CAIE Chemistry A-Level: 15: Halogen Compounds

CAIE Chemistry A-level
15: Halogen Compounds

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Halogenoalkanes
Halogenoalkanes are alkanes which contain a halogen atom covalently bonded to a carbon
atom. When naming halogenoalkanes, the prefix of the halogen
(fluoro-/chloro-/bromo-/iodo-) is put before the alkane name with a number to indicate which
carbon the halogen is bonded to. For example 1-bromopropane, 3-chlorohexane and
2-iodopentane.
Formation of Halogenoalkanes
Free radical substitution

This mechanism requires a free radical (a particle with an unpaired electron). A free
radical is denoted by having a dot next to the chemical symbol, e.g. Cl⠂. There are three
stages to free radical substitution: initiation, propagation and termination.
Example: The reaction of methane with chlorine

Initiation - Free radicals are produced. UV light is required to split the covalent bond in Cl2
and form two chlorine atoms each with an unpaired electron (free radicals):
Cl2 → 2Cl⠂
Propagation - The free radicals are used up and recreated in chain reactions:
Cl⠂+ CH4 → CH3⠂+ HCl
A methyl radical, CH3⠂, is produced which reacts with Cl2 to produce more radicals.
CH3⠂+ Cl2 → CH3Cl + Cl⠂
These reactions continually occur in a chain until the termination stage.
Termination - All the free radicals are completely used up. When two radicals react, they
form a covalent bond. Several termination reactions can take place:
Cl⠂+ CH3⠂ → CH3Cl
Cl⠂+ Cl⠂→ Cl2
CH3⠂+ CH3⠂→ C2H6
Electrophilic addition
The electron dense double bond in an alkene is susceptible to attack from electrophiles. This
leads to electrophilic addition reactions which can lead to the formation of halogenoalkanes.
Addition with halogens:

When alkenes react with halogens, covalent bonds form between the halogen atoms and the
carbons on either side of the double bond, producing a di-halogenoalkane. The mechanism
is called electrophilic addition and can be seen in ‘Electrophilic addition’ on the following
page.
Addition with hydrogen halides:

A hydrogen halide is polar due to the difference in electronegativity between hydrogen and
the much more electronegative halogen atom. This polarity means both the hydrogen and
the halide bond to carbon atoms in the alkene, forming a halogenoalkane.
Substitution of alcohol with hydrogen halide
● Primary and secondary alcohols react very, very slowly with hydrogen chloride,
HCl. Tertiary alcohols react rapidly with concentrated hydrochloric acid at room
temperature:
(CH3)3COH + HCl → (CH3)3CCl + H2O
● Hydrogen bromide reacts with alcohols. Typically the alcohol is treated with
potassium bromide and concentrated sulfuric acid as these two reactants will
produce hydrogen bromide:
CH3CH2OH + HBr → CH3CH2Br + H2O
● Hydrogen iodide reacts with alcohols. Typically the alcohol is treated with
potassium iodide and phosphoric(V) acid. Phosphoric(V) acid is used in this
reaction instead of sulfuric acid as sulfuric acid will readily oxidise the iodide ions
to iodine.
CH3CH2OH + HI → CH3CH2I + H2O
Nucleophilic Substitution of Halogenoalkanes

The carbon-halogen bond in halogenoalkanes is polar because there is a large difference in
electronegativity of these atoms. Halogens (particularly chlorine and fluorine) are much
more electronegative than carbon meaning that the bonding pair of electrons is drawn
towards the halogen. The polarity of this bond makes it relatively easy to break. When the
bond breaks, a positive carbocation intermediate is formed which attracts nucleophiles.
Nucleophiles donate electrons. Common nucleophiles are: OH-, CN- and NH3.
Hydrolysis
Hydrolysis occurs when a halogenoalkane undergoes nucleophilic substitution with a
hydroxide.
For example bromoethane reacts to form ethanol. Warm aqueous sodium hydroxide is
required:
Formation of nitriles
Nitriles are formed when a halogenoalkane reacts with cyanide. The reaction requires
warm, ethanolic potassium cyanide (ethanolic means dissolved in ethanol).
Formation of primary amines

Primary amines are formed when a halogenoalkane is warmed with excess ethanolic
ammonia under pressure.
Test for Halogenoalkanes

First the halogenoalkane is heated with some sodium hydroxide in a mixture with some
ethanol and water. This is then acidified by adding nitric acid, which prevents unreacted
hydroxide ions from reacting with the silver ions which would give a false positive precipitate.
As these precipitates are often hard to distinguish, adding ammonia can help to confirm the
result.
Silver Nitrate (In ethanol) Dilute NH3 Concentrated NH3
Cl- White precipitate Precipitate dissolves Precipitate dissolves
Br- Cream Precipitate Precipitate remains Precipitate dissolves
I- Yellow precipitate Precipitate remains Precipitate remains
Elimination of Halogenoalkane
Halogenoalkanes can also undergo an elimination reaction when they are heated under
reflux with ethanolic hydroxide ions. The hydroxide ions can’t be dissolved in water as
this would cause hydrolysis would occur.
SN1 and SN2 Mechanisms

