6.
HALOALKANES AND HALOARENES
Class 12 - Chemistry
Time Allowed: 3 hours Maximum Marks: 70
General Instructions:
Read the following instructions carefully.
(a) There are 33 questions in this question paper with internal choice.
(b) SECTION A consists of 16 multiple -choice questions carrying 1 mark each.
(c) SECTION B consists of 5 short answer questions carrying 2 marks each.
(d) SECTION C consists of 7 short answer questions carrying 3 marks each.
(e) SECTION D consists of 2 case - based questions carrying 4 marks each.
(f) SECTION E consists of 3 long answer questions carrying 5 marks each.
(g) All questions are compulsory.
(h) Use of log tables and calculators is not allowed.
Section A
1. Which reagent will you use for the following reaction?
CH3CH2CH2CH3 → CH3CH2CH2CH2Cl + CH3CH2CHClCH3
a) Cl2 gas in the presence of iron in dark b) NaCl + H2SO4
c) Cl2 gas in dark d) Cl2/UV light
2. IUPAC name of (CH3)3CCl is:
a) n – butyl chloride b) 3 – chloro butane
c) t – butyl chloride d) 2-chloro, 2-methyl propane
3. The preparation of alkyl chloride is carried out by:
a) constant boiling of alcohol with HCl. b) passing dry hydrogen chloride gas through a
solution of alcohol.
c) heating alcohol with potassium chloride. d) heating alcohol with sodium chloride.
4. Methyl bromide is converted into ethane by heating it in ether medium with:
a) Na b) Cu
c) Al d) Zn
5. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro compound C5H9Cl in bright
sunlight. The hydrocarbon is
1/6
a) Cyclopentene b) Cyclosporine
c) Cycloalkyne d) Cyclopentane
6. Inversion of configuration occurs in
a) SN1 as well as SN2 reaction b) SN1 reaction
c) Neither SN2 nor SN1 reaction d) SN2 reaction
7. The reaction of ammonia with a large excess of methyl chloride will yield mainly:
a) methylamine b) trimethylamine
c) tetramethylammonium chloride d) dimethylamine
8. In which of the following molecules carbon atom marked with an asterisk (*) is asymmetric?
a.
b.
c.
d.
a) (b), (c), (d) b) (a), (b), (c)
c) (a), (b), (c), (d) d) (a), (c), (d)
9. Which is the correct increasing order of boiling points of the following compounds?
1-Iodobutane, 1-Bromobutane, 1-Chlorobutane, Butane
a) Butane < 1-Iodobutane < 1-Bromobutane < b) Butane < 1-Chlorobutane < 1-Iodobutane <
1-Chlorobutane 1-Bromobutane
c) Butane < 1-Chlorobutane < 1-Bromobutane d) 1-Iodobutane < 1-Bromobutane < 1-
< 1-Iodobutane Chlorobutane < Butane
10. Which of the following isomer of pentane (C5H12) will give three isomeric monochlorides on photochemical
chlorination?
a) CH3
|
b) CH3 − C H − CH2 − CH3
|
CH3 − C CH3
|
CH3
c) CH3CH2CH2CH2CH3 d) CH3
CH3 − C − CH3
|
CH3
2/6
11. Chlorobenzene is formed by the reaction of chlorine with benzene in the presence of AlCl3. Which of the following
species attacks the benzene ring in this reaction?
a) AlCl3 b) [AlCl ]–
4
c) Cl+ d) Cl-
12. Hydrocarbons having double the number of carbon atoms than present in the original alkyl halide are produced by using:
a) Sandmeyer’ reaction b) Williamson’s synthesis
c) Fittig reaction d) Wurtz reaction
13. Assertion (A): Reaction of alcohol with SOCl2 is SNi reaction.
Reason (R): In SNi reaction inversion of configuration occur.
a) Both A and R are true and R is the correct b) Both A and R are true but R is not the
explanation of A. correct explanation of A.
c) A is true but R is false. d) A is false but R is true.
14. Assertion (A): Vinyl chloride is less reactive than alkyl chloride.
Reason (R): Stability of alkyl halide decreases as the strength of C-X bond decreases.
a) Both A and R are true and R is the correct b) Both A and R are true but R is not the
explanation of A. correct explanation of A.
c) A is true but R is false. d) A is false but R is true.
15. Assertion (A): Ethanol gives iodoform test while methanol does not.
Reason (R): Ethanol is less reactive than methanol towards nucleophilic addition reactions.
a) Both A and R are true and R is the correct b) Both A and R are true but R is not the
explanation of A. correct explanation of A.
c) A is true but R is false. d) A is false but R is true.
16. Assertion (A): Boiling point of RCl is greater than RF.
Reason (R): R-Cl is more stable than R-F.
a) Both A and R are true and R is the correct b) Both A and R are true but R is not the
explanation of A. correct explanation of A.
c) A is true but R is false. d) A is false but R is true.
Section B
17. How will you obtain monobromobenzene from aniline?
18. Why is the solubility of haloalkanes in water very low?
19. 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.
