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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Intext Exercise
Question 1:
Write structures of the following compounds:
(i) 2 - chloro-3methylpentane
(ii) 1- chloro- 4 - ethylcyclohexane
(iii) 4 - tert .Butyl-3- iodoheptane
(iv) 1, 4 -Dibromobut- 2 - ene
(v) 1-Bromo- 4 - sec/ butyl- 2 -methylbenzene.

Solution 1:
(i)

(ii)

(iii)

(iv)

(v)

Question 2:

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Why is sulphuric acid not used during the reaction of alcohols with Kl?

Solution 2:
H 2 SO4 is an oxidizing agent. It oxides Hl produced during the reaction to I2 and thus prevents
the reaction between an alcohol and HI to from alky iodide. In order to prevent this, a non-
oxidising acid like H 3 PO3 is used which prevents the oxidation of HI.
2 KI  H 2 SO4  2 KHSO4  2 HI  I2

Question 3:
Write structures of different dihalogen derivatives of propane

Solution 3:
Four isomers are possible. There are:
Br  CH 2 CH 2 CH 2  Br 1,3 ,-dibromopropane

Question 4:
Among the isomeric alkanes of molecular formula C5 H12 identify the one that one
photochemical chlorination yields
(i) A single monochloride
(ii) Three isomeric monochlorides.
(iii) Four isomeric monochlorides.

Solution 4:

(i) Neopentane As all the H-atoms are equivalent, the replacement of any
one of them give the same product
a b c b a
(ii) CH 3 CH 2 CH 2 CH 2 CH 3 n-pentane. a, b, c are the three sets of equivalent hydrogens.

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Therefore, three isomeric monochlorides are possible.

(iii) iso-pentane, there are four sets of equivalent hydrogens

designated as a,b,c,d. Thus, four isomeric monochlorides are possible.

Question 5:
Draw the structures of major monohalo products in each of the following reactions:
(i)

(ii)

(iii)

(iv)

(v) CH 3CH 2 Br  Nal 


(vi)

Solution 5:
(i)

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(ii)

(iii)

(iv)

(v) CH3CH 2 I  NaBr

(vi)

Question 6:
Arrange each set of compounds in order of increasing boiling points.
(i)Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(ii) Chloropropane, Isopropyl chloride, 1 -Chlorobutane.

Solution 6:
(i) Chloromethane < Bromomethane < Dibromomethane < Bromoform
The reason is:

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(a) for same alkyl group, B.Pt increases with size of halogen atom.
(b) B.Pt increases as number of halogen atoms increase
(ii) lsopropyl chloride < 1 - Chloropropane < 1 - Chlorobutane
Reason :
(a) For same halogen, B.Pt. increases as size of alkyl group increases.
(b) B.Pt. decreases as branching increases.

Question 7:
Which alkyl halide from the following pairs would you expect to react more rapidly by an
SN2 mechanism? Explain your answer.
(i) CH 3CH 2CH 2CH 2 Br or

(ii)

(iii)

Solution 7:
In SN2 mechanism, reactivity depends upon the steric hindrance around the C-atom carrying
the halogen. Lesser the steric hindrance, faster the reaction.
(i) CH 3CH 2CH 2CH 2 Br 1o alkyl halide
CH 3CH 2CH ( Br )CH 3 2o alkyl halide
As steric hindrance in 2o alkylhalide is more, thus reactivity of
CH 3CH 2CH 2CH 2 Br  CH 3CH 2CH ( Br )CH 3
(ii) CH 3CH 2CH ( Br )CH 3 2o alkyl halide (CH 3 ) CBr 3o alkyl halide
As steric hindrance in (CH 3 )3 CBr is more, thus it is less reactive than
CH 3CH 2CH ( Br )CH 3

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(iii) Both are2o alkylhalides but CH 3 group at C 2 is closer to Br atom than CH 3 - group at . C3
as a result CH 3CH 2CH (CH 3 )CH 2 Br suffers greater steric hindrance than
CH 3CH (CH 3 )CH 2CH 2 Br and will thus be less reactive in S N 2

Question 8:
In the following pairs of halogen compounds, which compound undergoes faster SN1
reaction?
(i)

(ii)

Solution 8:
Reactivity of SN1 is governed by stability of carbocations.

(i) reacts faster due to greater stability of 3o carbocation.

(ii) reacts faster due to greater stability of 2o carbocation over 1o

carbocation

Question 9:
Identify A, B,C,D,E,R and R1 in the following:

R  Br  Mg 
dry ether
 A 
H2O
B

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Solution 9:

NCERT EXERCISE
Question 1:
Name the following halides according to IUPAC system and classify them as alkyl, benzyl
(primary,secondary ,tertiary),vinyl or aryl halides:
(i) CH3  2 CHCH Cl  CH3
(ii) CH3CH2CH CH3  CH C2 H5  Cl
(iii) CH3CH2C CH3 2 CH2l
(iv)  CH3  3 CCH2CH  Br  C 6 H5
(v) CH3CH CH3  CH  Br  CH3

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(vi) CH3C C2 H5 2 CH2CH3

(vii) CH3CH  C Cl  CH2CH CH3 2
(ix) CH3CH  CHC  Br CH3 2
( x) P  ClC6 H4 CH2C CH3 2
( xi) m  ClCH2C6 H4 CH2C CH3 3
( xii) o  Br  C6 H4 CH CH3  CH2CH3

Solution 1:
(i) 2-Chloro-3methylbutane,2o alkyl halide
(ii) 3-Chloro-4methyl hexane,2o alkyl halide
(iii) 1 -Iodo-2, 2-dimethylbutane,1o alkyl halide
(iv) 1-Bromo-3, 3-dimethyl -1-phenylbutane, 2o benzylic halide
(v) 2-Bromo-3-methylbutane,2o alkyl halide
(vi) 1-Bromo-2-ethyl-2-methylbutane, 1o alkyl halide
(vii) 3-Chloro-3-methylpentane,3o alkyl halide
(viii) 3-Chloro-5-methylhex-2-ene, vinylic halide
(ix) 4-Bromo-4-methylpent-2-ene, allylic halide
(x)1-Chloro-4-(2-methylpropyl) benzene, aryl halide
(xi) l -Chloromethyl-3- (2,2-dimethylpropyl) benzene,1o benzylic halide.
(xii) 1-Bromo-2-(l-methylpropyl) benzene,aryl halide.

Question 2:
Give the IUPAC names of the following compounds:
i  CH3CH CI  CH  Br  CH3
ii  CHF2CBrCIF
iii  ClH2C  CCH2 Br
iv CCl3 3 CCl
 v  CH3C  p  CIC6 H4 2 CH3
 vi CH3 3 CCH  C CI  C6 H4 I  p

Solution 2:
(i) 2-Bromo-3-chorobutane
(ii) 1-Bromo-1–chloro-1, 2, 2-trifluoroethane
(iii) 1-Bromo-4-chlorobut- 2 - yne
(iv) 2-(Trichloromethyl)-|,1,1,2,3,3,3-heptachloropropane
(v) 2-Bromo-3,3-bis-(4-chlorophenyl) butane
(vi) 1-Chloro-| (4-iodophenyl)-3,3- dimethylbut-|-ene.

Question 3:

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Write the structures of the following organic halogen compounds:

(i) 2-Chloro-3-methylpentane
(ii) p-Bromochlorobenzene
(iii) l-Chloro-4-ethylcyclohexane
(iv) 2- (2-Chlorophenyl) -1- iodooctane
(v) 2-Bromobutane
(vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
(viii)l, 4-Dibromobut-2-ene

Solution 3:
(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

(viii) BrCH2 – CH = CH – CH2Br

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Question 4:
Which one of the following has the highest dipole moment?
(i) CH 3Cl2 (ii )CHCl3 (iii )CCl4

Solution 4:
The three dimensional structures of the three compounds along with the direction of dipole
moment in each of their bonds are given below:

CCl4 being symmetrical has zero dipole moment. In CHCl3 the resultant of two C  Cl dipole
moments is opposed by the resultant of C  H and C  Cl bonds. Since dipole moment of
latter resultant is expected to be smaller than the former, CHCl3 has a finite dipole (1.03 D)
moment. In CH 3Cl2 the resultant of two C  Cl dipole moment higher than that of CHCl3 .
Thus, CH 3Cl2 has highest dipole moment.

Question 5:
A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.

Solution 5:
The hydrocarbon with molecular formula can either be a cycloalkane or an alkene. Since the
compound does not react with Cl2 in the dark, therefore it cannot be an alkene but must be a
cycloalkane since the cycloalkane reacts with Cl2 in the presence of bright sunlight to give a
single monochloro compound C5 H 9Cl , therefore all the ten hydrogen atoms of the
cycloalkanes must be equivalent. Thus the cycloalkane is cyclopentane

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Question 6:
Write the isomers of the compound having formula C4 H 9 Br

Solution 6:
Double bond equivalent (DBE) for C4 H 9 Br
4(4  2)  9(1  2)  1(1  2)
= 1  0
2
So none of the isomer has a ring or unsaturation, so the isomers are position or chain isomers
(i) CH3CH 2CH 2CH 2 Br
1 Bromo butane

(ii)

(iii)

(iv)

Question 7:
Write the equations for the preparation of 1-iodoobutane from
(i) 1-butanol (ii)1-chlorobutane (iii) but-1-ene.

Solution 7:
i  CH3CH2CH2CH2OH  KI  H3PO4  CH3CH 2CH 2 I  H 2O  KH 2 PO4
(ii ) CH 3CH 2CH 2CH 2CI  KI 
Aceione
CH 3CH 2CH 2CH 2 I  KCl 

CH 3CH 2 CH 2 CH 2 Br
(iii ) CH 3CH 2  CH =CH 2  HBr  
peroxide

 NaI / Acetone
CH 3 CH 2 CH 2 CH 2 I + NaBr

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Question 8:
What are ambident nucleophiles? Explain with an example.

Solution 8:
Nucleophiles which can attack through two different sites are called ambident nucleophiles.
For example, Cyanide ion is a resonance hybrid of the following two structures:
 .. 
: C  N :: C  N :
It can attack through carbon to form cyanide and through N to form is isocyanide.

Question 9:
Which compound in each of the following pairs will react faster in SN 2 reaction with OH ?
(i) CH 3 Br or CH 3 I
(ii)  CH3 3 CCl or CH3Cl

Solution 9:
(i) Since I  ion is a better leaving group than Br  ion, therefore, CH3I reacts faster CH3Br in
SN2 reaction with OH  ion.
(ii) On steric grounds, methyl halide is more reactive than tert-alkyl halides in S N 2 reaction.
Therefore CH 3 Cl will react at a faster rate than  CH3 3 CCl in a S N 2 reaction with OH  ion

Question10:
Predict all the alkenes that would be formed by dehydrohalogenation of the following halides
with sodium ethoxide in ethanol and identify the major alkene:
(i) 1-Bromo-1-methylcyclohexane
(ii) 2-Chloro-2-methylbutane.
(iii) 2,2,3-Trimethyl-3-bromopentane.

Solution 10:
(i)

(ii)

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(iii)

Question 11:
How will you bring about the following conversioins?
(i) Ethanol to but-1-yne.
(ii) Ethane to bromoethane
(iii) Propene to 1-Nitropropane
(iv) toluene to benzyl alcohol
(v) propene to propyne
(vi) Ethanol to ethyl Fluoride
(vii) Bromomethane to propanone
(viii)But-1-ene to but-2-ene
(ix)1-Chlorobutane to n-octane
(x) Benzene to biphenyl

Solution 11:
(i) CH3CH2OH 
SOCl2 .Pyridine
SO2 . HCl
 CH3CH 2  Cl
Chlorethane (l)

CH  CH  NaNH 2 
Liq NH3 .196 K
 HC  C  Na 
Sodium acetylide (II)

CH3  CH2  Cl  HC  C  Na  
 CH3CH2  C  CH  NaCl
(I) (II)

(ii)
hv. 520  670 k
CH3  CH3  Br2   CH3CH 2  Br  HBr
Ethane Bromoethane
 / KOH(alc)

 CH 2  CH 2 
KOH(alc)
 HBr
 BrCH 2CH 2Br   CH 2  CHBr
Br2 / CCl4
 HBr
Bromoethane

(iii) CH 3  CH  CH 2 
 CH 3CH 2CH 2 Br 
HBr . ROOR
 CH 3CH 2CH 2 NO2
Peroxide effect
AgNO2 , C2 H5 OH / H 2 O

Propene 1 Bromopropane 1 nitropropane

(iv)

(v)

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(vi) CH 3CH 2OH 

SOCl2 , Pyridine
 SO2 ,  HCl
 CH 3CH 2Cl 
Hg2 F2
 Hg2 Cl2
 CH 3CH 3 F
Ethanol Ethyl chloride Ethylfuoride

(vii)

(viii)

(ix) 2CH3CH 2CH 2CH 2Cl  2 Na 

Dry ether
Wurtz reaction
CH3CH 2CH 2CH 2CH 2CH 2CH 2 CH 3  2NaCl
1 chlorobu tane n  Octane

(x)

Question 12:
Explain why
(i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
(ii) alkyl halides, though polar, are immiscible with water?
(iii) Grignard reagents should be prepared under anhydrous conditions?

