cl O O
 | 
2 KMnO4  3 H 2 SO 4  K2 SO 4  2 MnSO4
|
Cl  C  C  OH CH 3  C  OH

Cl 3 H 2 O  5[O]
– I effect + I effect 14. (c) Esters containing   hydrogens on treatment with a base
(Stronger acid) (Weaker acid) form a carbanion which brings about nucleophilic acyl
substitution at the carbonyl group of the other molecule of the
3. (c) Carboxylic acids (RCOOH ) dissolves in water due to
ester to form   keto esters.
hydrogen bonding between H-atom of COOH group and
O-atom of water. As alkyl portion R-is non polar and lyophobic,
this effect predominates as –R gets larger (over five carbon
atoms).
4. (b) As carboxylic acids are resonance stabilized they do not contain
true carbonyl group as is present in carbonyl compounds.

 :
:O  :
:O
  
R  C O   H  R  C  O  H
.. ..
5. (c) Formic acid is stronger than acetic acid
H  C  OH ⇌ H  C  O   H 
 
O O
CH 3  C  OH ⇌ CH 3  C  O   H 
 
O O
Presence of CH 3 group in acetate ion shows +I.E, and there
by intensifying charge on O  of acetate ion than formate ion
or acetate ion is destabilized. Thus formate ion is more stable
than acetate ion or HCOOH loses proton more easily than
CH 3 COOH .
6. (e) Both fumaric and maleic acids have two ionisable H  i.e.
protons. The maleate monoanion shows intramolecular H-
bonding and thus requires more energy to give maleate
dianion. It is therefore second dissociation of fumaric acid is
more than maleic acid since former does not show
intramolecular H-bonding.
7. (c) Larger is the size of alkyl group of ester, greater is the steric
effect and thus lesser will be rate of hydrolysis.

O O
  
CH 3  C  OH   CH 3  C  OH 
fast
H

 
O CH 3 O CH 3
CH 3 COOH  CH 3 OH
O O
  
CH 3  C  OH  CH 3  C  OH 
slow H

 
O C4 H 9 O C4 H 9
CH 3 COOH  C 4 H 9 OH