1 Carboxylic Acids & Derivatives

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

(a) 2-Bromo-3-methylbutanoic acid
Introduction to Carboxylic Acid and Its Derivatives
(b) 2-Methyl-3-bromobutanoic acid
1. The general formula for monocarboxylic acids is
(c) 3-Bromo-2-methylbutanoic acid
(a) CnH2nO (b) CnH2n+1O2
(d) 3-Bromo-2,3-dimethylpropanoic acid
(c) CnH2n+2O2 (d) CnH2nO2
Ans. (c)
Ans. (d)
Sol.
Sol. The general formula of mono carboxylic acids and esters
is Cn H 2n O 2 .

O
||
2. H  C  Cl is called
6. The IUPAC name of is
(a) Acetyl chloride (b) Formyl chloride
(c) Chloretone (d) Oxochloromethane (a) but-3-enoic acid (b) but-1-enoic acid
Ans. (b) (c) pen-4-enoic acid (d) prop-2-enoic acid
Ans. (a)
O
|| O
Sol. H  C  Cl is called formyl chloride
Sol.
3. The IUPAC name for
7. The IUPAC name of the molecule

is :-

(a) 1-Hydroxy-4-methylpentanoic acid is

(b) 1-Methyl-3-hydroxypentanoic acid
(c) 4-Hydroxy-2-methylpentanoic acid
(a) 4-oxo-2,3-dimethylpent-2-en-1-oic acid
(d) 4-Carboxypentanol-2.
(b) 3-carboxy-3-methylpent-2-en-3-one
Ans. (c)
(c) 4-carboxy-3-methylpent-3-en-2-one
(d) 2,3-dimethyl-4-oxopent-2-en-1-oic acid
Sol. Ans. (d)
4- Hydroxy -2- methyl pentatonic acid. Sol. 2,3-dimethyl-4-oxopent-2-en-1-oic acid
4. The IUPAC name of C6H5COCl is 8. Monocarboxylic acids are functional isomers of
(a) Chlorobenzyl ketone (a) Alcohols (b) Ethers
(b) Benzene chloroketone (c) Esters (d) Aldehydes and ketones.
(c) Benzoyl chloride Ans. (c)
(d) Chlorophenyl ketone Sol. Monocarboxylic acids and esters are functional isomers
Ans. (c)  Both have General formula as Cn H 2n O2
Sol. C6 H5 COCl  Benzoyl chloride. 9. The general formula CnH2nO2 could be for open chain
(a) diketones (b) carboxylic acids
(c) diols (d) dialdeydes
5. The IUPAC name of is
Carboxylic Acids & Derivatives 2

Ans. (b) 14. In the following reaction sequence.

Sol. Diketones - Cn H 2n  2 O 2 Carboxylic acid -C n H 2n O 2 , Diols- CuCN/Pyridine
C6 H5 Br  2 4 Y
 X 
Dil.H SO
523 K Boil
-Cn H2n+2O2 , Dialdehydes -Cn H n O2 , The product Y is
10. Which of the following does not contain a carboxyl group? (a) Benzonitrile (b) Benzene
(a) picric acid (b) aspirin (c) Benzoic acid (d) Benzamide
(c) benzoic acid (d) ethanoic acid Ans. (c)
Ans. (a) CuCN/Pyridine Dil.H SO
Sol. C6 H5 Br 
523K
C6H5  CN 
2 4 C H -COOH
Boil 6 5
Sol. Acidic character of phenol is enhaced by the introduction
of –NO2 group. Since in picric acid (2, 4, 6 trinitrophenol) 15. Ethanoic acid is prepared commercially from
there are three –NO2 groups, acidic character of phenol is (a) Ethyne (b) Ethanol
enhanced to such an extent that it behaves like carboxylic (c) Methanal (d) Both ethyne and ethanol.
acid, although it has no –COOH group. Ans. (d)
Preparation of Carboxylic Acid Sol. Ethanoic acid prepared commercially from both ethyne and
11. Hydrolysis of hydrogen cyanide results in the formation ethanol.
of C H  C H  K  C H 3 C O O H
M nO 4
ethyne
(a) Formic acid (b) Oxalic acid
(c) Formaldehyde (d) Acetaldehyde C H 3 CH 2 OH  [Link]
 nO 4
 CH 3 COOH
Ethenol
Ans. (a)
16. The major product obtained on interaction of phenol with
O sodium hydroxide and carbon dioxide is
||
Hydrolysis
Sol. H -C  N   H- C -OH (a) benzoic acid (b) salicylaldehyde
Hydrogen Formicacid
cyanide (c) salicylic acid (d) phthalic acid
12. Ethyl isocyanide on hydrolysis in acidic medium generates Ans. (c)
(a) ethylamine salt and methanoic acid
(b) propanoic acid and ammonium salt
(c) ethanoic acid and ammonium salt
(d) methylamine salt and ethanoic acid Sol.
Ans. (a)