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Solution 12:
(i) sp2-hybrid carbon in chlorobenzene is more electronegative than a sp3-hybrid carbon in
cyclohexylchloride, due to greater s-character. Thus, C atom of chlorobenzene has less
tendency to release electrons to Cl than carbon atom of cyclohexylchloride. As a result, C -
Cl bond in chlorobenzene is less polar than in cyclohexylchloride. Further, due to
delocalization of lone pairs of electrons of the Cl atom over the benzene ring, C-CI bond in
chlorobenzene acquires some double bond character while the C — Cl in cyclohexy chloride
is a pure single bond. In other words, C-Cl bond in chlorobenzene is shorter than in
cyclohexyl chloride.
Since dipole moment is a product of charge and distance. Therefore, chlorobenzene has lower
dipole moment than cyclohexylchloride due to lower magnitude of negative charge on the Cl
atom and shorter C- Cl distance.
(ii) Alkyl halides are polar molecules, therefore, their molecules are held together by dipole-
dipole attraction.
The molecules of H2O are hold together by H-bonds. Since the new forces of attraction
between water and alkyl halide molecules are weaker than the forces of attraction already
existing between alkyl halide - alkyl halide molecules and water-water molecules, therefore,
alkyl halides are immiscible (not soluble) in water.
Alkyl halide are neither able to form H- bonds with water nor are able to break the H-
bounding network of water
(iii) Grignard reagents are very reactive. They react with moisture present in the apparatus to
form alkanes
R  Mg  X  H  OH  R  H  Mg (OH ) X
Thus, Grignard reagents must be prepared under anhydrous conditions.

Question 13:
Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.

Solution 13:
Iodoform: It was earlier used as an antiseptic but the antiseptic properties are due to the
liberation of free iodine and not due to iodoform itself. Due to its objectionable smell, it has
been replaced by other formulations containing iodine.
Carbon tetrachloride:
Uses:
(i) As an industrial solvent for oil, fats. resins etc. and also in dry cleaning.
(ii) CCl4 vapours are highly non inflammable. Thus CC14 is used as a fire extinguisher under
the name pyrene.
(iii) Used in the manufacture of refrigerants and propellants for aerosol cans.
Freons: Freon-12 (CCl2F2) is most common freons in industrial use.
Uses For aerosol propellants, refrigeration and air conditioning purposes.
DDT (p -p' — Dichloro diphenyl — trichloro ethane):

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(i) The use of DDT increased enormously on a world wide basis after World War Il,
primarily because of its effectiveness against the mosquitoes that spreads malaria and other
insects which damages crops.
(ii) However, problems related to extensive use of DDT began to appear in the late 1940 s.
Many species of insects developed resistance to DDT, it was also discovered to have a high
toxicity towards fishes. DDT is not metabolised very rapidly by animals, instead is deposited
and stored in the fatty tissues. If the ingestion continues at a steady rate, DDT builds up
within the animals overtime.

Question 14:
Write the structure of the major organic product in each of the following reactions:
(i ) CH 3CH 2 CH 2 Cl  NaI 
Acetone heat

(ii ) (CH 3 )3 CBr  KOH 

Ethone heat

(iii ) CH 3CH ( Br )CH 2CH 3  NaOH  
Water

(iv) CH 3CH 2 Br  KCN 

aq .ethanol

(v) C6 H 5ONa  C2 H 5Cl 

(vi ) CH 3CH 2CH 2OH  SOCI 2 

Peroxide
(vii) CH 3CH 2CH  CH 2  HBr 

(viii ) CH 3CH  C (CH 3 ) 2  HBr 


Solution 14:
(i) CH3CH 2CH 2Cl  Nal 
acetone.heat
( Finkelstein reaction )
CH 3CH 2CH 2 I  NaCl
1 Chloropropane 1 Iodopropane

(ii)

(iii)

(iv) CH3CH 2 Br  KCN  aq.ethanol


(Nucleophilic substitution)
 CH 3CH 2CN  KBr
Propanenitrile

(v) C6 H5O  Na  C2 H 5Cl  C6 H 5  O  C2 H 5  NaCl

Williamson's
synthesis
Sodium phenoxide Ethylchloride Phenetole

(vi) CH3CH 2CH 2OH  SOCl2  CH 3CH 2CH 2Cl  HCl  SO2
Nucleophilic
substitution
Propan 1 ol 1 Chloropropane

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(vii) CH3CH 2CH  CH 2  HBr  Proxide


(Anti-Markownikoff's addition)
CH3CH 2CH 2CH 2 Br
But 1 ene 1 Bromobutane

(viii)

Question 15:
Write the mechanism of the following reaction:
EtoH  H2O
n  BuBr  KCN   n  BuCN

Solution 15:
KCN is a resonance hybrid of the following two contributing structures:

K    : C  N :: C  N : 
Thus, CN  ion is an ambident nucleophile. Therefore, it can attack the “carbon atom of
C  Br bond in n  BuBr either through C or N. Since C-C bond is stronger than C—N
bond, therefore, attack occurs through C to from n-butyl cyanide.

Question 16:
Arrange the compounds of each set in order of reactivity towards S N 2 displacement:
(i) 2-Bromo-2-Methyibutane, 1-Brompentane, 2-Bromopentane.
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane,3-Bromo-2-methylbutane
(iii)1-Bromobutane,1-Bromo-2,2-dimethypropane,1-Bromo-2-methylbutane,1-Bromo-3-
methyl butane.

Solution 16:
The S N 2 reactions reactivity depends upon steric hindrance. More the steric hindrance slower
the reaction. Thus the order of reactivity will be 1o  2o  3o
(i)

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(ii)

(iii)

Since in case of1o alkyl halides steric hindrance increases in the order) n-alkyl halides, alkyl
halides with a substituent at any position other than theβ- position, one substituent at theβ-
position, two substituents at theβ- position, therefore, the reactivity decreases in the same
order. Thus, the reactivity of the given alkyl bromides decreases in the order.
1-Bromobutane >l -Bromo-3-methylbutane >|-Bromo-2-methyjbutane >1-Bromo—2, 2-
dimethyl propane.

Question 17:
Out of¸ C6 H 5CH 2Cl and C6 H 5CHClC6 H 5 which is more easily hydrolysed by aqueous KOH

Solution 17:
C6 H 5CHCl is 10 aryl halide while C6 H5CH Cl  C6 H5 aryl halide In S N 1 reactions, the
reactivity depends upon the stability of carbocations.

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

Since the C6H5CH+C6H5 carbocation is more stable than C6 H 5 CH 2  carbocation, therefore,

C6 H 5CHClC6 H 5 gets hydrolysed more easily than C6 H 5CH 2Cl under S N 1 conditions.
However, under S N 2 conditions, C6 H 5CH 2Cl gets hydrolysed more easily than
C6 H 5CHClC6 H 5

Question 18:
p-Dichlorobenzene has higher m.p. and lower solubility than those of o-and m-isomers.
Discuss.

Solution 18:
The p-isomer being more symmetrical fits closely in the crystal lattice and thus has stronger
inter- molecular forces of attraction than o - and m- isomers. Since during melting or
dissolution, the crystal lattice breaks, therefore, a large amount of energy is needed to melt or
dissolve the p-isomer than the corresponding o-and m-isomers. In other words, the melting
point of the p-isomer is higher and its solubility lower than the corresponding o -and m-
isomers.

Question 19:
How the following conversions can be carried out:
(i) Propene to propan-l-ol
(ii) Ethanol to but-I-yne
(iii) I-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3,4-dimethylhexane
(x) 2-Methyl-1 -propene to 2-chk>ro-2- methylpropane.
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chlropropane to 1 -propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol

10. Haloalkanes and Haloarenes www.vedantu.com 19

Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(xvi) 2-Bromopropane to 1-bromopropane

(xvii) Chloroethane to butane ,
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide (xx) Aniline to phenylisocyanide

Solution 19:
Aq. KOH , 
(i) CH3CH  CH 2 
HBr / Peroxide
 CH3CH 2CH 2 Br 
Hydrolysis
 CH 3CH 2CH 2OH
Propane Propan-l-ol

(ii)

KOH (alc), 
(iii) CH3CH 2CH 2 Br 
Dehydrohalogenation
CH 3CH  CH 2 HBr
Mark. addition
CH 3  CHBr  CH 3
2  Bromopropane

(iv)

(v)

(vi)

10. Haloalkanes and Haloarenes www.vedantu.com 20

Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

P/I2 ,  KCN , Et  OH  H 2 O
(vii) CH 3CH 2OH   CH 3CH 2 I 
(Nucleophilic
 CH 3CH 2CN
Ethanol substitution) Propanenitrile

(viii)

(ix)

(x)


KCN , EtOH  H 2 O
(xi) CH 3CH 2Cl 
(Nucleophilic
 CH 3CH 2CN 
H / H2O
Hydrolysis
 CH 3CH 2COOH
Ethyl chloride substitution) Propanenitrile Propanoic acid

(xii)
CH 3CH 2CH  CH 2 
HBr / RCOOR
Anti-Mark. Addition
 CH 3CH 2CH 2CH 2 Br 
Nal , acetone
Finkelstein
CH 3CH 2CH 2CH 2 I
But 1 ene reaction n-Butyliodide

(xiii)

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Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(xiv)

(xv)

(xvi)

(xvii)

(xviii)

(xix)

10. Haloalkanes and Haloarenes www.vedantu.com 22

Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(xx)

Question 20:
The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in
the presence of alcoholic KOH, alkenes are major products. Explain.

Solution 20:
If aqueous solution, KOH is almost completely ionized to give OH  ions which being a
strong nucleophile brings about a substitution reaction on alkyl halides to form alcohols.
Further in the aqueous solution, OH  ions are highly solvated (hydrated). This solvation
reduces the basic character of OH  ions which, therefore, fails to abstract a hydrogen from
the P - carbon of the alkyl chloride to form alkenes. In contrast, an alcoholic solution of KOH
contains alkoxide  RO  ion which being a much stronger base than OH  ions perferentially
eliminates a molecule of HCI from an alkyl chloride to form alkenes.

Question 21:
Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b)
Compound (b) is reacted, with HBr to give (c) which is an isomer of (a). When (a) is reacted
with sodium metal it give compound (d), C8H18 which is different from the compound formed
when n-butyl bromide is reacted with sodium. Give the structural formula of (a) and write the
equations for all the reactions

Solution 21:
Ans. (i) There are two primary alkyl halides having the molecular formula, C4H9Br.

(ii) Since compound (a) when reacted with Na metal gave a compound (d) with molecular
formula C8H18 which was different from die compound obtained when n-butyl bromide was
reacted with Na metal, therefore, (a) must be isobutyl bromide and compound (d) must be
2,3- dimethylhexane.
2CH3CH 2CH 2 Br  2 Na 
Wurtz reaction
CH3CH 2CH 2CH 2CH 2CH 2CH 2CH 3
n  Octane

10. Haloalkanes and Haloarenes www.vedantu.com 23

Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(iii) If compound (a) is isobutyl bromide. Than the compound (b) which it gives on treatment
with alcoholic KOH must be 2-methyl-1-propane.

(iv) The compound (b) on treatment with HBr gives compound (c) in accordance with
Markownikoff rule. Therefore, compound (c) is tert-butyl bromide which is an isomer of
compound (a),i.e, isobutyl, bromide.

Thus,
(a) is isobutyl bromide,
(b) is 2-methyl-1-propane,
(c) is tert-butylbromide, and
(d) is 2,5-dimethylhexane.

Question 22:
What happens when.
(i) n-butyi chloride is treated with alcoholic KOH.
(ii) bromobenzene is treated with Mg in the presence of dry ether.
(iii) chlorobenzene is subjected to hydrolysis.
(iv) ethyl chloride is treated with aqueous. KOH
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN.

Solution 22:
(i)

CH 3CH 2  CH 2  CH 2  Cl  KOH (alc) 
Dehydrohalogenation
 CH 3CH 2CH  CH 2  KCl  H 2O
n  Butychloride But 1 ene

(ii)

10. Haloalkanes and Haloarenes www.vedantu.com 24

Class XII – NCERT – Chemistry Chapter 10
Haloalkanes and Haloarenes

(iii)

(iv) CH3CH 2  Cl  KOH (aq) 

Hydrolysis

CH 3CH 2  OH  KCl  H 2O
Ethylchloride Ethyl alcohol

(v) CH3  Br  2 Na  Br  CH 3 CH 3  CH 3  2NaBr

Dry ether
( wurtz reaction )
Methylbromide

Et  OH  H 2 O , 
(vi) CH 3  Cl  KCN 
Nucleophilic substitution
 CH 3C  N  KCl
Methyl Methyleyanide
chloride

10. Haloalkanes and Haloarenes www.vedantu.com 25

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Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers
NCERT Exercise

Question 1:
Write IUPAC names of the following compounds.
CH3
|
i  CH 3  CH  CH  C  CH 3
| | |
CH3 OH CH3
 ii  H 3C  CH  CH 2  CH  CH  CH 2  CH 3
| | |
OH OH C2H5
 iii  CH 3
 CH  CH  CH 3
| |
OH OH
 iv  HO  CH 2  CH
|
 CH 2  OH
OH

(v)

(vi)

(vii)

(viii)

11.Alcohols phenols and ethers www.vedantu.com 1

 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ix) CH 3  O  CH 2  CH  CH 3
|
CH3
(x) C6 H 5  O  C2 H 5
(xi)
C6H5-O-C7H15(n - )
(xii) CH3  CH 2  O  CH  CH 2  CH3
|
CH3

Solution 1:
(i) 2, 2, 4-Trimethylpentan-3-ol
(ii) 5-Ethylheptane-2, 4-diol
(iii) Butane-2, 3-diol
(iv) Propane-1, 2, 3-triol
(v) 2-Methylphenol
(vi) 4-Methylphenol
(vii) 2, 5-Dimethylphenol
(viii) 2, 6-Dimethylphenol
(ix) 1-Methoxy-2-methylpropane
(x) Ethoxybenzene
(xi) 1-Phenoxyheptane
(xii) 2-Ethoxybutane

Question 2:
Write structures of the compounds whose IUPAC names are as follows:
(i) 2-Methylbutan-2-ol
(ii) 1-Phenylpropan-2-ol
(iii) 3,5-Dimethylhexane -1, 3, 5-triol
(iv) 2,3 -Diethylphenol
(v) 1 -Ethoxypropane
(vi) 2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol
(x) 3-Chloromethylpentan- 1-ol.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Solution 2:
OH
|
i CH 3  C  CH 2  CH 3
|
CH3

(ii)

OH OH
| |
 iii  HO  CH 2  CH 2  C  CH 2  C  CH 3
| |
CH3 CH3

(iv)

 v CH3  CH2  O  CH2  CH2  CH3

CH3
|
(VI) CH3-CH2-O-CH-CH-CH2-CH3
|
CH3
(vii)

(viii)

11.Alcohols phenols and ethers www.vedantu.com 3

 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ix)

CH2Cl
|
(X) CH3-CH2-CH-CH2-CH2-OH

Question 3:
(i) Draw the structures of all isomeric alcohols of molecular formula C5 H12O and give their
IUPAC names.
(ii) Classify the isomers of alcohols in question 11.3 (i) as primary, secondary and tertiary
alcohols.

