5.HALOALKANES AND HALOARENES

SESSION 2024-25
AS PER NEW NTA SYLLABUS
CHAPTER 05
HALOALKANES AND
HALOARENES
Chemistry Smart Booklet

Theory + NCERT
MCQs+Topicwise Practice
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CHEMISTRY HALOALKANES AND HALOARENES
3|Page
HALOALKANES AND HALOARENES
Polyhalogen Compounds
Polyhalogen compounds: Carbon compounds containing more than one halogen atom
permolecule.
Polyhalogen compounds are useful in various industries and in agriculture.

Some important polyhalogen compounds:
Dichloromethane
(Methylene chloride)
p,p'-Dichlorodiphenyl- Trichloromethane
trichloroethane (DDT) (Chloroform)
Polyhalogen
Compounds
Freons Triiodomethane
(Iodoform)
Tetrachloromethane
(Carbon tetrachloride)
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Dichloromethane (Methylene chloride)
Uses:
Dichloromethane (methylene chloride) is used as a:
1. Solvent for paint removers

2. Propellant in aerosols
3. Process solvent in the manufacture of drugs
4. Metal cleaning and finishing solvent
Harmful effects:
1. It endangers the human central nervous system.

2. Exposure to lower levels of methylene chloride in air can lead to slightly
impaired hearing andvision.
3. High levels of methylene chloride in air cause dizziness, nausea, tingling and
numbness in thefingers and toes.
4. In humans, direct skin contact with methylene chloride causes intense
burning and mild rednessof the skin.
5. Direct contact with the eyes can burn the cornea.
Trichloromethane (Chloroform)
Uses:
1. Chemically, chloroform is used as a solvent for fats, alkaloids, iodine and other
substances.
2. The major use of chloroform today is in the production of the freon refrigerant
R-22.
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3. It was once used as a general anaesthetic in surgery but has been replaced
by less toxic, saferanaesthetics such as ether.
Harmful effects:
1. As might be expected from its use as an anaesthetic, inhaling chloroform vapour
depresses the central nervous system.
2. Breathing about 900 parts of chloroform per million parts of air (900 ppm) for a
short time can cause dizziness, fatigue and headache.
3. Chronic chloroform exposure may cause damage to the liver (where chloroform
is metabolised to phosgene) and to the kidneys. Some people develop sores
when the skin is immersed inchloroform.
4. Chloroform is slowly oxidised by air (oxygen) in the presence of light to an
extremely poisonous gas, carbonyl chloride, also known as phosgene.
It is therefore stored in closed dark-coloured bottles which are completely

filled so that air is keptout.
Triiodomethane (Iodoform)
Uses:
• It was used earlier as an antiseptic, but the antiseptic properties are due to
the liberation of freeiodine and not due to iodoform itself.
Drawback:
• Because of its objectionable smell, it has been replaced by other formulations
containing iodine.
Tetrachloromethane (Carbon tetrachloride)
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Uses:
1. It is produced in large quantities for use in the manufacture of refrigerants
and propellants foraerosol cans.
2. It is also used as feedstock in the synthesis of chlorofluorocarbons and
other chemicals, inpharmaceutical manufacturing and general solvent use.
3. Until the mid-1960s, it was also widely used as a cleaning fluid, both in
industry, as a degreasingagent, and in the home, as a spot remover and fire
extinguisher.
Harmful effects:
1. There is evidence that exposure to carbon tetrachloride causes liver cancer in
humans.
2. The most common effects are dizziness, light headedness, nausea and
vomiting, which cancause permanent damage to nerve cells.
3. In severe cases, these effects can lead rapidly to stupor, coma, unconsciousness
or death. Exposure to CCl4 can make the heart beat irregularly or stop.
4. The chemical may irritate the eyes on contact. When carbon tetrachloride is
released into the air,it rises to the atmosphere and depletes the ozone layer.
5. Depletion of the ozone layer is believed to increase human exposure to
ultraviolet rays, leading toincreased skin cancer, eye diseases and disorders, and
possible disruption of the immunesystem.
Freons
• The chlorofluorocarbon compounds of methane and ethane are collectively

known as freons.
• They are extremely stable, unreactive, non-toxic, non-corrosive and easily
liquefiable gases.
• They are manufactured from tetrachloromethane by Swarts reaction.
• By 1974, the total freon production in the world was about 2 billion pounds
annually.
Uses:
1. These are usually produced for aerosol propellants, refrigeration and air
conditioning purposes.
2. Freon 12 (CCl2F2) is one of the most common freons in industrial use.
3. Most freons, even those used in refrigeration, eventually make their way
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into the atmospherewhere it diffuses unchanged into the stratosphere.
Harmful Effect:
• In stratosphere, freons can initiate radical chain reactions which can upset
the natural ozonebalance.
p,p′-Dichlorodiphenyltrichloroethane (DDT)
DDT, the first chlorinated organic insecticide, was originally prepared in 1873.
However, it was not until 1939 that Paul Muller of Geigy Pharmaceuticals in
Switzerland discovered theeffectiveness of DDT as an insecticide.
Paul Muller was awarded the Nobel Prize in Medicine and Physiology in 1948
for this discovery.
Paul Muller
Uses:
• The use of DDT increased enormously worldwide after World War II,
primarily because of itseffectiveness against the mosquito which spreads
malaria and lice which carry typhus.
Harmful Effects:
Problems related to extensive use of DDT began to appear in the late 1940s.
1. Many species of insects developed resistance to DDT.
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2. It has a high toxicity towards fish.
3. The chemical stability of DDT and its fat solubility compounded the problem.
DDT is not metabolised very rapidly by animals. Instead, it is deposited and
stored in the fatty tissues. If ingestion continues at a steady rate, DDT builds up
within the animal over time.
The use of DDT was banned in the United States in 1973, although it is still in
use in some other parts ofthe world.
Preparation
Methods of Preparation of haloalkanes
By halogenations of alkanes in presence of light, catalyst or heat:
By halogenations of alkenes with HX :
Hunsdiecker reactions:
The Hunsdiecker reaction is an instance of a halogenation reaction which
involves an organic between silver salts of carboxylic acids and halogens
resulting in the formation of organic halides.
Allylic halogenations:
9
Preparation of alkyl halides from alcohols:
Treatment of alcohol with HCl in the presence of anhydrous ZnCl2 phosphorous

pentachloride, PX3(P4 + X2)or SOCl2 leads to the preparation of alkyl halide.
By the action of halogen acids:
1 and 2 degree alcohols require anhydrous ZnCl2 while alcohols do not require
ZnCl2. Mixture of conc. HCl and anhydrous ZnCl2 is called Lucas reagent.
Primary and secondary alkyl chlorides are prepared from their respective
alcohols by using HCl gas and anhydrous ZnCl2.
By the action of phosphorous halides:
3ROH + PX3 à 3RX + H3PO3.
Alkyl chlorides can be synthesized by the action of PCl3 or PCl5.
Methods of Preparation
There are primarily 4 different types of preparation techniques of Haloalkanes
and Haloarenes. They include Preparation of Haloalkanes and Haloarenes
from:
• Alcohols
• Hydrocarbons
• Alkenes by addition of hydrogen halides and halogens
• Halogen exchange reaction.
Preparation from Alcohols (Haloalkanes):
The most convenient method of preparation of haloalkane is from alcohols. R-
OH when reacts with suitable reagents, the reaction results in the formation of
R − X. The suitable reagents that help in the reaction are
Concentrated halogen acids (HX)
Phosphorus halides (PX5 or PX3)
Thionyl chloride (SOCl2)
i) The Reaction of Alcohols with Halogen Acid
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An organic compound derivative of alcohol reacts with halogen acid (H-X) to
form haloalkanes as the major product.
Example-Preparation of Chloroalkanes
Preparation of chloroalkane is an example of the reaction of an alcohol with
halogen acid to form haloalkane. In this case, primary alcohol and secondary
alcohol react with HCl acid gas to form haloalkane in the presence of
anhydrous ZnCl2, which act as a catalyst in this reaction.
Preparation of Bromoalkanes
Hydrogen bromide (HBr) reacts with alcohols to form bromoalkanes. Hydrogen
bromide synthesis of the reaction takes place by the reaction of sodium
bromide or potassium bromide and H2SO4 (sulphuric acid). In the reaction
below, NaBr and H2SO4 react to form HBr which further reacts with alcohol.
Example of Preparation of Bromoethane from Ethanol
The tertiary carbonation which occurs due to tertiary alcohols is more stable
than secondary and primary alcohols. Therefore tertiary carbocations offer
more stability in comparison to the primary and secondary form of the
compound. Hence, tertiary is more reactive than primary and secondary. The
order of reactivity is 30 > 20 > 10.
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Additionally, the reactivity of haloacids follows the order HI > HBr > HCl > HF.
HI is easily and highly reacting haloacid among all of them because the HI bond
is weaker than the other three. Therefore, it can be broken easily in
comparison to the other halogen bonds to form H+ and I− ions.
However, this preparation method will not be able to synthesize aryl
halides/haloarenes. C-OH bond in the phenol structure contains partial double
bond character because of the delocalization of lone pair of electrons present
on the oxygen atom of the benzene ring. Therefore, the bond formed in the
structure cannot be easily broken down by any sort of reaction with haloacids.
Ar – OH + HX → No reaction
ii) The Reaction of Alcohols with Phosphorus halides (PX5 or PX3)
This reaction helps in the formation of Chloroalkanes, bromoalkanes, and
iodoalkanes. In this reaction phosphorus halides interchange the functional
group of alcohols (–OH) with the corresponding halides. The reaction is as
follows:
ROH + PCl5 → RCl + POCL3 + HCl
The above reaction is for the formation of alkyl chloride. Similarly, alkyl
bromide or alkyl iodide formation is possible by the reaction of an alcohol with
phosphorus tribromide and triiodide. To achieve the reaction, red phosphorus
reacts with bromine or iodine by in-situ preparation (during the reaction) of
phosphorus tribromide and triiodide.
Note: Fresh preparation of the phosphorus tribromide and phosphorus

