NCERT Solution for Class 12

Chemistry
Chapter 10– Haloalkanes and Haloarenes

Intext Exercise

1. Write structures of the following compounds:

Ans: According to the name we can easily draw the structure.
(i) 2 - chloro-3methylpentane:
Ans: Main chain will be of five carbon atoms. At second position chlorine will be
present and at third position, methyl group will be present.

(ii) 1- chloro- 4 – ethylcyclohexane

Ans: A cyclic structure is present in which at 1st carbon there is chlorine present and at
the 4th position ethyl group is present.

(iii)4 - tert .Butyl-3- iodoheptane

Ans: Main chain will be of seven carbon atoms. At 4 th position tertiary butyl will be
present and at the 3rd position iodine will be present.

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(iv) 1, 4 -Dibromobut- 2 – ene
Ans: Main chain will be of 4 carbon atoms and it is an alkene. There are two bromine
atoms on the terminal carbon atoms.

(v) 1-Bromo- 4 - sec/ butyl- 2 -methylbenzene.

Ans: Main chain will be the benzene. Three substituents are present on benzene.

2. Why is sulphuric acid not used during the reaction of alcohols with KI ?
Ans: H 2SO4 is a powerful oxidizer. HI generated during the reaction is oxidized,
preventing the interaction between alcohol and HI from becoming alky iodide as a
result of the process. H3PO3 is utilized as a non-oxidizing acid to prevent the oxidation
of HI . The reaction is given below:
2KI + H2SO4  2KHSO4 + 2HI  I2

3. Write structures of different dihalogen derivatives of propane.

Ans: Propane is an alkane molecule containing three carbon atoms. Dihalogen
derivatives are propane that includes two halogen atoms. There are four potential
isomers. These are given below:
(i) 1,3-Dibromopropane

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(ii) 1,2-Dibromopropane

(iii)1,1-Dibromopropane

(iv) 2,2-Dibromopropane

4. Among the isomeric alkanes of molecular formula C5H12 identify the one that
one photochemical chlorination yields:
Ans: Isomeric alkane means that there will be different arrangements of substituents
around the carbon atom. C5H12 is pentane and it is analkane.

(i) A single monochloride

Isomer of pentane that will yield single monochloride is neopentane and its structure is
given below:

Due to the fact that all of the H-atoms are identical, replacing any one of them will
result in the same result.

(ii) Three isomeric monochlorides.

An isomer of pentane that will yield three isomeric monochlorides is n-pentane as given
below:

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In this, a, b, and c have three sets of equivalent hydrogen atoms.

(iii) Four isomeric monochlorides.

An isomer of pentane that will yield four isomeric monochlorides is iso-pentane which
is given below:

Because all the carbon atoms have different hydrogen atoms.

5. Draw the structures of major monohalo products in each of the following

reactions:
(i)

Ans: In this reaction, the hydroxyl group will be replaced with the chlorine atom. The
reaction is given below:

(ii)

Ans: In this reaction the amine group will be replaced with methyl bromide. The
reaction is given below:

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(iii)

Ans: In this reaction the hydroxyl group with the methyl group will be replaced with
the chlorine atom. The reaction is given below:

(iv)

Ans: In this reaction the iodine from the hydrogen iodide will attach the carbon atom
having the double bond as well as methyl group. The reaction is given below:

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(v) CH3CH2Br+NaI 
Ans: In this reaction the iodine atom will replace the bromine in the haloalkane. The
reaction is given below:
CH3CH2Br + NaI  CH3CH2I + NaBr

(vi)

Ans: In this reaction, the bromine atom will attack the alpha-carbon atom of the double
bond. The reaction is given below:

6. Arrange each set of compounds in order of increasing boiling points.

(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
Ans: As we can see that all the compounds given above are haloalkanes. The order will
be:
Chloromethane < Bromomethane < Dibromomethane < Bromoform
This is due to the fact that as the halogen size increases the boiling point will increase
and as the number of halogen atoms increases in the same chain, the boiling point will
increase.

(ii) Chloropropane, Isopropyl chloride, 1 -Chlorobutane.

Ans: In all the compounds there is chlorine atom present and the size of the alkyl chain
is different. The order will be:
Isopropyl chloride < 1- Chloropropane < 1 – Chlorobutane
This is due to the fact that as the branching of the chain increases the boiling point will
decrease and as the size of the chain increases the boiling point will increase.

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7. Which alkyl halide from the following pairs would you expect to react more
rapidly by an SN 2 mechanism? Explain your answer?
Ans: For the SN 2 reaction the order of reactivity is 1  2  3 , so we can solve the
question according to the order of the reactivity.

