HALOALKANES & HALOARENES

CASE-BASED/PASSAGE-BASED INTEGRATED QUESTIONS

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I. Read the given passage and answer the questions (c) Out of CH2==CH—CH2Cl and CH3CH2CH2Cl

that follow: which one undergoes SN1 mechanism faster?
Haloalkanes are colourless (when pure), sweet Ans. CH2==CH—CH2Cl because CH2—CH—CH2⊕ is

smelling liquids. CH3Cl, CH3Br and C2H5Cl and more stable due to resonance.
freons are gases. Boiling point increases with
(d) Complete the following:
increase in molecular weight and increase in carbon Cl
chain and decreases with branching. They are
Conc.
insoluble in water due to inability to form H-bonds D
+ H2SO4 →
LA
with water. Dipole moment increases with polarity,
density increases with increase in molar mass. They

Cl Cl
are non-inflammable, therefore, CCl4 is used as fire
extinguisher under the name pyrene. p-dichloro Conc.
heat
benzene has zero dipole moment, higher melting Ans. + H2SO4 →

point than o-dichloro benzene due to symmetry,
fits into crystal lattice readily. Haloalkanes undergo SO3H
nucleophilic substitution reaction by SN2 mechanism, Cl
1° > 2° > 3°, SN1 if carbocation formed is stable.
SO3H
They also undergo nucleophilic elimination reactions
+ + H2O
with alcoholic KOH. Haloarenes are less reactive
A
than haloalkanes towards nucleophilic substitution
due to resonance. Haloarenes undergo electrophilic (e) Why is chloroform stored in dark coloured

substitution reaction like nitration, sulphonation, bottles?
Friedel Crafts alkylation, acylation. Chloroform Ans. It is done so as to prevent formation of COCl2
is used as solvent, Freon is used as refrigerant,

which is poisonous.
dichloromethane is used as paint remover. Iodoform 1 Sunlight
B

is used as antiseptic. DDT is insecticide but non-
biodegradable.
(a) Arrange R—F, R—Br, R—I, R—Cl in
increasing order of boiling point.
Ans. R—F < R—Cl < R—Br < R—I
(b) A hydrocarbon ‘A’ (C 5H 10) gives only one
monochloro product on photo chlorination.
Identity ‘A’.
Cl
CHCl3 + O2 → COCl2 + HCl
2
(f) What is use of fully fluorinated organic
compounds?
Ans. They are used as blood substitute in surgery.
(g) Name the chlorine containing drug used in
treatment of coronavirus and malaria.
Ans. Hydroxychloroquine

hv
Ans. + Cl2 → + HCl

Cyclopentane

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 II. Read the given passage and answer the questions OC2H5 OH
that follow:
The substitution reaction of alkyl halides occurs Ans. + HI → + C2H5I


in SN1 or SN2 mechanism whatever mechanism
alkyl halide follow for substitution reaction to III. Observe the histogram related by comparison of
occur, the polarity of the carbon-halogen bond is boiling points of some alkyl halides and answer the
responsible for the substitution reaction. The rate questions that follow:
of SN1 reactions are governed by the stability of Chlorides Bromides Iodides
carbocation where as for SN2 reactions steric factor
is the deciding factor. If the starting material is a
400
chiral compound, we may end up with an inverted

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product or racemic mixture depending upon the type
of mechanism followed by alkyl halide. Cleavage

Boiling point (K)

300
of ethers with HI is also governed by steric factor
and stability of carbocation which indicates that in
organic chemistry, these two major factors help us 200
g g g
in deciding the kind of product formed. a a a
(a) Predict the stereochemistry of the product s s s
100

formed if optically active alkyl halide undergoes
LA
substitution reaction by SN1 mechanism.
Ans. Racemic mixture will be formed. 0
CH3X CH3CH2X CH3CH2CH2X

(b) Name the instrument used for measuring the Comparison of boiling points of some alkyl halides.

angle by which the plane polarised light is
rotated. (a) Name the alkyl halides in gaseous state.

Ans. CH3Cl (chloromethane), CH3Br (bromomethane),
Ans. Polarimeter

CH3CH2Cl (chloroethane)

(c) Predict the major product formed when
(b) Why do alkyl iodides have highest boiling points

2-bromopentane reacts with alcoholic KOH.

among alkyl halides?
Ans. Pent-2-ene will be major product. Ans. It is due to higher molar mass, bigger size, more

CH3—CH—CH2—CH2—CH3 + KOH(alc) →

van der Waals’ forces of attraction.
A
Br (c) How does boiling point vary with increase in

2-Bromopentane carbon chain?

CH3—CH==CH—CH2—CH3 + KBr + H2O Ans. As the carbon chain increases, surface area

Pent-2-ene increases, van der Waals’ forces of attraction
increases, hence boiling point increases.
(d) Write the structure of the products formed
(d) What is effect of branching on boiling point?

B

when anisole is treated with HI.

Why?
Ans. Phenol and CH3I are formed.
Ans. Boiling point decreases with branching because

OCH3 OH

surface area decreases, van der Waals’ forces of
attraction decreases.
+ HI → + CH3I (e) What happens to inflammability with increase

Iodomethane in halogen atoms? Illustrate with example.
Anisole Phenol
Ans. Inflammability decrease with increase in number of

(e) Write the structure of product formed when

halogen atoms e.g. CCl4 is used as fire extinguisher

ethoxy benzene is treated with HI. under the name pyrene.

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 IV. Observe the table in which physical data of Halomethane, polyhalogen derivative and haloarenes is given. Answer
the questions based on them.
Table: Some Physical Data of Halomethanes (CH3—X)

Bond C—X length Bond enthalpy Dipole moment

1. CH3F 139 452 1.847D
2. CH3Cl 178 351 1.860D
3. CH3Br 193 293 1.83D
4. CH3I 214 234 1.636D

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5. CH2Cl2 — — 1.62D
6. CHCl3 — — 1.03D
7. CCl4 — — Zero
Dipole moment Melting point
8. p-dichloro benzene Zero 325K
9. o-dichloro benzene 2.54D 216K
LA
10. m-dichloro benzene 1.72D 249K
Boiling point
11. C6H5F 1.60D 358K
12. C6H5Cl 1.69D 405K
13. C6H5Br 1.70D 429K
14. C6H5I 1.70D 462K

(a) Why is dipole moment of CH 3 F less than
CH3Cl?
A
Ans. It is because m = e × d, C—F bond distance is
less than C—Cl, therefore, product of charge and
distance is slightly lower in CH3F than CH3Cl.
(b) Why is CH3I more reactive than CH3Cl?
Ans. It is due to lower bond dissociation enthalpy of
C—I bond than C—Cl bond.
B
melting point. o-isomer has higher boiling point
due to higher dipole moment, more polarity than
p-isomer.
(d) Why does o-dichlorobenzene has higher dipole
moment than m-dichlorobenzene?
Ans. m = µ12 + µ 22 + 2µ1µ 2 cos θ , m1 and m2 are dipole
moments of C—X bonds m1 = m2 and cos 60 = 0.5

in o-isomer cos 120° = –0.5 in m-isomer.

(c) Why is melting point of p-dichlorobenzene (e) Why does C6H5I has higher dipole moment

higher than o-dichlorobenzene but boiling point

than C6H5F?
of o-isomer is higher than p-isomer?
Ans. It is due to C—I bond is longer than C—F bond
Ans. p-dichlorobenzene fits into crystal lattice more

and m = e × d.

readily than o-isomer, therefore, has higher

CLASSES BY ANKUR SIR 7983744732