SN1 and SN2 reactions are both types of nucleophilic substitution. In these reactions, a
nucleophile replaces a leaving group.
It is easier to understand if we look at SN2 first:
SN2
These reactions are a one step mechanism. The nucleophile attacks the substrate at the
same time as the leaving group leaves the substrate. The nucleophile attacks the carbon
atom from the back side, causing an inversion of the groups in the product. The
nucleophile attacks from the backside because the large halogen atom prevents the
attack from the other direction.
In the diagram below, :Nu is the nucleophile and X is a halogen:
SN1
These reactions are two step mechanisms. This type of reaction takes place in tertiary
and some secondary halogenoalkanes. If the nucleophile is unable to attack the back of the
carbon atom (for example if it is blocked by larger atoms / groups such as -CH3) a
carbocation intermediate is formed. The first step in the process is generating the
carbocation intermediate and the second step is the attack of the nucleophile on the
carbocation to form the product. The following diagram demonstrates the two steps:
Primary halogenoalkanes - SN2 mechanism
Secondary halogenoalkanes - SN1 and SN2 mechanism
Tertiary halogenoalkanes - SN1 mechanism
Effects of Alkyl Groups on Reactivity

The halogenoalkane reactivity trend for SN1 is: tertiary > secondary > primary.
This is because alkyl groups have a positive inductive effect which helps stabilise the
carbocation. This makes the tertiary carbocation most stable and therefore the most likely to
form.
The halogenoalkane reactivity trend for SN2 is: primary > secondary > tertiary
This is due to steric hindrance which is caused by side chains on the molecule preventing a
reaction occurring. Tertiary halogenoalkanes are less reactive because the alkyl groups
prevent the nucleophile attacking the back side of the carbon so substitution doesn’t occur.
Relative Strength of C-Hal Bond
Reactivities of Halogenoalkanes
The reactivity of a halogenoalkane depends on the strength of the carbon-halogen
bond. For a reaction to take place, the carbon-halogen bond needs to be broken. The
weaker the carbon-halogen bond is, the more reactive the halogenoalkane.
C-F has the highest bond enthalpy and so is the strongest carbon-halogen bond. This
makes fluoroalkanes the least reactive of halogenoalkanes so they react slowest.
C-I has the lowest bond enthalpy so is the weakest carbon-halogen bond. This makes
iodoalkanes the most reactive of halogenoalkanes so they will react fastest.
Carbon-halogen bond enthalpy decreases down the group, so reactivity increases.
Fluoroalkanes and Fluorohalogenoalkanes
Fluoroalkanes contain carbon and fluorine only. Fluorohalogenoalkanes contain carbon,
fluorine and hydrogen only.
Fluoroalkanes and fluorohalogenoalkanes are chemically inert. The C-F bond is very
strong and requires a lot of energy to break, making the compounds very unreactive.
Uses of fluoroalkanes and fluorohalogenoalkanes:

● Refrigerants
● Propellants for aerosols
● Solvents for dry cleaning
● Making expanded polystyrene

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CAIE Chemistry A-level

15: Halogen Compounds

This work by PMT Education is licensed under https://bit.ly/pmt-cc

Free radical substitution

Example​: The reaction of methane with chlorine

Addition with halogens:

Addition with hydrogen halides:

(CH​3​)​3​COH + HCl → (CH​3​)​3​CCl + H​2​O

CH​3​CH​2​OH + HI → CH​3​CH​2​I + H​2​O

Nucleophilic Substitution of Halogenoalkanes

Formation of primary amines

Test for Halogenoalkanes

Silver Nitrate (In ethanol) Dilute NH​3 Concentrated NH​3

Cl- White precipitate Precipitate dissolves Precipitate dissolves

Br- Cream Precipitate Precipitate remains Precipitate dissolves

I- Yellow precipitate Precipitate remains Precipitate remains

S​N​1 and S​N​2 Mechanisms

It is easier to understand if we look at S​N​2 first:

Effects of Alkyl Groups on Reactivity

Relative Strength of C-Hal Bond

Uses​ of fluoroalkanes and fluorohalogenoalkanes:

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Example: The reaction of methane with chlorine

(CH3)3COH + HCl → (CH3)3CCl + H2O

CH3CH2OH + HI → CH3CH2I + H2O

Silver Nitrate (In ethanol) Dilute NH3 Concentrated NH3

SN1 and SN2 Mechanisms

It is easier to understand if we look at SN2 first:

Uses of fluoroalkanes and fluorohalogenoalkanes: