CBSE Class 12 Chemistry Notes Chapter 10 Haloalkanes and Haloarenes Overview

CBSE Class 12 Chemistry Notes for Chapter 10 Haloalkanes and Haloarenes are created by the subject
experts of Physics Wallah. These notes provide an in-depth overview of haloalkanes and haloarenes,
focusing on their structure, properties, and reactions.

The notes are designed to help students master the key concepts and mechanisms involved, making
it easier to tackle exam questions and gain a solid grasp of the topic.

CBSE Class 12 Chemistry Notes Chapter 10 PDF

The PDF for CBSE Class 12 Chemistry Notes Chapter 10 Haloalkanes and Haloarenes is available
below. This detailed guide provides detailed insights into the chemistry of haloalkanes and
haloarenes, including their properties, reactions and applications.

The notes are designed to simplify complex concepts and help in effective exam preparation. By
reviewing this PDF students can enhance their understanding of the chapter and ensure they are
well-prepared for their exams.

CBSE Class 12 Chemistry Notes Chapter 10 Haloalkanes and Haloarenes PDF

CBSE Class 12 Chemistry Notes Chapter 10 Haloalkanes and Haloarenes

Here we have provided CBSE Class 12 Chemistry Notes Chapter 10 Haloalkanes and Haloarenes-

Introduction

Haloalkanes and Haloarenes are organic compounds formed by replacing hydrogen atoms in aliphatic
or aromatic compounds with halogen atoms. In haloalkanes, the halogen atom is bonded to a sp³
hybridized carbon atom in an alkyl group, whereas in haloarenes, it is attached to a sp² hybridized
carbon atom in an aryl group.

Haloalkanes (or alkyl halides) and Haloarenes (or aryl halides) are categorized based on the number
of halogen atoms present: mono-, di-, tri-, tetra-haloalkanes or haloarenes. They are further
classified by the type of carbon atom to which the halogen is attached: primary (1°), secondary (2°),
tertiary (3°), as well as allylic, benzylic, vinylic, and aryl derivatives.

This classification helps in understanding their chemical behavior and reactivity, which is crucial for
various applications in organic chemistry.
Classification of Haloalkanes and Haloarenes

Compounds Containing sp³ C–X Bond:

Alkyl Halides (Haloalkanes)

 General formula: R–X

 Halogen (X) is bonded to a sp³ hybridized carbon atom in an alkyl group.

Allylic Halides

 Halogen (X) is bonded to a carbon atom adjacent to a C–C double bond.

Benzylic Halides

 Halogen (X) is bonded to a carbon atom adjacent to a benzene ring.

Compounds Containing sp² C–X Bond:

Vinylic Halides

 Halogen (X) is bonded to a carbon atom within a C–C double bond.

Aryl Halides

 Halogen (X) is bonded to a carbon atom within a benzene ring.

This classification is important for understanding the reactivity and properties of these compounds in
organic chemistry.

Nature of C–X Bond

In haloalkanes and haloarenes, the carbon-halogen (C–X) bond is polarized due to the difference in
electronegativity between the carbon and halogen atoms. Halogens are more electronegative than
carbon, which causes the following effects:

 Polarity of the Bond: The C–X bond becomes polarized, with the carbon atom developing a
partial positive charge (δ+) and the halogen atom developing a partial negative charge (δ-).
This polarization occurs because the halogen atom attracts the bonding electrons more
strongly than the carbon atom.

 Impact on Reactivity: The partial positive charge on the carbon atom makes it more
susceptible to nucleophilic attack, influencing the chemical reactivity of haloalkanes and
haloarenes. The partial negative charge on the halogen atom makes it a good leaving group
in many reactions.

Methods Of Preparation Of Haloalkanes

Haloalkanes can be prepared from displacement of alcoholic group in alkyl alcohol by halogen acid,
PCl5 and PCl3. Haloalkanes can also be prepared by addition of halogen acids or halogens on alkene
and alkyne. Alkyl halides can aslo be prepared by free radical halogenation of alkene.

Finkelstein Reaction

Finkelstein Reaction
R−X+NaI→X=Cl,BracetoneR—I+NaXR−X+NaIacetoneX=Cl,BrR—I+NaX

Swarts Reaction

H3C−Br+AgF⟶H3C−F+AgBrH3C−Br+AgF⟶H3C−F+AgBr
Hg2F2, COF2 and SbF3 can also be used as a reagent for Swarts reaction.Hg2F2, COF2 and SbF3 can a
lso be used as a reagent for Swarts reaction.

