Halogen Derivatives

EUNOIA JUNIOR COLLEGE

H2 CHEMISTRY (9729) TEACHERS’ COPY
Organic Chemistry (2018 JC2)

Topic 5: Halogen Derivatives

Name: ___________________________________________ Civics Group: _________

Candidates should be able to:

(a) recall the chemistry of halogenoalkanes as exemplified by:

(i) the following nucleophilic substitution reactions of bromoethane: hydrolysis; formation
of nitriles; formation of primary amines by reaction with ammonia
(ii) the elimination of hydrogen bromide from 2-bromopropane
(b) describe and explain the mechanisms of nucleophilic substitutions in halogenoalkanes:
(i) SN1, in terms of stability of the carbocation intermediates
(ii) SN2, in terms of steric hindrance of the halogenoalkanes
(c) explain the stereochemical outcome in nucleophilic substitution involving optically active
substrates:
(i) inversion of configuration in SN2 mechanism
(ii) racemisation in SN1 mechanism
(d) interpret the different reactivities of halogenoalkanes, with particular reference to hydrolysis,
and to the relative strengths of the C-Hal bonds
(e) explain the unreactivity of chlorobenzene compared to halogenoalkanes towards nucleophilic
substitution, in terms of the delocalisation of the lone pair of electrons on the halogen and
steric hindrance
(f) suggest characteristic reactions to differentiate between:
(i) different halogenoalkanes
(ii) halogenoalkanes and halogenoarenes
e.g. hydrolysis, followed by testing of the halide ions
(g) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative
chemical inertness
(h) recognise the concern about the effect of chlorofluoroalkanes (CFCs) on the ozone layer
[the mechanistic details of how CFCs deplete the ozone layer are not required]

Recommended References:
1. Chemistry (for CIE AS & A Level) by Peter Cann & Peter Hughes
2. Cambridge International AS and A Level Chemistry Revision Guide by Judith
Potter and Peter Cann
3. Understanding Advanced Organic and Analytical Chemistry: The Learner’s Approach by
Chan Kim Seng and Jeanne Tan

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Lecture Content Page

1 Introduction to Halogen Derivatives 3
2 Nomenclature and Classification 3
2.1 Halogenoalkanes 3
2.2 Halogenoarenes 4
3 Physical Properties 6
3.1 Melting and Boiling Points 6
3.2 Solubility 6
3.3 Density 6
4 Preparation of Halogenoalkanes and Halogenoarenes 8
4.1 Free Radical Substitution of Alkanes 8
4.2 Electrophilic Addition of Alkenes 8
4.3 Nucleophilic Substitution of Alcohols 9
4.4 Preparation of Halogenoarenes 10
5 Nucleophilic Substitution Reactions of Halogenoalkanes 12
5.1 Mechanism of SN2 Reactions 12
5.2 Mechanism of SN1 Reactions 14
5.3 Comparison of SN2 and SN1 mechanisms 16
5.4 Reactivity of Halogenoalkanes by Nucleophilic Substitution Reactions 16
5.5 Formation of Alcohols 17
5.6 Formation of Nitriles 17
5.7 Formation of Amines 18
6 Elimination Reaction of Halogenoalkanes 19
7 Reactions of Halogenoarenes 20
7.1 Electrophilic Substitution of the Benzene Ring of Halogenoarenes 21
8 Distinguishing Test for Halogen Derivatives 22
9 Uses of Halogenoalkanes and the Impact on the Environment 23
9.1 Effect of CFCs on the Ozone Layer 23

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1. Introduction to Halogen Derivatives

Organic halogen compounds (or Halogen Derivatives) are organic compounds that contain
the C–X functional group (X = F, Cl, Br or I). Some of these halogen derivatives are naturally
occurring, such as CH3Cl and CH3Br, which are biosynthesised by termites and marine
organisms respectively. Halogen derivatives are also produced in humans, at they play an
important role in homeostasis, for example, thyroxine by the thyroid gland.