Solution 3:
(i) The structures of all isomeric alcohols of molecular formula, C5 H12O are shown below:
a CH3  CH 2  CH 2  CH 2  CH 2  OH

Pentan-1-ol 1
 b  CH 3  CH 2  CH
|
 CH 2  OH
CH3

2-Methylbutan-1-ol 1
 c  CH 3  CH
|
 CH 2  CH 2  OH
CH3

3-Methlbutan-1-ol 1
CH3
|
 d  CH 3  C  CH 2  OH
|
CH3

11.Alcohols phenols and ethers www.vedantu.com 4

 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

2, 2-Dimethylpropan-1-ol 1
OH
|
 e  CH 3  CH 2  CH 2  CH  CH 3
Pentan-2-ol  2
CH3 OH
| |
 f  CH 3  CH  CH  CH 3
3-Methylbutan-2-ol  2
OH
|
(g) CH 3  CH 2  CH  CH 2  CH 3

Pentan-3-ol  2
OH
|
 h  CH 3  CH 2  C  CH 3
|
CH3
2-Methylbutan-2-ol  3
(ii) Primary alcohol: Pentan-1-ol; 2-Methylbutan-1-ol;
3-Methylbutan-1-ol; 2, 2—Dimethylpropan- 1-ol
Secondary alcohol: Pentan-2-ol; 3-Methylbutan-2-ol;
Pentan-3-ol
Tertiary alcohol: 2-methylbutan-2-ol

Question 4:
Explain why propanol has higher boiling point than that of the hydrocarbon, butane?

Solution 4:
Propanol undergoes intermolecular H-bonding because of the presence of —OH group. On the
other hand, butane does not
     
H O H O H O
| | |
C3H7 C3H7 C3 H 7

Therefore, extra energy is required to break hydrogen bonds. For this reason, propanol has a
higher boiling point than hydrocarbon butane.

11.Alcohols phenols and ethers www.vedantu.com 5

 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 5:
Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular
masses. Explain this fact.

Solution 5:
Alcohols form H-bonds with water due to the presence of -OH group. However, hydrocarbons
cannot form H-bonds with water.

As a result, alcohols are comparatively more soluble in water than hydrocarbons of

Comparable molecular masses.

Question 6:
What is meant by hydroboration-oxidation reaction? Illustrate it with an example.

Solution 6:
The addition of borane followed by oxidation is known as the hydroboration-oxidation
reaction, For example, propan-l-ol is produced by the hydroboration-oxidation reaction of
propene. In this reaction, propene reacts with diborane  BH3 2 to form trialkylborane as an
addition product. This addition product is oxidized to alcohol by hydrogen peroxide in the
presence of aqueous sodium hydroxide.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 7:
Give the structures and IUPAC names of monohydric phenols of molecular formula, C7 H 8O .

Solution 7:

Question 8:
While separating a mixture of ortho and para nitrophenols by steam distillation, name the
isomer which will be steam volatile. Give reason.

Solution 8:
Intramolecular H-bonding is present in o-nitrophenol and p-nitrophenol. In p-nitrophenol, the
molecules are strongly associated due to the presence of intermolecular bonding. Hence, o-
nitrophenol is steam volatile.

Question 9:
Give the equations of reactions for the preparation of phenol from cumene.

Solution 9:
To prepare phenol, cumene is first oxidized in the presence of air of cumene hydroperoxide.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Then, cumene hydroxide is treated with dilute acid to prepare phenol and acetone as by
products.

Question 10:
Write chemical reaction for the preparation of phenol from chlorobenzene.

Solution 10:
Chlorobenzene is fused with NaOH (at 623 K and 320 atm pressure) to produce sodium
phenoxide, which gives phenol on acidification.

Question 11:
Write the mechanism of hydration of ethene to yield ethanol.

Solution 11:
The mechanism of hydration of ethene to form ethanol involves three steps.
Step 1: Protonation of ethene to form carbocation by electrophilic attack of H 3O  :

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

H 2O  H  
 H 3O 

Step 2: Nucleophilic attack of water on carbocation:

Step 3: Deprotonation to form ethanol :

Question 12:
You are given benzene, conc. H 2 SO4 and NaOH . Write the equations for the preparation of
phenol using these reagents.

Solution 12:

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 13:
Show how will you synthesize:
(I) 1-phenylethanol from a suitable alkene.
(ii) cyclohexylmethanol using an alkyl halide by an SN2 reaction.
(iii) pentan-1-ol using a suitable alkyl halide?

Solution 13:
(i) By acid-catalysed hydration of ethylbenzene (styrene), 1-phenylethanol can be synthesized

(ii) When chloromethylcyclohexane is treated with sodium hydroxide, cyclohexylmethanol is

obtained.

(iii) When 1-chloropentane is treated with NaOH , pentan-1-ol is produced.

CH3CH 2CH 2CH 2CH 2Cl  NaOH 
 CH 3CH 2CH 2CH 2CH 2OH  NaCl
1Chloropen tan e Pan tan 1ol

Question 14:
Give two reactions that show the acidic nature of phenol. Compare acidity of phenol with that
of ethanol.

Solution 14:
The acidic nature of phenol can be represented by the following two reactions:
(i) Phenol reacts with sodium to give sodium phenoxide, liberating H 2 .

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ii) Phenol reacts with sodium hydroxide to give sodium phenoxide and water as by products.

The acidity of phenol is more than that of ethanol. This is because after losing a proton, the
phenoxide ion undergoes resonance and gets stabilized whereas ethoxide ion does not.

Question 15:
Explain why is ortho nitrophenol more acidic than ortho methoxyphenol?

Solution 15:

The nitro-group is an electron-withdrawing group. The presence of this group in the ortho
position decreases the electron density in the O-H bond. As a result, it is easier to lose a
proton. Also, the o-nitrophenoxide ion formed after the loss of protons is stabilized by
resonance. Hence, ortho-nitrophenol is a stronger acid.
On the other hand, methoxy group is an electron-releasing group. Thus, it increases the
electron density in the O—H bond and hence, the proton cannot be given out easily. For this
reason, ortho-nitrophenol is more acidic than ortho-methoxyphenol.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 16:
Explain how does the -OH group attached to a carbon of benzene ring activate it towards
electrophilic substitution?

Solution 16:
The -OH group is an electron-donating group. Thus, it increases the electron density in the
benzene ring as shown in the given resonance structure of phenol.

As a result, the benzene ring is activated towards electrophilic substitution.

Question 17:
Give equations of the following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS 2 with phenol.
(iii) Dilute HNO3 with phenol.
(iv) Treating phenol with chloroform in presence of aqueous NaOH .

Solution 17:
CH 3CH 2CH 2OH 
alk KmnO4
 CH 3CH 2COOH
Propan-l-ol Propanic acid

(ii)

(iii)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(iv)

Question 18:
Explain the following with an example.
(i) Kolbe’s reaction.
(ii) Reimer-Tiemann reaction.
(iii) Williamson ether synthesis.
(iv) Unsymmetrical ether

Solution 18:
(i) Kolbe’s reaction:
When phenol is treated with sodium hydroxide, sodium phenoxide is produced. This sodium
phenoxide when treated with carbon dioxide, followed by acidification, undergoes
electrophilic substitution to give ortho-hydroxybenzoic acid as the main product. This reaction
is known as Kolbe’s reaction.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ii) Reimer-Tiemann reaction:

When phenol is treated with chloroform ( CHCl3 ) in the presence of sodium hydroxide, a-CHO
group is introduced at the ortho position of the benzene ring.

This reaction is known as the Reimer-Tiemann reaction.

The intermediate is hydrolysed in the presence of alkalis to produce salicylaldehyde.

(iii) Williamson ether synthesis

Williamson ether synthesis is a laboratory method to prepare symmetrical and unsymmetrical
ethers by allowing alkyl halides to react with sodium alkoxides.
R  X  R  ONa   R  O  R  NaX
Alkl halide Sodiumalkoxide Ether

This reaction involves SN2

attack of the alkoxide ion on the alkyl halide. Better results are
obtained in case of primary alkyl halides.

If the alkyl halide is secondary or tertiary, then elimination competes over substitution.
(iv) Unsymmetrical ether:
An unsymmetrical ether is an ether where two groups on the two sides of an oxygen atom
differ (i.e., have an unequal number of carbon atoms). For example: ethyl methyl ether
CH3  O  CH2CH3  .

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 19:
Write the mechanism of acid-catalyzed dehydration of ethanol to yield ethene.

Solution 19:
The mechanism of acid dehydration of ethanol to yield ethene involves the following three
steps:
Step 1:
Protonation of ethanol to form ethyl oxonium ion:

Step 2:
Formation of carbocation (rate determining step):

Step 3:
Elimination of a proton to form ethene:

The acid consumed in step 1 is released in Step 3. After the formation of ethene, it is removed
to shift the equilibrium in a forward direction.

Question 20:
How are the following conversions carried Out?
(i) Propene  Propan-2-ol
(ii) Benzyl chloride.  Benzyl alcohol
(iii) Ethyl magnesium chloride  Propan-l-ol.
(iv) Methyl magnesium bromide  2-Methylpropan-2-ol.

Solution 20:

11.Alcohols phenols and ethers www.vedantu.com 15

 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(i) If propene is allowed to react with water in the presence of an acid as a catalyst, then
propan-2-ol is obtained.

(ii) If benzyl chloride is treated with NaOH (followed by acidification) then benzyl alcohol is
produced.

(iii) When ethyl magnesium chloride is treated with methanal, an adduct is the produced which
gives propan-1-ol on hydrolysis.

(iv) When methyl magnesium bromide is treated with propane, an adduct is the product which
gives 2-methylpropan-2-ol on hydrolysis.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 21:
Name the reagents used in the following reactions:
(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) Oxidation of a primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-ol to propene.
(vi) Butan-2-one to butan-2-ol.

Solution 21:
(i) Acidified potassium permanganate
(ii) Pyridinium chlorochromate (PCC)
(iii) Bromine water
(iv) Acidified potassium permanganate
(v) 85% phosphoric acid at 440 K
(vi) NaBH 4 or LiAlH 4

Question 22:
Give reason for the higher boiling point of ethanol in comparison to methoxymethane.

Solution 22:
Ethanol undergoes intermolecular H-bonding due to the presence of —OH group, resulting in
the association of molecules. Extra energy is required to break these hydrogen bonds. On the
other hand, methoxymethane does not undergo H-bonding. Hence, the boiling point of ethanol
is higher than that of methoxymethane.

Question 23:
Give IUPAC names of the following ethers:
 i  C2 H5OCH 2  CH  CH 3
|
CH3
(ii) CH 3OCH 2CH 2Cl
(iii) O2 N  C6 H4  OCH3 p
(iv) CH 3CH 2CH 2OCH 3
(v)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(vi)

Solution 23:
(i) 1-Ethoxy-2-methylpropane
(ii) 2-Chloro-1-methoxyethane
(iii) 4-Nitroanisole
(iv) 1-Methoxypropane
(v) 1-Ethoxy-4, 4-dimethylcyclohexane
(vi) Ethoxybenzene

Question 24:
Write the names of reagents and equations for the preparation of the following ethers by
Williamson’s synthesis:
(I) 1-Propoxypropane
(ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane
(iv) 1-Methoxyethane

Solution 24:
(i) CH3CH 2CHONa CH3CH 2CH 2 Br 
 C2 H5CH 2  O  CH 2C2 H 5  NaBr
Sodium propoxide I  Bromopropane I  Pr opoxypropane

(ii)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

CH3 CH3
| |
 iii  CH 3  C  ONa  CH 3  Br 
|
 CH 3  C  OCH 3  NaBr
|
CH3 CH3
Sodium 2  methyl Bromomethane 2  methoxy  2  methylpropane
2  propoxide

(iv) CH3CH 2  ONa  CH3  Br 

 CH3CH 2  O  CH 3  NaBr
Sodium ethoxide Bromomethane I  Methoxyethane

Question 25:
Illustrate with examples the limitations of Williamson synthesis for the preparation of certain
types of ethers.