triiodide is made with red phosphorus and bromine or iodine due to the
instability of the compounds. Thus, alcohol reacts with phosphorus trihalides
(PX3) to obtain three molecules of alkyl halide. The general overall reaction is.
Example: Reaction of ethanol with PCl3 for the formation of chloroethane
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iii) The Reaction of Alcohols with Thionyl chloride as Suitable Reagent
This reagent is the most preferred and suitable in between the three reactions
of alcohols. Alcohol reacts with Thionyl chloride (SOCl2) to form alkyl chlorides.
However, the by-products formed in this reaction are gaseous in nature.
Therefore, the by-products can easily escape into the atmosphere, leaving the
pure alkyl halide. This method helps in the generation of pure alkyl halide.
2) Preparation of Haloalkanes & Haloarenes from Hydrocarbons

Preparation of Haloalkanes and haloarenes from hydrocarbons is possible by 3
different methods. They are
• Free radical halogenation of haloalkanes
• Electrophilic Substitution Reactions
• Sandmeyer reaction
i) Free Radical Halogenation
Alkyl bromides and alkyl chloride formation are possible by the free radical
halogenation reaction. However, radicals are very non-selective in nature.
Moreover, radicals are non-specific and highly reactive intermediates that
result in the formation of the mixture of products.
For instance bromination or chlorination of free radical results in the formation
of a number of haloalkanes. This causes difficulty in the isolation of a single
product. Therefore it is not the preferred method for the preparation of
haloalkanes. Example- When butane reacts with chlorine in the presence of
light as energy, a mixture of product formation takes place.
ii) Electrophilic Substitution Reaction

This method helps in the preparation of haloarenes such as aryl bromides and
aryl chlorides. Electrophilic substitution forms the aryl bromides and aryl
chlorides by using halogens such as chlorine and bromine in the presence of
Lewis acid. However, the reaction requires the following of certain specific
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condition for the generation of proper electrophile.
For example, the reaction should be conducted in presence of Lewis acid.
Additionally, the reaction must be carried out in the dark. The reactions to
obtain the electrophiles are
The electrophiles in the above reactions are Cl+ and Br+ and HCl and HBr are
the by-products of the reaction. Therefore, the electrophilic substitution
reaction for the preparation of aryl bromide and aryl chloride is
Mechanism of Electrophilic Substitution Reaction

In the above reaction, two different isomers of the aryl chlorides are formed.
They are Ortho and Para isomer. The π-electron in the benzene ring attacks the
Cl+ electrophile to produce an intermediate complex. However, the H+ bond
from the intermediate complex moves in order to compensate for the positive
charge of the carbon atom.
Thus the reaction forms two different isomers of the product-ortho and para.
The melting points of both the isomer differ significantly. And para-isomer has
the higher boiling point than ortho-isomer. Therefore, they can be easily
separated from each other.
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Preparation of aryl chloride and bromide is possible from this reaction. Aryl
fluoride formation is not possible due to the high reactivity of the halogen
fluorine. Additionally, iodine reaction is also not possible as iodine is reversible
in nature. Thus, it requires a strong oxidizing agent such as Conc. HNO3 or HIO4
for the oxidation of HI and converting it to I2. Therefore, driving the reaction in
forwarding direction is difficult and requires a strong oxidizing agent
iii) Sandmeyer’s Reaction
Sandmeyer’s Reaction is a two-step method which includes:
Diazonium salt formation
Diazonium salt reaction with a cuprous halide (Cu2X2)
Primary aromatic amine reacts with sodium nitrite in the presence of cold
mineral acid to form the diazonium salt. In this case, HNO2 is prepared within
the reaction by reacting sodium nitrite and HX in the temperature of 273-278K.
Mechanism of the Sandmeyer’s Reaction

In the first step
NaNO2 + HCl → HNO2 + NaCl
The HNO2 formed in the presence of H+ undergo protonation to form NO+ as
the electrophile. The lone pair of the atom from the primary amine will react
with the electrophile.to form an intermediate compound which further gives
diazonium salt after elimination of H2O. In the second step, the diazonium salt
reacts with cuprous halide to form the respective aryl halide
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3) Haloalkanes & Haloarenes from Alkenes
Haloalkanes and haloarenes preparation is possible by the addition of halogens
(X2) across the double bond of the alkene. It is also possible by the addition of
hydrogen halides (HX). In this halogen can be chlorine, bromine or even iodine.
i) Addition of HX
Alkene can be converted to haloalkane by an electrophilic addition reaction.
Alkene reacts with HX to form R-X. The order of reactivity of halides with
respect to alkenes follows the order HI > HBr > HCl > HF. The general reaction
will be
The reaction, in this case, is an example of a regioselective reaction. In this

type of reaction, we get products in major and minor quantity. Additionally,
the reaction follows Markovnikov′s rule of addition for the determination of
the major product by the addition of across the double bond of the alkene.
According to Markovnikov’s rule, in an addition reaction of unsymmetrical
alkenes, the negative part of the reagent or halogen will attach itself to the
carbon that contains less number of hydrogen atoms. For example, prop-1-ene
reacts with hydrogen bromide to form 2-bromopropane as a major product.
Peroxide effect (Kharash effect)
There is another possibility where the reaction contradicts Markovnikov’s rule.
This effect is known as Peroxide effect/ Kharash effect/ anti-markovnikov’s
rule. In this reaction, alkene reacts with HBr in the presence of peroxide. The
Br- or the negative part of the reagent will attach itself to the carbon having
more number of hydrogen atoms. For example, Prop-1-ene reacts with
hydrogen bromide to form 1-bromopropane as a major product in the
presence of peroxide.
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ii) Addition of Halogens
Similarly, alkenes can also react with halogens (X2). For example, Bromine
reacts with an alkene in the presence of carbon tetrachloride (CCl4) to form
vic-dibromide. It is a common test to determine a double bond or an alkene
compound. The reaction will release reddish brown colour during the reaction.
4) Haloalkanes and Haloarenes from Halogen exchange reaction

i) Finkelstein Reaction
The last method of preparation of haloalkane and haloarene is halogen
exchange reaction. In this reaction, an alkyl chloride or alkyl bromide reacts
with sodium iodide in acetone to form alkyl iodides.
The reaction is an equilibrium reaction so there is a possibility of forming other

products. The solubility difference of alkyl halides in acetone is used for driving
the reaction in the forward direction. We know that sodium iodide is soluble in
acetone but NaCl or NaBr are insoluble. Therefore, they precipitate out in the
reaction which is easy to remove from the reaction mixture.
ii) Swartz Reaction
In this reaction, alkyl fluorides formation is possible by heating of Alkyl
fluorides RBr/RCl. The reaction is carried out in the presence of metallic
fluoride such as SbF3, Hg2F2, AgF, CoF2.
Darzen method: Darzens halogenation is a chemical processs involving the

preparation of alkyl halides from alcohols by treating with reflux of thionyl
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chloride or bromide (SOX2) in the presence of small quantity of a nitrogen base
like tertiary amine or pyridine, or the equivalent hydrochloride.
Alkyl bromides and iodides cannot be prepared by this method. The reason
behind this is that thionyl bromide is unstable and thionyl iodide does not
exist. This method is preferred for preparing alkyl chlorides because here by-
products are gaseous SO2 and HCl which escape easily. But this does not
happen in the method involving phosphorous chloride; hence it is not used for
preparing alkyl chlorides.
Methods of Preparation of aryl halides
Nuclear halogenations:
This method can be used to prepare aryl chlorides and bromides. This is done
by treatment of arene with chlorine or bromine in the absence of sunlight and
in the presence of halogen carrier like AlCl3, FeCl3 etc. at low temperatures. It is
an electrophilic substitution.
From phenol:
However the yield of Chlorobenzene is very poor as the main product is