Thyroxine

Most of the halogen derivatives found are synthetically made. These serve many important
roles such as insecticides, herbicides, dry-cleaning agents, degreasers, fire-extinguishing
chemicals and polymers. Well-known examples are CFCs (chloroflurocarbons) as refrigerants
and vinyl chloride as the starting material of PVCs (polyvinylchlorides) plastics.

dichlorodifluoromethane and vinyl chloride

In the field of synthetic chemistry, these organic halogen derivatives make for very useful
intermediates that can be converted to important speciality chemicals. However, some
halogen derivatives are known to be either harmful to the environment or are carcinogenic.

In this topic, two main types of halogen derivatives will be discussed: halogenoalkanes and
halogenoarenes.

2. Nomenclature and Classification

2.1 Halogenoalkanes (Alkyl Halides)

Halogenoalkanes are alkane molecules which have one or more hydrogen atoms replaced by
halogen atoms. Thus, the halogen is considered a substituent of the hydrocarbon chain.
Therefore, these compounds are named similarly to alkanes, with the suffix ending with –ane
and the halogens as prefixes with the respective positional numbers. As such,
halogenoalkanes may exhibit structural and/or stereoisomerism. Below are some examples:

Bromoethane 1,1-dibromoethane 1,2-dibromoethane 3-chloropentane

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Halogenoalkanes are classified as primary (1°), secondary (2°) or tertiary (3°) depending
on the number of alkyl groups attached to the α–carbon bonded to the halogen atom.

Primary (1°) halogenoalkanes – each alkane molecule contains only one

alkyl or other carbon-containing group attached to the α–carbon to the
halogen atom

e.g. CH3CH2Br CH3CH(OH)CH2Cl

Secondary (2°) halogenoalkanes – each alkane molecule contains two

alkyl or other carbon-containing group attached to the carbon bonded to the
halogen atom

e.g.

Tertiary (3°) halogenoalkanes – each alkane molecule contains three

alkyl or other carbon-containing group attached to the α–carbon to the
halogen atom

e.g.

(X = halogen atom, R = alkyl group)

2.2 Halogenoarenes (Aryl halides)

Halogenoarenes are derivatives of benzene, with halogen atoms replacing the hydrogen
atoms present in the aromatic ring. Thus, the nomenclature is the same as arenes, with the
halogen substituent added as prefixes with the respective positional numbers. Numbering of
the positional number starts from the carbon atom bearing the principal functional group and
in the direction that utilises the lowest possible numbers for the substituents.

bromobenzene 2,4-dibromophenylamine

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Self-Assessment 1

1 a) Draw five isomers (both structural and stereoisomers) with the molecular formula,
C4H9Br. Annotate the chiral carbon with a * if any.
b) Give the IUPAC names of the five isomers.

2 Draw the structural formulae of the halogenoalkanes in the table and classify them as
primary, secondary or tertiary.
Classification
Name Structural formula
(primary, secondary or tertiary)

2-bromo-2-methylbutane Tertiary

iodocyclohexane Secondary

1-bromo-1-
Tertiary
methylcycloheptane

Pen down your notes/ questions/ thoughts on this section in the space below

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3. Physical Properties

3.1 Melting and Boiling points

With the presence of the halogen atom, one would expect the melting/boiling point of
halogenoalkanes to be higher than that of alkanes with the same chain length.

Similar to the trends for alkanes, both the melting point and boiling point of halogenoalkanes
with the same halogen atom:

➢ increases with increasing chain length due to the increasing size of the electron
cloud of the molecule.
➢ decreases with increasing degree of branching due to the decreasing surface area
of the molecule.

When comparing halogenoalkanes of the same chain length but with different halogen atoms,
the melting point was observed experimentally to increase from F to Cl to Br and to I.

