index

Classification

Nucleophilic Substitution Reaction

Elimination Reaction

Substitution vs Elimination

Preparation of alkyl halide

Physical Properties

Polyhalogen compounds
 Real life importance of Alkyl Halide

Alkyl halide compounds used as a solvent, a paint remover, a propellant in

aerosols, and in the manufacture of drugs. It is also used in the
manufacture of refrigerants and a.c.

College related importance of alkyl halide

Haloalkanes are used in the lab as intermediate in making other

molecule.
 JEE Main Exam

HALOGEN DERIVATIVES
10.23%

Organic Chemistry
 JEE Advanced Exam
Organic Chemistry: Relative Weightage (2019-23)

HALOGEN
DERIVATIVES
11.8%
Pre-requisite chapters

General organic chemistry (GOC)

Isomerism

Hydrocarbon
 j
Classification of Alkyl and Aryl Halides

On the basis of On the basis of

On the basis of
compounds compounds
number of
containing containing
Halogen atoms
sp3 C-X sp2 C-X
C2H5Cl
CH2 == CH—CH2—Cl CH2 == CH—Cl :
CH2X
CH2X X:
CH2—X
R—CHX2

CHCl3
 Nucleophilic Substitution Reaction

Θ
— C—L.G. + NuΘ — C—Nu + L.G.

The reaction has been found to proceed by different mechanisms.

S N1 SN i

SN 2 SNNGP
 SN2 (Bimolecular Nucleophilic Substitution)

Nu + R—X R—Nu + X

Mechanism

Nu + R—X R—Nu + X
Nucleophile Substrate

Characteristics:

It is a one step reaction.

Nucleophile attacks on the substrate from just opposite side to the

leaving group.
Kinetics of the reaction

ROR  [ R—X] [ Nu]

ROR = k [ R—X ] [ Nu]

order = 2
Molecularity = 2

SN2 reaction is favored by polar aprotic solvent. (Ex: DMSO, DMF ,

acetone etc.).

In SN2 reaction, transition state (T.S.) is formed .

In transition state (T.S.), partly bond formation and bond breaking

is involved.

In SN2 reaction, transition state (T.S.) is negatively charged .

 StereoChemistry & Mechanism of reaction

R
R d– d– R
+ Cl
HO + C Cl HO C Cl HO C
D sp3 sp2 sp3 D
H HD H
Transition state
(Penta-coordinated)

Inversion of configuration
(Walden Inversion)
Note

SN2 reaction completes with almost 100% inversion of configuration.

 EXAMPLE

The major product formed in the following reaction is :

Et
OH—
Me Br

H
CH3

C CH3O—/DMSO
H
Cl
Cl
C CH3O—/DMSO
CH3
H
Factor's affecting the rate of SN2 reaction

Substrate 1
Rate of SN2 reaction ∝ Branching at alpha and beta carbon
(Steric Crowding)
X

CH3—X > H3C—CH2—X > H3C—CH—X > H3C—C—CH3

CH3 CH3
CH3

H3C—CH2—CH2—X > H3C—CH—CH2—X > H3C—C—CH2—X

CH3 CH3

Electron withdrawing groups (e.g. Carbonyl Group) at 𝛼 carbon

increases the stability of transition state due to presence of
negative charge in the T.S Hence rate of SN2 increases.
 Factor's affecting the rate of SN2 reaction

ROR  [ Nu]

Nucleophile As nucleophilicity of nucleophile increases, rate of

SN2 reaction increases.
Aq. KOH/NaOH shows SN2/SN1 reaction depending
upon the substrate.

Solvent Polar aprotic Solvent favors SN2 Reaction

Leaving Group
R I > R Br > R Cl > R F
 Compounds Don’t show SN2 Reaction

H2C=CH—X X

Vinyl halide Aryl halide

CH3 X
CH3
H3C—C—X H3C—C—CH2—X
CH3 CH3
Bredt’s rule
3° alkyl halide Neopentyl halide violation
 EXAMPLE

The major product formed in the following reaction is :

Br
NH3
Br

Solution

NH2
Ans.
Br
 EXAMPLE

The major product formed in the following reaction via SN2 is :

K2CO3
[JEE (Main)-2021]
+ Cl
OH Acetone

Solution

Ans.
O
 EXAMPLE

The major product formed in the following reaction is :