Triphenyl phosphate.
By Hunsdiecker reaction:
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Raschig process:
Sandmeyer reaction:
Diazonium salts are highly reactive compounds used to prepare arene
derivatives. Treating diazonium salt with copper (I) chloride (Cu2Cl2) or copper
(I) bromide (Cu2Br2) leads to the formation of corresponding haloarene. This
reaction is known as Sandmeyer reaction.
Gattermann reaction:
Haloarenes can also be prepared by reaction of benzene diazonium chloride
with copper powder in the presence of corresponding halogen acid. This
reaction is termed as Gattermann reaction.
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Physical Properties of haloalkanes
o Alkyl halides are colorless in pure state. Bromides and iodides cultivate colour on
exposure to light
o Volatile halogen compounds possess a sweet smell.
o Intermolecular forces of attraction of halogen derivatives are stronger due to greater
polarity and molecular mass as well compared to the parent hydrocarbon thereby
resulting in higher boiling points of chlorides, bromides and iodides compared to
hydrocarbons of equivalent molecular mass.
o The boiling points of alkyl halides for same alkyl group follow the order: RI> RBr> RCl>
RF due to the increase in size and mass of halogen atom thereby increasing the extent
of van der Waal forces.
In isomeric haloalkanes the boiling points decreases with increase in branching.
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o Para-isomers possess high melting point compared to ortho and meta-isomers due to
the symmetry of para-isomers fitting in crystal lattice better than ortho- and meta-
isomers.
o Density increases with increase in number of carbon atoms, halogen atoms and
atomic mass of the halogen atoms. Consequently the density of Bromo, iodo and
polychloro derivatives of hydrocarbons is greater than water.
o The haloalkanes are only very slightly soluble in water due to release of less energy
during the setup of new attractions between the haloalkane and the water molecules
which in turn is insufficient to overcome the attractions between the haloalkane
molecules and break the hydrogen bonds between water molecules.
o Haloalkanes dissolves easily in organic solvents due to the new intermolecular forces
of attractions between haloalkanes and solvent molecules having equivalent strength
as the one that is broken in separate haloalkane and solvent molecules.
Problem: Arrange each set of compounds in order of increasing boiling points.
1. Bromomethane, Bromoform, Chloromethane, Dibromomethane.
2. 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.

Solution:
Haloalkanes are hydrocarbons in which hydrogen in a normal alkane is replaced by a

halogen (group 17 elements). In this article, we will discuss the physical properties of
haloalkanes. The physical properties of haloalkanes are mostly like a normal covalent
compound. Halogens not being much reactive functional group as a carboxyl group or
aldehyde doesn’t affect the overall physical properties by much. Still, few differences
can be seen as we move down in the homologous series of haloalkanes group due to
the difference in atomic masses of the compound.
Chemical Properties of Haloalkanes

Haloalkanes are quite reactive compounds. They undergo substitution,
elimination and reduction reactions. They also react with some metals to form
organometallic compounds. The reactivity of haloalkanes is mainly due to the
polar nature of the carbon halogen bond.
The stability of alkyl halides generally decreases as the strength of the C-X
bond decreases. Iodides generally liberate iodine due to their low stability and
acquire brown or violet colour.
2R-I → R-R + I2
Iodoform shows the antiseptic properties due to the liberation of iodine.
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NCERT LINE BY LINE QUESTIONS

(1.) Consider the following reactions [Page: 307]
Here A+B is
(a.) Racemic mixture (b.) Inversion
(c.) Retention (d.) None of these
(2.) In which of the following solvents, the solubility of haloalkanes is low? [Page: 299]
(a.) water (b.) ethanol
(c.) benzene (d.) chloroform
(3.) Which of the following reaction is Sandmeyer’s reaction?

(b.) H3C — Br + AgF ⎯⎯
→ H3C — F + AgBr
(a.)
(d.) H3C — X + NaI ⎯⎯
→ H3C — I + Nax
(c.)
(4.) Consider the following reaction [Page: 301]
The reaction represents

(a.) SN 2 mechanism (b.) SN1 mechanism
(c.) SNi mechanism (d.) none of these
(5.) Which of the following is in correct [QR code, NCERT Exemplar, Page: 304]
(b.)
(a.)
(c.)
(d.)
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(6.) An alkyl chloride produces a single alkene on reaction with sodium ethoxide and ethanol. The
alkene further undergoes hydrogenation to yield 2-methylbutane. Identify the alkyl chloride
from amongst the following.
(a.) ClCH 2 ( CH3 )2 CH3 (b.) ClCH2CH2CH2CH3
(c.) ClCH 2CH ( CH3 ) CH 2CH3 (d.) CH3C ( Cl )( CH3 ) CH 2CH3
(7.) Which of the following statement is incorrect? [Page: 291]

(a.) The common name of alkyl halides are (b.) For monohalogen substituted derivatives
derived by naming the alkyl group of benzene, common and IUPAC names
followed by the name of halide. are used.
(c.) For dihalogen derivatives, the prefixes o-, (d.) The dihaloalkanes having the same type
mand p- are used in IUPAC system. of halogen atoms are named as alkylide.
Here, ‘X’ is
(a.) Br CH2 − CH2 Br (b.) CH3 - CH2 Br
(d.) both (a) and (b)
(c.)
(9.) Carbon compounds containing more than one halogen atom are usually referred to as [Page:
317]
(a.) polyhalogen compounds (b.) hydrocarbon
(c.) haloalkane (d.) haloarene
(10.) Match the organic compounds given in column I with their effects given in column II. [Page:
289]
(Column I) (Column I)
Organic compounds Effects
(I) Chloramphenicol (p) treatment of malaria
(II) Thyroxine (q) antibiotic
(III) Chloroquine (r) Iodine containing hormone
(IV) Halothane (s) Anaesthetic
Codes
I II III IV
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(a.) r q p s (b.) p q r s
(c.) q r p s (d.) p q s r
The type of reaction shown by the reaction is

(a.) nucleophilic substitution (b.) electrophilic substitution
(c.) addition reaction (d.) elimination reaction
(12.) Match the following. [Page: 292]
Column I (IUPAC) (Name) Column II
(p) Bromobutane
(i)
(q) 1-Bromo-2-methylbutane
(ii)
(iii) CH3 − CH2CH2CH2 Br (r) 3-bromopentane
Codes
I II III
(a.) r p q (b.) p q r
(c.) q p r (d.) q r p
(13.) C7 H8 ⎯⎯ ⎯⎯
3Cl2 ,Heat
→ A ⎯⎯⎯
Zn/Br2
→ B ⎯⎯⎯
Zn/HCl
→ , Here, the correct compound C is
(a.) 3-Bromo-2,4,6-trichlorotoluene (b.) o-bromotoluene
(c.) p-bromotoluene (d.) m-bromotoluene
(14.) Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to
[Page: 311]
(a.) Resonance effect (b.) Difference in hybridisation
(c.) Instability of phenyl cation (d.) All of these
(15.) An alkene ‘A’ on reaction with O2 and Zn / H2O gives propanone and ethanol in equimolar
ratio. Addition of HCI to alkene ‘A’ gives ‘B’ as the major product. [NEET-2019]
The structure of product ‘B’ is
(a.)
(b.)
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(d.)
(c.)
(16.) The number of isomers for the compound with molecular formula C2BrClFI is
(a.) 3 (b.) 4
(c.) 5 (d.) 6
(17.) The reagent ‘Y’ in the reaction is [Page: 296]
(a.) Fe dark
(b.) Fe + sunlight
(c.) FeCl3
(d.) FeBr3
(18.) Thionyl chloride is preferred because [Page: 294]

(a.) alkyl halide and H3PO3 formed (b.) alkyl halide is formed along with SO2 and
HCl gas
(c.) alkyl halide and POCl3 are formed (d.) alkyl halide and H 2O are formed
(19.) Chlorination of toluene in presence of light and heat followed by treatment with aq. NaOH and
acidification gives
(a.) o-cresol (b.) p-cresol
(c.) 2,4-dihydroxytoluene (d.) benzoic acid
(20.) The alkane that gives only one mono-chloro product on chlorination with Cl2 in presence of
diffused sunlight is [Odisha NEET-2019]
(a.) 2,2-dimethylbutane (b.) neopentane
(c.) n-pentane (d.) isopentane
(21.) Name the polyhalogen compound which is employed as a solvent for fats, alkaloids, iodine and
other substances. [Page: 317]
(a.) chloroform (b.) methylene chloride
(c.) iodoform (d.) None of these
(22.) Consider the following statements [Page: 292]

(I) The dihalo compounds is classified as geminal halide.
(II) In common system, gem-dihalides are named as alkylidene halides.
(III) Vic-dihalides are named as alkylene dihalides.
(IV) IUPAC name of H3C − CHCl2 is ethylidene chloride.
Choose the correct option.
(a.) I and II (b.) I and III
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(c.) II, III and IV (d.) II and III
(23.) Which of the following has highest boiling point? [Page: 298]
(a.) CH3CH2CH2CH2CH2Br
(b.)
(c.) (d.)
(24.) When a compound rotates the plane of plane polarised light to the right, then it is called [Page:
305]
(a.) racemised (b.) leavorotatory
(c.) dextrorotatory (d.) inverated
(25.) The product of the following reaction [Page: 297]
(a.)
(b.)
(c.)
(d.)
(26.) Which of the following is used as feedstock in the synthesis of chlorofluorocarbons and other
chemicals in pharmaceutical manufacturing? [Page: 317]
(a.) CCl4 (b.) Iodoform
(c.) Chloroform (d.) Methylene chloride
(27.) The compound C7H8 undergoes the following reactions: [NEET-2018, Page: 296]
The product ‘C’ is
(a.) 3-bromo-2,4,6-trichlorotoluene (b.) o-bromotoluene
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(c.) m-bromotoluene (d.) p-bromotoluene
(28.) Assertion: Vinyl chloride is less reactive than alkyl chloride.

