FREE RADICAL SUBSTITUTION

1. What do you understand by the following terms?

a) free radical

An atom or group of atoms with unpaired electrons. The unpaired electrons make them very reactive.

Free radical substitution occurs in the reactions of alkenes with halogens. Alkanes have single bonds and
are saturated. So the hydrogen atoms are substituted with the halogens.

b) photochemical reaction

A photochemical reaction is a reaction that is triggered by exposure to light.

c) chain reaction
A chain reaction is a series of reaction in which an initial reaction leads to another and continues until
completion.

2. The free radical substitution reaction between methane and chlorine to produce chloromethane and

hydrogen chloride goes through the following reactions:

Initiation:

Propagation:

Termination:

a) Explain in words what is happening at each of these stages, including the significance of the

words propagation and termination.

Initiation: The presence of ultraviolet light causes the Cl—Cl bond in chlorine to break by homolytic
fission and produce two radicals. Homolytic fission is the separation of a bond to form atoms with the
same electrons each.

Propagation: this occurs in two steps. The highly reactive chlorine radicals attack the relatively
unreactive methane and from the methyl free radical, CH3, as well as HCL.

CH4 + Cl• → CH3• + HCl

The methyl free radical then attacks another chlorine molecule and forms the chlorine radical and a
chain reaction takes place.

CH3• + Cl2 → CH3Cl + Cl•

If there is excess chlorine this process can continue until all the hydrogen

atoms in the methane have been replaced.

CH3Cl + Cl• → CH2Cl• + HCl

In summary: You take out a H in step one. A radical is formed. Then in stop two you add a CL to the
radical.

Termination: Two free radicals combine to form a single molecule. Recombination of two free radicals.

For example:

CH3• + Cl• → CH3Cl or CH3• + CH3• → CH3CH3

This stops the chain reaction in the propagation step. The reaction

finishes when there are no more free radicals left to react.

b) The rest of this question assumes that you know about multiple substitution.

Chloromethane undergoes further substitution to give dichloromethane, CH2Cl2, trichloromethane,

CHCl3, and tetrachloromethane, CCl4.

Write the equations for the propagation reactions which result in the formation of

(i) dichloromethane from chloromethane;

CH3CL + CL• → CH2CL• + HCl

CH2CL• + Cl2 → CH2Cl2 + Cl•

(ii) trichloromethane from dichloromethane;

CH2CL2 + CL• → CHCL2• + HCl

CHCL2• + Cl2 → CHCl3 + Cl•

(iii) tetrachloromethane from trichloromethane

CHCL3 + CL• → CCL3• + HCl

CCL3• + Cl2 → CCl4 + Cl•

3. This question concerns the substitution of hydrogen by chlorine in the methyl group of

methylbenzene. If you haven't actually needed to read the page about methylbenzene, try it anyway.

That's why you are learning about mechanisms – so that you can work out what would happen in an

unfamiliar case.

The reaction we are concerned with is:

Write the mechanism for this reaction in the following stages:

a) Write the equation for the initiation reaction, explaining why UV light is involved.

b) Write the equations for the propagation reactions.

c) Write the equations for any two chain termination reactions.

ELECTROPHILIC ADDITION – SYMMETRICAL ALKENES

1. Ethene reacts with an electrophile XY to undergo an addition reaction represented by this

mechanism, known as electrophilic addition:

a) Explain the term addition reaction.

Addition reactions form single products from two reactant molecules. An alkene is unsaturated and has
a double bond. In an addition reaction, this double bond will break and other atoms can then be added
onto the carbon atoms.

b) An electrophile is a something that is attracted to an electron-rich region of another molecule or ion.

(i) Explain why ethene is attractive to an electrophile.

The double bond in ethene is an electron-rich area and is susceptible to attacks by positively charged
reagents such as an electrophile.

(ii) A simple example of a molecule of the type XY might be HCl. Explain why HCl might

behave as an electrophile.

HCl might behave as an electrophile because it is a polar molecule and the positively charged H+ is
attracted to areas of high electron densities while the CL ion is .

HCl may act as an electrophile because it is a polar molecule and it has a delta positive partial charge on
the H atom and a delta negative partial charge on the Cl atom. So the delta positive H will be attracted
to the electron rich area of the double bond

c) What name is given to ions such as the one formed in the middle of the mechanism in which a

carbon atom carries a positive charge?

The name given is carbocation.

d) Describe briefly in words what is happening during the two stages of the mechanism.

An electron pair from the double bond in ethene forms a bond with the H atom to form a positively
charged carbocation. At the same time the Br atom gains control of the electron pair in the HBr to form
a Br ion. The H—Br bond breaks heterolytically. The Br ion then attacks the + carbocation and the
addition product, bromoethane, is formed.
2. Draw the mechanism for the reaction between ethene and bromine. How or why does bromine act
like an electrophile in this reaction?

As Br2 approaches the ethene molecule the high electron density in ethene’s C=C bond repels the
electron pair in the Br2 single bond and this causes the Br2 molecule to be polarised and the positive
end attacks the area of high electron density in the double bond.