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How are halogenoalkanes made?


There are several ways by which halogenoalkanes can
be made, including:

free radical substitution of an alkane:


CH4 + Cl2 CH3Cl + HCl

electrophilic addition of HX or X2 to an alkene:


C2H4 + HBr C2H5Br
C2H4 + Br2 C2H4Br2

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Free radical substitution: Cl2 + CH4

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Other products of chain reactions


If an alkane is more than two carbons in length then any of
the hydrogen atoms may be substituted, leading to a mixture
of different isomers. For example:

1-chloropropane

2-chloropropane

The mixture of products is difficult to separate, and this is


one reason why chain reactions are not a good method of
preparing halogenoalkanes.
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Further substitution in chain reactions


Some chloromethane molecules formed during free radical
substitution between methane and chlorine will undergo
further substitution to form dichloromethane. Further
substitution can occur until all hydrogens are substituted.

The further substituted chloroalkanes are impurities that


must be removed. The amount of these molecules can be
decreased by reducing the proportion of chlorine in the
reaction mixture.
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Chain reactions and ozone

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Free radical reactions: true or false?

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Bonding in alkenes

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Structure of alkenes summary

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Double bonds and electrophiles


The double bond of an alkene is an area of high electron
density, and therefore an area of high negative charge.
The negative charge of the double bond may be attacked
by electron-deficient species, which will accept a lone pair
of electrons.
These species have either a full positive charge or slight
positive charge on one or more of their atoms. They are
called electrophiles, meaning electron loving.
Alkenes undergo addition reactions when attacked by
electrophiles. This is called electrophilic addition.
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Electrophilic addition mechanism: 1


In the first stage of electrophilic addition,
the positive charge on the electrophile is
attracted to the electron density in the
double bond.
+

As the electrophile approaches the


double bond, electrons in the AB
bond are repelled towards B.

The pi bond breaks, and A bonds to the


carbon, forming a carbocation an ion
with a positively-charge carbon atom.
The two electrons in the AB bond
move to B forming a B- ion.
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Electrophilic addition mechanism: 2


In the second stage of electrophilic
addition, the B- ion acts as a nucleophile
and attacks the carbocation.

The lone pair of electrons on the B- ion


are attracted towards the positivelycharged carbon in the carbocation,
causing B to bond to it.

Because both electrons in the bond that joins B- to the


carbocation ion come from B-, the bond is a co-ordinate bond.
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More on the bromine water test


A simple equation for the bromine water test with ethene is:
CH2=CH2 + Br2 + H2O CH2BrCH2Br + H2O
However, because water is present in such a large
amount, a water molecule (which has a lone pair) adds to
one of the carbon atoms, followed by the loss of a H + ion.
CH2=CH2 + Br2 + H2O CH2BrCH2OH + HBr
The major product of the test is not 1,2-dibromoethane
(CH2BrCH2Br) but 2-bromoethan-1-ol (CH2BrCH2OH).

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Electrophilic addition reactions

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Addition to unsymmetrical alkenes


When an electrophile
(e.g. HBr) attacks an
alkene with three or
more carbon atoms
(e.g. propene), a mix
of products is
formed. This is
because these
alkenes are
unsymmetrical.

minor product:
1-bromopropane

HBr

major product:
2-bromopropane

Unequal amounts of each product are formed due to the


relative stabilities of the carbocation intermediates.
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Structure of carbocations
A chain of carbon atoms can be represented by R when
drawing organic structures. This is an alkyl group (general
formula CnH2n+1).

Primary (1) carbocations have


one alkyl group attached to the
positively-charged carbon.

Secondary (2) carbocations


have two alkyl groups attached
to the positively-charged carbon.

Tertiary (3) carbocations have


three alkyl groups attached to
the positively-charged carbon.
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Stability of carbocations
The stability of carbocations increases as the number of alkyl
groups on the positively-charged carbon atom increases.

primary

secondary

tertiary

increasing stability
The stability increases because alkyl groups contain a
greater electron density than hydrogen atoms. This
density is attracted towards, and reduces, the positive
charge on the carbon atom, which has a stabilizing effect.
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Structure of carbocations

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Electrophiles: true or false?

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Polar bonds and nucleophiles


The carbonhalogen bond in halogenoalkanes is polar
because all halogens are more electronegative than carbon.
+

The polar bond means that the carbon atom has a small
positive charge (+), which attracts substances with a lone
pair of electrons. These are nucleophiles, meaning
nucleus (positive charge) loving. Examples include:

ammonia
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cyanide

hydroxide
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Reaction with nucleophiles


+

Nucleophiles (Nu-) attack the carbon


of a carbonhalogen (CX) bond,
because the electron pair on the
nucleophile is attracted towards the
small positive charge on the carbon.
The electrons in the CX bond are
repelled as the Nu- approaches the
carbon atom.

The Nu- bonds to the carbon and the CX


bond breaks. The two electrons move to
the halogen, forming a halide ion.
The halide is substituted, so this is a
nucleophilic substitution reaction.
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Nucleophilic substitution reactions

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Rate of nucleophilic substitution


The rate of a nucleophilic substitution reaction depends on
the strength of the carbonhalogen bond rather than the
degree of polarization in the bond.
Bond

Strength (kJ mol-1)

CF

484

CCl

338

CBr

276

CI

238

The CI bond is the weakest and so most readily undergoes


nucleophilic substitution. The rate of reactions involving
iodoalkanes is the highest.
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Nucleophilic substitution

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Elimination in halogenoalkanes
In the reaction with a strong base, halogenoalkanes will
undergo not only nucleophilic substitution but also
elimination reactions, forming alkenes and water.

The OH- acts as both a base and a nucleophile. When acting


as a base, the OH- removes H+ from the halogenoalkane,
which also results in the formation of a halide ion.
The reaction between a halogenoalkane and a strong base
usually results in the formation of a mixture of substitution
and elimination products.
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Elimination mechanism

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Mixture of elimination products


If the carbon chain is four or more carbons in length and
the halogen is not attached to a terminal carbon, a
mixture of positional isomers may be formed.

attack at A

but-2-ene
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attack at B

but-1-ene
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Conditions are important


The conditions for the reaction that favour substitution or
elimination are different.

Base strength: the stronger the base used, the more


elimination is favoured. Sodium hydroxide in aqueous
solution contains OH-, but when dissolved in ethanol,
CH3CH2O- is also present, which is a stronger base.
Therefore elimination is favoured by NaOH in ethanolic
solution, and substitution is favoured by NaOH in
aqueous solution.

Temperature: elimination is favoured at hotter


temperatures whereas substitution is favoured by warm
conditions.
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Primary, secondary or tertiary?


Primary halogenoalkanes favour substitution whereas
tertiary halogenoalkanes favour elimination.

primary

secondary

tertiary

substitution more likely


elimination more likely

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Elimination or substitution?

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Glossary

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Whats the keyword?

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Multiple-choice quiz

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