Reason: Stability of alkyl halide decreases as the strength of C − X bond decreases. [Page: 293]
(a.) Both A and R are correct and R is correct (b.) Both A and R are correct but R is not
explanation of A. correct explanation of A.
(c.) A is correct but R is incorrect. (d.) Both A and R are false.
(29.) Assertion: Chloral reacts with phenylchloride to form DDT. [Page: 318]
Reason: It is an electophilic substitution reaction.
(30.) Assertion: Low member of alkyl halides are colourless gases.

Reason: Alkyl iodides in general turn black on exposure to air and light. [Page: 297]
(31.) Consider the following statements: [Page: 303]

(I) In SN1 , the rate of reaction depends upon the concentration of only one reactant.
(II) SN1 reaction occur in two steps.
(III) The rate of reaction depends only on the concentration of R − X and not on the
concentration of hydroxide ion.
Read the given statements and then choose the correct option
(a.) Only I (b.) Only II
(c.) Both I and II (d.) All of these
(32.) Which of the following is not correct match? [Page: 291]
(b.) Benzylic halide-

(a.) Allylic halide -
(d.) Vinyl halide -

(c.) Aryl halide -
(33.) Assertion: CCl4 is a fire extinguisher.

Reason: CCl4 is insoluble in water. [Page: 317]
27
(34.) The hydrolysis reaction that takes place at the slowest rate, among the following is
(a.)
(b.) H3C − CH2 − Cl ⎯⎯⎯⎯
aq. NaOH
→ H3C − CH2 − OH
(c.) H2C = CH − CH2 − Cl ⎯⎯⎯⎯
aq. NaOH
→ H2C = CH − CH2OH
(d.)
(35.) The boiling points of chlorides are higher than those of hydrocarbons of comparable molecular
mass. It is due to [Page: 298]
(a.) dipole−dipole forces of attraction (b.) van der Waal’s attraction
(c.) Both (a) and (b) (d.) none of these
(36.) Replacement of Cl of chlorobenzene to give phenol requires drastic conditions but chlorine of
2,4-dinitrochlorobenzene is readily replaced because
(a.) NO2 makes the electron rich ring at ortho (b.) NO2 withdraw electrons at metaposition
and para positions
(c.) NO2donates electrons at m-position (d.) NO2withdraws electrons at ortho and
para positions

CH3CH 2CH 2CH3 ⎯⎯⎯⎯⎯
Cl2 / UVLight
or heat
→‘X’ and ‘Y’
Product ‘X’ and ‘Y’ are
(b.) CH3CH2CH2CH2Cl and CH3CH2CHClCH3
(a.) and
(c.) CH3CH2CHCl2CH3 only (d.) CH3CH2CH2CH2Cl only
(38.) Which of the following is the correct order of reactivity of alkyl halides toward SN1 reaction?
[Page: 303]
(a.) 3  2  1  CH3X (b.) 2  3  1  CH3X
(c.) 1  2  3  CH3X (d.) CH3X  1  2  3
(39.) The compound in which the halogen atom is bonded to an sp3 hybridised carbon atom adjacent
to C = C double bond is
(a.) Benzylic halide (b.) Aryl halide
(c.) Allylic halide (d.) Vinylic halide
(40.) Assertion: Alkyl iodide can be prepared by treating alkyl chloride/bromide with NaI in
acetone. Reason: NaCl/NaBr are soluble in acetone while NaI is not. [Page: 295]
28
(41.) Match the following. [Page: 315]

Column I (Reactant) Column II (Product)
(A)
(p)
(B) (q)
(C) (r)
(D)
(s)
ABCD
(a.) rsqp
(b.) qrsp
(c.) qprs
(d.) pqrs
(42.) Which of the following is not an electrophilic substitution reaction? [Page: 314]
Column I (Reactant)
(a.) (b.)
(c.) (d.)
(43.) Freons is manufactured from tetrachloromethane by [Page: 318]

(a.) Frankland reaction (b.) Wurtz reaction
(c.) Swarts reaction (d.) Sandmeyer reaction
29
(44.) Assertion: Boiling point of alkyl halide increases with increase in molecular weight. Reason:
Boiling point of alkyl halides is in the order RI  RBr  RCl  RF . [Page: 298]
(45.) Assertion: p-dichlorobenzene has higher melting point than o-dichlorobenzene.

Reason: Stronger the van der Waal’s forces of attraction, higher is the melting point. [Page: 298]
This reaction is called

(a.)  − elimination (b.)  − elimination
(c.) substitution (d.) free radical
(47.) Identify the set of reagents/reaction condition ‘X’ and ‘Y’ in the following set of transformations
(a.) X = dil. aqueous NaOH, 20°C Y = (b.) X = conc. alcoholic NaOH, 80°C Y =
HBr/acetic acid 20°C HBr/acetic acid 20°C
(c.) X = dil. aqueous NaOH, 20°C Y = (d.) X = conc. alcoholic NaOH, 80°C Y=
Br2/CHCl3, 0°C Br2/CHCl3, 0°C
(48.) The correct IUPAC name of the following structure is [Page: 293]
(a.) 4-bromopent-2-ene (b.) 3-bromo-2-methylbutene

(c.) 1-bromobut-2-ene (d.) 3-bromo-2-methylpropene
(49.) How much chloroform can cause dizziness for a short time? [Page: 317]
(a.) 100 parts per million (b.) 200 parts per million
(c.) 900 parts per million (d.) only 1 part per million
(50.) The reaction of C6H5CH = CHCH3 with HBr produces [CBSE AIPMT-2015, Page: 296]
(a.) C6 H5CH ( Br ) CH 2CH3 (b.) C6 H5CH 2CH ( Br ) CH3
(c.) C6 H5CH2CH2CH2 Br (d.)
30
TOPIC WISE PRACTICE QUESTIONS

TOPIC 1: General Characteristics of Haloalkanes and Haloarenes
1. Read the following statements and choose the correct option.
(i) The general formula of alkyl halides is CnH2n+1 X
(ii) The general formula of aryl halides is Cn Hn–1 X
(iii) In alkyl halides halogen atom(s) is attached to sp2 hybridised carbon atom
(iv) In aryl halides halogen atom(s) is attached to sp2 hybridised carbon atom.
1) (i), (ii) and (iii) are correct 2) (i), (ii) and (iv) are correct
3) (ii), (iii) and (iv) are correct 4) (i), (ii), (iii) and (iv) are correct
2. Which one of the following is not an allylic halide?
1) 4-Bromopent-2-ene 2) 3-Bromo-2-methylbut-1-ene
3) 1-Bromobut-2-ene 4) 4-Bromobut-1-ene
3. The compound which contains all the four 1°, 2°, 3° and 4° carbon atoms is
1) 2, 3-dimethylpentane 2) 2, 3, 3-trimethylpentane 3) 2, 3, 4-trimethylpentane 4) 3,3-dimethylpentane
4. Benzene hexachloride is
1) 1, 2, 3, 4, 5, 6-hexachlorocyclohexane 2) 1, 1, 1, 6, 6, 6-hexachlorocyclohexane
3) 1, 6-phenyl-1, 6-chlorohexane 4) 1, 1-phenyl-6, 6-chlorohexane
5. In the following groups :
–OAc (I) –OMe (II)
– OSO2 Me (III) –OSO2CF3 (IV)
the order of leaving group ability is
1) I > II > III > IV 2) IV > III > I > II 3) III > II > I > IV 4) II > III > IV > I
6. Phosgene is a common name for
1) phosphoryl chloride 2) thionyl chloride
3) carbon dioxide and phosphine 4) carbonyl chloride
7. Match the columns
Column - I Column - II
1) CH2 = CH – CH2Cl (p) gem-Dichloride
2) CH2 = CHX (q) Vinylic halide
3) CH3CHCl2 (r) vic-Dichloride
4) CH2Cl CH2Cl (s) Allylic halide
1) A – (r), B – (q), C – (p), D – (s) 2) A – (q), B – (p), C – (s), D – (r)
3) A – (s), B – (q), C – (p), D – (r) 4) A – (r), B – (p), C – (s), D – (q)
8. The IUPAC name of the compound shown below is
1) 2-bromo-6-chlorocyclohex-1-ene 2) 6-bromo-2-chlorocyclohexene
3) 3-bromo-1-chlorocyclohexene 4) 1-bromo-3-chlorocyclohexene
9. A compound is formed by substitution of two chlorine for two hydrogens in propane. The number of
possible isomeric compounds is
1) 4 2) 3 3) 5 4) 2
10. Arrange the following halides in the decreasing order of SN1 reactivity :
1) I > II > III 2) II > I > III 3) II > III > I 4) III > II > I
31
TOPIC 2 : Preparation and Properties of Haloalkanes
11. Which of the following will give vinyl chloride ?
12. Comment on the following reactions