Solution 25:
The reaction of Williamson synthesis involves S N 2 attack of an alkoxide ion on a primary
alkyl halide.
CH3 CH3
|  |
CH 3  C  O Na  CH 3  Cl 
 CH 3  O  C  CH 3  NaCl
| |
CH3 CH3
But if secondary or tertiary alkyl halides are taken in place of primary alkyl halides, then
elimination would compete over substitution. As a result, alkenes would be produced.
This is because alkoxides are nucleophiles as well as strong bases. Hence, they react
with alkyl halides, which results in an elimination reaction.
CH3
|
CH 3  C  Cl  NaO  CH 3  CH 3  C  CH 2  CH 3OH  NaCl
| |
CH3 CH3
Teritary alkyl halide Alkene

Question 26:
How is 1-propoxypropane synthesised from propan-1-ol? Write mechanism of this reaction.

Solution 26:
1-propoxypropane can be synthesized from propan-1-ol by dehydration Propan-1-ol undergoes
dehydration in the presence of protic acids (such as H 2 SO4 , H 3 PO4 ) to give 1-propoxypropane.

2CH3CH 2CH 2  OH 
H
CH3CH3CH 2  O  CH 2CH 2CH3
Propan-1-ol 1-propoxypropane
The mechanism of this reaction involves the following three steps:
Step 1: Protonation
H
CH 3CH 2CH 2  O  H  
 CH 3CH 2CH 2  O   H
popan 1 ol

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Step 2: Nucleophilic attack

Step 3:Deprotonation

Question 27:
Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable
method. Give reason.

Solution 27:
The formation of ethers by dehydration of alcohol is a bimolecular reaction ( S N 2 ) involving
the attack of an alcohol molecule on a protonated alcohol molecule. In the method, the alkyl
group should be unhindered. In case of secondary or tertiary alcohols, the alkyl group is
hindered. As a result, elimination dominates substitution. Hence, in place of ethers, alkenes are
formed.

Question 28:
Write the equation of the reaction of hydrogen iodide with:
(i) 1-propoxypropane
(ii) Methoxybenzene and
(iii) Benzylethylether

Solution 28:
(i) C2 H5CH 2  O  CH 2C2 H5  HI 
373 K
 CH3CH 2CH 2  OH  CH 3CH 2CH 3  I
I  Pr opoxypropane Pr opan 1ol I  Iodopropane

(ii)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(iii)

Question 29:
Explain the fact that in aryl alkyl ethers.
(i) The alkoxy group activates the benzene ring towards electrophilic substitution and
(ii) It directs the incoming substituents to ortho and para positions in benzene ring.

Solution 29:
(i)

In aryl alkyl ethers, due to the +R effect of the alkoxy group, the electron density in the
benzene ring increases as shown in the following resonance structure.

Thus, benzene is activated towards electrophilic substitution by the alkoxy group.

(ii)It can also be observed from the resonance structures that the electron density increases
more at the ortho and para positions than at the meta position. As a result, the incoming
substituents are directed to the ortho and para positions in the benzene ring.

Question 30:
Write the mechanism of the reaction of HI with methoxymethane.

Solution 30:
The mechanism of the reaction of HI with methoxymethane involves the following steps:
Step 1: Protonation of methoxymethane:

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Step2: Nucleophilic attack of I :

(Iodide ion is a good nucleophile. It attacks the least substituted carbon of the oxonium ion
formed in step 1 and displaces an alcohol molecule by SN2 reaction)

Step 3:
When HI is in excess and the reaction is carried Out at a high temperature, the methanol
formed in the second step reacts with another HI molecule and gets converted to methyl iodide


I   CH 3  O H 2 
 CH 3  I  H 2O

Question 31:
Write equations of the following reactions:
(i) Friedel-Crafts reaction —alkylation of anisole.
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Craft’s acetylation of anisole.

Solution 31:
(i)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ii)

(iii)

(iv)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 32:
Show how would you synthesize the following alcohols from appropriate alkenes?
(i)

(ii)

(iii)

(iv)

Solution 32:
The given alcohols can be synthesized by applying Markovnikov’s rule of acid-catalysed
hydration of appropriate alkenes.
(i)

(ii)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(iii)

Acid-catalysed hydration of pent-2-ene also produces pentan-2-ol but along with pentan-3-ol.

Thus, the first reaction is preferred over the second one to get pentan-2-ol.
(iv)

Question 33:
When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place:
Br
|
CH 3  CH  CH  CH 3  
HBr
 CH 3  C  CH 2  CH 3
| | |
CH3 OH CH3

Give a mechanism for this reaction.

(Hint: The secondary carbocation formed in step II rearranges to a more stable tertiary
carbocation by a hydride ion shift from 3rd carbon atom.

Solution 33:
The mechanism of the given reaction involves the following steps:
Step 1: Protonation

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers


CH 3  CH  CH  CH 3 
H
 CH 3  CH  CH  CH 3
| | | |
CH3 OH CH3 OH 2

3 Methylbu tan  2 ol

Step 2: Formation of 2° carbocation by the elimination of a water molecule

Step 3: Re-arrangement by the hydride-ion shift

Step 4: Nucleophilic attack

Text solution

Question 1:
Classify the following as primary, secondary and tertiary alcohols:
(i)
CH3
|
CH 3  C  CH 2OH
|
CH3

(ii) H 2C  CH  CH 2OH
(iii) CH 3  CH 2  CH 2  OH
(iv)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(v)

(vi)

Solution 1:
Primary alcohol  (i), (ii), (iii)
Secondary alcohol  (iv), (v)
Tertiary alcohol  (vi)

Question 2:
Identify allylic alcohols in the above examples.

Solution 2:
The alcohols given in (ii) and (vi) are allylic alcohols.

Question 3:
Name the following compounds according to IUPAC system.
CH 2OH
|
 i  CH 3  CH 2  CH  CH  CH  CH 3
| |
CH 2Cl CH3
CH 2OH
|
 ii  CH 3  CH
|
 CH 2  CH 
|
CH  CH 3
CH3 OH
(iii)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

 iv  H 2C  CH  CH  CH 2  CH 2  CH 3
|
OH
 v  CH3  C  C  CH 2OH
| |
CH3 Br

Solution 3:
(i) 3-Chloromethyl-2-isopropylpentan- 1-ol
(ii) 2, 5-Dimethylhexane-1, 3-diol
(iii) 3-Bromocyclohexanol
(iv) Hex-1-en-3-ol
(v) 2-Bromo-3-methylbut-2-en-1-ol

Question 4:
Show how are the following alcohols prepared by the reaction of a suitable Grignard reagent
on methanal?
 i  CH 3  CH  CH 2OH
|
CH3

(ii)

Solution 4:
(i)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ii)

Question 5:
Write structures of the products of the following reactions:
(i)

(ii)

(iii)

Solution 5:
(i)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ii)

(iii)

Question 6:
Give structures of the products you would expect when each of the following alcohol reacts
with (a) HCl  ZnCl2 (b) HBr and (c) SOCl2 .
(i) Butan-1-ol
(ii) 2-Methylbutan-2-ol

Solution 6:
(a)

(i)

Primary alcohols do not react appreciably with Lucas’ reagent  HCl  ZnCl2  at room
Temperature.

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

OH Cl
| |
HCl  ZnCl2
(ii) CH 3  CH 2  C  CH 3  CH 3  CH 2  C  CH 3  H 2O
| |
CH3 CH3
 
2  Methylbu tan  2  ol 3o 2  cloro  2  Methylbu tan e
White turbidity 

Tertiary alcohols react immediately with Lucas’ reagent.

(b)
(i) CH3CH 2CH 2CH 2OH  HBr  CH3CH 2CH 2CH 2 Br
Bu tan 1ol I  Bromobu tan e

OH Br
| |
(ii) CH 3  CH 2  C  CH 3  HBr 
 CH 3  CH 2  C  CH 3  H 2O
| |
CH3 CH3
 
2  Methylbu tan  2  ol 3o 2  Bromo  2  Methy l bu tan e

(c)
(i) CH3CH 2CH 2CH 2OH  SOCl2 
CH3CH 2CH 2CH 2Cl  SO2  HCl
Bu tan 1ol I Chlorobu tan e

(ii)

Question 7:
Predict the major product of acid catalyzed dehydration of
(i) 1-methylcyclohexanol and
(ii) butan-1-ol

Solution 7:
(i)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(ii) CH3CH 2CH 2CH 2OH 

Dehydration

 CH 3CH  CHCH 3  H 2O
Bu tan 1ol H But  2ene
 Major product 

Question 8:
Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures
of the corresponding phenoxide ions.

Solution 8:

Resonance structure of the phenoxide ion

Resonance structures of p-nitrophenoxide ion

11.Alcohols phenols and ethers www.vedantu.com 32

 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Resonance structures of o-nitrophenoxide ion

It can be observed that the presence of nitro groups increases the stability of phenoxideion.

Question 9:
Write the equations involved in the following reactions:
(I) Reimer-Tiemann reaction
(ii) Kolbe’s reaction

Solution 9:
i. Reimer-Tiemann reaction

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

ii. Kolbe’s reaction

Question 10:
Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from
ethanol and 3-methylpentan-2-ol

Solution 10:
In Williamson synthesis, an alkyl halide reacts with an alkoxide ion. Also, it is an S N 2
reaction. In the reaction, alkyl halides should be primary having the least steric hindrance.
Hence, an alkyl halide is obtained from ethanol and alkoxide ion from 3- methylpentan-2-ol.
C2 H5OH  
HBr
 C2 H5 Br
Ethanol Bromoethane

CH 3  CH 2  CH  CH  CH 3 
Na
 CH 3  CH 2  CH  CH  ONa
| | | |
CH3 OH CH3 CH3
3 Methylpen tan  2  ol Sodium 3 methylpen tan  2  oxide

CH 3  CH 2  CH  CH  ONa  C2 H 5 Br 
 CH 3  CH 2  CH  CH  OC2 H 5  NaBr
| | | |
CH3 CH3 CH3 CH
3
2  Ethoxy 3 methylpen tan e

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

Question 11:
Which of the following is an appropriate set of reactants for the preparation of 1- methoxy-4-
nitrobenzene and why?
(i)

(ii)

Solution 11:
Set (ii) is an appropriate set of reactants for the preparation of 1-methoxy-4- nitrobenzene.

In set (i), sodium methoxide ( CH 3ONa ) is a strong nucleophile as well as a strong base.
Hence, an elimination reaction predominates over a substitution reaction.

Question 12:
Predict the products of the following reactions:
(i) CH 2  CH 2  CH 2  O  CH 3  HBr 
(ii)

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 Class XII – NCERT – Chemistry Chapter 11
Alcohols phenols and ethers

(iii)

(iv)  CH3 3 C  OC2 H2 

HI


Solution 12:
(i) CH3  CH 2  CH 2  O  CH 3  HBr 
 CH 3  CH 2  CH 2  OH  CH 3  Br
n  propylmethyl ether Pr opanol Bromomethane

(ii)

(iii)

(iv)  CH 3 3 C  OC2 H 5 
HI
  CH 3 3 C  I  C2 H 5OH
tert  Butvl ethvl ether tert  Butvilodide Ethanol

11.Alcohols phenols and ethers www.vedantu.com 36

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

NCERT Exercise

Question 1:
What is meant by the following terms? Give an example of the reaction in each case.
(i) Cyanohydrin
(ii) Acetal
(iii) Semicarbazone
(iv) Aldol
(v) Hemiacetal
(vi) Oxime
(vii) Ketal
(vii) Imine
(ix) 2,4-DNP-derivative
(x) Schiff’s base

Solution 1:
(i) Cyanohydrin:
Cyanohydrins are organic compounds having the formula RR′C(OH)CN, where R and R′can
be alkyl or aryl groups.

Aldehydes and ketones react with hydrogen cyanide (HCN) in the presence of excess sodium
cyanide ( NaCN ) as a catalyst to field cyanohydrin. These reactions are known as cyanohydrin
reactions.
NaCN
RR ' C  O  HCN   RR ' C  OH  CN
Ketone Cyanodydrin

Cyanohydrins are useful synthetic intermediates.

(ii) Acetal:
Acetals are gem-dialkoxy alkanes in which two alkoxy groups are present on the terminal
carbon atom. One bond is connected to an alkyl group while the other is connected to a
hydrogen atom.
H
|
R C  OR'
|
OR"
General Structure of an acetal

When aldehydes are treated with two equivalents of a monohydric alcohol in the presence of

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

dry HCl gas, hemiacetals are produced that further react with one more molecule of alcohol to
yield acetal.

(iii) Semicarbarbazone:
Semicarbazones are derivatives of aldehydes and ketones produced by the condensation
reaction between a ketone or aldehyde and semicarbazide.

Semicarbazones are useful for identification and characterization of aldehydes and ketones.
(iv) Aldol:
A β-hydroxy aldehyde or ketone is known as an aldol. It is produced by the condensation
reaction of two molecules of the same or one molecule each of two different aldehydes or
ketones in the presence of a base.

(v) Hemiacetal:
Hemiacetals are α−alkoxyalcohols

Aldehyde reacts with one molecule of a monohydric alcohol in the presence of dry HCl gas.

(vi) Oxime:
Oximes are a class of organic compounds having the general formula RR′CNOH, where R is
an organic side chain and R′ is either hydrogen or an organic side chain. If R′ is H, then it is
known as aldoxime and if R′ is an organic side chain, it is known as ketoxime.