(i) CH3CH2CH2CH2Br or

Ans: In the first compound the alkyl halide is primary halide while the second
compound is a secondary halide. So, the first compound will react more rapidly.

(ii)

Ans: In the first compound the alkyl halide is secondary halide while the second
compound is a tertiary halide. So, the first compound will react more rapidly.

(iii)

Ans: Both compounds are secondary halides but the steric hindrance by the CH3 the
group will have more effect in the second compound so, the first compound will react
more rapidly.

8. In the following pairs of halogen compounds, which compound undergoes

faster SN 1 reaction?
Ans: For the SN1 reaction the order of reactivity is 3  2  1 , so we can solve the
question according to the order of the reactivity.
(i)

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Ans: The first compound is tertiary compound and the second compound is secondary
compound. So, first compound will undergo faster SN1 reaction.

(ii)

Ans: The first compound is a secondary compound and the second compound is
primary compound. So, first compound will undergo faster SN1 reaction.

9. Identify A, B, C, D, E, R and R 1 in the following:

Ans: The compound A in the reaction is cyclohexylmagnesium bromide, compound B

is Cyclohexane.
Compound R –Br will be 2-Bromopropane and the compound C is given below:

The third part of the question is incorrect because the tertiary-alkyl halides do not
undergo wurtz reaction but they undergo dehydrohalogenation to give alkenes.
So, the compound R1 -Br is given below:
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Compound D is Tertiary butyl magnesium bromide and compound E is 2-
Methylpropane.
The complete reaction is given below:

NCERT EXERCISE

1. Name the following halides according to IUPAC system and classify them as
alkyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides:

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(i) (CH3 )2CHCH(Cl)CH3
Ans: The name of the compound is 2-Chloro-3-methyl butane and it is a secondary
alkyl halide.

(ii) CH3CH2CH(CH3 )CH(C2H5 )Cl

Ans: The name of the compound is 3-Chloro-4-methyl hexane and it is a secondary
alkyl halide.

(iii) CH3CH2C(CH3 )2CH2I

Ans: The name of the compound is 1-Iodo-2,2-dimethyl butane and it is a primary
alkyl halide.

(iv) (CH3 )3CCH2CH(Br)C6H5

Ans: The name of the compound is 1-Bromo-3,3-dimethyl-1-phenylbutane and it is a
secondary benzylic halide.

(v) CH3CH(CH3 )CH(Br)CH3

Ans: The name of the compound is 2-bromo-3-methyl butane and it is a secondary
alkyl halide.

(vi) CH3C(C2H5 )2CH2CH3

Ans: The name of the compound is 1-bromo-2-ethyl-2-methyl butane and it is a
primary alkyl halide.

(vii) CH3C(Cl)(C2H5 )CH2CH3

Ans: The name of the compound is 3-Chloro-3-methyl pentane and it is a tertiary alkyl
halide.

(viii) CH3CH=C(Cl)CH2CH(CH3 )2
Ans: The name of the compound is 3-Chloro-5-methyl hex-2-ene and it is a vinylic
halide.

(ix) CH3CH=CHC(Br)(CH3 )2
Ans: The name of the compound is 4-bromo-4-methyl pent-2-ene and it is allylic
halide.

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(x) p-ClC6H4CH2C(CH3 )2
Ans: The name of the compound is 1-Chloro-4-(2-methylpropyl) benzene and it is an
aryl halide.

(xi) m-ClCH2C6H4CH2C(CH3 )3
Ans: The name of the compound is 1-Chloromethyl-3-(2,2-dimethylpropyl) benzene
and it is a primary benzylic halide.

(xii) o-Br-C6H4CH(CH3 )CH2CH3

Ans: The name of the compound is 1-Bromo-2-(1-methylpropyl) benzene and it is an
aryl halide.

2. Give the IUPAC names of the following compounds:

(i) CH3CH(Cl)CH(Br)CH3
Ans: The IUPAC name of this compound is 2-Bromo-3-chlorobutane.

(ii) CHF2CBrClF
Ans: The IUPAC name of this compound is 1-Bromo-1-chloro-1, 2, 2- trifluoroethane.

(iii) ClH2C  CCH2Br

Ans: The IUPAC name of this compound is 1-Bromo-4-chlorbut-2-yne.

(iv) (CCl 3 )3CCl

Ans: The IUPAC name of this compound is 2-(Trichloromethyl)- 1, 1, 1, 2, 3, 3, 3-
heptachloropropane.