(i) CH3OH + NaCl → (ii) CH3OH + HCl →
1) Both reactions take place easily. 2) Only reaction (ii) takes place.
3) Reaction (ii) takes places faster than (i) . 4) None of the two reactions in possible.
13. When chlorine is passed through propene at 400°C, which of the following is formed ?
1) PVC 2) Allyl chloride 3) Alkyl chloride 4) 1, 2-Dichloroethane
14. When CH3CH2CHCl2 is treated with NaNH2, the product formed is
15. The reaction of tert-butyl bromide with sodium methoxide produces mainly –
1) iso-butane 2) iso-butylene 3) tert-butyl methyl ether 4) sodium tert butoxide
16. Ethylidene bromide on heating with metallic sodium in ether solution yields
1) ethene 2) ethyne 3) 2-butene 4) 1-butene
17. Vinyl chloride undergoes
1) only addition reactions 2) only elimination reactions
3) substitution reactions 4) both (1) and (2)
18. In the following sequence of reactions
1) n-propyl amine 2) isopropylamine 3) ethylamine 4) ethylmethyl amine

19. The number of structural and configurational isomers of a bromo compound, C5H9Br, formed by the
addition of HBr to 2-pentyne respectively are
1) 1 and 2 2) 2 and 4 3) 4 and 2 4) 2 and 1
20. During debromination of meso-2,3-dibromobutane, the major compound formed is
1) n-butane 2) 1-butene 3) cis-2-butene 4) trans-2-butene
21. Halogenation of alkanes is
1) a reductive process 2) an oxidative process
3) an isothermal process 4) an endothermal process
22. Which of the following reagent produces pure alkyl halides when heated with alcohols?
1) PCl5 2) PCl3 3) SOCl2 4) dry HCl
23. Which of following can be used as solvent for Grignard reagent ?
1) H2O 2) C2H5OH 3) CH3OH 4) C2H5OC2H5
24. To prepare 3-ethylpentan-3-ol, the reagents needed are –
1) CH3CH2MgBr + CH3COCH2CH3 2) CH3MgBr + CH3CH2CH2COCH2CH3
3) CH3CH2MgBr + CH3CH2COCH2CH3 4) CH3CH2CH2MgBr + CH3COCH2CH3
25. Rate of SN2 will be negligible in :
32
26. Identify Z in the following series
1) CH3CH2CN 2) NCCH2–CH2CN 3) BrCH2–CH2CN 4) BrCH=CHCN

27. The compound most reactive towards SN1 reaction is
1) Me3COCH2Cl 2) MeOCH2Cl 3) C6H5CH2CH2Cl 4)

28.
Which of the following is correct?

1) A on reaction with aq. KOH gives HOCH2CH2COOK
2) B can be resolved into d– and l –forms
3) Both (1) and (2) 4) Neither (1) nor (2)
29. Which of the following order is not correct ?
1) MeBr > Me2CHBr > Me3CBr > Et3CBr(SN2)
2) PhCH2Br > PhCHBrMe > PhCBrMe2 > PhCBrMePh(SN1)
3) MeI > MeBr > MeCl > MeF (SN2) 4) All the above are correct
30. Isopropyl chloride undergoes hydrolysis by
1) SN1 mechanism 2) SN2 mechanism
3) SN1 and SN2 mechanisms 4) Neither SN1 nor SN2 mechanism
31. Mg reacts with RBr best in
1) C2H5OC2H5 2) C6H5OCH3 3) C6H5N(CH3)2 4) Equally in all the three
32. Ethylene dichloride can be prepared by adding HCl to
1) ethane 2) ethylene 3) acetylene 4) ethylene glycol
33. ( CH3 )3 CC1 ⎯⎯⎯→ A ⎯⎯⎯⎯
NaCN dil.H 2SO4
→ B compound B is
1) ( CH3 )3 CCOOH 2) ( CH3 )3 COH 3) ( CH3 )3 COC ( CH3 )3 4)all the three
34.
1) 3-Chloropropene 2) 2-Chloropropene 3) 1-Chloropropene 4) 1, 2-Dichloropropane

35. A solution of (+) –2–chloro–2–phenylethane in toluene racemises slowly in the presence of small
amount of SbCl5, due to the formation of
1) carbanion 2) carbine 3) free-radical 4) carbocation
36. The best method for the conversion of an alcohol into an alkyl chloride is by treating the alcohol with
1) PCl5 2) dry HCl in the presence of anhydrous ZnCl2
3) SOCl2 in presence of pyridine 4) none of these
37. A Grignard reagent may be made by reacting magnesium with
1) Methyl amine 2) Diethyl ether 3) Ethyl iodide 4) Ethyl alcohol
33
38. Silver acetate Br2 ⎯⎯→
CS2
. The main product of this reaction is
1) CH3 - Br 2) CH3COH 3) CH3COOH 4) None of these
39. Which of the following will have the maximum dipole moment?
1) CH3F 2) CH3Cl 3) CH3Br 4) CH3I
40. Dehydrohalogenation by strong base is slowest in
41.
The above transformation proceeds through

1) electrophilic-addition 2) benzyne intermediate
3) activated nucleophilic substitution 4) SN1
42. Which of the following is liquid at room temperature (b.p. is shown against it)?
1) CH3I 42 °C
2) CH3Br 3 °C
3) C2H5Cl 12 °C
4) CH3F –78 °C
43. The decreasing order of boiling points of alkyl halides is
1) RF > RCl > RBr > RI 2) RBr > RCl > RI > RF 3) RI > RBr > RCl > RF 4) RCl > RF > RI > RBr
44.
45. C – Cl bond of chlorobenzene in comparison to C – Cl bond in methyl chloride is

1) Longer and weaker 2) Shorter and weaker
3) Shorter and stronger 4) Longer and stronger
TOPIC 3: Preparation and Properties of Haloarenes
46. Benzene reacts with n-propyl chloride in the presence of anhydrous AlCl3 to give
1) 3 – Propyl – 1 – chlorobenzene 2) n-Propylbenzene
3) Isopropylbenzene 4) No reaction occurs
47. Aryl halides cannot be prepared by the reaction of aryl alcohols with PCl3, PCl5 or SOCl2 because
1) Phenols are highly stable compounds.
2) carbon-oxygen bond in phenols has a partial double bond character.
3) carbon-oxygen bond is highly polar 4) all of these
48. In the preparation of chlorobenzene from aniline, the most suitable reagent is
1) Chlorine in the presence of ultraviolet light
2) Chlorine in the presence of AlCl3
3) Nitrous acid followed by heating with Cu2Cl2 4) hCl and Cu2Cl2
34
49. The correct kinetic rate equation for the addition- elimination mechanism of nucleophilic aromatic
substitution
1) Rate = k [aryl halide] [nucleophile] 2) rate = k [aryl halide]
3) Rate = k [aryl halide] [nucleophile]2 4) rate = k [nucleophile]
50. How many isomeric naphthylamines are expected in the following reaction?
1) Two 2) only single product 3) four 4) three

51.
The reagent R may be
52. What is the product of the following reaction?
1) N, N-dimethyl aniline 2) phenyl-lithium (C6H5Li)