Fluoroethane Chloroethane Bromoethane Iodoethane

Structural formula

Boiling point (°C) –37.1 12.3 38.3 71.0

Although the listed halogenoalkanes are polar molecules, the size of the electron cloud due to
the respective halogen atoms play a more dominating factor. Thus, the intermolecular forces
of attraction between the molecules are dominantly id-id attractions. The id-id attraction
becomes stronger from F < Cl < Br < I due to the increasing number of electrons of the
halogen atoms.

3.2 Solubility

Halogenoalkanes/halogenoarenes although polar, have poor solubility in water, especially

for molecules with higher molecular weight. This is due to energetic considerations.

➢ Hydrogen bonds between water molecules will have to be overcome first before the
water molecules can interact with halogen compounds
➢ The interaction between the halogen compounds and free water molecules are much
weaker than hydrogen bonding (whether pd-pd or id-id attractions)
➢ The energy released from the interaction between the halogen compounds and water
is insufficient in overcoming the strong hydrogen bond between water molecules

However, halogenoalkanes/halogenoarenes are soluble in non-polar solvents. This is due

to the presence of the alkyl group/hydrophobic benzene ring of the respective compounds,
which are hydrophobic in nature and thus have similar id-id attractions with the non-polar
solvent molecules.

3.3 Density

Halogenoalkanes/halogenoarenes are generally denser than both water and the alkane which
they are derived from. This is due to the presence of the halogen atom, which increases the
molecular mass.

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Self-Assessment 2

The boiling points of some organic compounds are given below.

Compound Structural formula Name Boiling point / °C

A CH3CH2CH2CH3 butane –1
B CH3CH2CH2CH2Cl 1-chlorobutane 78
C CH3CH2CH2CH2Br 1-bromobutane 101
D CH3CH2CH2CH2I 1-iodobutane 130

Explain each of the following.

(a) The boiling point of compound B is higher than that of A.

More energy is required to overcome the stronger permanent dipole-permanent dipole
interactions between polar 1-chlorobutane molecules of B as compared to the weaker
instantaneous dipole-induced dipole interactions between the non-polar butane
molecules of A.
OR
More energy is required to overcome the stronger instantaneous dipole-induced dipole
interactions between the 1-chlorobutane molecules of B compared to the butane
molecules of A because of the increased number of electrons/size of electron cloud
due the chlorine atom.

(b) The boiling point increases in the order of B < C < D.

From B to D, the increasing size of the halogen electron cloud becomes more easily
distorted and results in the increasing strength of the instantaneous dipole-induced
dipole interactions between molecules. Thus, there is an increase in energy needed
to overcome the increasingly stronger intermolecular forces of attractions. Hence,
boiling point increases from B to D.

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4. Preparation of Halogenoalkanes and Halogenoarenes

4.1 Free Radical Substitution of Alkanes

Reagents and condition: Cl2(g) or Br2(l); UV light or heat

Observations: Greenish yellow Cl2(g) or reddish-brown Br2(l) decolourises

Free radical substitution of alkanes is seldom used due to the formation of a mixture of
products.

4.2 Electrophilic Addition of Alkenes

4.2.1 Addition of hydrogen halides

Reagents and condition: Dry HCl(g), HBr(g) or HI(g); room temperature

Markovnikov’s rule can be used to predict the major product in the addition of HX to an
unsymmetrical alkene.

4.2.2 Addition of halogen

Reagents and condition: Cl2 in CCl4 or Br2 in CCl4; room temperature, in the dark

Observation: Pale-yellow Cl2 (CCl4) or orange-red Br2 (CCl4) decolourises

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4.3 Nucleophilic Substitution of Alcohols (will revisit in Topic 6: Hydroxyl Cpds)

4.3.1 Preparation of chloroalkanes

(a) Phosphorus (V) chloride PCl5

Reagents and condition: anhydrous PCl5(s); heat

Observation: white fumes of HCl observed

(b) Phosphorus (III) chloride PCl3

Reagents and condition: anhydrous PCl3(l); heat with reflux

No white fumes evolved when alcohols react with PCl3.