Hunsdiecker Reaction

CH3COOAg+Br2→CCl4CH3Br+AgBr+CO2CH3COOAg+Br2CCl4CH3Br+AgBr+CO2

Free Radical halogenat ion of alkane s

Addition of hydrogen halides on alkene s

Physical Properties Of Haloalkanes

 Boiling point orders 1. R-I > R – Br > R-Cl > R -F

 CH3–(CH2)2–CH2Br > (CH3)2CHCH2Br > (CH3)3CBr

 CH3CH2CH2 > CH3CH2X > CH3X

 Bond strength of haloalkanes decreases as the size of the halogen atom increases. Thus, the
order of bond strength is CH3F > CH3Cl > CH3Br > CH3I.

 Dipole moment decreases as the electronegativity of the halogen decreases.

 Haloalkanes though polar but are insoluble in water as they do not form hydrogen bonding
with water.

 Density order is RI> RBr > RCl > RF (for the same alkyl group) CH3I > C2H5I > C3H7I

Chemical Properties Of Haloalkanes

Relative reactivity of alkyl halides for same alkyl group is RI > RBr > RCI> RF

(I) Nucleophilic Substitution R eactions (S N reactions)

Nucleophilic Substitution Reactions

Nucleophilic substitution reactions involve the replacement of a leaving group (usually a halogen) in
a molecule with a nucleophile. These reactions can proceed via two main mechanisms: SN1 and SN2.
Each mechanism has distinct characteristics:

Characteristics of SN1 Mechanism:

 Kinetics: Follows first-order kinetics. The rate of the reaction is given by the equation: rate =
k[RX], where RX is the substrate.

 Mechanism: Occurs in two steps. First, the leaving group departs to form a carbocation
intermediate, followed by the nucleophile attacking the carbocation.

 Stereochemistry: Features a trigonal planar carbocation intermediate, leading to

racemization at a single stereogenic center due to the formation of a planar intermediate.

 Identity of R: More substituted halides (tertiary) react fastest, as the formation of a stable
carbocation is favored.

 Rate: The order of reactivity is R₃CX > R₂CHX > RCH₂X > CH₃X.

Characteristics of SN2 Mechanism:

 Kinetics: Follows second-order kinetics. The rate of the reaction is given by the equation: rate
= k[RX][Nu], where RX is the substrate and Nu is the nucleophile.

 Mechanism: Occurs in a single step. The nucleophile attacks the carbon atom from the
backside while the leaving group departs simultaneously.

 Stereochemistry: Involves a backside attack by the nucleophile, leading to inversion of

configuration at the stereogenic center.

 Identity of R: Unhindered halides (methyl or primary) react fastest, as steric hindrance

inhibits the nucleophile’s attack.

 Rate: The order of reactivity is CH₃X > RCH₂X > R₂CHX > R₃CX.
(II) Eliminat ion Reactions

Dehydrohalogenation is a -elimination reaction in which halogen is from α carbon atom and the
hydrogen from the β carbon according to Saytzeff rule, e.g.,

(III) Reduction

C2H5—Br+H2→Ni, 575 KC2H6+HBrC2H5I+HI→Red P, 420 KC2H6+I2C2H5—Br+H2Ni, 575 KC2H6

+HBrC2H5I+HIRed P, 420 KC2H6+I2

(IV) R eaction with Metals

(1) Wurtz reaction: RX+2Na+XR→DryetherR—R(alkane)+2NaXRX+2Na+XRDryetherR—R(alkane)+2NaX

(2) Wurtz-Fitting
C6H3—Cl+2Na+ClCH3→DryetherC6H5—CH3+2NaClC6H3—Cl+2Na+ClCH3DryetherC6H5—
reaction:

C2H5Br+Mg→DryetherC2H5—Mg—Br(Grignard’sreagent)C2H5Br+MgDryether(Grignard
(3) Reaction with Mg:
Mg—Br

Methods Of Preparation Of Haloarenes

(a) By Electrophilic Substitution Reaction:

(b) Sandmeyer’s Reaction

(c) Gattermann Reaction:

(d) In the presence of KI

(e) Balz-Schiemann reaction:

Chemical Properties Of Haloarenes

Aromatic nucleophilic s ubstitution reaction Haloarenes do not undergo nucleophilic substitution

reaction readily. This is due to C–X bond in aryl halide is short and strong and also the aromatic ring is
a centre of high electron density. The halogen of haloarenes can be substituted by OH-, NH2 -, or CN-
with appropriate nucleophilic reagents at high temperature and pressure. For Example :

C6H5Cl+NaOHChlorobenzene→300atm350°CC6H5OH+NaClChlorobenzeneChlorobenzeneC6H5
Cl+NaOH350°C300atmChlorobenzeneC6H5OH+NaCl