Sol. C2 H5  NC 
H
H2 O
 C2 H5 NH3  HCOOH 17. Acetic acid is obtained when
13. The compound formed as a result of oxidation of ethyl (a) Methyl alcohol is oxidised with potassium permanganate
benzene by KMnO4 is (b) Formaldehyde is oxidised with potassium dichromate
(a) benzophenone (b) acetophenone and sulphuric acid
(c) benzoic acid (d) benzyl alcohol (c) Acetonitrile is hydrolysed with a dilute mineral acid
Ans. (c) (d) Glycerol is heated with sulphuric acid.
Ans. (c)
C H 3 C N  H 2 O  HC
 l
 CH 3 C ON H 2
Sol. Sol.  H
HC l
O
 C H 3 C OO H  NH 3
2
Ethanoic acid

When oxidises with alkaline KMnO4 or acidic Na2Cr2O7,  CH3 2 CO 

+

 HCl   A  B
NaCN H3 O
18.
the entire side chain (in benzene homologues) with at least
one H at α carbon, regardless of length is oxidised to in the above sequence of reactions A and B are
-COOH. (a) (CH3)2C(OH)CN, (CH3)2CHCOOH
(b) (CH3)2C(OH)CN, (CH3)2C(OH)2
(c) (CH3)2C(OH)CN, (CH3)2C(OH)COOH
(d) (CH3)2C(OH)CN, (CH3)2 C = O
 3 Carboxylic Acids & Derivatives

Ans. (c) Sol.

Sol.

19. The acid D obtained through the following sequence of

reactions is
[Link] Br KCN H O
C2 H5 Br   A 
CCl  B 
2
(excess)  C  D
3
4

(a) Succinic acid (b) Malonic acid

(c) Maleic acid (d) Oxalic acid
Ans. (a) Physical and Chemical properties of Carboxylic
Acids
21. Which of the following has the highest boiling point ?
(a) CH3OCH2CH3 (b) CH3CH2CH2OH
(c) CH3COOH (d) CH3CH2CH2CH3
Sol. Ans. (c)
Sol. The higher boiling point of acids is due to formation of a
stable, hydrogen-bonded dimer.
20. p-cresol reacts with chloroform in alkaline medium to give 22. The carboxylic acid which has maximum solubility in water
the compound A which adds hydrogen cyanide to form the is
compound B. The latter, on acidic hydrolysis gives chiral (a) Phthalic acid (b) Succinic acid
carboxylic acid. The structure of the carboxylic acid is
(c) Malonic acid (d) Salicylic acid
Ans. (c)
Sol.
(a)

(b) Phthalic acid Succinic acid Malonic acid Salicylic acid

Malonic acid has less hydrocarbon and it is dicarboxylic
acid so its solubility is maximum is water.
23. In the anion HCOO the two carbon-oxygen bonds are
found to be of equal length. What is the reason for it.
(c)
(a) Electronic orbitals of carbon atom are hybridised
(b) The C = O bond is weaker than C – O bond
(c) The anion HCOO– has two resonating structures.
(d) The anion is obtained by removal of a proton form the
(d) acid molecule
Ans. (c)
Ans. (c)
Carboxylic Acids & Derivatives 4
Sol. H
28. The reaction, CH3COOH + CH3OH   CH3COOCH3 +
H2O is called
(a) Acidification reaction
(b) Dehydration reaction
(c) Dehydrogenation reaction
In this the two carbon-oxygen bonds are found to be of
equal length. (d) Esterification reaction
24. The weakest acid among the following is Ans. (d)