MeNH2
Cl
Cl

Solution

N
Ans.
 EXAMPLE

Major product ‘P’ formed in the following reaction is :-

OH Br2
P
NaHCO3
O
Major Product [JEE (Main)-2023]

Br Br
Br OH O Br OH OH
(1) (2) (3) (4)
O O O O
Solution

OH Br2
NaHCO3
O

Ans. (2)
 EXAMPLE

The decreasing order of reactivity of the following compounds

towards nucleophilic substitution reaction (SN2) is
CH2Cl CH2Cl CH2Cl CH2Cl
NO2

NO2 NO2 NO2 NO2

(I) (II) NO2 (III) (IV)

[JEE (Main)-2020]
Solution

CH2Cl CH2Cl CH2Cl CH2Cl

NO2

NO2 NO2 NO2 NO2

(I) (II) NO2 (III) (IV)

Ans. (ii > iii > iv > i )

 EXAMPLE

The reaction of 4-methyloct-ene (P, 2.52 g) with HBr in the presence of

(C6H5CO)2O2 gives two isomeric bromides in a 9 : 1 ratio, with combined
yield of 50%. Of these, the entire amount of the primary alkyl bromide
was reacted with an appropriate amount of diethylamine followed by
treatment with eq. K2CO3 to given a non-ionic product S in 100% yield.
The mass (in mg) of S obtained is __.
[Use molar mass (in g mol–1) : H = 1, C = 12, N = 14, Br = 80]
[JEE-Advanced 2023]
 The reaction of 4-methyloct-ene (P, 2.52 g) with HBr in the
Solution
presence of (C6H5CO)2O2 gives two isomeric bromides in a 9 :
1 ratio, with combined yield of 50%. Of these, the entire
amount of the primary alkyl bromide was reacted with an
appropriate amount of diethylamine followed by treatment
with eq. K2CO3 to given a non-ionic product S in 100% yield.
The mass (in mg) of S obtained is __.
[Use molar mass (in g mol–1) : H = 1, C = 12, N = 14, Br = 80]

Ans. (1791)
 EXAMPLE

Which of the following compounds will show retention in configuration

on nucleophic substitution by OH⊝ ion ? Br
CH3–CH–CH2Br CH3–CH–Br CH3–CH–Br CH3–C–H

(A) C2H5 (B) C2H5 (C) CH3 (D) C6H13

[JEE (Main)-2020]
Solution

Ans. (A)
 SN1 (unimolecular Nucleophilic Substitution)

R—X + H–A R— A + H–X

(Solvent)

Reaction in which only solvent act as reagent are called solvolysis

reaction.

Mechanism

slow
R—X + solvent R+X Step 1
rds

R + H–A Fast R—A

–H+ Step 2
Characteristics:

It is a two step reaction.

Kinetics of the reaction

ROR  [R—X ]
Rate = k[ R—X ]
order = 1

Molecularity = 1

Rate is independent of concentration of nucleophile.

In SN1 reaction, intermediate i.e. Carbocation formed so

Rearrangement may be possible.
 EXAMPLE

The graph which represents the following reaction is :

⊖
OH
(C6H5)3C—Cl (C6H5)3C—OH
Pyridine

rate rate rate rate

(1) (2) (3) (4)

[(C6H5)3C–Cl] [OH–] [(C6H5)3C–Cl] [Pyridine]

[JEE (Main)-2023]
Solution

Ans. (3)
 EXAMPLE

The major product formed in the following reaction is :

CH3OH

Cl

Solution

Ans.
OCH3
 Stereochemistry & Mechanism of Reaction

H–A R–X H–A (ionisation of R—X)

⊕
H–A R A–H (stabilization of charges)
⊖
A–H X H–A

R= chiral Centre R–A + A–R

Retention inversion

Key Point

In SN1 reaction racemic mixture is obtained.

Inversion product > retention product

 Energy Profile Diagram for SN1

Intermediate

TS(1)
TS(2)

 ⊝
R +X
Free energy
R–X

R–A
Progress of reaction
 Factor's affecting the rate of SN1 reaction

X
H3C—CH2—X > H3C—CH—X > H3C—C—CH3

CH3 CH3
Substrate
Rate of SN1 reaction Stability of carbocation intermediate

ROR  [ RX]
Nucleophile Rate is independent of concentration of
Nucleophile

Solvent Polar protic Solvent favors SN1 Reaction

Leaving Group
R I > R Br > R Cl > R F
 Compounds Don’t show SN1 Reaction

H2C=CH—X

:
Vinyl halide
Partial double
bond
character

:
Aryl halide
Partial double
bond
character
X

Bredt’s rule
violation
 EXAMPLE

Which of the following plots is(are) correct for the given reaction?
([P]0 is the initial concentration of P)
CH3 CH3

H3C Br+ NaOH H3C OH + NaBr [JEE-Advanced 2020]

CH3 CH3
(P) (Q)

Initial rate
(Q)
(A) t1/2 (B) (C) (D) In P
P 0 P 0

[P]0 [P]0 time time

Solution

Ans. (A)
 EXAMPLE

Choose the halogen which is most reactive towards SN1 reaction in the
given compounds (A, B, C & D)
Br(a)

A. B. I(a) I(b) C. D. Br(b)

Br(b) Br(a)
Br(b) Br(a)

(1) A-Br(b) ; B-I(b) ; C-Br(b) ; D-Br(b) (2) A-Br(a) ; B-I(a) ; C-Br(b) ; D-Br(a)
(3) A-Br(b) ; B-I(a) ; C-Br(a) ; D-Br(a) (4) A-Br(b) ; B-I(a) ; C-Br(a) ; D-Br(a)
[JEE (Main)-2023]
Solution

Ans. (2)
Test with aqueous AgNO3

R–X + AgNO3 AgX + R

It follows SN1 reaction

Ppt of AgX formed only when stable carbocation is formed.

Aryl and vinyl halides do not form precipitate of silver halide with
ethanolic silver nitrate solution.
 EXAMPLE

The major product formed in the following reaction is :

CH3

H — C — CH2 —I Aq. AgNO3

Solution CH3
Ans. HO — C — CH3
 Miscellaneous reaction
EXAMPLE

The decreasing order of reactivity of the following organic molecules

towards AgNO3 solution is :
Cl Cl
CH3CHCH3 CH3CHCH2NO2
Cl Cl
(A) (B) (C) (D)
OMe

(1) (A) > (B) > (D) > (C) (2) (A) > (B) > (C) > (D)

(3) (C) > (D) > (A) > (B) (4) (B) > (A) > (C) > (D)
 Solution

Cl Cl
CH3CHCH3 CH3CHCH2NO2
Cl Cl
(A) (B) (C) (D)
OMe

Ans. (4)
 Comparison between SN1 and SN2

Factor SN 1 SN 2
Substrate 2,3 (requires formation Methyl > 1> 2
of a relatively stable (requires
carbocation) unhindered
substrate)
Nucleophile neutral molecule OR Strong Lewis base,
nucleophile may be the rate increased by
solvent (solvolysis) high concentration
of nucleophile
Solvent Polar protic (e.g., Polar aprotic
alcohols, water) (e.g., DMF, DMSO)
Leaving I > Br > Cl > F for both SN1 and SN2
group (the weaker the base after the group departs,
the better the leaving group)
 EXAMPLE

2-Methyl propyl bromide reacts with C2H5O– and gives ‘A’ whereas on
reaction with C2H5OH it gives ‘B’. The mechanism followed in these
reactions and the products ‘A’ and ‘B’ respectively are:
(1) SN2, A = iso-butyl ethyl ether; SN1, B= tert-butyl ethyl ether
(2) SN1, A = tert-butyl ethyl ether; SN1, B = 2- butyl ethyl ether
(3) SN1, A = tert-butyl ethyl ether; SN2, B = iso-butyl ethyl ether
(4) SN2, A =2-butyl ethyl ether; SN2, B= iso-butyl ethyl ether
[JEE (Main)-2023]
Solution

Ans. (1)
 EXAMPLE Consider the following reaction.

List - I List - II
(P) (-)-1-Bromo-2-ethylpentane aq. NaOH
(1) Inversion of configuration
(single enantiomer) SN2 reaction
(Q) (-)-2-Bromopentane aq. NaOH (2) Retention of configuration
(single enantiomer) SN2 reaction
(R) (-)-3-Bromo-3-methylhexane aq. NaOH (3) Mixture of enantiomers
(single enantiomer) SN1 reaction
(4) Mixture of structural isomers
aq. NaOH
(S) Me HMe Br
SN1 reaction (5) Mixture of diastereomers
(Single enantiomer)

(A) P → 1; Q → 2; R → 5; S → 3 (B) P → 2; Q → 1; R → 3; S → 5
(C) P → 1; Q → 2; R → 5; S → 4 (D) P → 2; Q → 4; R → 3; S → 5
[JEE-Advanced 2023]
 Solution

List - I
(P) (-)-1-Bromo-2-ethylpentane aq. NaOH
(single enantiomer) SN2 reaction
(Q) (-)-2-Bromopentane aq. NaOH
(single enantiomer) SN2 reaction
(R) (-)-3-Bromo-3
aq. NaOH
-methylhexane
SN1 reaction
(single enantiomer)
aq. NaOH
(S) Me HMe Br SN1 reaction
(Single enantiomer)

Ans. (B)
 EXAMPLE

Match List I with List II

1 - Bromopropane is reacted with reagents in List I to give product in
LIST I - LIST II -
Reagent Product
A. KOH (alc) I. Nitrile
B. KCN (alc) II. Ester
C. AgNO2 III. Alkene
D. H3CCOOAg IV. Nitroalkane

(1) A-IV, B-III, C-II, D-I (2) A-III, B-I, C-IV, D-II
(3) A-I, B-II, C-III, D-IV (4) A-I, B-III, C-IV, D-II
[JEE (Main)-2023]
Solution

Ans. (2)
 SNNGP Nucleophilic substitution by Neighbouring Group
Participation

When substrate contains a group with an unshared pair of electron

beta to the leaving group or sometimes further away then it is called
neighbouring group participation or SNNGP.

“
Example
“ 14
S CH2—OH

: :
Ph CH2
14
S CH2—Cl
: :
aq. KOH +
Ph CH2
S CH2—OH

: :
14
Ph CH2
Mechanism:
Ph

14
⊕
S
S CH2—Cl

: :
aq. KOH ⊖
Ph CH2 H2C—CH2 + Cl
14

⊖
⊖
OH OH

14
S CH2—OH S CH2—OH

: :

: :
14
Ph CH2 Ph CH2
Characteristics:

SNNGP is faster than SN1 & SN2

SNNGP consists essentially of two SN2 substitutions, each causing

an inversion each so the net result is retention of configuration.
 EXAMPLE

Find product of given below reaction : [JEE-Advanced 2015]

O
||
C—OH NaNO2 +aq. HCl

0℃
NH2
O
NH2 ||
(a) C—OH
(b)
OH
OH

COOH NH2
(c) (d)
OH OH
Solution

Ans. (c)
Elimination reaction

E1 E2

Steps Two One

⊖
H—C—C—X B
H

—C—C—
⨁ ⨁
H—C—C +X

–H
⊕ X

C=C

:
C=C + X
⊖
BH +
 Elimination reaction

E1 E2

First order Second order

Kinetic unimolecular biomolecular
⊖
R=k[RX] R=k[RX][B ]

Alkyl 3° >2° >1° 3° >2° >1°

group

Base External base are not

High Concentration of
required. Only
strong base are required.
solvent act as base.
Eg. Alc. KOH/NaOH, bulky
Eg. ROH/𝚫, ⊖
base t-BuO ,NaNH2 etc.
Conc. H2SO4/H3PO4
 Substitution vs Elimination
Strongly basic, Strongly basic,
Poor nucleophile Weakly basic
unhindered hindered nucleophile
(e.g. H2O, ROH) in nucleophile
nucleophile (e.g. DBU, DBN, t-
acid medium (e.g. I¯ , RS¯)
(e.g. RO¯) BuO¯)
Methyl
H3C No reaction SN2 SN2 SN2
X
Primary (unhindered)
No reaction SN 2 SN 2 E2
X
Primary (hindered)
X No reaction SN 2 E2 E2
Secondary
SN1, E1 (slow) SN 2 E2 E2
X
tertiary
X
E1 or SN1 SN1 or E1 E2 E2

b to anion-stabilizing
group O X
𝛽
E1cB E1cB E1cB E1cB
𝛼
 Effect of Temperature

Since elimination forms more product than the substitution hence

Elimination reaction is entropically driven at high temperature.

Br OH
45°C
+ HO¯ ⎯⎯⎯⎯⎯→ + + H2O + Br¯
CH3CH2OH/H2O

47% 53%

Br OH
100°C
+ HO¯ ⎯⎯⎯⎯⎯→ + + H2O + Br¯
CH3CH2OH/H2O

29% 71%
 EXAMPLE

The major product formed in the following reaction given below is:
CH3 [JEE (Main)-2021]
Cl NaOH
C2H5OH

Solution

Ans.
 EXAMPLE

The major product formed in the following reaction given below is:

CH3CH2CHCH2Br [JEE (Main)-2021]

CH3O—
CH3OH

Solution

H3C – H2C – CH = CH2

Ans.
 EXAMPLE

The major product of the following reaction is : [JEE (Main)-2019]

CH2CH3
NaOEt
H3C C Cl
∆
COOCH2CH3

CH2CH3 OCH2CH3

(1) H3 C C OCH2CH3 (2) H3CH2C C CO2CH2CH3

COOCH2CH3 CH3

CO2CH2CH3 CH3CH2C = CH2

(3) (4)
CH3C = CHCH3 CO2CH2CH3

Solution Ans. (4)

 EXAMPLE
CH3CH2CH2Z + Br⊝
ks

For the following reactions : CH3CH2CH2Br + Z⊝

CH3 ke
where CH3CH=CH2 + HZ + Br⊝
Z⊝ = CH3CH2O⊝ (A) or H3C–C–O⊝ (B),
CH3
ks and ke , are , respectively, the rate constants for the
substitution and elimination, and m =ks/ke , the correct options is -

(A) mB > mA and ke(B) > ke(A) (B) mB > mA and ke(A) > ke(B)
(C) mA > mB and ke(B) > ke(A) (D) mA > mB and ke(A) > ke(B)
[JEE (Main)-2020]
Solution

Ans. (C)
 Reaction with metal

ether
R – X + Mg R – Mg X

Reactivity order :- R–I > R – Br > R– Cl

Diethyl ether (Et2O) dimethoxyethane(DME),dioxane and

tetrahydrofuran (THF) are generally used as solvent and it is
lewis base.

CH2―CH2 & are not used as solvent because they react with
O O Grignard reagent to minimise angle strain.

Grignard reagent do not form pure carbanion but it has tendency to

form carbanion by heterolytic cleavage so act as nucleophile or base.
 Acid-Base reaction

Compounds having active hydrogen give acid base reaction with

Grignard reagent
X
R ― MgX + H ― A RH + Mg
A
“
Example
“
R ― SO3H, R ―COOH, ROH, RSH, NH3, R ―NH2, R2NH, H2O, Ph ―OH
,
O
R ―CCH, active methylene compound, R ―C ―NH2 , D2O, react with
Grignard reagent
Reaction with aq. KNO2 & aq. AgNO2 Reaction with aq. KCN & aq. AgCN

O
•• ||
R–NO2 Ag–O–N=O Ag–C≡N: H+/H2O
R–NC R–NH2 + H–C–OH
R—X
KNO2 KCN

R–CN
R–O–N = O
H+/H2O

O
||
R–C–OH
 Preparation of alkyl halide

Photo halogenation

hn hn
CH4 + Cl2 CH3Cl + HCl CH4 + Cl2 CCl4
(Excess) (excess)

CH3 CH3
Cl2
CH3—CH—CH2Cl + CH3—C—CH3
hn
Cl
CH3 64.28% 35.72%
CH3—CH—CH3
CH3 CH3
CH3—CH—CH2Br + CH3—C—CH3
Br2
hn 1% Br
more 99%
From Alkene

HBr
A

HCl
B

HBr
C
Peroxide

HCl
D
Peroxide
From Alkene

X2
CCl4

X2
H2O
CH2=CH2
ICl
CCl4

NOCl
From Alcohol with HX

R—O—H+H—X R — X + H2O

Rate of HX with R—OH is HI > HBr > HCl > HF

Rate of ROH according to SN1

OH

H3C—CH2—OH H3C—CH—OH H3C—C—CH3

> >

CH3 CH3
1° 2° 3°

H3C—CH2—OH < H3C—OH

 EXAMPLE

The major product formed in the following reaction is :

OH
HBr
Conc. H2SO4

HI

OH

Me

Pr HI
OH

Et
From Alcohol and SOCl2

SNi
ROH + SOCl2 R Cl + SO2↑ + HCl ↑

OH

SOCl2
No reaction

R C—OH SOCl2 R C—Cl

O O
 EXAMPLE

The major product formed in the following reaction is :

OH [JEE (Main)-2021]

SOCl2

HOH2C OH

Solution
OH
Ans.