(v) CH3C(p-ClC6H4 )2CH3

Ans: The IUPAC name of this compound is 2-Bromo-3, 3-bis-(4-chlorophenyl)
butane.

(vi) (CH 3 )3CCH=C(Cl)C6 H 4I -p

Ans: The IUPAC name of this compound is 1-Chlor-1-(4-iodophenyl)-3, 3-
dimethylbut-1-ene.

3. Write the structures of the following organic halogen compounds:

(i) 2-Chloro-3-methylpentane

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Ans: The structure of this compound will be:

(ii) p-Bromochlorobenzene
Ans: The structure of this compound will be:

(iii) l-Chloro-4-ethylcyclohexane
Ans: The structure of the compound will be:

(iv) 2- (2-Chlorophenyl) -1- iodooctane

Ans: The structure of the compound will be:

(v) 2-Bromobutane
Ans: The structure of the compound will be:

(vi) 4-tert-Butyl-3-iodoheptane
Ans: The structure of the compound will be:

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(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
Ans: The structure of the compound will be:

(viii) l, 4-Dibromobut-2-ene
Ans: The structure of the compound will be:
BrCH2 -CH=CH-CH2Br

4. Which one of the following has the highest dipole moment?

CH2Cl 2 , CHCl 3 or CCl 4
Ans: Below are the three-dimensional structures of the three compounds, as well as the
direction of each bond's dipole moment:

CCl4 has no dipole moment since it is symmetrical. When two C-Cl dipole moments
are added to CHCl3 , the C-H and C-Cl bonds oppose each other. CHCl3 has a limited
Class XII Chemistry www.vedantu.com 13
dipole moment (1.03 D) because the dipole moment of the second resultant is
anticipated to be less than that of the first. This means that in CH 2Cl2 , the resulting
dipole moment of C-Cl pairs is greater than in CHCl3 . Due to its dipole moment,
CH 2Cl2 is the strongest.

5. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single
monochloro compound C5H9Cl in bright sunlight. Identify the hydrocarbon.
Ans: The molecular formula of the hydrocarbon might be either cycloalkane or alkene.
Since the molecule does not react with Cl2 in the dark, it must be a cycloalkane. Since
the cycloalkane interacts with Cl2 in the presence of strong sunshine to form a single
monochloro compound, C5H9Cl , all ten hydrogen atoms in the cycloalkanes must be
equivalent. Thus, cyclopentane is the cycloalkane.

6. Write the isomers of the compound having formula C4H9Br .

Ans: First we have find the Double bond equivalent (DBE) for C4H9Br . It is given
below:
4(4-2) + 9(1-2) + 1(1-2)
= +1=0
2
The answer is zero which means that there is no ring or unsaturation in the isomers of
the given compound, all the isomers will be either branched or straight chain. So, there
will be four isomers and these are given below:
(i) 1- Bromobutane:
CH3CH2CH2CH2Br

(ii) 1-Bromo-2-methylpropane:

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(iii)2-Bromo butane:

(iv) 2-Bromo-2-methylpropane:

7. Write the equation for the preparation of 1-iodobutane from:

(i) 1-Butanol
Ans: 1-Butanol will react with potassium iodide and phosphoric acid to form the 1-
Iodobutane. The reaction is given below:
CH3CH2CH2CH2OH + KI + H3PO4  CH3CH2CH2CH2I + H2O + KH2PO4

(ii) 1-Chlorobutane
Ans: 1-Chlorobutane will react with potassium iodide in the presence of acetone to
form the 1-Iodobutane. The reaction is given below:
CH3CH 2CH 2CH 2Cl + KI  Acetone
CH3CH 2CH 2CH 2 I + KCl

(iii)But-1-ene
Ans: But-1-ene will react with hydrogen bromide in the presence of peroxide to give
1-Bromobutane and then it reacts with sodium iodide in the presence of acetone to give
1-Iodobutane. The reaction is given below:
CH3CH 2 -CH=CH 2 + HBr  peroxide
CH3CH 2CH 2CH 2 Br
CH3CH 2CH 2CH 2Br + NaI  Acetone
CH3CH 2CH 2CH 2 I + NaBr

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8. What are ambident nucleophiles? Explain with an example.
Ans: Ambident nucleophiles are nucleophiles that can attack at two distinct locations.
It is a resonance hybrid of the following two structures (for example, the cyanide
ion).Cyanide ion is a resonance hybrid of the following two structures:

It may attack carbon to produce cyanide, and nitrogen to form isocyanide, depending
on the chemical.