(a) CH3COOH (b) Cl2CHCOOH Sol. CH 3 COOH  CH 3 OH H CH 3 COOCH 3  H 2 O is
(c) ClCH2COOH (d) Cl3CCOOH called Esterification reaction.
Ans. (a) 29. Heating a mixture of ethyl alcohol and acetic acid in presence
Sol. +I effect groups decreases the acidity and -I effect groups of conc. H2SO4 produces a fruity smelling compound. This
increases the acidity. reaction is called
25. When CH 2  CH  COOH is reduced with LiAlH4, the (a) Neutralisation (b) Ester hydrolysis
compound obtained will be (c) Esterification (d) Williamson’s synthesis
(a) CH3— CH2— COOH (b) CH 2  CH  CH 2 OH Ans. (c)
(c) CH3— CH2— CHO O O
H  CH  C OEt
|| ||
Sol. CH 3  C OH  HO  Et 
(d) CH3  CH 2  CH 2  OH 3

Ans. (b) 30. Which reagent will bring about the conversion of
carboxylic acids into esters
Sol. LiAlH 4 is a strong reducing agent, it reduces carboxylic
(a) C2H5OH (b) Dry HCl + C2H5OH
group into primary alcoholic group without affecting the
basic skeleton of compound. (c) LiAlH4 (d) Al(OC2H5)3
LiAlH 4
Ans. (b)
CH 2  CH  COOH 
 
CH 2  CH  CH 2 OH
H
  O O
|| ||
26. Sodium formate on heating yields H+
Sol. CH3  C  OH  HO  C2 H5 
 CH3  C  O  C2 H5
(a) oxalic acid and H2 +H2 O
(b) sodium oxalate and H2
31. In esterification, OH  ion for making H2O comes from
(c) CO2 and NaOH
(d) sodium oxalate. (a) Acid (b) Alcohol
Ans. (b) (c) Ketone (d) Carbohydrate
Sol. Ans. (a)
O O
|| ||
Sol. CH 3  C OH  HOC2 H 5  CH 3  C O  C 2 H 5
32. Which of the following would be expected to be the most
27. Treatment of benzoic acid with Cl2/FeCl3 will give
highly ionized in water ?
(a) p-chlorobenzoic acid
(a) ClCH2CH2CH2COOH (b) CH3CCl2CH2COOH
(b) o-chlorobenzoic acid
(c) CH3CH2CCl2COOH (d) CH3CH2CHClCOOH
(c) 2,4-dichlorobenzoic acid
(d) m-chlorobenzoic acid Ans. (c)
Ans. (d) Sol. i. Increase in the number of halogen atoms increases the
acidity.
ii. Increase in the distance of halogen from COOH
Sol. decreases acidity.
iii. Chlorine atom has high-I effect so when attached to
Since - COOH is meta directing group. closest carbon, it increases acidity thus is more acidic.
Therefore option c is correct.
 5 Carboxylic Acids & Derivatives

33. Rewrite the following in the increasing order of acidity ? benzoic acid, o-isomer will have higher acidity then
(i) Benzoic acid (ii) p-methoxybenzoic acid corresponding m and p isomer due to ortho-effect.
(iii) o-methoxybenzoic acid
As M group (i.e. NO 2 ) at p- position have more
(a) (i) < (ii) < (iii) (b) (iii) < (i) < (ii)
pronounced electron withdrawing effect than as -NO2
(c) (ii) < (i) < (iii) (d) (iii) < (ii) < (i).
group at m- position (-I effect)
Ans. (c)
 Correct order of acidity is ii  iii  iv  i.
Sol. order of acidity O-methoxybenzoicacid > Benzoic 37. The strongest acid amongst the following compounds is

due toorthoeffect (a) CH3COOH (b) HCOOH
acid > p- methoxybenzoic acid (c) CH3CH2CH(Cl)CO2H (d) ClCH2CH2CH2COOH
34. The increasing order of acidity of ,  and – chlorobutyric Ans. (c)
acids is
Sol. CH 3 CH 2 CH(Cl)COOH is the strongest acid due to -I
(a)  <  <  (b)  <  <  effect of Cl
(c)  <  <  (d)  <  <  Also, Increases in the distance of halogen from COOH
Ans. (d) decreases the acidity e.g. This is due to the fact that
Sol. Increase in the distance of halogen from COOH decreases inductive effect decreases with increasing distance.
the acidity e.g. This is due to the fact that inductive effect correct answer is (c).
decreases with increasing distance 38. Among the following, the acid which undergoes fastest
35. Which of the following is the weakest acid decarboxylation is
O O
|| ||
(a) (b) CH3COOH (a) Ph  C COOH (b) Ph  C  CH 2  COOH

(c) PhCOOH (d) Ph  CHOH  COOH

(c) HCOOH (d) Ans. (b)

Ans. (a) Sol. β -Keto acids undergo decaboxylication through a cylic

transtion state the thermal decomposition of beta keto
acids is easy.
Sol. 39. In the reaction,
LiAlH4 PCl
[Link]
Formic acid is stronger than benzoic acid because it has a CH3COOH   A 
5
 B   C,
lower pKa value (formic acid pKa = 3.751; benzoic acid pKa
= 4.204; Acid dissociation constant). the product C is :
A large Ka value indicates a strong acid because it means (a) Acetylene (b) Ethylene
the acid is largely dissociated into its ions. (c) Acetyl chloride (d) Acetaldehyde
A small Ka value means little of the acid dissociates, then it
Ans. (b)
is a weak acid.
LiAlH 4 PCl5
36. Consider the acidity of the carboxylic acids : Sol. CH3 COOH  CH3 CH2 OH  
(i) C6H5COOH (ii) o–NO2C6H4COOH .
(iii) p–NO2C6H4COOH (iv) m–NO2C6H4COOH CH3CH 2 Cl 
[Link]
 CH 2  CH 2
Which of the following order is correct ?
2 Cl ,RedP
Alc. KOH
(a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iv) > (iii) > (i) 40. CH3 CH 2 COOH  X  Y
(c) (ii) > (iv) > (i) > (iii) (d) (ii) > (iii) > (iv) > (i) Compound Y is
Ans. (d) (a) CH3CH2OH (b) CH3CH2CN
(c) CH 2  CHCOOH (d) CH3CHClCOOH

Sol. Ans. (c)

Electron withdrawing group increases the acidity of

Carboxylic Acids & Derivatives 6
Sol. 44. Which of the following will not undergo Hell - volhard
Zelinsky (HVZ) reaction ?
(a) HCOOH (b) CH3COOH
(c) CH3CH2COOH (d) CH3CHBrCOOH
Ans. (a)
Sol. Carboxylic acid with  hydrogen will undergo Hell-
volhard - Zelinsity(HVZ) reaction. So in formic acid there
is no  - hydrogen so no reaction.
45. When propionic acid is treated with aqueous sodium
41. Propanoic acid or its sodium salt can be converted into
bicarbonate CO2 is liberated. The ‘C’ of CO2 comes from
alkanes by reduction with Hl/red P or decarboxylation
(a) Methyl group (b) Carboxylic acid group
reaction or kolbe’s reduction. Which of the following
alkanes is not formed in any of these reactions ? (c) Methylene group (d) Bicarbonate
(a) Methane (b) Ethane Ans. (d)
(c) Propane (d) Butane
Ans. (a) Sol.
Sol.