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

On treatment with hydroxylamine in a weakly acidic medium, aldehydes or ketones

formoximes.

(vii) Ketal:
Ketals are gem-dialkoxyalkanes in which two alkoxy groups are present on the same carbon
atom within the chain. The other two bonds of the carbon atom are connected to two alkyl
groups.
R'
|
R  C  OR"
|
OR''
General structure of a ketal
Ketones react with ethylene glycol in the presence of dry HCl gas to give a cyclic product
known as ethylene glycol ketals.

(viii) Imine:
Imines are chemical compounds containing a carbon nitrogen double bond.

Imines are produced when aldehydes and ketones react with ammonia and its derivatives.

(ix) 2, 4−DNP−derivative:
2, 4−dinitrophenylhydrazones are 2, 4−DNP−derivatives, which are produced when aldehydes
or ketones react with 2, 4−dinitrophenylhydrazine in a weakly acidic medium.

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

To identify and characterize aldehydes and ketones, 2, 4−DNP derivatives are used.
(x) Schiff’s base:
Schiff’s base (or azomethine) is a chemical compound containing a carbon-nitrogen double
bond with the nitrogen atom connected to an aryl or alkyl group-but not hydrogen. They have
the general formula R1R2C  NR3 . Hence, it is an imine. It is named after a scientist, Hugo
Schiff.

Aldehydes and ketones on treatment with primary aliphatic or aromatic amines in the presence
of trace of an acid yields a Schiff’s base.

Question 2:
Name the following compounds according to IUPAC system of nomenclature:
(i) CH3CH CH3  CH2CH2CHO
(ii) CH3CH2COCH C2 H5  CH2CH2Cl
(iii) CH 3CH  CHCHO
(iv) CH 3COCH 2COCH 3
(v) CH3CH CH3  CH2C CH3 2 COCH3
(vi)  CH3 3 CCH2COOH
(vii) OHCC6 H 4CHO  p

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

Solution 2:
(i) 4-methylpentanal
(ii) 6-Chloro-4-ethylhexan-3-one
(iii) But-2-en-1-al
(iv) Pentane-2,4-dione
(v) 3,3,5-Trimethylhexan-2-one
(vi) 3,3-Dimethylbutanoic acid
(vii) Benzene-1,4-dicarbaldehyde

Question 3:
Draw the structures of the following compounds.
(i) 3-Methylbutanal (ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde (iv) 4-Methylpent-3-en-2-one 4-chloropentan-2-one
(vi) 3-Bromo-4-phenylpentanoic acid (vii) p, p ' -Dihydroxybenzophenone
(viii) Hex-2-en-4-ynoic acid

Solution 3:
CH3 O
| ||
 3
i H C  CH  CH 2  C H

(ii)

(iii)

O CH 3
|| |
 iv  H 3C  C  CH  C  CH 3
O Cl
|| |
 v  H 3C  C  CH 2  CH  CH 3
C6 H5 Br O
| | ||
 vi  H 3C  CH  CH  CH 2  C  OH
(vii)

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

O
||
 viii  H 3C  C  C  CH  CH C  OH

Question 4:
Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also
common names.
 i  CH 3CO  CH 2 4 CH 3  ii  CH 3CH 2CHBrCH 2CH CH 3  CHO
 iii  CH 3  CH 2 5 CHO  iv  Ph  CH  CH  CHO
(v)

(vi) PhCOPh

Solution 4:
(i) CH3CO  CH2 4 CH3
IUPAC name: Heptan-2-one
Common name: Methyl n-propyl ketone
(ii) CH3CH2CHBrCH2CH CH3  CHO
IUPAC name: 4-Bromo-2-methylhaxanal
Common name: (γ-Bromo-α-methyl-caproaldehyde)
(iii) CH3  CH2 5 CHO
IUPAC name: Heptanal
(iv) Ph  CH  CH  CHO
IUPAC name: 3-phenylprop-2-enal
Common name: β-Pheynolacrolein
(v)

IUPAC name: Cyclopentanecarbaldehyde

(vi) PhCOPh
IUPAC name: Diphenylmethanone
Common name: Benzophenone

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Question 5:
Draw structures of the following derivatives.
(i) The 2,4-dinitrophenylhydrazone of benzaldehyde
(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal
(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde

Solution 5:

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Question 6:
Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents.
(i) PhMgBr and then H 3O 
(ii)Tollens’ reagent
(iii) Semicarbazide and weak acid
(iv)Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid

Solution 6:

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Question 7:
Which of the following compounds would undergo aldol condensation, which the Cannizzaro
reaction and which neither? Write the structures of the expected products of aldol
condensation and Cannizzaro reaction.
(i) Methanal
(ii) 2-Methylpentanal
(iii) Benzaldehyde
(iv) Benzophenone
(v) Cyclohexanone
(vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde
(viii) Butan-1-ol
(ix) 2, 2-Dimethylbutanal

Solution 7:
Aldehydes and ketones having at least one α-hydrogen undergo aldol condensation. The
compounds (ii) 2−methylpentanal, (v) cyclohexanone, (vi) 1-phenylpropanone, and
(vii)phenylacetaldehyde contain one or more α-hydrogen atoms. Therefore, these undergo
aldol condensation.
Aldehydes having no α-hydrogen atoms undergo Cannizzaro reactions. The compounds
(i)Methanal,(iii) Benzaldehyde, and (ix) 2, 2-dimethylbutanal do not have any
α- hydrogen.Therefore, these undergo cannizzaro reactions. Compound (iv) Benzophenone is a
ketone having no α-hydrogen atom and compound (viii) Butan-1-ol is an alcohol. Hence, these
compounds do not undergo either aldol condensation or cannizzaro reactions.
Aldol condensation (ii)

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2,2-Dimethylbutan-1-o Sodium2,2-dimethylbutanoate

Question 8:
How will you convert ethanal into the following compounds?
(i) Butane-1, 3-diol (ii) But-2-enal (iii) But-2-enoic acid

Solution 8:
(i) On treatment with dilute alkali, ethanal produces 3-hydroxybutanal gives butane-1, 3-diol
on reduction.

Ethanal 3-Hydroxybutanal Butane-1,3-diol

(ii) On treatment with dilute alkali, ethanal gives 3-hydroxybutanal which on heating
produces but-2-enal.
OH
|

CH 3CHO 
dil NaOH
 CH 3  C  CH 2  CHO 
 H 2O
 CH 3  CH  CH  CHO
Ethanal 3 Hydrocybu tan al But  2  enal

(iii) When treated with Tollen’s reagent, But-2-enal produced in the above reaction
produces but-2-enoic acid.

 Ag  NH   OH 
CH3  CH  CH  CHO 
 3 2
Tollen ' s reagent
 CH 3CH  CHCOOH
But  2enal But  2enoic acid

Question 9:
Write structural formulas and names of four possible aldol condensation products from
propanal and butanal. In each case, indicate which aldehyde acts as nucleophile and which as
electrophile.

Solution 9:
(i) Taking two molecules of propanal, one which acts as a nucleophile and the other as an
electrophile.
OH CH3
| |
2CH 3CH 2CHO 
dil NaOH
 CH 3CH 2  CH  CH  CHO
Pr opanal 3 hydroxy  2 methylpen tan al

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(ii) Taking two molecules of butanal, one which acts as a nucleophile and the other as an
electrophile.

(iii) Taking one molecule each of propanal and butanal in which propanal acts as a nucleophile
and butanal acts as an electrophile.
OH CH3
| |
CH 3CH 2CH 2CHO  CH 3CH 2CHO 
 CH 3CH 2CH 2  CH  CH  CHO
Bu tan al Pr opanal 3 Hydroxy  2  methylpen tan al
 Electrophile   Nucleophile 
(iv) Taking one molecule each of propanal and butanal in which propanal acts as an
electrophile and butanal acts as a nucleophile.

Question 10:
An organic compound with the molecular formula C9H10O forms 2, 4-DNP derivative, reduces
Tollens’ reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives
1, 2-benzenedicarboxylic acid. Identify the compound.

Solution 10:
It is given that the compound (with molecular formula C9 H10O ) forms 2, 4-DNP derivative and
reduces Tollen’s reagent. Therefore, the given compound must be an aldehyde. Again, the
compound undergoes cannizzaro reaction and on oxidation gives 1,2-benzenedicarboxylic
acid. Therefore, the −CHO group is directly attached to a benzene ring and this benzaldehyde
is ortho-substituted. Hence, the compound is 2-ethylbenzaldehyde.

The given reactions can be explained by the following equations.

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Question 11:
An organic compound (A) (molecular formula C8 H16O2 ) was hydrolysed with dilute sulphuric
acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid
produced (B). (C) on dehydration gives but-1-ene.Write equations for the reactions involved.

Solution 11:
An organic compound A with molecular formula C8 H16O2 gives a carboxylic acid (B) and an
alcohol (C) on hydrolysis with dilute sulphuric acid. Thus, compound A must be an ester.
Further, alcohol C gives acid B on oxidation with chromic acid. Thus, B and C must contain
equal number of carbon atoms. Since compound A contains a total of 8 carbon atoms, each of
B and C contain 4 carbon atoms. Again, on dehydration, alcohol C gives but-1-ene. Therefore,
C is of straight chain and hence, it is butan-1-ol. On oxidation, Butan-1-ol gives butanoic acid.
Hence, acid B is butanoic acid. Hence, the ester with molecular formula C8 H16O2 is
butylbutanoate.
O
||
CH 3CH 2CH 2  C  OCH 2CH 2CH 2CH 3
Butylbu tan oate

All the given reactions can be explained by the following equations.

O O
|| ||
CH 3CH 2CH 2  C  OCH 2CH 2CH 2CH 3 
dil H 2 SO4
 CH 3CH 2CH 2  C  OH  CH 3CH 2CH 2CH 2OH
Butylbu tan oate Bu tan oic acid Bu tan 1ol
 A  B C 

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Question 12:
Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards
HCN)
(ii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH,
CH3CH2CH2COOH(acid strength)

(iii)
Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid
strength)

Solution 12:
(i) When HCN reacts with a compound, the attacking species is a nucleophile, CN  Therefore,
as the negative charge on the compound increases, its reactivity with HCN decreases. In the
given compounds, the +I effect increases as shown below. It can be observed that steric
hindrance also increases in the same

Hence, the given compounds can be arranged according to their increasing reactivities toward
HCN as:

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Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone < Acetaldehyde
(ii) After losing a proton, carboxylic acids gain a negative charge as shown:
R  COOH   R  COO  H 
Now, any group that will help stabilise the negative charge will increase the stability of the
carboxyl ion and as a result, will increase the strength of the acid. Thus, groups having +Ieffect
will decrease the strength of the acids and groups having −I effect will increase the strength of
the acids. In the given compounds, - CH 3 group has +I effect and Br− group has−I effect.
Thus, acids containing Br− are stronger. Now, the +I effect of isopropyl group is more than
that of n-propyl group.
Hence,  CH3 2 CHCOOH is a weaker acid than CH 3CH 2CH 2COOH .
Also, the −I effect grows weaker as distance increases. Hence, CH3CH  Br  CH2COOH is a
weaker acid than CH3CH2CH  Br  COOH .
Hence, the strengths of the given acids increase as:
CH3 2 CHCOOH  CH3CH2CH2COOH  CH3CH  Br  CH2COOH  CH3CH2CH  Br  COOH
(iii) As we have seen in the previous case, electron-donating groups decrease the strengths of
acids, while electron-withdrawing groups increase the strengths of acids. As methoxy group is
an electron-donating group, 4-methoxybenzoic acid is a weaker acid than benzoic acid. Nitro
group is an electron-withdrawing group and will increase the strengths of acids. As 3,4-
dinitrobenzoic acid contains two nitro groups, it is a slightly stronger acid than 4-nitrobenzoic
acid. Hence, the strengths of the given acids increase as:
4-Methoxybenzoic acid < Benzoic acid < 4-Nitrobenzoic acid < 3,4-Dinitrobenzoic acid

Question 13:
Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and Propanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal

Solution 13:
(i) Propanal and propanone can be distinguished by the following tests.
(a) Tollen’s test
Propanal is an aldehyde. Thus, it reduces Tollen’s reagent. But, propanone being a ketone does
not reduce Tollen’s reagent.

