QUESTION BANK

CLASS: XII, CHEMISTRY

UNIT 4: HALOALKNAES & HALOARENES

CASE STUDY BASED QUESTIONS

NATURE OF C–X BOND, SUBSTITUTION REACTIONS
(DIRECTIVE INFLUENCE OF HALOGEN IN MONOSUBSTITUTED COMPOUNDS ONLY)

Sl.No. Read the passage given below and answer the following questions.
CASE STUDY -I
Methyl chloride, methyl bromide, ethyl chloride and some chlorofluoromethanes are gases at room
temperature. Higher members are liquids or solids. As we have already learnt, molecules of organic
halogen compounds are generally polar. Due to greater polarity as well as higher molecular mass as
compared to the parent hydrocarbon, the intermolecular forces of attraction (dipole-dipole and van der
Waals) are stronger in the halogen derivatives. That is why the boiling points of chlorides, bromides
and iodides are considerably higher than those of the hydrocarbons of comparable molecular mass. The
attractions get stronger as the molecules get bigger in size and have more electrons. For the same alkyl
group, the boiling points of alkyl halides decrease in the order: RI> RBr> RCl> RF. This is because
with the increase in size and mass of halogen atom, the magnitude of van der Waal forces increases.
The boiling points of isomeric haloalkanes decrease with increase in branching . For example, 2-
bromo-2- methylpropane has the lowest boiling point among the three isomers. Boiling points of
isomeric dihalobenzenes are very nearly the same.
(i) Boiling point and melting point of alkyl halides increase as
(a) Alkyl group increases in size
(b) Size of halogen atom increases
(c) Branching decreases
(d) All of the above
(ii) The intermolecular forces of attraction are stronger in halogen derivatives of
alkanes. The kind of intermolecular forces are
(a) Dipole dipole interaction
(b) Van der waals force of attraction
(c) Both of above
(d) None of these
(iii) Which of the following has the highest boiling point?
(a) Chlorobutane
(b) Iodobutane
(c) Bromobutane
(d) Flourobutane
(iv) Which of the following gas is an environmental hazard?

ZIET, Bhubaneswar, 6-Oct-21 1

 (a) Methyl chloride
(b) Ethyl bromide
(c) Methyl bromide
(d) Chlorofluoromethane

CASE STUDY -II

Read the passage given below and answer the following questions :
A primary alkyl halide (A) C4H9Br reacted with alcoholic KOH to give compound B .
Compound B reacted with HBr to give compound (C) which is an isomer of (A). when (A)
reacted with sodium metal , it gave a compound (D) C8H18 that is different than the
compound obtained when n-butyl bromide reacted with sodium metal.
(i) Compound (A) is
a. 1-bromobutane
b. 1-bromo-2-methylpropane
c. Tert-butyl bromide
d. 1-bromopropane

(ii) Which type of isomerism is present in compound (A) & (C)?

a. position
b. function
c. Chain
d. Both a and c

(iii) Compound (B) is :

a. 2-methylpropene
b. But-2-ene
c. But-1-ene
d. None of these

(iv) IUPAC name of compound (D) is:

a. n-octane
b. 2,5-dimethylhexane
c. 2-methylhepatne

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 d. 3,4-dimethylhexane

(v) When compound ( C) is treated with alc.KOH and then treated with HBr in presence of
peroxide , the compound obtained is :
a. Tert-butyl bromide
b. 1-bromo-2-methylpropane
c. n-butyl bromide
d. 1-bromo-1-methylbutane