Preparation of Carboxylic Acid Derivatives

46. Acetic anhydride is obtained from acetyl chloride by the

reaction of
42. CCl4 , Reflux
The reaction : RCOOAg + Br2   (a) P2O5 (b) H2SO4
R – Br + AgBr + CO2 (c) CH3COONa (d) HOCl
is called Ans. (c)
(a) Wurtz reaction O O O
|| || ||
Sol. CH 3  C Cl  CH 3 COONa  CH3  C O  C CH 3
(b) Hunsdiecker reaction
(c) Friedel-Crafts reaction 47. Identify Z in the following reaction sequence.
(d) Kolbe’s reaction
Ans. (b)

Sol. CCl4 , Reflux

RCOOAg  Br2   R  Br  AgBr  CO2 (a) CH3COCH2COONa
Hunsdicker reaction. (b) (CH3CO)2O
43. The reaction, (c) CH3CO – O – COCH2Cl2
(d) CH3CO – OCOCHCl2
H  or OH 
RCOOR   R OH (excess)  RCOOR   R 
Ans. (b)
OH is called
Sol.
(a) Esterification (b) Trans-esterification
(c) Saponification (d) Hydrolysis
Ans. (b)
+ -
Sol. RCOOR +R  OH( excess )    RCOOR"
H or OH

 R  OH is called Trans- esterification 48. Which will not give acetamide on reaction with ammonia
In organic chemistry, Trans- esterification is the process (a) Acetic acid (b) Acetyl chloride
of exchanging the organic group R' of an ester with the (c) Acetic anhydride (d) Methyl formate
organic group R’’ of an alcohol. These reactions are often Ans. (d)
catalyzed by the addition of an acid or base catalyst.
 7 Carboxylic Acids & Derivatives
Sol. Chemical Properties of Carboxylic Acid Derivatives
53. Benzoyl chloride on treatment with ammonia gives
(a) Benzamide (b) Acetamide
(c) Benzylamine (d) Benzoic acid
Ans. (a)
Sol.

49. Among the following acids which have the lowest pKa
value:
(a) CH3COOH (b) HCOOH
(c) (CH3)2COOH (d) CH3CH2COOH 54. Ethyl acetate reacts with CH3MgBr to form
Ans. (b) (a) Secondary alcohol (b) Tertiary alcohol
Sol. HCOOH is the most acidic. So it has the lowest pKa value. (c) Primary alcohol and acid
Hence option (b) is the answer. (d) Acid
Ans. (b)
50. Hydrolysis of acetamide produces Sol.
(a) Acetic acid (b) Acetaldehyde
(c) Methylamine (d) Formic acid
Ans. (a)
O O
|| ||
Hydrolysis
CH 3  C NH 2   
 CH3  C OH
Sol. Acetamide AceticAcid
(Acid derivative)

51. In the following reaction, product P is

O
|| H2 55. The decreasing order of reactivity of
R  C Cl 
Pd BaSO
P
4 (i) CH3COCl (ii) CH3COOC2H5
(a) RCH2OH (b) RCOOH (iii) CH3CONH2 (iv) (CH3CO)2O
(c) RCHO (d) RCH3 Towards nucleophilic acyl substitution is
Ans. (c) (a) (i) > (iv) > (iii) > (ii)
O (b) (i) > (iv) > (ii) > (iii)
||
H2
Sol. R  C Cl RCHO (c) (iv) > (iii) > (i) > (ii)
Pd  BaSO 4
(d) (iii) > (i) > (iv) > (ii)
52. Sodium ethoxide has reacted with ethanoyl chloride. The Ans. (b)
compound that is produced in the above reaction is
Sol. Reactivity order of derivative of carboxylic acids.

(a) diethyl ether (b) 2-butanone O O O O O

|| || || || ||
(c) ethyl chloride (d) ethyl ethanoate R  C  Cl  R  C  O  C  R  R  C  OR '  R  C  NH 2
Ans. (d)
H2
56. CH 3 COCl 
Pd / BaSO 4
 CH 3CHO  HCl;
C2 H 5 O  Na   CH 3  C  Cl The above reaction is called
||
O (a) Reimer-Tiemann reaction
 (b) Cannizzaro reaction
Sol.
C 2 H 5  O  C CH 3 (c) Rosenmund reaction
||
O
(d) Reformatsky reaction
Ans. (c)
Carboxylic Acids & Derivatives 8
Sol. Rosenmund reduction is the hydrogenation of an acyl 59. Which of the following reaction is appropriate for
chloride to an aldehyde, in preence of catalyst (Pd converting acetamide to methanamine?
supported on barium sulphate.)
(a) Hoffmann bromamide reaction
57. Consider the following compounds:
(b) Stephen’s reaction
(i) C6H5COCl
(c) Gabriel phthalimide synthesis
(d) Carbylamine reaction
(ii)
Ans. (a)
Sol.
(iii)