3) para-chloro-N, N-dimethyl aniline 4) meta-chloro-N, N-dimethyl aniline
TOPIC 4: Some Important Polyhalogen Compounds
53. Which of the following is responsible for depletion of the ozone layer in the upper strata of the
atmosphere?
1) Polyhalogens 2) Ferrocene 3) Fullerenes 4) Freons
54. Freon-12 is commonly used as
1) insecticide 2) refrigerant 3) a solvent 4) a fire extinguisher
55. Which of the following is used in fire extinguishers
1) CH4 2) CHCl3 3) CH2Cl2 4) CCl4
56. If chloroform is left open in air in the presence of sunlight, it gives
1) carbon tetrachloride 2) carbonyl chloride 3) mustard gas 4) lewisite
57. The product formed by heating iodoform with KOH is :
1) HCHO 2) HCOOK 3) CH3COOK 4) CH3CHO
58. Ethyl alcohol is used as a preservative for chloroform because it :
1) Prevents aerial oxidation of chloroform
2) Prevents decomposition of chloroform
3) Decomposes phosgene to CO and Cl2
4) Removes phosgene by converting it to ethyl carbonate
59. Uses of dichloromethane is
1) paint remover 2) solvent in drugs manufacturing
3) metal cleansing and finishing solvent 4) All of the above
60. On warming with silver powder, chloroform is converted into
1) acetylene 2) hexachloroethane
3) 1,1,2,2-tetrachloroethane 4) ethylene
61. AgNO3 does not give precipitate with chloroform because :
1) CHCl3 does not ionise in water 2) CHCl3 is insoluble in water
35
3) AgNO3 is insoluble in CHCl3 4) CHCl3 is an organic compound
62. CHCl3 and KOH on heating with a compound forms a bad smelling product (X), X is
1) C2H5CN 2) C2H5NC 3) C2H5OH 4) C2H5NH2
63. The compound which forms acetaldehyde when heated with dilute NaOH, is
1) 1, 1-dichloroethane 2) 1, 1, 1-trichloroethane 3) 1-chloroethane 4) 1, 2-dichloroethane
64. Which one of the following has antiseptic property?
1) Dichloromethane 2) Trifluoromethane 3) Triiodomethane 4) Tetrachloromethane
65. The major product formed when 1, 1, 1-trichloro-propane is treated with aqueous potassium hydroxide
is:
1) Propyne 2) 1-Propanol 3) 2-Propanol 4) Propionic acid
NEET PREVIOUS YEARS QUESTIONS

1. The compound C7H8 undergoes the following reactions:
The product 'C' is [2018]

1) m-bromotoluene 2) o-bromotoluene
3) p-bromotoluene 4) 3-bromo-2,4,6-trichlorotoluene
2. Identify A and predict the type of reaction [2017]
3. Which of the following biphenyls is optically active? [2016]
4. For the following reactions :-
36
Which of the following statements is correct? [2016]

1) (1) and (2) are elimination reaction and (3) is addition reaction
2) (1) is elimination, (2) is substitution and (3) is addition reaction
3) (1) is elimination, (2) and (3) are substitution reactions
4) (1) is substitution, (2) and (3) are addition reaction
5. Which of the following reaction (s) can be used for the preparation of alkyl halides? [2015]
1) (I), (III) and (IV) only 2) (I) and (II) only 3) (IV) only 4) (III) and (IV) only
6. What products are formed when the following compounds is treated with Br2 in the presence of FeBr3?
[2014]
7. Which of the following compounds will undergo racemisation when solution of KOH hydrolyses?
[2014]
1) (i) and (ii) 2) (ii) and (iv) 3) (iii) and (iv) 4) (iv)
37
8. Among the following, the reaction that proceeds through an electrophilic substitution is : [2019]
(1)
(2)
(3)
(4)
9. Which of the following will NOT undergo SN1 reaction with OH ? [2020-COVID-19]
(1) CH2 = CH − CH2Cl (2) ( CH3 )3 CCl
(3) (4)
10. The major product formed in dehydrohalogenation reaction of 2-Bromo pentane is Pent-2-ene. This
product formation is based on? [NEET-2021]
1) Hund’s Rule 2) Hofmann Rule 3) Huckel’s Rule 4) Saytzeff’s Rule
11. The correct sequence of bond enthalpy of ‘C-X’ bond is [NEET-2021]
1) CH3 − F  CH3 − Cl  CH3 − Br  CH3 − I 2) CH3 − F  CH3 − Cl  CH3 − Br  CH3 − I
3) CH3 − Cl  CH3 − F  CH3 − Br  CH3 − I 4) CH3 − F  CH3 − Cl  CH3 − Br  CH3 − I
12. Which compound amongst the following is not and aromatic compound? [NEET-2022]
1) 2) 3) 4)
13. Which of the following sequence of reactions is suitable to synthesize chlorobenzene?
[NEET-2022]
1) Benzene, Cl2 , anhydrous FeCl3 2) Phenol, NaNO2 , HCl , CuCl
NH2
, HCI , HCI, Heating

3) 4)
38
14. The incorrect statement regarding chirality is [NEET-2022]
1) SN1 reaction yields 1: 1 mixture of both enantiomers
2)The product obtained by SN2 reaction of haloalkane having chirality at the reactive site shows
inversion of configuration
3)Enantiomers are superiomposable mirror images on each other
4)A racemic mixture shows zero optical rotation
15. The correct IUPAC name of the following compound is: [NEET-2022]
1) 1-bromo-5-chloro-4-methylhexan-3-ol
2) 6-bromo-2-chloro-4-methylhexan-4-ol
3) 1-bromo-4-methyl-5-chlorohexan -3-ol
4) 6-bromo-4-methyl-2-chorohexan-4-ol
NaO+?
CH3 CH2 COOO− Na+ →
16. Heat
CH3 CH3 + Na2 CO3
Consider the above reaction and identify the missing reagent/chemical.
(a) B2 H6 (b) Red phosphorus
(c) CaO (d) DIBAL-H
17. The compound C7 H8 undergoes the following reactions :

3Cl2 /Δ Br/Fe Zn/HCl
C7 H8 → A → B → C
The product ' 𝐶 is
(a) 3-bromo-2, 4, 6-trichlorotoluene
(b) o-bromotoluene
(c) m-bromotoluene
(d) p-bromotoluene
NCERT LINE BY LINE QUESTIONS – ANSWERS