CASE STUDY -III

Polarity of carbon-halogen bond is responsible for the nucleophilic substitution reactions of
alkyl halides which mostly occur by SN1 and SN2 mechanisms. The rates of SN2 reactions
among other things are governed by the steric factor while that of SN1 reactions are governed
by stability of intermediate carbocations. Chirality has a profound role in understanding the
mechanism of SN1& SN2 reactions. Whereas SN2 reactions of chiral alkyl halides are
accompanied by inversion of configuration, SN1 reactions are characterised by racemisation.
(i) Solvolysis of neopentyl chloride in ethanol mainly gives
(a) neo pentyl alcohol
(b) tert butyl ethyl ether
(c) 2-methylbutan-2-ol
(d) 2-ethoxy-2-methylbutane
(ii) Which of the following are true for SN1 reactions?
(a) Favoured by polar solvent.
(b) Tertiary alkyl halides generally react by SN1 mechanism.
(c) the rate of the reactiondoes not depend upon the molar concentration of nucleophile.
(d) All statements are correct.
(iii) Which of the following statement are not true about SN2 reactions?
(a) They occur through a single transition state.
(b) They are favoured by polar protic solvents.
(c) They are stereo specific reactions.
(d) They are stereo selective reaction.
(iv) Reaction of C6H5CH2Br with aqueous NaOH follows
(a) SN1 mechanism
(b) SN2 mechanism
(c) any one of the above two depending upon the temperature.

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 (d) Saytzeff rule.
CASE STUDY -IV
Nucleophilic substitution reactions are of two types; substitution nucleophilic bimolecular
(SN2) and substitution nucleophilic unimolecular (SN1) depending on molecules taking part in
determining the rate of reaction. Reactivity of alkyl halide towards SN1 and SN2 reactions
depends on various factors such as steric hindrance, stability of intermediate or transition state
and polarity of solvent. SN2 reaction mechanism is favoured mostly by primary alkyl halide or
transition state and polarity of solvent, SN2 reaction mechanism is favoured mostly by primary
alkyl halide then secondary and then tertiary. This order is reversed in case of SN1 reactions.
(i)Which of the following is most reactive towards nucleophilic substitution reaction?
(a) C6H5Cl
(b) CH2=CHCl
(c) ClCH2CH=CH2
(d) CH3CH=CHCl

(ii) Isopropyl chloride undergoes hydrolysis by

(a) SN1 mechanism
(b) SN2 mechanism
(c) Either SN1 and SN2 mechanism depends upon solvent
(d) neither SN1 nor SN2 mechanism

(iii) The most reactive nucleophile among the following is

(a) CH3O-
(b) C6H5O-
(c) (CH3)2CHO-
(d) (CH3)3CO-

(iv) Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of
(a) insolubility
(b) instability
(c) inductive effect
(d) steric hindrance

(v)Which of the following is the correct order of decreasing SN2 reactivity?

(a) RCH2X > R2CHX > R3CX

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 (b) R3CX > R2CHX >RCH2X
(c) R2CHX >R3CX > RCH2X
(d) RCH2X >R3CX >R2CHX

Answers of case study questions

NATURE OF C–X BOND,
ANSWER KEY
SUBSTITUTION REACTIONS
(DIRECTIVE INFLUENCE OF HALOGEN IN MONOSUBSTITUTED COMPOUNDS ONLY)

CASE Answers CASE Answers CASE Answers CASE Answers

STUDY -I STUDY - STUDY - STUDY -
II III IV
(i) d (i) b (i) c (i) c
(ii) c (ii) a (ii) d (ii) c
(iii) b (iii) a (iii) b (iii) b
(iv) d (iv) b (iv) a (iv) d
(v) b (v) a

The questions submitted by the PGTs (Chemistry) of KVs of Bhubaneswar, Guwahati, Kolkata,
Ranchi, Silchar and Tinsukia Regions.
Vetted by:
Mr. Alok Kumar Pandey, PGT (Chemistry), KV Paradip Port, Bhubaneswar Region.
Email: chemalok1734@gmail.com Ph No. 93865975535

ZIET, Bhubaneswar, 6-Oct-21 5

 QUESTION BANK
CLASS: XII, CHEMISTRY
UNIT 4: HALOALKNAES & HALOARENES
CASE/SOURCE BASED QUESTIONS
IUPAC NAME, NATURE OF C-X BOND AND REACTIVITY TOWARD NUCLEOPHILIC
SUBSTITUTION REACTION