CH 3CH 2 CHO  2  Ag  NH 3 2   3OH   CH 3CH 2COO   Ag   4 NH 3  2H 2O
Propanal Tollen’s reagent Propanoate ion silver mirror

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(b) Fehling’s test

Aldehydes respond to Fehling’s test, but ketones do not. Propanal being an aldehyde reduces
Fehling’s solution to a red-brown precipitate of Cu2O, but propanone being a ketone does not.
CH 3CH 2CHO  2Cu 2  5OH  
 CH 3CH 2COO   Cu2O  3H 2O
Pr opanal Pr opanoate ion Cuprous oxide
 Re d brown ppt 
(c) Iodoform test:
Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom
respond to iodoform test. They are oxidized by sodium hypoiodite (NaOI) to give iodoforms.
Propanone being a methyl ketone responds to this test, but propanal does not.
CH 3COCH 3  3NaOI   CH 3COONa  CHI 3  2 NaOH
Pr opanone Sodium acetate Iodoform
 yellow ppt 
(ii) Acetophenone and Benzophenone can be distinguished using the iodoform test.
Iodoform test:
Methyl ketones are oxidized by sodium hypoiodite to give yellow ppt. of iodoform.
Acetophenone being a methyl ketone responds to this test, but benzophenone does not.
C6 H 5COCH 3  3NaOI   C6 H 5COONa  CHI 3  2 NaOH
Acetophenone Sodium Sodium Iodoform
hypoiodite
 yellow ppt benzoate

C6 H 5COCH 3  NaOI 
 No yellow ppt of CHI 3
Benzophenone
(iii) Phenol and benzoic acid can be distinguished by ferric chloride test.
Ferric chloride test:
Phenol reacts with neutral FeCl3 to form an iron-phenol complex giving violet colouration.
3
  Fe  OC6 H 5    3H   3Cl 
6C6 H 5OH  FeCl3 
Phenol 
6 
Iron  phenol complex
Violet color 
But benzoic acid reacts with neutral FeCl3 to give a buff coloured ppt. of ferric benzoate.
  C6 H 5COO  Fe 3HCl
3C6 H 5OH  FeCl3 
Benzonicacid 3
Ferric benzoate
 Buff coloured ppt 
(iv) Benzoic acid and Ethyl benzoate can be distinguished by sodium bicarbonate test.
Sodium bicarbonate test:
Acids react with NaHCO3 to produce brisk effervescence due to the evolution of CO2 gas.
Benzoic acid being an acid responds to this test, but ethylbenzoate does not.
C6 H5COOH  NaHCO3   C6 H5COONa  CO2   H 2O
Benzoic acid Sodium benzoate

C6H5COOC2H5 + NaHCO3 ------------→ No effervercense due to evolution of CO2

gas

(v) Pentan-2-one and pentan-3-one can be distinguished by iodoform test.

Iodoform test:
Pentan-2-one is a methyl ketone. Thus, it responds to this test. But pentan-3-one not being a
methyl ketone does not respond to this test.

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(vi) Benzaldehyde and acetophenone can be distinguished by the following tests.

(a) Tollen’s Test
Aldehydes respond to Tollen’s test. Benzaldehyde being an aldehyde reduces Tollen’s
reagent to give a red-brown precipitate of Cu2O, but acetophenone being a ketone does not.

(b) Iodoform test

Acetophenone being a methyl ketone undergoes oxidation by sodium hypoiodite ( NaOI ) to
give a yellow ppt. of iodoform. But benzaldehyde does not respond to this test.
C6 H5COCH3  3NaOI   C6 H 5COONa  CHI 3  2NaOH
Acetophenone Sodium benzoate Iodoform
 yellow ppt 
(vii) Ethanal and propanal can be distinguished by iodoform test.
Iodoform test
Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom
responds to the iodoform test. Ethanal having one methyl group linked to the carbonyl carbon
atom responds to this test. But propanal does not have a methyl group linked to the carbonyl
carbon atom and thus, it does not respond to this state.
CH3CHO 3NaOI   HCOONa CHI3  2NaOH
Ethanal Sodium Iodoform
methanoate
 yellow ppt 

Question 14:
How will you prepare the following compounds from benzene? You may use any inorganic
reagent and any organic reagent having not more than one carbon atom
(i) Methyl benzoate (ii) m-Nitrobenzoic acid
(iii) p-Nitrobenzoic acid (iv) Phenylacetic acid
(v) p-Nitrobenzaldehyde.

Solution 14:

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Question 15:
How will you bring about the following conversions in not more than two steps?
(i) Propanone to Propene
(ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal
(iv) Benzene to m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone
(vi) Bromobenzene to 1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
(viii) Benazaldehyde to α-Hydroxyphenylacetic acid
(ix) Benzoic acid to m- Nitrobenzyl alcohol

Solution 15:

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O OH
|| |
 i  CH3  C  CH 3  CH 3  CH  CH 3 
NaBH3 conc , H 2 SO4

CH 3  CH  CH 2
Pr opene

(ii)

OH
|
 iii  CH 3  CH 2  OH 
CrO3
 CH 3CHO 
 Aldol condensation  CH 3
dil . NaOH
C HCH 2CHO
Ethanol 3 hydroxybu tan al

(iv)

(v)

(vi)

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Question 16:
Describe the following:
(i) Acetylation
(ii) Cannizzaro reaction
(iii) Cross aldol condensation
(iv) Decarboxylation

Solution 16:
(i) Acetylation
The introduction of an acetyl functional group into an organic compound is known as
acetylation. It is usually carried out in the presence of a base such as pyridine, dimethylaniline,
etc. This process involves the substitution of an acetyl group for an active hydrogen atom.
Acetyl chloride and acetic anhydride are commonly used as acetylating agents.
For example, acetylation of ethanol produces ethyl acetate.
CH 3 CH 2OH  CH 3COCl  Pyridine
 CH 3COOC2 H 5  HCl
Ethanol Acetyl Ethylacetate
Chloride

(ii) Cannizzaro reaction:

The self oxidation-reduction (disproportionation) reaction of aldehydes having no
α -hydrogen’s on treatment with concentrated alkalis is known as the Cannizzaro reaction. In
this reaction, two molecules of aldehydes participate where one is reduced to alcohol and the
other is oxidized to carboxylic acid.
For example, when ethanol is treated with concentrated potassium hydroxide, ethanol and
potassium ethanoate are produced.

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(iii) Cross-aldol condensation:

When aldol condensation is carried out between two different aldehydes, or two different
ketones, or an aldehyde and a ketone, then the reaction is called a cross-aldol condensation. If
both the reactants contain α-hydrogens, four compounds are obtained as products.
For example, ethanal and propanal react to give four products.

(iv) Decarboxylation:
Decarboxylation refers to the reaction in which carboxylic acids lose carbon dioxide to form
hydrocarbons when their sodium salts are heated with soda-lime.

Decarboxylation also takes place when aqueous solutions of alkali metal salts of carboxylic
acids are electrolyzed. This electrolytic process is known as Kolbe’s electrolysis.

Question 17:
Complete each synthesis by giving missing starting material, reagent or products.
(i)

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(iii) C6 H 5CHO 

H 2 NCONHNH 2

(iv)

(vii)
C6H5CHO
dil , NaOH
  
CH3CH2CHO
i  NaBH4
(viii) CH 3COCH 2COOC2 H 5  
ii  H 

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Solution 17:

O
||
(iii) C6 H 5CHO  H 2 NCONHNH 2 
 C6 H 5CH  NNH C  NH 2  H 2O
Benzaldehyde Semicarbazide Benzaldehyde semicarbazone

(iv)

(vi)

(vii)

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
 CH 3CH  OH  CH 2COOC2 H 5
i NaBH
(viii) CH 3COCH 2COOC2 H 5 
 ii  H 
4

Ethyl 3oxobu tan ote Ethyl 3 hydroxybu tan oate

(ix)

(x)

(xi)

Question 18:
Give plausible explanation for each of the following:
(i) Cyclohexanone forms cyanohydrin in good yield but 2, 2, 6- trimethylcyclohexanone does
not.
(ii) There are two - NH 2 groups in semicarbazide. However, only one is involved in the
formation of semicarbazones.
(iii) During the preparation of esters from a carboxylic acid and an alcohol in the presence of
an acid catalyst, the water or the ester should be removed as soon as it is formed.

Solution 18:
(i) Cyclohexanones form cyanohydrins according to the following equation.

In this case, the nucleophile CN  can easily attack without any steric hindrance. However, in
the case of 2, 2, 6- trimethylcyclohexanone, methyl groups at α-positions offer steric

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hindrances and as a result, CN  cannot attack effectively.

For this reason, it does not form a cyanohydrin.

(ii) Semicarbazide undergoes resonance involving only one of the two –NH2 groups, which is
attached directly to the carbonyl-carbon atom.

Therefore, the electron density on − NH 2 group involved in the resonance also decreases.
As a result, it cannot act as a nucleophile. Since the other - NH 2 group is not involved in
resonance; it can act as a nucleophile and can attack carbonyl-carbon atoms of aldehydes and
ketones to produce semicarbazones.
(iii) Ester along with water is formed reversibly from a carboxylic acid and an alcohol in
presence of an acid.

RCOOH  R ' CH 
H
 RCOOR ' H 2O
carboxylic acid Alcohol Ester water
If either water or ester is not removed as soon as it is formed, then it reacts to give back the
reactants as the reaction is reversible. Therefore, to shift the equilibrium in the forward
direction i.e., to produce more ester, either of the two should be removed.

Question 19:
An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The
molecular mass of the compound is 86. It does not reduce Tollens’ reagent but forms an
addition compound with sodium hydrogensulphite and give positive iodoform test. On
vigorous oxidation it gives ethanoic and propanoic acid. Write the possible structure of the
compound.

Solution 19:
% of carbon = 69.77 %
% of hydrogen = 11.63 %
% of oxygen = {100 − (69.77 + 11.63)}%
= 18.6 %
Thus, the ratio of the number of carbon, hydrogen, and oxygen atoms in the organic compound
can be given as:

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69.77 11.63 18.6

C : H :O  : :
12 1 16
 5.81:11.63:1.16
 5 :10 :1
Therefore, the empirical formula of the compound is C5 H10O . Now, the empirical formula
mass of the compound can be given as:
5 12  10 1  116
 86
Molecular mass of the compound = 86
Therefore, the molecular formula of the compound is given by C5 H10O .
Since the given compound does not reduce Tollen’s reagent, it is not an aldehyde. Again,the
compound forms sodium hydrogen sulphate addition products and gives a positive iodoform
test. Since the compound is not an aldehyde, it must be a methyl ketone. The given compound
also gives a mixture of ethanoic acid and propanoic acid. Hence, the given compound is
pentan−2−ol.
O
||
CH 3  C  CH 2  CH 2  CH 3
Pen tan  2ol
The given reactions can be explained by the following equations:

Question 20:
Although phenoxide ion has more number of resonating structures than carboxylate
ion,carboxylic acid is a stronger acid than phenol. Why?

Solution 20:
Resonance structures of phenoxide ion are:

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

It can be observed from the resonance structures of phenoxide ion that in II, III and IV, less
electronegative carbon atoms carry a negative charge. Therefore, these three structures
contribute negligibly towards the resonance stability of the phenoxide ion. Hence, these
structures can be eliminated. Only structures I and V carry a negative charge on the more
electronegative oxygen atom.
Resonance structures of carboxylate ion are:

In the case of carboxylate ion, resonating structures I′ and II′ contain a charge carried by a
more electronegative oxygen atom.Further, in resonating structures I′ and II′, the negative
charge is delocalized over two oxygen atoms. But in resonating structures I and V of the
phexoxide ion, the negative charge is localized on the same oxygen atom. Therefore, the
resonating structures ofcarboxylate ion contribute more towards its stability than those of
phenoxide ion. As a result, carboxylate ion is more resonance-stabilized than phenoxide ion.
Hence, carboxylic acid is a stronger acid than phenol.

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

INTEXT SOLUTION

Question 1:
Write the structures of the following compounds.
(i) α-Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec-butyl ketone
(vi) 4-Fluoroacetophenone

Solution 1:
H3COO
| ||
(i) H 3C  CH  C  H
OH O
| ||
(ii) H 3C  CH  CH 2  C  H
(iii)

O
||
(iv) CH 3  C  CH 2  CH 2  CHO
CH3 O CH3
| || |
(v) CH 3CH 2 CH  C  CH  CH 2CH 3
(vi)

Question 2:
Write the structures of products of the following reactions;
(i)

12.Aldehydes, Ketones and Carboxylic Acids www.vedantu.com 29

 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

(ii)  C6 H5CH2 2 Cd  2CH3COCl 


(iii)

(iv)

Solution 2:
(i)

(ii)

(iii)

(iv)

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

Question 3:
Arrange the following compounds in increasing order of their boiling points.
CH 3CHO, CH 3CH 2OH , CH 3OCH 3 , CH 3CH 2CH 3

Solution 3:
The molecular masses of the given compounds are in the range 44 to 46. CH 3CH 2OH
Undergoes extensive intermolecular H-bonding, resulting in the association of molecules,
Therefore, it has the highest boiling point. CH 3CHO is more polar than CH 3OCH 3 and so
CH 3CHO has stronger intermolecular dipole − dipole attraction than CH 3OCH 3 , CH 3CH 2CH 3
has only weak van der Waals force. Thus, the arrangement of the given compounds in the
increasing order of their boiling points is given by:
CH 3CH 2CH 3  CH 3OCH 3  CH 3CHO  CH 3CH 2OH

Question 4:
Arrange the following compounds in increasing order of their reactivity in nucleophilic
addition reactions.
(i)Ethanal, Propanal, Propanone, Butanone.
(ii)Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint: Consider steric effect and electronic effect.