9. Which compound in each of the following pairs will react faster in SN 2 reaction
with OH- ?
(i) CH 3Br or CH 3I
Ans: Both the compounds are alkyl halide but the iodide ion is a larger atom than
bromide ion. So, I- ion is better leaving group than Br - ion. Therefore, CH3I will react
faster than CH3Br towards SN 2 reaction with hydroxyl ion.

(ii) (CH3 )3CCl or CH3Cl

Ans: In SN 2 reaction the steric hindrance should be very less. (CH3 )3CCl has very
high steric hindrance and CH3Cl has less steric hindrance. So, CH3Cl will react faster
to the SN 2 reaction with hydroxyl ion.

10. 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
Ans: The major product when 1-Bromo-1-methylcyclohexane reacts with sodium
ethoxide in ethanol will give 1-Methylcyclohexene. The reaction is given below:

(ii) 2-Chloro-2-methylbutane.

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Ans: 2-Chloro-2-methyl butane has two different sets of equivalent beta-hydrogen and
hence, in principle, can give two alkenes. But according to Satzeff’s rule, more highly
substituted alkene is more stable and is the major product. The reaction is given below:

(iii) 2, 2, 3-Trimethyl-3-bromopentane.
Ans: 2, 2, 3-Triethyl-3-bromopentane has two different sets of equivalent beta-
hydrogen and hence, in principle, can give two alkenes. But according to Satzeff’s rule,
more highly substituted alkene is more stable and is the major product. The reaction is
given below:

11. How will you bring about the following conversions?

(i) Ethanol to but-1-yne.
Ans: Ethanol will react with SOCl2 and pyridine to Chloroethane. Acetylene will react
with NaNH2 to form sodium acetylide. Now Chloroethane and Sodium acetylide will
react to form But-1-yne. The reactions are given below:

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CH3CH 2OH 
SOCl2 , Pyridine
 CH3CH 2 -Cl
CH  CH + NaNH 2 
Liq. NH3 , 196K
 HC  C- Na +
CH3CH 2Cl + HC  C- Na +  CH3CH 2 -C  CH + NaCl

(ii) Ethane to bromoethene

Ans: Ethane will react with bromine to form bromoethane. Now, this bromoethane will
react with KOH to form ethene and then there will be the formation of 1, 2-
Dibromoethane. Now, 1, 2-Dibromoethane will react with alcoholic KOH to form
Bromoethene. The reactions are given below:
CH3 -CH3 + Br2  hv, 520-670K
 CH3CH 2 -Br 
KOH(alc.)
 CH 2 =CH 2
CH 2 =CH 2 Br2 /CCl4
 BrCH 2 -CH 2 Br KOH(alc.)
 CH 2 =CHBr

(iii) Propene to 1-Nitropropane

Ans: Propene will react with Hydrogen bromide in peroxide effect to form 1-
Bromopropane. Now, 1-Bromopropane will react with silver nitrite to given 1-
Nitropropane. The reaction is given below:
CH3 -CH=CH 2  
HBr
 CH3CH 2CH 2 Br AgNO2
 CH3CH 2CH 2 NO2

(iv) toluene to benzyl alcohol

Ans: Toluene will react with chlorine in the presence of light to give benzyl chloride
and this benzyl chloride will react with aqueous KOH to give benzyl alcohol. The
reaction is given below:

(v) propene to propyne

Ans: Propene will react with bromine in the presence of carbon tetrachloride to give 1,
2-Dibromopropane. Now, 1, 2-Dibromopropane will react with NaNH2 and liquid
ammonia to give propyne. The reaction is given below:

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(vi) Ethanol to ethyl Fluoride
Ans: Ethanol will react with SOCl2 and pyridine to form ethyl chloride. Now, ethyl
chloride will react with Hg 2F2 to form Ethyl fluoride. The reaction is given below:
CH3CH 2OH  SOCl2 , pyridine
 CH3CH 2 -Cl 
Hg 2 F2
 CH3CH 2 -F

(vii) Bromomethane to Propanone

Ans: Bromomethane will react with KCN in the presence of ethanol to form
acetonitrile. Acetonitrile will react with CH3MgBr in the presence of ether and then
with water to give Propanone. The reaction is given below:

(viii) But-1-ene to but-2-ene

Ans: But-1-ene will react with Hydrogen bromide to form 2-Bromobutane and this will
react with alcoholic KOH to form But-2-ene. The reaction is given below:

(ix) 1-Chlorobutane to n-octane

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Ans: 1-Chlorobutane will react with sodium and dry ether to form n-octane. The
reaction is given below:
2 CH3CH 2CH 2CH 2Cl + 2 Na 
Dry ether
 CH3 (CH 2 )6CH3 + 2 NaCl