(iv)

The correct decreasing order of their reactivity towards

hydrolysis is
(a) (i) > (ii) > (iii) > (iv) 60. Acetic anhydride reacts with excess of ammonia to form
(b) (iv) > (ii) > (i) > (iii) (a) 2CH3COON4 (b) 2CH3CONH2
(c) (ii) > (iv) > (i) > (iii) (c) CH3CONH2 + CH3COONH4
(d) (ii) > (iv) > (iii) > (i) (d) 2CH3COOH
Ans. (c) Ans. (c)
Sol. The ease of hydrolysis depends upon the magnitude of
the +ve charge on the carbonyl group. Electron withdrawing O O
|| ||
groups increase the magnitude of positive charge and CH3  C O  C CH3  NH3
electron donating groups decrease the magnitude of positive excess

charge. Hence, the decreasing order of reactivity towards Sol. O O

|| ||
hydrolysis is 
CH3  C  NH2 +CH3 - C -ONH4

Tests of Carboxylic Acids and Its Derivatives

61. Which one of the following compounds forms a red

coloured solution on treatment with neutral FeCl3 solution
(a) CH3COCH3 (b) CH3OCH3
58. Self condensation of two moles of ethyl acetate in
presence of sodium ethoxide yields (c) CH3CH2OH (d) CH3COOH
(a) ethyl propionate Ans. (d)
(b) ethyl butyrate Sol. CH3 COOH 
Neutral
FeCl
 Red colour
3
(c) acetoacetic ester
62. Phenol can be distinguished from acetic acid by
(d) methyl acetoacetate.
(a) Blue litmus test (b) Sodium bisulphite test
Ans. (c)
(c) With FeCl3 solution (d) Tollen’s reagent test.
Sol. Ethyl acetate undergoes Claisen condensation in presence
Ans. (c)
of sodium exthoxide involving hydrogen atom in which
two molecules of ethyl acetate combine together to form Sol. With FeCl3 solution phenol can be distinguished from
acetoacetic ester. acetic acid.
CH 3COOC 2 H 5  CH 3 COOC 2 H 5 
C2 H 2 ONa
 Phenol  FeCl3  violet colour
CH 3 COCH 2 COOC2 H 5  C2 H 5 OH Acetic acid  FeCl3  Red colour
Acetoacetic ester
 9 Carboxylic Acids & Derivatives

63. Tollen’s reagent in not reduced by (c) II, III (d) II only
(a) Formic acid (b) Acetaldehyde Ans. (a)
(c) Benzaldehyde (d) Acetic acid Sol. Fehling solution will not oxidise benzaldehyde until it is
Ans. (d) attached with an electron withdrawing group. Solution will
oxidise formic acid (HCOOH) , formaldehyde (HCHO)
Sol. Tollen’s reagent is valid for aldehyde.
and acetaldehyde (CH3 CHO) .
But formic acid reduces tollen’s reagent and
65. Formic acid can reduce
oxidize to CO 2 since it has both aldehyde and
carboxylic group. (a) Tollen’s reagent (b) Mercuric chloride
This test is not given by other carboxylic acids. (c) KMnO4 (d) All of these
64. Fehling’s solution can make distinction between following Ans. (d)
pairs Sol. The reducing property of formic acid is due to presence of
carbonly (-C=O) group.
I : CH3COOH, HCOOH II : CH3COOH,HCHO
Thus, Formic acid reduces tollen's reagent solution,
III : C6H5CHO, HCHO IV : CH3CHO, HCHO mercuric chloride and potassium permangante.
Select correct pairs :
(a) I, II, III (b) II, III, IV