Solution 4:
(i)

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

The +I effect of the alkyl group increases in the order:

Ethanal<Propanal<Propanone< Butanone
The electron density at the carbonyl carbon increases with the increase in the +I effect. As a
result, the chances of attack by a nucleophile decrease. Hence, the increasing order of the
reactivities of the given carbonyl compounds in nucleophilic addition reactions is:
Butanone <Propanone<Propanal<Ethanal.
(ii)

The +I effect is more in ketone than in aldehyde. Hence, acetophenone is the least reactive in
nucleophilic addition reactions. Among aldehydes, the +I effect is the highest in
p-tolualdehyde because of the presence of the electron-donating CH 3 group and the lowest
in p-nitrobezaldehyde because of the presence of the electron-withdrawing  NO2 group.
Hence, the increasing order of the reactivities of the given compounds is:
Acetophenone<p-tolualdehyde< Benzaldehyde <p-Nitrobenzaldehyde

Question 5:
Predict the products of the following reactions:
(i)

(ii)

O
|| 
(iii) R  CH  CH  CHO  NH 2  C  NH  NH 2 
H

(iv)

Solution 5:

12.Aldehydes, Ketones and Carboxylic Acids www.vedantu.com 32

 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

(i)

(ii)

(iii)

(iv)

Question 6:
Give the IUPAC names of the following compounds:
 i  PhCH 2CH 2COOH
 ii  CH 3 2 C  CHCOOH
(iii)

(iv)

Solution 6:
(i) 3-Phenylpropanoic acid
(ii) 3-Methylbut-2-enoic acid
(iii) 2-Methylcyclopentanecarboxylic acid
(iv)2,4,6-Trinitrobenzoic acid

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 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

Question 7:
Show how each of the following compounds can be converted to benzoic acid.
(i) Ethylbenzene (ii) Acetophenone
(iii) Bromobenzene(iv) Phenylethene (Styrene)

Solution 7:
(i)

(ii)

(iii)

(iv)

12.Aldehydes, Ketones and Carboxylic Acids www.vedantu.com 34

 Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

Question 8:
Which acid of each pair shown here would you expect to be stronger?
 i  CH3CO2 H or CH 2 FCO2 H
 ii  CH 2 FCO2 H or CH 2ClCO2 H
 iii  CH 2 FCH 2CH 2CO2 H or CH 3CHFCH 2CO2 H

iv
Solution 8:
O|| O
||
 i  CH3  C  O  H F  CH 2  C  O H
The +I effect of CH 3 group increases the electron density on the O-H bond. Therefore,
release of proton becomes difficult. On the other hand, the −I effect of F decreases the electron
density on the O-H bond. Therefore, proton can be released easily. Hence, CH 2 FCO2 H is a
stronger acid than CH 3CO2 H .
O O
|| ||
 ii  F  CH 2  C  O H Cl  CH 2  C O H
F has stronger −I effect than Cl. Therefore, CH 2 FCO2 H can release proton more easily than
CH 2ClCO2 H . Hence, CH 2 FCO2 H is stronger acid than CH 2ClCO2 H .
O
||
 iii  F  CH 2  CH 2  CH 2  C  O  H
O
||
F CH  CH 2  C  O  H
|
CH3
Inductive effect decreases with increase in distance. Hence, the +I effect of F in
CH 3CHFCH 2CO2 H is more than it is in CH 2 FCH 2CH 2CO2 H . Hence, CH 3CHFCH 2CO2 H is
stronger acid than CH 2 FCH 2CH 2CO2 H .
(iv)

Due to the −I effect of F, it is easier to release proton in the case of compound (A). However,
in the case of compound (B), release of proton is difficult due to the +I effect of CH 3 group.
Hence, (A) is a stronger acid than (B).

12.Aldehydes, Ketones and Carboxylic Acids www.vedantu.com 35

Class XII – NCERT – Chemistry Chapter 12
Aldehydes, Ketones and Carboxylic Acids

12.Aldehydes, Ketones and Carboxylic Acids www.vedantu.com 36

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Class XII – NCERT – Chemistry Chapter 13 – Amines

INTEX QUESTIONS

Question 1:
Classify the following amines as primary, secondary and tertiary:

(iii) (C2 H 5 ) 2 CHNH 2

(iv) (C2 H 5 )2 NH

Solution 1:
(i) 1 (ii) 3 (iii) 1(iv) 2

Question 2:
(i) Write the structures of different isomeric amines corresponding to the molecular formula, .
C4H11N
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?

Solution 2:
(i), (ii) The structures and their IUPAC names of different isomeric amines corresponding to the
molecular formula, C4H11N are given below:
(a) CH3-CH2-CH2-CH2-NH2 Butanamine (10 )

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Class XII – NCERT – Chemistry Chapter 13 – Amines

(iii) Position isomers : (a) and (b); (e) and (g)

Chain isomers: (a) and (c); (a) and (d); (b)and(c); (b)and(d)
Metamers: (e) and (f). (f) and (g)
Functional isomers: All 10 amines are functional isomers of 20 and 30 amines and vice-versa

Question 3:
How will you convert:
(i)Benzene into aniline
(ii)Benzene into N,N-dimethylaniline
(iii) Cl  (CH 2 )4  Cl into Hexane -1, 6- diamine

13.Amines www.vedantu.com 2
Class XII – NCERT – Chemistry Chapter 13 – Amines

Solution 3:

Question 4:
Arrange the following in increasing order of their basic strength:
(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
(ii) C2H5NH2, (C2H5)2 NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2, (CH3)2 NH, (CH3)3N, C6H5NH2, C6H5CH2NH2

Solution 4:
(i) Considering the inductive effect of alkyl groups, NH3, C2H5NH2, and (C2H5)2NH can be
arranged in the increasing order of their basic strengths as:

Again, C6H5NH2 has proton acceptability less than NH3. Thus, we have:

Due to the −I effect of C6H5 group, the electron density on the N-atom in C6H5CH2NH2 is lower
than that on the N-atom in C2H5NH2, but more than that in NH3. Therefore, the given compounds
can be arranged in the order of their basic strengths as:

(ii) Considering the inductive effect and the steric hindrance of the alkyl groups, C2H5NH2,
(C2 H5)2NH2, and their basic strengths as follows:

13.Amines www.vedantu.com 3
Class XII – NCERT – Chemistry Chapter 13 – Amines

Again, due to the −R effect of C6H5 group, the electron density on the N atom in C6H5 NH2 is
lower than that on the N atom in C2H5NH2. Therefore, the basicity of C6H5NH2 is lower than that
of C2H5NH2. Hence, the given compounds can be arranged in the increasing order of their basic
strengths as follows:

(iii) Considering the inductive effect and the steric hindrance of alkyl groups, CH3NH2,
(CH3)2NH, and (CH3)3N can be arranged in the increasing order of their basic strengths as:

In C6H5NH2, N is directly attached to the benzene ring. Thus, the lone pair of electrons on the
N−atom is delocalized over the benzene ring. In C6H5CH2NH2, N is not directly attached to the
benzene ring. Thus, its lone pair is not delocalized over the benzene ring. Therefore, the
electrons on the N atom are more easily available for protonation in C6H5CH2NH2 than in
C6H5NH2 i.e., C6H5CH2NH2 is more basic than C6H5NH2. Again, due to the −I effect of C6H5
group, the electron density on the N−atom in C6H5CH2NH2 is lower than that on the N−atom in
(CH3)3N. Therefore, (CH3)3N is more basic than C6H5CH2NH2. Thus, the given compounds can
be arranged in the increasing order of their basic strengths as follows.

Question 5:
Complete the following acid-base reactions and name the products:
(i) CH3CH2CH2NH2 + HCl  
(ii) (C2H5)3N+HCl  

Solution 5:

Question 6:

13.Amines www.vedantu.com 4
Class XII – NCERT – Chemistry Chapter 13 – Amines

Write reactions of the final alkylation product of aniline with excess of methyl iodide in the
presence of sodium carbonate solution.

Solution 6:
Aniline reacts with methyl iodide to produce N, N-dimethylaniline.

With excess methyl iodide, in the presence of Na2CO3 solution, N, N-dimethylaniline produces
N, N, N−trimethylanilinium carbonate.

Question 7:
Write chemical reaction of aniline with benzoyl chloride and write the name of the product
obtained.

Solution 7:

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Class XII – NCERT – Chemistry Chapter 13 – Amines

Question 8:
Write structures of different isomers corresponding to the molecular formula, C3H9N. Write
IUPAC names of the isomers which will liberate N2 gas on treatment with nitrous acid.

Solution 8:
In all, four structural isomers are possible. These are:

only 1 amines react with HNO2 to liberate N2 gas

CH3CH 2CH 2 NH 2  HNO2  CH3CH 2CH 2OH  N 2  H 2O
Propan-1-amine Propan-1-ol

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Class XII – NCERT – Chemistry Chapter 13 – Amines

Question 9:
Convert:
(i)3-Methylaniline into 3-nitrotoluene
(ii)Aniline into 1,3,5- Tribromo benzene

Solution 9:

NCERT EXERCISES
Question 1:
Write IUPAC names of the following compounds and classify them into primary, secondary and
tertiary amines.
(i) (CH3)2 CHNH2
(ii) CH3 (CH2)2 NH2
(iii) CH3 NHCH (CH3)2
(iv) (CH3)3 CNH
(v) C6 H5 NHCH
(vi) (CH3 CH2)2 NCH3
(vii) m-BrC6 H4 NH2

Solution 1:
(i) 1-Methylethanamine (10 amine)
(ii) Propan-1-amine (10 amine)

13.Amines www.vedantu.com 7
Class XII – NCERT – Chemistry Chapter 13 – Amines

(iii) N−Methyl-2-methylethanamine (20 amine)

(iv) 2-Methylpropan-2-amine (10 amine)
(v) N−Methylbenzamine or N-methylaniline (20 amine)
(vi) N-Ethyl-N-methylethanamine (30 amine)
(vii) 3-Bromobenzenamine or 3-bromoaniline (10 amine)

Question 2:
Give one chemical test to distinguish between the following pairs of compounds:
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
(v) Aniline and N-Methylaniline.

Solution 2:
(i) Methylamine and methylamine can be distinguished by carbylamine test.

CH 3 NH 2  CHCl3  3KOH   CH 3 NC  2 KCl  3H 2O
1 Amine Methylisocyanide
(offencive smell)

CHCl3 / KOH ( alc )

(CH3 )2 NH   No reaction
(ii) Secondary and tertiary amine can be distinguished by Liebermann’s nitroamine test.
Secondary amines gives Liebermann nitroamine test while tertiary amines do not.
HCl  NaNO2
(CH 3CH 2 )2 NH  HO  N  O   (CH 3CH 2 )2 N  N  O  H 2O
Diethylamine Yellow colour
(2  Amine)

[(CH 3CH 2 )3 NH ] NO2

(CH 3CH 2 )3 N  HNO2 
Triethylamine Triethylammonium nitrite
(3 Amine) (Soluble)

(iii) Ethylamine and aniline can be distinguished by azo test:

273  278 K
C2 H 5 NH 2  HONO  HCl   C2 H 5OH  CH 2  CH 2  CH 3CH 2Cl  N 2

(iv) Aniline and benzylamine can be distinguished by nitrous acid test:

 
C6 H 5CH 2 NH 2 
HONO
HCl
 C6 H 5CH 2 N 2Cl   H2O
Decomposes
 C6 H 5CH 2OH  N 2   HCl
Benzylamine  Unstable 

13.Amines www.vedantu.com 8
Class XII – NCERT – Chemistry Chapter 13 – Amines

(v) Aniline and N-methylaniline can be distinguished by carbylamines test:


C6 H 5 NH 2  CHCl3  3KOH   C6 H 5 NC  3KCl  3H 2O
Aniline Offensive smaell
CHCl3  3KOH
C6 H5  NH  CH3 
 No reaction

Question 3:
Account for the following
(i) pKb of aniline is more than that of methylamine
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o and p — directing in aromatic electrophilic substitution
reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesizing primary amines.

Solution 3:
(i) In aniline, the lone pair of electrons on the N-atom is delocalised over the benzene ring. As a
result, electron density on the nitrogen atom decreases. Whereas in CH3NH2,+ I-effect of –CH3
group increases the electron density on the N-atom. Therefore, aniline is a weaker base than
methylamine and hence its pKb value is higher than that of methylamine.
(ii) Ethylamine dissolves in water due to intermolecular H-bonding. However, in case of aniline,
due to the large hydrophobic part, i.e., hydrocarbon part, the extent of H-bonding is very less
therefore aniline is insoluble in water.

(iii) Methylamine being more basic than water, accepts a proton from water liberating OH- ions.

These OH-ions combine with Fe3+ ions

present in H2O to form brown precipitate of hydrated ferric oxide.

13.Amines www.vedantu.com 9
Class XII – NCERT – Chemistry Chapter 13 – Amines

2Fe3  6OH  
 2Fe(OH )3 or Fe2O3.3H 2O
( Brown ppt .)

(iv) Nitration is usually carried out with a mixture of conc HNO3+ conc H2SO4. In presence of
these acids, most of aniline gets protonated to form anilinium ion. Therefore, in presence of
acids, the reaction mixture consist of aniline and anilinium ion. Now, -NH2 group in aniline is
activating and o, p-directing while the +NH3 group in anilinium ion is deactivating and m-
directing: Nitration of aniline (due to steric hindrance at o-position) mainly gives p-nitroaniline,
the nitration of anilinium ion gives m-nitroaniline. In actual practice, approx a 1:1 mixture of p-
nitroaniline and m-nitroaniline is obtained. Thus, nitration of aniline gives a substantial amount
of m-nitroaniline due to protonation of the amino group.

(v) Aniline being a Lewis base reacts with Lewis acid AlCl3 to form a salt.

As a result, N of aniline acquires positive charge and hence it acts as a strong deactivating group
for electrophilic substitution reactions. Consequently, aniline does not undergo Fridel Crafts
reaction.
(vi) The diazonium salts of aromatic amines are more stable than those of aliphatic amines due to
dispersal of the positive charge on benzene ring as a result of resonance.

(vii) Gabriel phthalimide reaction gives pure primary amines without any contamination of
secondary and tertiary amines. Therefore, it is preferred for synthesising primary amines.