20. Give the structure of 1,3-dichloro -2-(bromomethyl) propane
21. How may methyl bromide be preferentially converted to methyl cyanide and methyl isocyanide?
OR
Explain ambident nucleophiles with the help of examples.
Section C
3/6
22. In each of the following pairs of compounds, identify the compound which will undergo SN1 reaction faster.
i. and
ii. and
23. Write the structures of the following organic halogen compounds.
i. 2-(2-Chlorophenyl)-1-iodooctane
ii. 2-Bromobutane
iii. 4-tert-Butyl-3-iodoheptane
24. Write a test to detect the presence of a double bond in a molecule.
25. Haloarenes are less reactive than haloalkanes and haloalkenes. Explain.
26. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro compound C5H9Cl in bright
sunlight. Identify the hydrocarbon.
27. Compound A with molecular formula C4H9Br is treated with aq. KOH solution. The rate of this reaction depends upon
the concentration of the compound A only. When another optically active isomer B of this compound was treated with
aq. KOH solution, the rate of reaction was found to be dependent on concentration of compound and KOH both.
i. Write down the structural formula of both compounds A and B.
ii. Out of these two compounds, which one will be converted to the product with inverted configuration.
28. Which compound in each of the following pairs will react faster in SN2 reaction with OH-?
i. CH3Br or CH3I
ii. (CH3)3CCl or CH3Cl
OR
Elimination reactions (especially β-elimination) are as common as the nucleophilic substitution reaction in case of
alkyl halides. Specify the reagents used in both cases.
Section D
29. Read the text carefully and answer the questions:
Nucleophilic Substitution
Nucleophilic Substitution reaction of haloalkane can be conducted according to both SN1 and SN2 mechanisms. SN1
is a two step reaction while SN2 is a single step reaction. For any haloalkane which mechanism is followed depends
on factors such as structure of haloalkane, properties of leaving group, nucleophilic reagent and solvent.
Influences of solvent polarity : In SN1 reaction, the polarity of the system increases from the reactant to the transition
state, because a polar solvent has a greater effect on the transition state than the reactant, thereby reducing activation
energy and accelerating the reaction. In SN2 reaction, the polarity of the system generally does not change from the
reactant to the transition state and only charge dispersion occurs. At this time, polar solvent has a great stabilizing
effect on Nu than the transition state, thereby increasing activation energy and slow down the reaction rate. For
example, the decomposition rate (SN1) of tertiary chlorobutane at 25oC in water (dielectric constant 79) is 300000
times faster than in ethanol (dielectric constant 24). The reaction rate (SN2) of 2-Bromopropane and NaOH in ethanol
containing 40% water is twice slower than in absolute ethanol. Hence the level of solvent polarity has influence on
4/6
both SN1 and SN2 reaction, but with different results. Generally speaking weak polar solvent is favourable for SN2
reaction, while strong polar solvent is favourable for SN1. Generally speaking the substitution reaction of tertiary
haloalkane is based on SN1 mechanism in solvents with a strong polarity (for example ethanol containing water).
(a) Why racemisation occurs in SN1?
(b) Why is ethanol less polar than water?
(c) Which one of the following in each pair is more reactive towards SN2 reaction?
i. CH3 - CH2 - I or CH3CH2 - Cl
ii. or
(d) Arrange the following in the increasing order of their reactivity towards SN1 reactions:
i. 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
ii. 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane
30. Read the text carefully and answer the questions:
The substitution reaction of alkyl halides occurs in S N
1
or S N
2
mechanism. Whatever mechanism alkyl halide follow
for substitution reaction to occur, the polarity of the carbonhalogen bond is responsible for the substitution reaction.
The rate of S N
1
reactions are governed by the stability of carbocation where as for S N
2
reactions steric factor is the
deciding factor. If the starting material is a chiral compound, we may end up with an inverted product or racemic
mixture depending upon the type of mechanism followed by alkyl halide. Cleavage 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
in deciding the kind of product formed.
(a) Predict the stereochemistry of the product formed if optically active alkyl halide undergoes substitution
reaction by S N
1
mechanism.
OR
Which will undergo SN2 reaction faster?
(CH3)3CCl or CH3Cl
(b) Name the instrument used for measuring the angle by which the plane polarised light is rotated.
OR
What is chirality?
(c) Predict the major product formed when 2-bromopentane reacts with alcoholic KOH.
OR
Predict the major product formed when 2,2,3-Trimethyl-3-bromopentane reacts with alcoholic KOH.
(d) Write the structure of the products formed when anisole is treated with HI.
OR
Write the structure of the product formed when t-butyl chloride is treated with Na.
Section E
31. Why are aryl halides less reactive towards nucleophilic substitution reactions than alkyl halides? How can we
enhance the reactivity of aryl halides?
OR
Convert:
i. Benzene to Aniline
ii. Benzene to m-Nitrochlorobenzene
5/6
iii. Benzene to Diphenyl
iv. Benzene to p-Chlorotoluene
32. Wurtz reaction fails in case of tert-alkyl halides. Explain.
OR
Diphenyls are potential threat to the environment. How are these produced from arylhalides?
33. 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 gives compound (d), C
8 H18
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.
OR
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?
6/6
