IMPORTANT QUESTIONS CLASS – 12 &+(0,675<
CHAPTER – 6 HALOALKANES AND HALOARENES
i
Question 1- Among the following pairs which one undergoes SN2 substitution
reaction faster. State reasons.
rth
(i)
(ii)
Answer: (i) It undergoes SN2 reaction faster as it is a primary
halide.
(ii) Due to its large size, Iodine is a better leaving group,
ya
therefore, in the presence of an incoming nucleophile, it will
be released at a faster rate.
Question 2- Among the following pairs which one undergoes SN1
substitution reaction faster. State reasons.
id
(i)
(ii)
Answer: i) Tertiary halide reacts faster than secondary halide
because of the greater stability of tert-carbocation.
eV
(ii) Because of the greater stability of secondary
carbocation than primary.
Question 3- How can the following
conversions be carried out?
(i) Methyl magnesium bromide to 2-methyl- propan-2-ol
(ii) Benzyl chloride to benzyl alcohol
(iii) 2-Bromopropane to 1-bromopropane
https://www.evidyarthi.in/
(iv) Benzene to p-chloronitrobenzene
Answer: (i)
i
(ii)
rth
(iii)
(iv)
ya
Question 4- Although chlorine is an electron-withdrawing group, yet it is ortho-,
id
para- directing in electrophilic aromatic substitution reactions. Why?
Answer: Chlorine withdraws electrons through inductive effect and releases electrons
through resonance. Through inductive effect, chlorine destabilised the intermediate
carbocation formed during the electrophilic substitution. Through resonance, halogen tends
to stabilise the carbocation and the effect is more pronounced at the ortho- and para-
eV
positions. The inductive effect is stronger than resonance and causes net electron withdrawal
and thus causes net deactivation. The resonance effect tends to oppose the inductive effect
for the attack at the ortho- and para positions and hence makes the deactivation less for
ortho- and para attack. Reactivity is thus controlled by the stronger inductive effect and
orientation is controlled by resonance effect.
https://www.evidyarthi.in/
i
rth
Question 5- State reasons for:
(i) p-dichlorobenzene has a higher melting point than its o- and m-isomers.
(ii) (±)-Butan-2-ol is optically inactive.
ya
(iii) The C–Cl bond length in chlorobenzene is shorter than that in CH3–Cl.
(iv) Chloroform is stored in closed dark brown bottles.
(v) Alkyl halides, though polar, are immiscible with water.
Answer: (i) p-isomers are comparatively more symmetrical, fits closely in the crystal lattice.
Therefore, they require more heat to break the strong forces of attraction. As a result, p-
id
isomers have a higher melting point than o- and m-isomers.
(ii) In a racemic mix, one type of rotation is cancelled by
another. Therefore, (±)-Butan-2-ol is optically inactive.
(iii) The C–Cl bond length in chlorobenzene is shorter than
eV
that in CH3–Cl as in haloalkanes, the halogen atom is
attached to sp3 hybridized carbon whereas in haloarenes it is attached to sp2 hybridized
carbon whose size is smaller than sp3 orbital carbon.
(iv) Chloroform is stored in closed dark brown bottles because chloroform gets slowly
oxidised by air in the presence of light and forms an extremely poisonous gas (carbonyl
chloride), popularly known as phosgene.
https://www.evidyarthi.in/
(v) Alkyl halides are polar molecules
that are held together by dipole-dipole
interaction. The molecules of H2O are
held together by H- bonds. The forces
of attraction between water and alkyl
halide molecules are weaker than the
existing forces of attraction between
i
alkyl halide-alkyl halide molecules and water-water molecules.
rth
Question 6- Identify chiral and achiral molecules in each of the following pair
of compounds:
(i)
(ii)
(iii)
Answer: (i)
(ii)
(iii)
ya
id
eV
Question 7- Define:
(i) ambident nucleophiles
(ii) racemic mixture
(iii) Sandmeyer’s reaction
https://www.evidyarthi.in/
Answer: (i) Groups like cyanides and nitrites possess two nucleophilic centres and are
called ambident nucleophiles. Cyanide group is a hybrid of two contributing structures and
can act as a nucleophile in two different ways [VC≡N ↔ :C=NV], i.e., linking through carbon
atoms resulting in alkyl cyanides and through nitrogen atoms leading to isocyanides.
(ii) A mixture containing two enantiomers in equal proportions will have zero optical
rotation, as the rotation due to one isomer will be cancelled by the rotation due to the other
i
isomer. Such a mixture is known as a racemic mixture or racemic modification. A racemic
mixture is represented by prefixing dl or (±) before the name, for example (±) butan-2-ol.
rth
The process of conversion of enantiomer into a racemic mixture is known as racemisation.
(iii) When a primary aromatic amine, dissolved or suspended in cold aqueous mineral acid,
is treated with sodium nitrite, a diazonium salt is formed. Mixing the solution of the freshly
prepared diazonium salt with cuprous chloride or cuprous bromide 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.
ya
id
Question 8- Write the structures
for the following:
eV
(i) 4-tert-Butyl-3-iodoheptane
(ii) 4-Bromo-3-methylpent-2-ene
(iii) p-Bromochlorobenzene
(iv) 1-Chloro-4-ethylcyclohexane
Answer: (i)
https://www.evidyarthi.in/
(ii)
(iii)
(iv)
Question 9- Give reasons:
i
(i) Grignard’s reagents should be
prepared under anhydrous conditions.
rth
(ii) n-Butyl bromide has a higher boiling
point than f-butyl bromide.
Answer: (i) Grignard’s reagents react with alcohol, water, amines etc.
to form the corresponding hydrocarbon and thus, must be prepared
under anhydrous conditions.
R-MgX + HOH → RH + Mg(OH)X
ya
(ii) n-Butyl bromide has a higher boiling point than f-butyl bromide as
it has a larger surface area. Therefore, it has more Van der Waals’ forces.
Question 10- What happens when:
(i) Chlorobenzene is treated with Cl2/FeCl3
(ii) Ethyl chloride is treated with AgNO2
id
(iii) 2-bromopentane is treated with alcoholic KOH
Answer: (i)
(ii)
eV
(iii)
https://www.evidyarthi.in/