C6H5Cl+2NH3Chlorobenzene→50atm250°CC6H5NH2+NH4ClAnilineChlorobenzeneC6H5Cl+2NH3
250°C50atmAnilineC6H5NH2+NH4Cl

C6H5Cl+CuCNChlorobenzene→Pyridine250°CC6H5CN+CuClPhenylcyanideChlorobenzeneC6H5
Cl+CuCN250°CPyridinePhenylcyanideC6H5CN+CuCl

Polyhalogen Compounds: Uses and Environmental Effects

(i) Dichloromethane (Methylene Chloride):

Dichloromethane is widely used as a solvent in various applications, including paint removal, aerosol
propellants, and as a process solvent in drug manufacturing. It is also employed in metal cleaning
and finishing due to its effective dissolving properties.

(ii) Triiodomethane (Iodoform):

Triiodomethane, commonly known as Iodoform, serves primarily as an antiseptic. Its antiseptic
properties arise from the liberation of free iodine rather than from Iodoform itself.

(iii) Trichloromethane (Chloroform):

Trichloromethane, or Chloroform, has been used as an anesthetic. When inhaled in pure form, it
affects the heart, which necessitates its use in combination with ether and other anesthetics for safe
anesthesia administration.

(iv) Tetrachloromethane (Carbon Tetrachloride):

Carbon Tetrachloride is utilized in the manufacture of refrigerants, aerosol propellants, and
chlorofluorocarbons. It also finds applications in pharmaceuticals due to its versatile chemical
properties.

(v) Freons:
Freons are chlorofluorocarbons derived from methane and ethane. They are characterized by their
stability, non-corrosiveness, and non-toxicity, making them ideal for use as refrigerants and
propellants. However, their environmental impact has raised concerns due to their role in ozone
depletion.

(vi) P,P’-Dichlorodiphenyltrichloroethane (DDT):

DDT, one of the first chlorinated organic insecticides, is highly toxic to various living organisms. It
accumulates in fatty tissues due to its slow metabolism in animals, leading to significant
environmental and health concerns. Its use has been restricted or banned in many countries due to
these adverse effects.

Polyhalogen Compounds: Uses and Environmental Effects

(i) Dichloromethane (Methylene Chloride):

Dichloromethane is widely used as a solvent in various applications, including paint removal, aerosol
propellants, and as a process solvent in drug manufacturing. It is also employed in metal cleaning
and finishing due to its effective dissolving properties.

(ii) Triiodomethane (Iodoform):

Triiodomethane, commonly known as Iodoform, serves primarily as an antiseptic. Its antiseptic

properties arise from the liberation of free iodine rather than from Iodoform itself.

(iii) Trichloromethane (Chloroform):

Trichloromethane, or Chloroform, has been used as an anesthetic. When inhaled in pure form, it
affects the heart, which necessitates its use in combination with ether and other anesthetics for safe
anesthesia administration.

(iv) Tetrachloromethane (Carbon Tetrachloride):

Carbon Tetrachloride is utilized in the manufacture of refrigerants, aerosol propellants, and

chlorofluorocarbons. It also finds applications in pharmaceuticals due to its versatile chemical
properties.

(v) Freons:

Freons are chlorofluorocarbons derived from methane and ethane. They are characterized by their
stability, non-corrosiveness, and non-toxicity, making them ideal for use as refrigerants and
propellants. However, their environmental impact has raised concerns due to their role in ozone
depletion.

(vi) P,P’-Dichlorodiphenyltrichloroethane (DDT):

DDT, one of the first chlorinated organic insecticides, is highly toxic to various living organisms. It
accumulates in fatty tissues due to its slow metabolism in animals, leading to significant
environmental and health concerns. Its use has been restricted or banned in many countries due to
these adverse effects.

Benefits of CBSE Class 12 Chemistry Notes Chapter 10 Haloalkanes and Haloarenes

 Comprehensive Coverage: These notes provide a thorough overview of Haloalkanes and

Haloarenes, covering essential concepts such as their classification, bonding nature, and
chemical reactions. This ensures a solid understanding of the topic.
 Clarity and Simplicity: The notes are written in simple language, making complex chemical
concepts more accessible to students.

 Detailed Reaction Mechanisms: The notes include detailed explanations of nucleophilic

substitution reactions, elimination reactions, and the behavior of polyhalogen compounds.
This helps students grasp the mechanisms and applications of these reactions.

 Visual Aids: Diagrams and reaction schemes are incorporated to visually represent the
chemical processes, aiding in better comprehension and retention of the material.

 Application of Knowledge: By studying these notes students gain insights into the practical
uses and environmental impacts of various haloalkanes and haloarenes, linking theoretical
knowledge with real-world applications.