(1.) a (2.) a (3.) c (4.) a (5.) b
(6.) c (7.) c (8.) a (9.) a (10.) c
(11.) a (12.) d (13.) d (14.) d (15.) b
(16.) d (17.) a (18.) b (19.) d (20.) a
(21.) a (22.) c (23.) a (24.) c (25.) a
(26.) a (27.) c (28.) b (29.) c (30.) c
(31.) d (32.) d (33.) b (34.) a (35.) c
(36.) d (37.) b (38.) a (39.) c (40.) c
39
(41.) b (42.) d (43.) c (44.) b (45.) b
(46.) b (47.) b (48.) a (49.) c (50.) b
TOPIC WISE PRACTICE QUESTIONS - ANSWERS
1) 2 2) 4 3) 2 4) 1 5) 2 6) 4 7) 3 8) 3 9) 3 10) 3
11) 4 12) 2 13) 2 14) 2 15) 2 16) 3 17) 4 18) 4 19) 2 20) 4
21) 2 22) 3 23) 4 24) 3 25) 3 26) 2 27) 2 28) 3 29) 2 30) 3
31) 1 32) 4 33) 2 34) 1 35) 4 36) 3 37) 3 38) 1 39) 2 40) 3
41) 3 42) 1 43) 3 44) 3 45) 3 46) 3 47) 2 48) 3 49) 1 50) 1
51) 3 52) 1 53) 4 54) 2 55) 4 56) 2 57) 2 58) 4 59) 4 60) 1
61) 1 62) 2 63) 1 64) 3 65) 4
NEET PREVIOUS YEARS QUESTIONS-ANSWERS
1) 1 2) 4 3) 2 4) 2 5) 1 6) 3 7) 4 8) 2 9) 3 10) 4
11) 1 12) 4 13) 1 14) 3 15) 1 16)c 17)c
NCERT LINE BY LINE QUESTIONS – SOLUTIONS
(1.) (a) Product ‘A+B’ is racemic mixture and process involved is racemisation Here, 50:50 mixture of A
and B is obtained.
(2.) (a) Solubility of haloalkanes in water is low. In order to dissolve, energy is required to overcome the
attractions between haloalkane molecules and break the hydrogen bonds between water molecules.
However, it tends to dissolve in organic solvents.
(3.) (c) Reaction (c) is Sandmeyer’s reaction
(4.) (a) The reaction between CH3Cl and hydroxide ion to yield methanol and chloride ion follows a second
order kinetics, i.e. the rate depends upon the concentration of both reactants.
(5.) (b) Boiling point of isomeric haloalkanes decreases with increase in branching as with increase in
branching surface area decrease which leads to decrease in intermolecular forces.
(6.) (c)
(7.) (c) Statement (c) is incorrect.
For dihalogen derivatives, the prefixes o-, m- and p- are used in common system but in IUPAC system,
the numerals 1,2; 1,3 and 1,4 are used.
(8.) (a) The product ‘X’ is BrCH2−CH2Br. The reaction is as follows:
(9.) (a) Carbon compounds containing more than one halogen atom are usually referred to as polyhalogen
compounds.
(10.) (c) I → q, II → r, III → p, IV → s
• Chloramphenicol is an antibiotic produced by microorganisms used in treatment of typhoid fever.
• Iodine containing hormone is thyroxine.
• Chloroquine is used for the treatment of malaria.
• Halothane is used as an anaesthetic during surgery.
40
(11.) (a) The given reaction is nucleophilic substitution reaction. In this reaction, a nucleophile replaces
already existing nucleophile in a molecule.
(12.) (d) I → q, II → r, III → p
(13.) (d)
(14.) (d) Arylhalides are extremely less reactive towards nucleophilic substitution reactions due to following
reasons
• Resonance effect
• Difference in hybridisation of carbon atom in C−X bond
• Instability of phenyl cation
(15.) (b) The product of ozonolysis can give an idea about probable alkene. These are represented as follows
Complete reaction is as follows
(16.) (d) Six isomers are possible.
(17.) (a) Arylchloride can be easily prepared by electrophilic substitution of arenes with chlorine in the
presence of Lewis acid catalyst like iron or iron (III) chloride
(18.) (b) Thionyl chloride is preferred because in this reaction alkyl halide is formed along with gases SO2
and HCl. The two gaseous products are escapable
41
(19.) (d)
(20.) (a) An alkene is connected to corresponding alkyl halide by reaction with hydrogen chloride. The
reaction proceed via addition of hydrogen halides.
(21.) (a) Chloroform is the polyhalogen compound which is employed as a solvent for fats, alkaloids, iodine
and other substances.
(22.) (c) Statements II, III and IV are correct while statement I is incorrect. The dihalo compounds having
both the halogen atoms are further classified as geminal halides or gem-dihalides and vic-dihalides.
(23.) (a) The boiling points of isomeric haloalkanes decrease with increase in branching.
(24.) (c) When the compound rotates the plane of plane polarised light to the right i.e. clockwise direction,it
is called dextrorotatory or the d-form and is indicated by placing a positive sign before the degree of
rotation.
(25.) (a)
(26.) (a) CCl4 (tetrachloromethane) is used as feedstock in the synthesis of chlorofluorocarbons and other
chemicals, pharmaceutical manufacturing.
(27.) (c) The reaction is as follows:
(28.) (b) Vinyl chloride itself shows resonance structure and thus stabilised. As vinyl chloride has partial
double bond character thus breaking of C−Cl bond is difficult which makes vinyl chloride less reactive
than alkyl chloride.
(29.) (c)When chlorobenzene is heated with chloral in the presence of conc. H2SO4, a powerful insecticide,
DDT is formed with the elimination of H2O molecule.
(30.) (c) Alkyl iodides in general turn brown due to liberation of I2 on decomposition by the action of air and
light.
(31.) (d) All given statements are correct
(32.) (d) Option (d) does not show a correct match. Vinyl halide are the compounds in which a halogen atom
is bonded to a sp2 hybridised carbon atom of a carbon–carbon double bond ( C = C )
42
and
(33.) (b) CCl4 is used as a fire extinguisher. The dense, non-combustible vapours cover the burning substance
and prevents the availability of oxygen around burning material.
(34.) (a) is a benzylic halide. There is a partial double bond character between sp3hybridised C
atom next to an aromatic ring and Cl. It is most difficult to break this bond .Hence, it undergoes
hydrolysis with slowest rate.
(35.) (c) 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 bimolecular forces of attraction are
stronger in the halogen derivatives. That is why the boiling points of chlorides are higher than those of
the hydrocarbons of comparable molecular mass.
(36.) (d) NO2 groups withdraw electrons at orthoand para-position and then deactivate the ring. This
deactivation of ring stabilises the negatively charged intermediates formed during the reaction and
therefore, increases the reactivity towards replacement.
(37.) (b) The products obtained are CH3CH2CH2CH2Cl and CH3CH2CHClCH3. The reaction proceed in a free
radical chlorination of alkanes. Complete reaction is as follows:
CH3CH 2CH 2CH3 ⎯⎯⎯⎯⎯ Cl2 / UV Light
or heat
→ CH3CH 2CH 2CH 2Cl + CH3CH 2CHClCH3
(38.) (a) SN1 reaction depends on the stability of carbocation, greater will be its ease of formation from alkyl
halide and faster will be the rate of reaction. In case of alkyl halides 3°alkyl halide undergo SN1 reaction
very fast because of high stability of 3°carbocations.
(39.) (c) Allylic halide are the compounds in which the halogen atom is bonded to an sp3 hybridised carbon
atom adjacent to C − C double bond ( C − C ) i.e. to an allylic carbon.
(40.) (c) Given reaction is known as a Finkelstein reaction. NaI is soluble in acetone and NaCl, NaBr are not,
the equilibrium is shifted by the precipitation of insoluble salt
MX’
R−X Ma
R − X’
(41.) (b)
(42.) (d) Reaction (d) is nucleophilic substitution while others are electrophilic substitution.
(43.) (c)
(44.) (b) Greater the molecular mass, stronger the van der Waal’s forces of attraction and hence, higher is the
melting point or boiling point.
(45.) (b) Among dichlorobenzenes, the p-isomer being symmetrical packs closely in the crystal lattice and
hence, has much higher melting point than o- and m-isomers.
(46.) (b) In the given reaction, the haloalkane on reaction with hydrogen atom is heated with alc. solution of
KOH. There is elimination of hydrogen atom from -carbon and a halogen atom -carbon atom.
(47.) (b)
(48.) (a) The correct name of the given compound is
43
(49.) (c) Breathing about 900 parts of chloroform per million parts of air (900 parts per million ) for a short
time can cause dizziness, fatigue and headache.
(50.) (b) The reaction of C6H5CH CHCH3 with HBr produces .

TOPIC WISE PRACTICE QUESTIONS - SOLUTIONS
1. (2) In alkyl halides halogen atom(s) is attached to sp3 hybridised carbon atom.
2. (4) 4-Bromobut-l-ene is not an allylic halide
3. 2)
4. 1)
5. 2) Weaker the base, better the leaving group. Hence
6. 4)
7. 3) In allylic halides hydrogen atom is bonded to sp3hybridized carbon atom. Whereas in vinylic halide,
hydrogen atom is bonded to sp2 hybridized carbon atom.
8. 3)
9. 3) The compound is C3H6Cl2 and the number of possible isomeric compounds is 5
10. 3) Stability of the three corresponding carbocations
11. 4) All given reactions give the vinyl chloride by substitution 1), by dehydrohalogenation 2) and by
addition 3)
44
12. (2) Reaction (i) is not possible because OH– is a stronger base than Cl–; hence it can’t be replaced by Cl–
+
. However, in reaction (ii) OH group is first protonated to form R O H 2 in which H2O, being a very
weak base, is easily replaced by Cl–.
13. (2) At high temp. i.e., 400°C substitution occurs in preference to addition.
14. 2)
15. 2) 3° alkyl halides on reaction with strong base (CH3O- ) undergo elimination reaction and forms alkene
as major product.
16. 3)
17. 4)
18. 4)
19. 2) Addition of HBr to 2-pentyne gives two structural isomers (I) and (II)
Each one of these will exist as a pair of geometrical isomers. Thus, there are two structural and four
configurational isomers.
20. 4) Debromination is a trans-elimination reaction. meso- 2, 3-Dibromobutane on debromination gives
trans-2-butene.
21. 2)
22. 3) Thionyl chloride is preferred because the other two products formed in the reaction are escapable
gases. Hence the reaction gives pure alkyl halides
ROH + SOCl2 → R − Cl + SO2  +HCl 
23. 4) Except 4) all contain abstractable proton
24. (3)
25. (3) At a bridge head position SN1 and SN2 do not takes place.
26. 2)
45
27. 2)
Though (ii) contains +ve charge on oxygen. Since octet around each atom is complete the structure II is
more stable than I.
28. (3) The compound A is
centre and can be resolved into d and l form.