(x) Benzene to biphenyl

Ans:Benzene will react with Bromine in the presence of FeBr3 to form Bromobenzene.
Bromobenzene will react with sodium to form Biphenyl. The reaction is given below:

12. Explain why

(i) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
Ans: S-character increases electronegative properties of chlorobenzene sp 2 -hybrid
carbon. Because of this, the chlorobenzene C atom is less likely than the cyclohexyl
chloride C atom to release electrons to Cl. C-Cl link in chlorobenzene is hence less
polar than cyclohexyl chloride. In addition, the C-Cl bond in chlorobenzene has a
double bond character due to the delocalization of Cl's lone electron pairs across the
benzene ring as opposed to cyclohexyl chloride, which has a pure single bond. Or to
put it another way, the chlorobenzene C-Cl bond is shorter than that of the cyclohexyl
chloride. Considering that the dipole moment is a function of charge and distance.
C-Cl distance is shorter in chlorobenzene, therefore it has a smaller dipole moment
than cyclohexyl chloride.

(ii) Alkyl halides, though polar, are immiscible with water?

Ans: Dipole-dipole attraction holds alkyl halides together.
H-bonds hold the molecules of H2O together. Alkyl halides are not soluble in water
because the new forces of attraction between water and alkyl halide molecules are
lower than the existing forces of attraction between alkyl halide - alkyl halide
molecules and water-water molecules.
In addition, alkyl halides are unable to establish hydrogen bonds with water or to
disrupt the H-bonding network that exists in water.

(iii)Grignard reagents should be prepared under anhydrous conditions?

Ans: The reactivity of the Grignard reagent is very high. When they come in contact
with water they readily react and form alkanes. The general reaction is given below:
Class XII Chemistry www.vedantu.com 20
R-Mg-X + H-OH  R-H + Mg(OH)X
Therefore, the Grignard reagent should be made in anhydrous condition.

13. Give the uses of Freon-12, DDT, carbon tetrachloride and iodoform.
Ans:
Iodoform:
Early on it was considered to be an antiseptic, however the characteristics are
attributable to the free iodine that is released, not the substance itself. It has been
superseded by other iodine-containing formulations due to its offensive odour.

Carbon tetrachloride:
For oil, fats, and resins in the industrial sector, as well as in dry cleaning.
In addition, CCl4 vapours are extremely inflammable, according to the manufacturer.
As a result, CCl4 is sold as pyrene, a fire extinguishing agent.
Used in the production of aerosol can refrigerants and propellants.

Freons:
Industry uses Freon-12 ( CCl2F2 ), which is the most prevalent form of refrigerant.
Refrigerant or air-conditioning components, aerosol propellants

DDT:
Its efficacy against mosquitoes that carry malaria and other insects that harm crops led
to a dramatic increase in its usage worldwide following World War II.
DDT, on the other hand, has been widely used since the 1940s. Toxic for fishes, DDT
acquired tolerance in many insect species. When it comes to animals, DDT is not
readily metabolised, but instead accumulates and is retained in fatty tissues. As long as
the animals continue to eat DDT at the same rate, it builds up in their bodies.

14. Write the structure of the major organic product in each of the following
reactions:
(i) CH 3CH 2CH 2Cl + NaI  Acetone, heat

Ans: The Chlorine atom from the alkyl halide by iodine. The major product of the
reaction is 1-Iodopropane. The reaction is given below:
CH3CH 2CH 2Cl + NaI Acetone, heat
 CH 3CH 2CH 2I + NaCl

(ii) (CH 3 )3CBr + KOH 

Ethanol

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Ans: There will be Dehydrohalogenation and the major product of the reaction is 2-
methylpropene. The reaction is given below:

(iii) CH 3CH(Br)CH 2CH 3 + NaOH  Water


Ans: The bromine atom will be replaced with the hydroxyl ion. The major product will
be Butan-2-ol. The reaction is given below:

(iv) CH 3CH 2Br + KCN  aq.ethanol


Ans: The bromide ion will be replaced with the cyanide ion. The major product will
be propanenitrile. The reaction is given below:
CH3CH 2 Br  KCN  aq.ethanol
 CH3CH 2CN  KBr

(v) C6H5ONa + C2H5Cl 

Ans: The major product in the above reaction will be Phenetole. The reaction is given
below:
C6H5ONa + C2H5Cl  C6H5 -O-C2H5 + NaCl