Question 4:

13.Amines www.vedantu.com 10
Class XII – NCERT – Chemistry Chapter 13 – Amines

Arrange the following:

(i) In decreasing order of pKb values:.
C6H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength:
C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
(iii) In increasing order of basic strength:
(a)Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2
(iv) In decreasing order of basic strength in gas phase:
C6H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point:
C5H5OH, (CH3)2 NH, C2H5NH2
(vi) In increasing order of solubility in water:
C6H5NH2, (C5H5)2NH, C2H5NH2

Solution 4:
(i) In C2H5NH2, only one −C2H5 group is present while in (C2H5)2NH, two −C2H5 groups are
present. Thus, the +I effect is more in (C2H5)2NH than in C2H5NH2. Therefore, the electron
density over the N-atom is more in (C2H5)2NH than in C2H5NH2. Hence, (C2H5)2NH is more
basic than C2H5NH2. Also, both C6H5NHCH3 and C6H5NH2 are less basic than (C2H5)2NH and
C2H5NH2 due to the delocalization of the lone pair in the former two. Further, among
C6H5NHCH3 and C6H5NH2, the former will be more basic due to the +I effect of −CH3 group.
Hence, the order of increasing basicity of the given compounds is as follows:
C6H5NH2 < C6H5NHCH3 < C2H5NH2 < (C2H5)2NH.
We know that the higher the basic strength, the lower is the pKb values.
C6H5NH2 > C6H5NHCH3 > C2H5NH2 > (C2H5)2NH

(ii) Among CH3CH2 and (C2H5)2NH, primarily due to the greater +1-effect of the two –C2H5
groups over one –CH3 group, (C2H5)2NH is more basic than CH3NH2. In both C6H5NH2 and
C6H5N(CH3)2 lone pair of electrons present on N-atom is delocalized over the benzene ring but
C6H5N(CH3)2 is more basic due to +1 effect of two –CH3 groups.
 (C2 H 5 )2 NH  CH 3 NH 2  C6 H 5 N (CH 3 )2  C6 H 5 NH 2
  Decreasing basic strength
(iii) (a) The presence of electron donating –CH3 group increases while the presence of electron
withdrawing NO2 group decreases the basic strength of amines.
p-nitroaniline< aniline < p-toluidine
  Increasing basic strength
(b) In C6H5NH2 andC6H5NHCH3, N is directly attached to the benzene ring. As a result, the lone
pair of electrons on the N-atom is delocalised over the benzene ring. Therefore, both C6H5NH2

13.Amines www.vedantu.com 11
Class XII – NCERT – Chemistry Chapter 13 – Amines

and C6H5NHCH3are weaker base in comparison to C6H5CH2NH2. Among C6H5NH2 and

C6H5NHCH3, due to +1 effect of –CH3 group C6H5NHCH3 is more basic.
 C6 H 5 NH 2  C6 H 5 NHCH 3  C6 H 5CH 2 NH 2
  Increasing basic strength
(iv) In gas phase or in non-aqueous solvents such as chlorobenzene etc, the solvation effects
i. e. the stabilization of the conjugate acid due to H-bonding are absent. Therefore, basic strength
depends only upon the +1-effect of the alkyl groups. The +1-effect increases with increase in
number of alkyl groups. Thus correct order of decreasing basic strength in gas phase is,
 (C2 H 5 )3 N  (C2 H 5 )2 NH  C2 H 5 NH 2  NH 3
  Decreasing basic strength
(v) Since the electronegativity of O is higher than that of N, therefore, alcohols form stronger H-
bonds than amines. Also, the extent of H-bonding depends upon the number of H-atoms on the
N-atom, thus the extent of H-bonding is greater in primary amine than secondary amine.
 (CH 3 )2 NH  C2 H 5 NH 2  C2 H 5OH
  Increasing boiling point
(vi) Solubility decreases with increase in molecular mass of amines due to increase in the size of
the hydrophobic hydrocarbon part and with decrease in the number of H-atoms on the N-atom
which undergo H-bonding.
 C6 H 5 NH 2  (C6 H 5 )2 NH  C2 H 5 NH 2

 Increasing solubility

Question 5:
How will you convert:
(i) Ethanoic acid into methanamine
(ii) Hexanenitrile into 1-aminopentane
(iii) Methanol to ethanoic acid.
(iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid
(vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine
(viii) Propanoic acid into ethanoic acid

Solution 5:
(i) CH3COOH 
SOCl2
 SO2 ,  HCl
CH 3COCl 
NH 4 Cl

NH3 ( excess )
CH 3CONH 2 
Br2 / NaOH
CH 3 NH 2

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Class XII – NCERT – Chemistry Chapter 13 – Amines


(iii) CH 3OH 
PCl5
 POCl3
CH 3Cl 
KCN ( alc )
 CH 3CN 
H 3O
 CH 3COOH

CHCl3 .KOH 
(vii) CH3 NO2 
Sn / HCl
CH3 NH2  CH3 NC 
LiAIH4
CH3 NHCH3

Question 6:
Describe a method for the identification of primary, secondary and tertiary amines. Also write
chemical equations of the reactions involved.

Solution 6:
The three type of amines can be distinguished by Hinsberg test. In this test, the amine is shaken
with benzenesulphonyl chloride (C6H5SO2Cl) in the presence of excess of aqueous NaOH or
KOH. A primary amine reacts to give a clear solution, which on acidification yields an insoluble
compound.

A secondary amine forms an insoluble compound, which remains insoluble even on

acidification.

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Class XII – NCERT – Chemistry Chapter 13 – Amines

A tertiary amine does not react with the reagent, but dissolves is acid.

C6 H5 SO2Cl  R3 N 
OH
 No reaction

Question 7:
Write short notes on the following:
(i) Carbylamine reaction
(ii) Diazotisation
(iii) ‘Hofmann’s bromamide reaction
(iv) Coupling reaction
(v) Ammonolysis
(vi) Acetylation
(vii) Gabriel phthalimide synthesis

Solution 7:
(i) Carbylamine reaction: Both aliphatic and aromatic primary amines when warmed with
chloroform and an alcoholic solution of KOH, produces isocyanides or carbylamines which have
very unpleasant odours. This reaction is called carbylamine reaction.

(ii) Diazotisation: The process of conversion of a primary aromatic amino compound into a
diazonium salt, is known as diazotisation. This process is carried out by adding an aqueous
solution of sodium nitrite to a solution of primary aromatic amine (e.g., aniline) in excess of at a
temperature below 5°C. HCl

273  278 K
ArNH 2  NaOH 2  2 HX   Ar N 2 X   NaX  2H 2O
1 amine Arene Diazonium
salt

(iii) Hoffmann’s bromamide reaction: When an amide is treated with bromine in alkali
solution, it is converted to a primary amine that has one carbon atom less than the starting amide.
This reaction is known as Hoffmann’s bromamide degradation reaction.
Br2  NaOH
C6 H5CONH2  C6 H5 NH2
(iv) Coupling reaction: In this reaction, arenediazonium salt reacts with aromatic amino
compound (in acidic medium) or a phenol (in alkaline medium) to form brightly coloured azo
compounds. The reaction generally takes place at para position to the hydroxy or amino group. If
para position is blocked, it occurs at ortho position and if both ortho and para positions are
occupied, than no coupling takes place.

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Class XII – NCERT – Chemistry Chapter 13 – Amines

(v) Ammonolysis: It is a process of replacement of either halogen atom in alkyl halides (or aryl
halides) or hydroxyl group in alcohols (or phenols) by amino group. The reagent used for
ammonolysis is alcoholic ammonia. Generally, a mixture of primary, secondary and tertiary
amine is formed.
Al2 O3 .
ROH  NH 3 
Hightemp. Prerssure
 RNH 2  H 2O
 R  OH  R  OH  R  OH
R  NH 2 
 H2O
 R2 NH 
 H2O
 R3 N   R4 N OH 
(1 ) (2 ) (3 )

(vi) Acetylation: The process of introducing an acetyl (CH3CO-) group into molecule using
acetyl chloride or acetic anhydride is called acetylation.

(vii) Gabriel phthalimide synthesis: It is a method of preparation of pure aliphatic and aralkyl
primary amines. Phthalimide on treatment with ethanolic KOH gives potassium phathalimide
which on heating with a suitable alkyl or aralkyl halides gives N-substituted phthalimides, which
on hydrolysis with dil HCl or with alkali give primary amines.

Question 8:
Accomplish the following conversions:
(i) Nitrobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline

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Class XII – NCERT – Chemistry Chapter 13 – Amines

(vii) Aniline to p-bromoaniline

(viii)Benzamide to toluene
(ix) Aniline to benzyl alcohol.

Solution 8:

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Class XII – NCERT – Chemistry Chapter 13 – Amines

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Class XII – NCERT – Chemistry Chapter 13 – Amines

Question 9:
Give the structures of A, B and C in the following reaction:


(ii) C6 H5Cl 
CuCN
 A 
H2O / H
 B 
NH3

C
(iii) CH3CH 2 Br 
KCN
 A 
LiAlH 4
 B 
HNO2
C
C

NH3
(v) CH3COOH 

 A 
NaOBr
 B 
NaNO2 / HCl
C
(vi) C6 H5 NO2 
Fe / HCl
 A 
HNO2
273 K
 B 
C6 H5OH
C

Solution 9:

(ii) A  C6 H 5CN , B  C6 H 5COOH and C  C6 H 5CONH 2

(iii) A  CH 3CH 2CN , B  CH 3CH 2CH 2 NH 2 and C  CH 3CH 2CH 2OH
(iv) A  C6 H 5 NH 2 , B  C6 H 5 N   NCl   C6 H 5OH
(v) A  CH 3CONH 2 , B  CH 3 NH 2 and C  CH 3OH

Question 10:
An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms compound
‘B’ which on heating with Br2 and KOH forms a compound ‘C. of molecular formula C6H7N.
Write the structures and IUPAC names of compounds A, B and C.

Solution 10:
Since the compound C with molecular formula C6H7N is formed from compound B on treatment
with Br2 and KOH ,therefore, compound ‘B’ must be an amide and ‘C’ must be an amine. The
only amine having the molecular formula C6H7N, i.e., C6H5NH2 is aniline. Since ‘C is aniline,
therefore, the amide from which it is formed must be benzamide (C6H5CONH2). Thus,
compound ’B’ is benzamide. Since compound ‘B is formed from compound with aqueous
ammonia and heating, therefore, compound ‘A’ must be benzoic acid.

Question 11:

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Class XII – NCERT – Chemistry Chapter 13 – Amines

Complete the following reactions:

(i ) C6 H 5 NH 2  CHCl3  alc KOH
(ii ) C6 H 5 N 2Cl  H 3 PO2  H 2O 


(iv) C6 H 5 N 2Cl  C2 H 5OH 


(v) C6 H 5 NH 2  Br2 (aq ) 


(vii) C6 H5 N2Cl  ( i ) HBF4

( ii ) NaNO2 / Cu .


Solution 11:

(i ) C6 H 5 NH 2  CHCl3  3KOH (alc)   C6 H 5 N  C  3KCl  3H 2O

Question 12:
Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?

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Class XII – NCERT – Chemistry Chapter 13 – Amines

Solution 12:
The success of Gabriel phthalimide reaction depends upon the nucleophilic attack by the
phthalimide anion on the organic halogen compound. Since aryl halides do not undergo
nucleophilic substitution reactions easily, therefore, arylamines, i.e. aromatic, primary amines
cannot be prepared by Gabriel phthalimide reaction.

Question 13:
Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid.

Solution 13:
Both aromatic and aliphatic primary amines react with HNO2 at 273-278 K to form aromatic and
aliphatic diazonium salts respectively. But aliphatic diazonium salts are unstable even at this low
temperature and thus decompose readily to form a mixture of compounds. Aromatic and
aliphatic primary amines react with HNO2as follows

273  278 K   Decomposes

CH 3CH 2 NH 2  HONO  HCl 
 H2O
 CH 3 CH 2  N   NCl   
273  278 K
 CH 3CH 2OH  CH 2  CH 2  CH 3CH 2Cl  N 2
 (Unstable ) 

Question 14:
Give plausible explanation for each of the following:
(i) Why are amines less acidic than alcohols of comparable molecular masses?

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Class XII – NCERT – Chemistry Chapter 13 – Amines

(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii)Why are aliphatic amines stronger bases than aromatic amines?

Solution 14:
i) Loss of proton from an amine gives an amide ion while loss of a proton from alcohol give an
alkoxide ion.
R  NH 2  R  NH   H 
R  O  H  R  O  H 
Since O is more electronegative than N, so it will attract positive species more strongly in
comparison to N. Thus, RO is more stable than RNH-. Thus, alcohols are more acidic than
amines. Conversely, amines are less acidic than alcohols.
(ii) Due to the presence of two H-atoms on N-atom of primary amines, they undergo extensive
intermolecular H-bonding while tertiary amines due to the absence of H-atom on the N-atom do
not undergo H-bonding. As a result, primary amines have higher boiling points than tertiary
amines of comparable molecular mass.
(iii) Aromatic amines are far less basic than ammonia and aliphatic amines because of following
reasons:
(a)Due to resonance in aniline and other aromatic amines, the lone pair of electrons on the
nitrogen atom gets delocalized over the benzene ring and thus it is less easily available for
protonation. Therefore, aromatic amines are weaker bases than ammonia and aliphatic amines.
(b)Aromatic amines are more stable than corresponding protonated ion; Hence, they have very
less tendency to combine with a proton to form corresponding protonated ion, and thus they are
less basic.

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