29. 2) The more is the stability of intermediate carbonium ion, the more is the chance of SN1 mechanism.
+ + + +
The intermediates obtained will be . Ph C H 2 ( i ) Ph C H − Me (ii), Ph C− Me 2 (iii), Ph C MePh (iv) .The
stabilty is of the order iv > iii > ii > i.
30. (3) Isopropyl chloride, being 2° alkyl halides, can undergo SN1 as well as SN2 mechanism.
31. (1) Although all the three compounds can be used for preparing Grignard reagents, diethyl ether is
considered as the best because it provides electron pairs to Mg of the reagent fully for coordination, in
case of C6H5OCH3 and C6H5N(CH3)2 electron pair on O and N are partialy delocalised over the benzene
and hence are less available for coordination with Mg.
32. (4) Ethylene dichloride can be prepared by adding HCl to ethylene glycol (CH2OH. CH2OH).
33. (2) CN– is a strong base and since the substrate is a terthalide, it mainly udnergoes elimination reaction
forming alkene 1). In presence of dil. H2SO4, alkenes undergo hydration in Markovnikov’s way.
34. 1)
46
35. 4) Occurrence of racemization points towards the formation of carbocation as intermediate, which being
planar can be attacked from either side.
36. 3) R − OH + SOCl2 ⎯⎯⎯→

Pyridine
RCl + SO2  +HCl 
SO2 and HCl being gases escape leaving behind pure alkyl halide.
37. 3)
38. 1) CH3COOAg + Br2 ⎯⎯→ CS2
CH2 Br + AgBr + CO2
39. 2) CH3Cl has higher dipole moment than CH3F due to much longer C–Cl bond length than the C–F
bond. The much longer bond length of the C–Cl bond outweighs the effect produced by lower
electronegativity of Cl than that of F.
40. (3)
41. (3)
42. (1) Boiling point of CH3I is 42°C which indicates that it is liquid at room temperature. CH3I is larger
molecule so it has stronger vander Waal’s force of attraction than others.
43. (3) 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's forces increases.
44. 3)
45. 3) Due to resonance in chlorobenzene

46. 3)
47. 2) This method is not applicable for the preparation of aryl halides because the C–O bond in phenol has
a partial double bond character and is difficult to break being stronger than a single bond.
48. 3)
49. 1)
47
50. 1)
51. 3) Organomagnesium and organolithium compounds can’t be prepared from the alkyl (or aryl) halide
having –NO2 group. On the other hand, organocopper and organocadmium compounds, do not react
with the –NO2 group.
52. 1)
53. 4) 54. 2)
55. 4) CCl4 vapours are non-inflammable (i.e. do not catch fire). Hence used as fire extinguishers under the
name pyrene.
56. 2)
57. 2)
58. 4) CHCl3 on exposure to air forms phosgene which is poisonous gas and removed by converting it into
diethyl carbonate (which is non-poisonous substance).
59. (4) Dichloromethane is widely used as solvent as a paint remover, as a propellant in aerosols and as a
process solvent in the manufacture of drugs. It is also used as a metal cleansing and finishing solvent.

60. 1) HCCl3 + 6Ag + HCCl3 ⎯⎯ → HC  CH + 6AgCl
61. (1) Since CHCl3 is covalent compound it does not produce Cl– ion in H2O, hence no white ppt is formed
during reaction with AgNO3
62. (2) This is carbylamine reaction which is used to detect presence of 1° amine in organic compounds.
The bad smelling compound is isocyanide.
63. 1) 1, 1-dichloroethane on heating with dil. NaOH gives acetaldehyde.
48
64. (3) Triiodomethane (CHI3) when comes in contact with organic matter decomposes easily to free iodine
which has antiseptic property.
65. 4)
NEET PREVIOUS YEARS QUESTIONS-EXPLANATIONS

1. 1)
2. 4)
More stable as –ve charge is close to electron withdrawing group. Also, incoming nucleophile gets
attached on same 'C' on which 'Br' (Leaving group) was present.  not a cine substitution reaction
3. 2)
is optically active due to absence of plane of symmetry and center of symmetry

4. 2) a)
This is dehydrohalogenation reaction which is an example of elimination reaction.
49
b)
Replacement of Br– by OH– is substitution reaction thus it is a nucleophilic substitution reaction.
c)
Above reaction involves addition of Br2 across double bond. Thus it is called addition reaction
5. a) ZnCl2 is a lewis acid and interact with alcohol.
Carbocation is formed as intermediate in the S1N mechanism which these reaction undergoes.
In the absence of ZnCl2 formation of primary carbocation is difficult which is the case with (ii) while
(i) undergoes reaction. (iii) Tertiary carbocation casily formed due to the stability
6. 3) Methyl group is ortho para directing but due to steric hinderce effect, generated by two CH3 groups
substitution will not take place on position (I). Hence only two products are possible.
i.e.
7. (4) Out of the given four compounds only (iv) compound is chiral and hence only this compound will
undergo racemisation.
8. 2)Halogenation (Electrophilic substitution reactions ) : Arenes react with halogens in the
50
presence of a Lewis acid like anhydrous AlCl3
9 3) Reactivity in case of SN1 reaction depends upon formation of carbocation.
10. 4)Major product formed in dehydrohalogenation reaction of 2-bromopentane is pent-2-ene because

according to Saytzeff's rule, in dehydrohalogenation reactions, the preferred product is that alkene which
has greater number of alkyl group(s) attached to the doubly bonded carbon atoms.
11. 1)The size of halogen atom increases from F to I hence bond length from C – F to C – I increases
Bond enthalpy from CH3 – F to CH3 – I decreases
12. ( 4n + 2 )  e− is not equal to 6
13.
The reaction is aromatic electrophilic substitution reaction

14. Enantiomers are not super imposable mirror images of each other
15. 1-bromo, 5 – chloro 4- methyl hexan – 3 ol
1+3+4+5-13/2+3+4+6-
16.Ans.(c)
51
In this reaction, removal of carbon dioxide takes place. So, this is a decarboxylation reaction. A decarboxylation
reaction takes place with soda lime (NaOH + CaO) So, missing reagent is CaO
17.Ans. (c)
Given
3Cl2 /Δ Br2 /Fe Zn/HCl
C7 H8 → A → B → C
The reaction in the above road map can be explained by the following steps
Step I Toluene (A) undergoes side chain halogenation with excess of chlorine to give benzotrichloride(A)
Step II In compound (A), the substituent CCl3 is an electron withdrawing group, so the electrophile will attack
at m-position. Thus, benzotrichloride reacts with bromine in presence of Fe- catalyst to give 𝑚-
bromobenzotrichloride (B).
m-bromobenzotrichloride
Step III m-bromobenzotrichloride undergoes reduction with Zn in presence of HCl to give 𝑚-bromotoluene ( 𝐶
).
52

5.HALOALKANES AND HALOARENES

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SESSION 2024-25

AS PER NEW NTA SYLLABUS

Chemistry Smart Booklet

Polyhalogen compounds are useful in various industries and in agriculture.

Dichloromethane (Methylene chloride)

1. Solvent for paint removers

1. It endangers the human central nervous system.

It is therefore stored in closed dark-coloured bottles which are completely

• The chlorofluorocarbon compounds of methane and ethane are collectively

Methods of Preparation of haloalkanes

By halogenations of alkanes in presence of light, catalyst or heat:

By halogenations of alkenes with HX :

Treatment of alcohol with HCl in the presence of anhydrous ZnCl2 phosphorous

By the action of halogen acids:

Example of Preparation of Bromoethane from Ethanol

Note: Fresh preparation of the phosphorus tribromide and phosphorus

Example: Reaction of ethanol with PCl3 for the formation of chloroethane

2) Preparation of Haloalkanes & Haloarenes from Hydrocarbons

ii) Electrophilic Substitution Reaction

Mechanism of Electrophilic Substitution Reaction

Mechanism of the Sandmeyer’s Reaction

The reaction, in this case, is an example of a regioselective reaction. In this

4) Haloalkanes and Haloarenes from Halogen exchange reaction

The reaction is an equilibrium reaction so there is a possibility of forming other

Darzen method: Darzens halogenation is a chemical processs involving the

Methods of Preparation of aryl halides

However the yield of Chlorobenzene is very poor as the main product is

In isomeric haloalkanes the boiling points decreases with increase in branching.

2. 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.

Haloalkanes are hydrocarbons in which hydrogen in a normal alkane is replaced by a

Chemical Properties of Haloalkanes

NCERT LINE BY LINE QUESTIONS

(3.) Which of the following reaction is Sandmeyer’s reaction?

(4.) Consider the following reaction [Page: 301]

The reaction represents

(7.) Which of the following statement is incorrect? [Page: 291]

(8.) Consider the following reaction [Page: 295]

Organic compounds Effects

(I) Chloramphenicol (p) treatment of malaria

(II) Thyroxine (q) antibiotic

(III) Chloroquine (r) Iodine containing hormone

(IV) Halothane (s) Anaesthetic

(11.) Consider the following reaction [Page: 300]

The type of reaction shown by the reaction is

(12.) Match the following. [Page: 292]

Column I (IUPAC) (Name) Column II

(iii) CH3 − CH2CH2CH2 Br (r) 3-bromopentane

(17.) The reagent ‘Y’ in the reaction is [Page: 296]

(18.) Thionyl chloride is preferred because [Page: 294]

(22.) Consider the following statements [Page: 292]

(25.) The product of the following reaction [Page: 297]

(28.) Assertion: Vinyl chloride is less reactive than alkyl chloride.

(30.) Assertion: Low member of alkyl halides are colourless gases.

(31.) Consider the following statements: [Page: 303]

(32.) Which of the following is not correct match? [Page: 291]

(b.) Benzylic halide-

(d.) Vinyl halide -

(33.) Assertion: CCl4 is a fire extinguisher.

(37.) Consider the following reaction [Page: 295]

(41.) Match the following. [Page: 315]