(vi) CH3CH2CH2OH + SOCl 2 

Ans: The hydroxyl ion in the alkyl halide will be replaced with chloride ion. The major
product of the reaction will be 1-Chloropropane. The reaction is given below:
CH3CH2CH2OH + SOCl2  CH3CH2CH2Cl + SO2 + HCl

(vii) CH 3CH 2CH=CH 2 + HBr  peroxide

Ans: Since peroxide is used in the reaction, there will be Anti-Markovnikov's addition.
The major product in the reaction will be 1-Bromobutane. The reaction is given below:
CH3CH 2CH=CH 2 + HBr  peroxide
CH3CH 2CH 2CH 2 Br

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(viii) CH3CH=C(CH3 )2 + HBr 
Ans: In this reaction there will be Markovnikoff’s addition. The major product of the
reaction will be 2-Bromo-2-methylbutane. The reaction is given below:

15. Write the mechanism of the following reaction:

n-BuBr + KCN  EtoH-H 2O
 n-BuCN
Ans: There are two contributing resonance hybrid structures of KCN due the
cyanide ion present. It is given below:
K + [-:C=N:  :C=N:- ]
So, as we can see that the CN- ion is an ambident nucleophile. Therefore, it can attack
from either C atom or from N atom towards n-BuBr. The strength of C-C bond is
stronger than C-N bond, therefore, the attack will take place from C atom towards n-
Butyl bromide to form n-butyl cyanide. The reaction is given below:

16. Arrange the compounds of each set in order of reactivity towards SN 2

displacement:
Ans: For the SN 2 reaction the order of reactivity is 1  2  3 , so we can solve the
question according to the order of the reactivity.

(i) 2-Bromo-2-Methylbutane, 1-Bromopentane, 2-Bromopentane.

First let us draw all the structures of the compound.
2-Bromo-2-Methyl butane:

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1-Bromopentane:
CH3CH2CH2CH2CH2 -Br

2-Bromopentane:

The order will be:

1-Bromopentane > 2-Bromopentane > 2-Bromo-2-methyl butane.

(ii) 1-Bromo-3-methylbutane,2-Bromo-2-methylbutane,3-Bromo-2-
methylbutane
Ans: The structures of the compounds are given below:
1-Bromo-3-methylbutane:

2-Bromo-2-methylbutane:

3-Bromo-2-methylbutane:

The order of the reactivity will be:

1-Bromo-3-methylbutane > 3-Bromo-2-methylbutane > 2-Bromo-2-methyl butane.

(iii)1-Bromobutane, 1-Bromo-2,2-dimethypropane, 1-Bromo-2-methylbutane, 1-

Bromo-3-methyl butane.

Class XII Chemistry www.vedantu.com 24

Ans: The structure of the compounds are given below:
1-Bromobutane:
CH3CH2CH2CH2Br
1-Bromo-2, 2-dimethylpropane:

1-Bromo-2-methylbutane:

1-Bromo-3-methylbutane:

The order of reactivity will be:

1-Bromobutane > 1-Bromo-3-methylbutane > 1-Bromo-2-methylbutane > 1-Bromo-2,
2-dimethylpropane.
This is decided by the fact that steric hindrance should be less for SN 2 for the
reactivity.

17. Out of C6H5CH2Cl and C6H5CHClC6H5 which is more easily hydrolyzed by

aqueous KOH.
Ans: C6H5CH2Cl is a primary aryl halide but C6H5CHClC6H5 is a secondary aryl
halide. If reaction with aqueous KOH is a SN1 reaction then it is based on the stability
of the carbocation. The formation of carbocation is given below:

Class XII Chemistry www.vedantu.com 25

Secondary carbocation is more stable than primary carbocation so, the
C6H5CHClC6H5 will react faster.
But if the reaction is SN 2 then C6H5CH2Cl will react faster because the reactivity is
of opposite order.

18. p-Dichlorobenzene has higher m.p. and lower solubility than those of o-and
m-isomers. Discuss.
Ans: There are greater molecular forces of attraction between p-isomers and o-isomers
due to it being more symmetrical and fitting into the crystal lattice more tightly. Due
to the fact that the crystal lattice breaks during melting or dissolution, a greater amount
of energy is required to melt or dissolve the p-isomer than the o- and m-isomers. This
means that p-isomers have higher melting points and lower solubilities than their
equivalent o- and m-isomers.