(c) Sulfur dichloride oxide or thionyl chloride SOCl2

Reagents and condition: anhydrous SOCl2(l); heat with reflux

Observation: white fumes of HCl observed

This method is better as the by-products SO2 and HCl gases can be readily separated from
the liquid RCl product.

(d) Hydrogen chloride

Reagents and condition: conc HCl(aq); ZnCl2 catalyst and heat with reflux

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4.3.2 Preparation of bromoalkanes

(a) Phosphorus (III) bromide PBr3

Reagents and condition: anhydrous PBr3(l); heat with reflux

(b) Hydrogen bromide

Reagents and condition: NaBr(s) or KBr(s); conc H2SO and heat with reflux

4.3.3 Preparation of iodoalkanes

(a) Phosphorus (III) iodide, PI3

Reagents and condition: anhydrous PI3; heat

(b) Hydrogen iodide

Reagents and condition: NaI(s) or KI(s); conc H3PO4 and heat

4.4 Preparation of Halogenoarenes (electrophilic substitution)

Reagents and condition: X2 with anhydrous FeX3 or anhydrous AlX3

or Fe as catalyst; room temperature [X = Cl or Br]

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Self-Assessment 3

(a) Draw the structures of four possible organic products that may be obtained when
propane, CH3CH2CH3, is reacted with chlorine in UV light.

(b) Draw the structure of the organic compound in each box below.

(i)

CH3CH2CHClCH3

(ii)

(iii) (iv)

(c) Draw the structure of the organic product obtained when the alcohol below is reacted
with each chemical below.

(i) anhydrous thionyl chloride; room temperature

(ii) red phosphorus, iodine; heat

(i)

(ii)

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5 Nucleophilic Substitution Reactions of Halogenoalkanes

δ–

δ+

Halogenoalkanes are polar molecules with the C atom of the C–X bond bearing the partial
positive charge. Nucleophilic substitution reactions occur when a nucleophile (electron-
rich species) is attracted to the electron-deficient C atom, which is then susceptible to
attack by these nucleophiles, where the nucleophile substitutes the halogen atom.

The overall reaction for nucleophilic substitution can be represented as:

Nucleophilic substitution reactions can proceed by either a one-step mechanism (SN2) or a

two-step mechanism (SN1). Generally, primary halogenoalkanes undergo nucleophilic
substitution via the one-step mechanism while tertiary halogenoalkanes undergo nucleophilic
substitution via the two-step mechanism. Secondary halogenoalkanes may proceed via both
mechanism.

5.1 Mechanism of SN2 reactions (one-step bimolecular nucleophilic substitution)

δ+ δ- δ- δ-

➢ The OH– nucleophile, attacks the δ+C atom from the side opposite to that of the C–Br
bond in what is known as the “backside” attack.
➢ The OH– donates one of its lone pair to the carbon atom, a bond begins to form
between O of OH– and the C of the halogenoalkane
➢ Simultaneously, the C–Br bond is weakened, and the bond begins to break
(heterolytic cleavage). Both the bonding electrons in the C–Br bond are gradually
transferred to the Br atom to form Br–, the leaving group.
➢ The simultaneous bond breaking and bond formation gives rise to the pentavalent
transition state (or pentavalent activated complex), where the entering nucleophile
(OH–) and the departing leaving group (Br–) are partially bonded to the same
pentavalent carbon atom. This is a one-step mechanism.

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If the halogenoalkane has a chiral α–carbon – due to the direction of the “backside” attack,
there will be an inversion of stereochemistry, where the configuration of the α–carbon is
inverted. This is also known as the Walden inversion.

* δ+ δ- *

* chiral carbon

The derived rate equation for this mechanism is rate = k[RX][nucleophile], where the rate is
dependent on the concentration of both RX and the nucleophile.

➢ The mechanism is known as SN2 (Substitution, Nucleophilic, bimolecular), because

two species are involved in the rate-determining step

The energy profile diagram for the SN2 mechanism is given below.