Cl—H2C Cl
From Alcohol and SOCl2 with pyridine

Me Me
C + SOCl pyridine C + SO2(g) + HCl (g)
2
H OH SN2 Cl H
R
R
 Reaction of R-OH with PCl3 & PCl5

SN2
3R OH + PCl3 3R Cl + H3PO3
or inversion
Red P/X2

SN2
R–OH + PCl5 R–Cl + POCl3 + HCl↑
inversion

Characteristics:

Reaction follow SN2 path, thus inversion product is formed.

Driving force of this reaction is strong affinity of phosphorous

with O.
 Some other reaction of PCl5

O
R' R + PCl5 RCl + R'Cl + POCl3
ether
O O

R—C—OH + PCl5 R—C—Cl + HCl + POCl3

Carboxylic acid

O
R C OR' + PCl5 RCOCl + R'Cl + POCl3

O O O O

R—C—O—C—R’ + PCl5 R—C—Cl + R’—C—Cl + POCl3

(Anhydride)
 Some other reaction of PCl5

O Cl Cl
Cl Cl
Cl
C POCl3
C + P +
R' R
R' R Cl Cl

R—C—NH2 + PCl5 R—C ≡ Nሷ

O Cl Cl

R—C—H+ PCl5 R—C—H + POCl3

 EXAMPLE
OH
red phosphorous
Consider the following reaction. R (major product)
Br2
Br
On estimation of bromine in 1.00 g of R using Carius method, the amount
of AgBr formed (in g) is ______.
[Given : Atomic mass of H = 1, C = 12, O = 16, P = 31, Br = 80, Ag = 108]

[JEE-Advanced 2022]
Solution

Ans. (1.50)
 Halogen Exchange Reaction
Finkelstein Reaction

Preparation of Alkyl iodides by the reaction of alkyl chlorides/

bromides with NaI in dry acetone is known as Finkelstein reaction.

Dry
R X + NaI R I + NaX
acetone
X = Cl, Br

Note

(1) NaCl or NaBr is precipitated in dry acetone, which is driving force.

(2) NaCl & NaBr are insoluble in dry acetone while NaI is soluble.

(3) SN2 mechanism is involved and hence inversion takes place.

 EXAMPLE

For the reaction:

Acetone
RCH2Br+I − RCH2 I + Br −
major

[JEE (Main)-2023]
The correct statement is :
(1) The transition state formed in the above reaction is less polar
than the localised anion.
(2) The reaction can occur in acetic acid also.
(3) The solvent used in the reaction solvates the ions formed in rate
determining step.
(4) Br– can act as competing nucleophile.

Solution

Ans. (1)
 EXAMPLE

In the following reaction sequence, the correct structure(s) of X is

(are):
Me N3
1) PBr3,Et2O
X
2) Nal, Me2CO
3) NaN3, HCONMe2
Enantiomerically pure
Me OH Me
OH
[JEE-Advanced 2018]
(A) (B)

(C) (D)
Me OH
Me OH
 Solution

1) PBr3,Et2O Me N3
X
2) Nal, Me2CO
3) NaN3, HCONMe2

Ans. (B)
 Swarts Reaction

The synthesis of alkyl fluorides is best accomplished by heating

an alkyl chloride/ bromide in presence of metallic fluoride such as

AgF, Hg2F2, HgF2, CoF2 or SbF3.

DMSO
CH3 –X + AgF CH3 –F + AgX

X = Br, Cl, I

F is a good nucleophile in polar aprotic solvent hence this reaction

⊝

occurs via SN2 mechanism.

 Physical
Properties

Boiling point &

Melting point

Solubility

Density

Dipole moment
 Boiling point

Boiling point
of Haloalkanes
depends on

Polarity & molar mass of the compound

Branching of parent chain

 Boiling point of Haloalkanes

Boiling point of Haloalkanes is directly proportional to the van der

Waals force of attraction.

Higher the molecular mass more will be its boiling point

EXAMPLE

Compare boiling point of given below compounds

CH3F , CH3Cl , CH3Br , CH3I

Solution

Ans. H3CI > CH3Br > CH3Cl > CH3F

 For isomeric haloalkane, boiling point decreases as branching
increases.
1
Boiling Point of isomeric haloalkanes  Branching

Example
CH3
Br
CH3—C—Br

—
CH3—CH2—CH2—CH2—Br CH3—CH—CH2—CH3
CH3

1-bromobutane 2-bromobutane 2- bromo-2- methyl

propane

375 K 364 K 346 K

 EXAMPLE

The correct order of melting point of dichlorobenzenes is

Cl Cl Cl Cl Cl Cl
Cl Cl
(A) > > (B) > >
Cl Cl
Cl Cl
Cl Cl Cl Cl Cl Cl
Cl Cl
(C) > > (D) > >
Cl Cl
Cl Cl
[JEE (Main)-2023]
Solution
Cl Cl Cl
Cl

M.P 256 K 249 K 323 K

Cl
B.P 453 K 446 K 448 K Cl Ans. (D)
 Solubility

Haloalkanes are very slightly soluble in water and easily soluble in

organic solvent,

Density

Density  Number of carbon atoms  Number of halogen atoms

Density  atomic mass of halogen atoms

 EXAMPLE

Identify the correct order for the given property for following
compounds
Cl
(A) Boiling Point : Cl < < Cl
Cl
(B) Density : Br < < I
Br Br Br
(C) Boiling Point Br < Br < Br
I Br Cl
(D) Density : < <

Br
(E) Boiling point : Cl
Cl
< <
Cl
[JEE (Main)-2023]
 EXAMPLE

Choose the correct answer from the option given below :-

(1) (B), (C) and (D) only (2) (A), (C) and (E) only
(3) (A), (C) and (D) only (4) (A), (B) and (E) only
[JEE (Main)-2023]
Solution

Ans. (2)
 EXAMPLE

The pair from the following pairs having both compounds with net non-
zero dipole moment is
(1) Benzene, anisidine
(2) 1,4-Dichlorobenzene, 1,3-Dichlorobenzene
(3) CH2Cl2, CHCl3
(4) cis-butene, trans-butene [JEE (Main)-2023]

Solution

Ans. (3)
 Dipole moment

𝛍=qxd
“
“ Example
the order of dipole moment of CH3X, where X=F, Cl, Br, I, is given
below.
Due to charge factor

CH3Cl > CH3F > CH3Br > CH3I

Due to size factor

Order of Polarity of C—X bond Order of C—X bond length

C — I < C — Br < C — Cl < C—F C — I > C — Br > C — Cl > C—F

 Polyhalogen Compounds

Iodoform

It is yellow crustallline solid and insoluble in water but soluble in

solvents like ethanol, chloroform, and ether.

Iodoform was used earlier as an antiseptic but the antiseptic

properties are due to the liberation of free iodine and not due to
the iodoform itself.

skin
CHI3 I2 (has antiseptic properties)
contact
Freons (CFC)

The chlorofluorocarbon compounds of methane and ethane are

collectively known as freons and it contains C, F and Cl.
“
“ Example CCl2F2 , C2F4Cl2 etc.

They are extremely stable, unreactive, non-toxic, non-corrosive and

easily liquefiable gases.

Freon 12 or R-12 (CCl2F2) is one of the most common. It is

manufactured from tetrachloromethane by Swarts reaction.

These are usually produced for aerosol propellants, refrigeration

and air conditioning purposes.
 p,p-Dichlorodiphenyltrichloroethane (DDT)

It was the first chlorinated organic insecticide prepared in 1873.

Prepared by heating chloral and chlorobenzene in the presence of

conc. H2SO4 .

Cl Cl
Cl Cl Cl Cl

CH

O
H H
H+
Cl Cl
-H2O
Cl Cl (DDT)
 EXAMPLE

Which of the following is true about freons ?

(1) These are chlorofluorocarbon compounds
(2) These are chemicals causing skin cancer
(3) These are radicals of chlorine and chlorine monoxide
(4) All radicals are called freons [JEE (Main)-2023]

Solution

Ans. (1)
 EXAMPLE

In the following halogenated organic compounds the one with maximum

number of chlorine atoms in its structure is :
(1) Chloral (2) Gammaxene
(3) Chloropicrin (4)Freon -12 [JEE (Main)-2023]

Solution

Ans. (2)
 EXAMPLE

Which of the following compounds is an example of Freon?

(1) C2Cl2F2 (2) C2HF3 (3) C2H2F2 (4) C2F4

[JEE (Main)-2023]
Solution

Ans. (1)
Post-requisite chapters

Alcohol, Phenol, Ether

Carbonyl Compounds

Carboxylic Acids and its derivatives

Amine

Aromatic compounds
Key takeaways

To predict product based on SN2 and SN1 reaction.

Intermediate and Transition state

Effect of temperature on chemical reaction

Why the solvent matters.