19. How the following conversions can be carried out:

(i) Propene to propan-1-ol
Ans: Propene will react with hydrogen bromide in the presence of peroxide to give 1-
Bromopropane. Now, this 1-Bromopropane will react with aqueous KOH to form
Propan-1-ol. The reaction is given below:
CH3CH=CH 2  HBr/peroxide
 CH3CH 2CH 2 Br 
Aq.KOH
 CH3CH 2CH 2OH

(ii) Ethanol to but-2yne

Ans: Ethanol will react with iodine and phosphorus to form Iodoethane then it will
convert to ethene. Now ethene will react with bromine in the presence of carbon
tetrachloride to form1, 2-Dibromoethane, this on dehydrohalogenation and reaction

Class XII Chemistry www.vedantu.com 26

with NaNH2 will form disodium acetylide. Later this reaction with methyl iodide will
give But-2-yne. The reaction is given below:

(iii)1-Bromopropane to 2-bromopropane
Ans: 1-Bromopropane will react with alcoholic KOH to form propene. Propene will
react with HBr to form 2-Bromopropane. The reaction is given below:
CH3CH 2CH 2 Br Alc.KOH
 CH3CH=CH 2  
HBr
 CH3 -CH(Br)-CH3

(iv) Toluene to Benzyl alcohol.

Ans: Toluene will react with chlorine in the presence of light to give benzyl chloride
and this benzyl chloride will react with aqueous KOH to give benzyl alcohol. The
reaction is given below:

(v) Benzene to 4-bromonitrobenzene

Class XII Chemistry www.vedantu.com 27

Ans: Benzene will react with Bromine in the presence of FeBr3 to form
Bromobenzene. Bromobenzen will react with concentrated nitric acid and concentrated
sulfuric acid to form 4-Bromonitrobenzene. The reaction is given below:

(vi) Benzyl alcohol to 2-phenylethanoic acid

Ans: Benzyl alcohol will react with SOCl2 to form Benzyl chloride. Benzyl chloride
will react with KCN to form Benzyl cyanide. Now, benzyl cyanide on hydrolysis will
give 2-Phenylethanoic acid. The reaction is given below:

(vii) Ethanol to Propanenitrile

Ans: Ethanol will react with iodine in the presence of phosphorus to form Iodoethane.
Iodoethane will react with KCN in the presence of aqueous ethanol to give
Propanenitrile. The reaction is given below:
CH3CH 2OH  P/I2
CH3CH 2 I 
KCN/aq.Ethanol
 CH3CH 2CN

(viii)Aniline to Chlorobenzene

Class XII Chemistry www.vedantu.com 28

Ans: Aniline will undergo diazotization to form Benzene diazonium chloride. The
Benzene diazonium chloride will react with copper chloride in the presence of
hydrochloric acid to give Chlorobenzene. The reaction is given below:

(ix) 2-Chlorobutane to 3, 4-Dimethylhexane

Ans: 2-Chlorobutane will react with sodium in the presence of dry ether to form 3, 4-
Dimethylhexane. The reaction is given below:

(x) 2-Methyl-1-propene to 2-Chloro-2-methylpropane

Ans: 2-Methyl-1-propene will react with Hydrogen chloride to give 2-Chloro-2-
methylpropane. The reaction is given below:

(xi) Ethyl chloride to propanoic acid

Ans: Ethyl chloride will react with KCN to give propanenitrile. Propanenitrile on
hydrolysis will give propanoic acid. The reaction is given below:
CH3CH2Cl  KCN
 CH3CH 2CN  H+ /H2O
 CH3CH 2COOH

(xii) But-1-ene to n-butyl iodide

Ans: But-1-ene will react with HBr in the presence of peroxide to form 1-
Bromobutane. 1-Bromobutane will react with NaI in the presence of Acetone to give
n-butyl iodide. The reaction is given below:

Class XII Chemistry www.vedantu.com 29

CH 3CH 2CH  CH 2 
HBr
peroxide
CH 3CH 2CH 2CH 2 Br 
NaI
Acetone
CH 3CH 2CH 2CH 2 I

(xiii)2-Chloropropane to 1-propanol
Ans: 2-Chloropropane will undergo dehydrohalogenation to give propene. Propene
will react with HBr in the presence of peroxide to give 1-bromopropane. 1-
Bromopropane will react with KOH to form 1-Propanol. The reaction is given below:

(xiv) Isopropyl alcohol to Iodoform

Ans: Isopropyl alcohol will react with iodine and sodium hydroxide to give Iodoform.
The reaction is given below:

(xv) Chlorobenzene to p-nitrophenol

Ans: Chlorobenzene will react with concentrated nitric acid and concentrated sulfuric
to give p-Chloronitrobenzene. p-Chloronitrobenzene will react with 15% sodium
hydroxide and hydrochloric acid to give p-nitrophenol. The reaction is given below:

Class XII Chemistry www.vedantu.com 30

(xvi) 2-Bromopropane to 1-bromopropane
Ans: 2-Bromopropane will react with alcoholic KOH to form Propene. Now, propene
will react with HBr in the presence of peroxide to form 1-Bromopropane. The reaction
is given below:

(xvii) Chloroethane to butane

Ans: Chloroethane will react with sodium in the presence of butane. The reaction is
given below:
2CH3CH 2 -Cl + 2Na 
Dryether
CH3CH 2CH 2CH3 + 2NaCl

(xviii) Benzene to diphenyl

Ans:Benzene will react with Bromine in the presence of FeBr3 to form Bromobenzene.
Bromobenzene will react with sodium to form Biphenyl. The reaction is given below:

(xix) Tert-Butyl bromide to isobutyl bromide

Ans: Tert-butyl bromide will react with alcoholic KOH to form 2-Methyl-1-propene.
2-Methyl-1-propene will react with HBr in the presence of peroxide to form isobutyl
bromide. The reaction is given below:

(xx) Aniline to phenylisocyanide

Ans: Aniline will react with chloroform and alcoholic KOH to form Phenyl isocyanide.
The reaction is given below:

Class XII Chemistry www.vedantu.com 31

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.
Ans: Because of its high nucleophilicity, KOH is nearly fully deionized in water to
generate OH - ions, which then undergo substitution reactions with alkyl halides to
form alcohols.
OH - ions are strongly solvated in the aqueous solution (hydrated). A result of this
process is that alkyl chloride fails to extract a hydrogen from its p-carbon in order to
create alkenes. While an alcohol-based solution of KOH contains an ion known as the
alkoxide ( RO- ), this strong base preferentially removes HCI from an alkyl chloride to
produce alkenes.

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.
Ans: C4H9Br is the chemical formula for two main primary alkyl halides. These are
given below:
n-butyl bromide: CH3CH2CH2CH2Br
and Isobutyl bromide:

As compound (a) when reacted with Na metal generated a compound (d) with a
molecular formula C8H18 which was different from the molecule obtained when n-
butyl bromide was reacted with Na metal, hence (a) must be isobutyl bromide and
compound (d) must be n-butyl bromide.
Class XII Chemistry www.vedantu.com 32
The reaction will be:
2 CH3CH 2CH 2CH 2Br + 2 Na 
Wurtz reaction
 CH3 (CH 2 )6CH3

Isobutyl bromide is compound (a). Because of this, 2-methyl-1-propane must be the

chemical (b) that it yields after being treated with alcohol KOH. The reaction is given
below:

On treatment with HBr, compound (b) transforms into compound (c) in line with the
Markownikoff rule To summarise: Compound (c), also known as tert- butyl bromide,
is an isomer of compound (a), also known as isobutyl bromide.

Therefore, (a) is isobutyl bromide, (b) is 2-Methyl-1-propane, (c) is tert-butyl bromide,

and (d) is 2, 5-Dimethylhexane.

22. What happens when.

(i) n-butyl chloride is treated with alcoholic KOH.
Ans: When n-butyl chloride is treated with alcoholic KOH, then there will be
dehydrohalogenation and the product will be But-1-ene. The reaction is given below:

(ii) Bromobenzene is treated with Mg in the presence of dry ether.

Class XII Chemistry www.vedantu.com 33

Ans: When bromobenzene is treated with Mg in the presence of dry ether there will be
the formation of Phenylmagnesium bromide. The reaction is given below:

(iii)Chlorobenzene is subjected to hydrolysis.

Ans: When chlorobenzene is hydrolyzed then there will be no reaction.

(iv) Ethyl chloride is treated with aqueous KOH

Ans: When ethyl chloride is treated with aqueous KOH then the product will be Ethyl
alcohol. The reaction is given below:

CH3CH 2Cl + KOH(aq) 

Hydrolysis
 CH3CH 2OH + KCl

(v) Methyl bromide is treated with sodium in the presence of dry ether.
Ans: When methyl bromide is treated with sodium in the presence of dry ether then
Wurtz reaction will take place and the product of the reaction will be Ethane. The
reaction is given below:

(vi) Methyl chloride is treated with KCN.

Ans: When methyl chloride is treated with KCN then there will be a Nucleophilic
substitution reaction and the product will be Methyl cyanide. The reaction is given
below:
CH3 -Cl + KCN  ethanol
 CH3 -C  N + KCl

Class XII Chemistry www.vedantu.com 34