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Steric hinderance increases as additional alkyl groups are bonded to the α–carbon. Hence, it
is expected for the rates of the reaction to decrease from methyl > 1° > 2° > 3°
halogenoalkane. This explains why primary halogenoalkanes undergo SN2 reactions more
readily and tertiary halogenoalkanes do not.

X X X X

5.2 Mechanism of SN1 reactions (two-step unimolecular nucleophilic substitution)

Step 1: Formation of carbocation

δ+ δ-

Step 2: Nucleophile attacks the carbocation to form final product

➢ The first step, which is the slow step, involves the heterolytic cleavage of the C–Br
bond in the halogenoalkane to produce a carbocation intermediate and free Br– ion.
➢ The electron-donating alkyl groups help to stabilise the carbocation.
➢ The second step, which is the fast step, involves nucleophilic attack by the
nucleophile (OH–) on the highly reactive carbocation to form the product.

As the carbocation intermediate is trigonal planar with respect to the cationic carbon, this
allows the nucleophile to approach from two faces with equal probability, top and bottom.

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If nucleophilic attack to the electron-deficient carbon gives rise to a chiral carbon, this would
result in a racemic mixture as both enantiomers would be formed equally.

The derived rate equation for this mechanism is rate = k[RX], where the rate is dependent on
the concentration of both RX only.

➢ The mechanism is known as SN1 (Substitution, Nucleophilic, unimolecular), because

only one species is involved in the rate-determining step

The energy profile diagram for the SN1 mechanism is given below.

The rate of the SN1 reaction is dependent on the stability of the carbocation intermediate.
The presence of alkyl groups on the positively charged carbon will help stabilise it via
electron-donating inductive effect. Thus, the rate of reaction decreases from 3° > 2° > 1° >
methyl halogenoalkane. This explains why from tertiary halogenoalkanes undergo SN1
reactions more readily and primary halogenoalkanes does not.

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5.3 Comparison of SN2 and SN1 mechanisms

➢ The attacking nucleophile approaches the electron-deficient α–carbon

from the side opposite to the leaving halide.
➢ The other 3 groups attached to the α–carbon would hinder the approach
of the nucleophile if they are large and bulky (steric hindrance).
SN2 ➢ 1° halogenoalkanes usually undergo nucleophilic substitution through SN2
mechanism and 3° halogenoalkanes do not. (CH3 > 1° > 2° > 3°)
➢ An optically active reactant would produce an optically active product
with inverted stereochemistry.
➢ Electron-donating alkyl groups attached to the electron-deficient α–carbon
of a halogenoalkane help to stabilise the incipient carbocation
intermediate.
SN1 ➢ 3° halogenoalkanes usually undergo nucleophilic substitution through SN1
mechanism and 1° halogenoalkanes do not. (CH3 < 1° < 2° < 3°)
➢ An optically active reactant would produce 2 enantiomers in equimolar
amounts; hence the resultant racemic mixture is optically inactive.

For 2° halogenoalkanes, nucleophilic substitution can proceed via both SN1 and SN2
mechanisms.
5.4 Reactivity of Halogenoalkanes by Nucleophilic Substitution Reactions

The reactivity of halogenoalkanes by SN1 and SN2 reactions depends on the ease of the
cleavage of the C–X bond. The stronger the bond, the harder it is for cleavage to occur.

Bond Bond Energy / kJ mol–1

C–F 485
C–Cl 340
C–Br 280
C–I 240

As the size of the halogens get bigger from F to I, the valence orbital used for bonding
becomes larger and more diffused. Thus, the orbital overlap between the halogen and
carbon atoms becomes less effective. Therefore, this accounts for the weaker bond strength
and lower bond energies. Hence, the reactivity decreases in the order of CH3I > CH3Br >
CH3Cl > CH3F. Due to the very strong C–F bond, fluoroalkanes are generally unreactive and
do not undergo nucleophilic substitution.