Sl.No. Read the passage given below and answer the following questions……..
1 CASE STUDY -I
Haloarenes are less reactive than haloalkanes. The low reactivity of haloarenes can be
attributed to
o Resonance effect
o sp2 hybridisation of C – X bond
o polarity of C – X bond
o instability of phenyl cation
o repulsion between the electron rich attacking nucleophiles and electron rich arenes.
Reactivity of haloarenes can be increased or decreased by the presence of certain groups at
certain positions for example, nitro( –NO2) group at -o and -p positions increases the
reactivity of haloarenes towards nucleophilic substitution reactions.
(i) Aryl halides are less reactive towards nucleophilic substitution reaction as compared
to alkyl halides due to
(a) the formation of less stable carbonium ion
(b) resonance stabilization
(c) larger carbon – halogen bond
(d) inductive effect
(ii) Which of the following aryl halides is the most reactive towards nucleophilic
substitution?
(a)

(b)

(c)

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 (d)

(iii) Which of the following will react fastest with aqueous NaOH?
(a)

(b)

(c)

(d)

(iv) Which chloro derivative of benzene among the following would undergo hydrolysis
most readily with aqueous sodium hydroxide to furnish the corresponding hydroxy
derivative?
(a) (b)

(c)

(v) The reactivity of the compounds (i) MeBr, (ii) PhCH₂Br, (iii) MeCl, (iv) p-MeOC6H4Br
decreases as

(a) (i) > (ii) > (iii) > (iv)

(b) (iv) > (ii) > (i) > (iii)
(c) (iv) > (iii) > (i) > (ii)
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 (d) (ii) > (i) > (iii) > (iv)
(vi) The reactivity of the compounds (i)p-NO2C6H4Br (ii) PhCH2Br (iii) p-
NO2C6H4Cl (iv) m-NO2C6H4Br towards nucleophilic substitution decreases as

(a) (i) > (ii) >(iii) > (iv)

(b) (iv) > (ii) >(i) > (iii)

(c) (iv) > (iii) >(i) > (ii)

(d) (ii) > (i) > (iii) > (iv)

CASE STUDY -II
Marine organisms that can use chloride and bromide available in the ocean waters are
capable of producing haloarenes. Haloarenes is present widely in nature and they have been
known to exhibit several medicinal properties. Thus, various reactions of haloarenes occur
artificially as well as in nature. Many other chlorinated and brominated aromatic compounds
such as tryptophan, tyrosine and many other derivatives of pyrrole are also present in nature.
Haloarenes undergo the usual electrophilic reactions of the benzene ring such as
halogenation, nitration, sulphonation and Friedel-Crafts reactions.
Due to –I effect (electron withdrawing nature) of halogen, benzene ring gets somewhat
deactivated towards electrophilic substitution reaction.
Thus, these reactions occur slowly and require more drastic conditions as compared to those
2.
in benzene.
Due to its various resonating structures, there’s an excess of electron or negative charge over
ortho- and para- positions of the ring than the meta- position. Thus, haloarenes are o- and p-
directive towards electrophilic substitution reaction.
Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes
with chlorine and bromine respectively in the presence of Lewis acid catalysts. But
preparation of aryl iodides requires presence of an oxidising agents such as HgO, HNO3
whichare used to remove HI produced in the reaction as follows:
4HI + 2HNO3 → 2N2O3 + 2I2
Choose the most appropriate answer:
(i)Toluene reacts with Br2 in the presence of sunlight to give
(a) o-bromo toluene
(b) p-bromotoluene
(c) m-bromotoluene
(d) Benzylbromide
(ii)A compound ‘A’ with molecular formula, C7H8 is treated with Cl2 in the presence of
FeCl3. Compound A is
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 (a) p-chlorotoluene
(b) m-chlorobenzene
(c) benzylchloride
(d) None of these
(iii)The ortho and para isomers formed by electrophilic substitution of arenes can be easily
separated due to the large difference in their …
(a) Densities
(b) Solubilities
(c) Melting points
(d) Boiling points
(iv)In the iodination of benzene, which compound causes the reduction of iodobenzene back
to benzene?
(a) Iodic acid
(b) Hydogen iodide
(c) Nitric acid
(d) Mercuric oxide

Case-Study answer:
Case-Study Case-Study
I II
(i) b (i) d
(ii) d (ii) a
(iii) c (iii) c
(iv) a (iv) b
(v) c
(vi) a

The questions submitted by the PGTs (Chemistry) of KVs of Bhubaneswar, Guwahati,

Kolkata, Ranchi, Silchar and Tinsukia Regions.
Vetted by:
Mr Alok Kumar Pandey, PGT (Chemistry), KV Paradip Port, Bhubaneswar Region.
Email: chemalok1734@gmail.com Ph No. 93865975535

ZIET Bhubaneswar, 06 October 2021 4

 QUESTION BANK
CLASS: XII, CHEMISTRY
UNIT 4: HALOALKNAES & HALOARENES
CASE/SOURCE BASED QUESTIONS:
ELECTROPHILIC SUBSTITUTION REACTION AND THEIR TYPES
Sl.No. Read the passage given below and answer the following questions……..

CASE STUDY -I
1.
Halobenzenes give electrophilic reactions like benzene as it increases the electron
density on benzene. It gives many electrophilic reactions likeNitration, Halogenation,
Sulphonation, Friedel Craft reactions. It gives a few nucleophilic reactions as well
but in drastic conditions it gives many more.
(i)What is the name of electrophile which formed when nitration on Benzenes occurs in
electrophilic substitution reactions?
a) Nitronium b) Nitride
c) Nitrite d) Azide
(ii)In which of the following electrophilic reactions involve a neutral electrophile?
a) Halogenation b) Sulphonation
c) Friedel craft Alkylation d) Friedel craft acylation
(iii)Which of the following effects is/are shown by halogen when present on benzene ring
a) -I b) +R
c) Both a and b d) +I and -R
(iv) Which of the following statements is correct about the -I and +R effect of Cl and Br?
a) -I effect of Cl is stronger than +R b) -I effect of Cl is weaker than +R
c) Both are stronger d) Both are weaker

CASE STUDY -II

Haloarenes can be prepare by following methods:
By electrophilic substitution
Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes
with chlorine and bromine respectively in the presence of Lewis acid catalysts like iron or
2. iron(III) chloride. The ortho and para isomers can be easily separated due to large
difference in their melting points. Reactions with iodine are reversible in nature and
require the presence of an oxidising agent (HNO3, HIO4) to oxidise the HI formed during
iodination. Fluoro compounds are not prepared by this method due to high reactivity of
fluorine.

Sandmeyer’s reaction
When a primary aromatic amine, dissolved or suspended in cold aqueous mineral acid, is
treated with sodium nitrite, a diazonium salt is formed (Unit 13, Class XII). Mixing the
solution of freshly prepared diazonium salt with cuprous chloride or cuprous bromide
ZIET Bhubaneswar, 06-10-21 1
 results in the replacement of the diazonium group by –Cl or –Br.
Replacement of the diazonium group by iodine does not require the presence of cuprous
halide and is done simply by shaking the diazonium salt with potassium iodide.

(i).The reagent used in Gatterman reaction is

(a) Cu/HBr (b) CuBr/HCl (c) CuCl2/HCl (d) KI

(ii).Toluene on reaction with Cl2 in presence of Fe gives

(a) 1,2-diChloro toluene (b) O,& p chlorotoluene (c) Bromobenzene (d) benzene

(iii).Preparation od diazonium salt from aniline is known as

(a) chlorination (b) Swartreaction (c) Diazotization (d) Free radical halogenation

(iv).Side chain halogenation of haloarenes takes place in presence of

(a) HNO3 (b) Sunlight or hv (c) in dark (d) HCl

Case-Study answer:
Case-Study I Case-Study II
(i) a (i) a
(ii) b (ii) b
(iii) c (iii) c
(iv) a (iv) b

The questions submitted by the PGTs (Chemistry) of KVs of Bhubaneswar, Guwahati,

Kolkata, Ranchi, Silchar and Tinsukia Regions.
Vetted by: BHUBANESWAR REGION

ZIET Bhubaneswar, 06-10-21 2