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Self-Assessment 4

Bromoethane, CH3CH2Br, reacts with methanol under suitable conditions to form

CH3CH2OCH3. Name and describe the mechanism for the reaction given that the attacking
nucleophile is CH3O–. [This reaction produces an organic compound containing a functional
group called ether]

Name of mechanism: SN2 nucleophilic substitution

δ+ δ-

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5.5 Formation of Alcohols

Reagents and condition: NaOH(aq) or KOH(aq); heat

This reaction is also known as alkaline hydrolysis, which is carried out in an aqueous
medium.

5.6 Formation of Nitriles

Reagents and condition: ethanolic NaCN or KCN; heat

Nitriles are a class of useful reagents in organic synthesis. Through the formation of a nitrile,
the carbon chain length is extended by one C atom (step-up reaction). The nitrile product
can be hydrolysed to form carboxylic acids (Topic 8: Carboxylic Acids and Derivatives) or
be reduced to form amines (Topic 9: Nitrogen Compounds).

Hydrolysis and Reduction of Nitriles

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5.7 Formation of Amines

Reagents and condition: excess ethanolic NH3; heat in sealed tube

A primary amine (RNH2) is formed in the above reaction. Excess ammonia is used to ensure
high yield of the primary amine. Without excess ammonia, secondary and tertiary amines
(R2NH and R3N respectively), or even quaternary ammonium salts (R4N+X−) may be obtained
as the primary amine formed are stronger nucleophiles than ammonia and further nucleophilic
substitution reaction may occur.

Equations for their formation are as shown below.

RX + RNH2 R2NH + HX (secondary amine formed)

RX + R2NH R3N + HX (tertiary amine formed)
RX + R3N R4N+ X− (quaternary ammonium salt formed)

Self-Assessment 5

A reaction scheme using 2-bromobutane is given below. Which of the reactions does not take
place?

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6 Elimination Reaction of Halogenoalkanes

Halogenoalkanes take part in elimination reactions, producing alkenes.

Reagents and condition: ethanolic NaOH(aq) or ethanolic KOH(aq); heat

➢ In an ethanolic solution, OH– acts as a base and deprotonates the H atom on the C
atom adjacent to the C–X bond.
➢ The C–X bond breaks simultaneously, and the alkene is formed.
➢ More than one alkene product can be formed when the carbon bonded to the halogen
has more than one adjacent carbon with hydrogen atom(s) bonded to it, resulting
in structural and cis-trans isomers.
➢ Like the reactivity of halogenoalkanes in nucleophilic substitution reactions, the ease
of elimination reaction is dependent on the strength of the C–X bond

Self-Assessment 6

Draw the structural formulae of the three alkenes formed when 2-bromobutane undergoes
elimination with hot ethanolic NaOH.

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7 Reactions of Halogenoarenes

In general, halogenoarenes do not undergo nucleophilic substitution.

The lack of reactivity towards nucleophilic attack is due to the following reasons.

1) The C–X bond is strengthened and not easily cleaved. (Main reason)

The p-orbital of the halogen atom can have a side-on overlap with the π electron cloud of the
benzene ring. As a result, the lone pair of electrons on the halogen atom can delocalise into
the benzene ring. Therefore, there is partial double bond character in the C–X bond and is
thus stronger than the C–X bond in halogenoalkanes.

2) Steric hinderance

The C in the C–X bond is less accessible to nucleophilic attack. As nucleophile is an electron-
rich species, it will face inter-electronic repulsion between the electron-rich benzene ring
and therefore its approach is sterically hindered.

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7.1 Electrophilic Substitution of the Benzene Ring of Halogenoarenes

Halogenoarenes undergo electrophilic substitution of benzene ring just like any other arenes.

➢ Electrophilic substitution of halogenoarenes happen at a lower rate because the

halogen substituents being electronegative (–I effect), diminishes π electron
density of the ring.
➢ Electrophilic attacks are 2–, 4–directed as this leads to the formation of a more stable
arenium intermediate.

Self-Assessment 7
Complete the table below by writing Yes or No.

Compound CH3CH2Cl

Delocalisation of electrons
No Yes No
from chlorine

Nucleophilic substitution Yes No Yes

Elimination Yes No No

Electrophilic substitution No Yes Yes

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8 Distinguishing Test for Halogen Derivatives

To determine if an organic compound is a halogenoalkane (or has a halide functional group),

the following chemical test can be done:

➢ Add NaOH(aq) and heat

o Nucleophilic substitution reaction occurs
➢ Subsequently add excess dilute HNO3 after cooling (Cannot use HCl and H2SO4)
o Removal of excess OH–(aq)
➢ Add AgNO3(aq) and observe for any precipitation that may occur
o Ag+(aq) + X–(aq) → AgX(s)

The expected observations are given in the table below.

Type of Halide Cl–(aq) Br–(aq) I–(aq)

White precipitate Cream precipitate Yellow precipitate
Observations
observed. observed. observed.
AgCl (s) formed. AgBr(s) formed. AgI(s) formed.
Conclusion
C–Cl is present. C–Br is present. C–I is present.

This chemical test can also be used to distinguish between halogenoalkanes and
halogenoarenes. Since halogenoarenes do not undergo nucleophilic substitution in general,
there will be no formation of precipitates.

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9 Uses of Halogenoalkanes and the Impact on the Environment

Halogenoalkanes have many commercial uses. For example, chlorofluorocarbons (CFCs) are
used as refrigerants, aerosol propellants and in fire extinguishers in view of their properties:
inert, non-flammable, odourless and can be liquefied under pressure and vaporise readily
when that pressure is released. CFCs and fluoroalkanes are much less reactive (inert) due to
stronger C F bonds. A common commercial fluorohydrocarbon is polytetrafluoroethene or
Teflon®. After the widespread commercial uses, many halogenoalkanes have also been
shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been
shown to lead to ozone depletion.

9.1 Effect of CFCs on the Ozone Layer - Depletion of the ozone layer

CFCs in aerosol sprays deplete the ozone (O3) layer and expose us to ultraviolet (UV) radiation
from the sun. The O3 layer absorbs UV rays and thus screens the earth from excessive UV
radiation. Overexposure to UV radiation causes skin cancer in humans and widespread crop
failure.

Being chemically inert, CFCs can drift upwards to an altitude 20 km above sea level and enter
the stratosphere. When exposed to UV radiation ( = 200–250 nm) at this altitude, photolysis
takes place. (Bond energies: C–Cl = 351 vs. C–F = 452 kJ mol–1)
uv
CF3Cl Cl• + •CF3

In the stratosphere, O2 molecules decompose to oxygen atoms upon absorbing UV light.

O2 2O

The oxygen atoms then react readily with O2 to produce ozone. However, O3 decompose to
reform oxygen atoms and O2 molecules by absorbing UV light and equilibrium is set up
between the two processes.

formation of ozone : O + O2 O3
depletion of ozone : O3 O + O2

Chlorine atom, Cl• , disrupts the equilibrium by acting as a homogeneous catalyst in the
destruction of ozone:

Cl• + O3 ClO• + O2 -----------(1)

ClO• + O Cl• + O2 -----------(2)

As shown by equations (1) and (2), the formation of Cl• is detrimental as it destroys O3 as well
as removes O, one of the reactants for O3 formation. Notice that Cl• is regenerated and thus
plays the role of catalyst.

Measures to reduce ozone depletion

▪ Reduce use of CFCs in industrial and household applications. Since 1987, at the Montreal
Protocol, the use of CFCs has been increasingly banned many countries.
▪ Substitutes such as hydrocarbons, hydrofluorocarbons or fluorocarbons have been used
in place of CFCs. For example, most aerosols use propane or butane as propellant
instead of CFCs. However, alkanes are highly flammable and pose a fire hazard.

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Summary
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