1. www.soran.edu.iq Organic and biochemistry Assistance Lecturer amjad ahmed jumaa  Hydrolysis and heterolysis Free radical. Chlorination of methane. 1

2. www.soran.edu.iq Homolysis and heterolysis:  Homolysis: Thus, of the two electrons making up the covalent bond, one goes to each fragment.  Heterolysis, in which both bonding electrons go to the same fragment.

3. www.soran.edu.iq Free radicals: chlorination of methane  Under the influence of ultraviolet light or at a temperature of 250-400º a mixture of two gases, methane and chlorine, reacts vigorously to yield hydrogen chloride (HCl) and a compounds of formula (CH 3 Cl). (CH 3 Cl) is called chloromethane or methyl chloride.  CH 3 = methyl group. Free radicals: chlorination of methane  Under the influence of ultraviolet light or at a temperature of 250-400º a mixture of two gases, methane and chlorine, reacts vigorously to yield hydrogen chloride (HCl) and a compounds of formula (CH 3 Cl). (CH 3 Cl) is called chloromethane or methyl chloride.  CH 3 = methyl group.

4. www.soran.edu.iq 4  Among the facts that must be accounted for are these: (a) Methane and chlorine do not react in the dark at room temperature, (b) Reaction takes place readily, however, in the dark at temperatures over 250, or (c) under the influence of ultraviolet light at room temperature, (d) When the reaction is induced by light, many (several thousand) molecules of methyl chloride are obtained for each photon of light that is absorbed by the system, (e) The presence of a small amount of oxygen slows down the reaction for a period of time, after which the reaction proceeds normally; the length of this period depends upon how much oxygen is present.

5. www.soran.edu.iq 5  The mechanism that accounts for these facts most satisfactorily, and hence is generally accepted, is shown in the following equation :

6. www.soran.edu.iq 6  The first step is the breaking of a chlorine molecule into two chlorine atoms. Like the breaking of any bond, this requires energy, the bond dissociation energy, in this case the value is 58 kcal/mole. The energy is supplied as either heat or light.  The chlorine molecule undergoes homolysis that is, cleavage of the chlorine-chlorine bond takes place in a symmetrical way, so that each atom retains one electron of the pair that formed the covalent bond.

7. www.soran.edu.iq 7  Collision with another chlorine atom is quite unlikely simply because there are very few of these reactive, short-lived particles around at any time. Of the likely collisions, that with a chlorine molecule causes no net change; reaction may occur, but it can result only in the exchange of one chlorine atom for another:

8. www.soran.edu.iq 8  Collision of a chlorine atom with a methane molecule is both probable and productive. The chlorine atom abstracts a hydrogen atom, with one electron, to form a molecule of hydrogen chloride :

9. www.soran.edu.iq 9  Now, what is this methyl radical most likely to do? Like the chlorine atom, it is extremely reactive, and for the same reason: the tendency to complete its octet, to lose energy by forming a new bond. Again, collisions with chlorine molecules or methane molecules are the probable ones, not collisions with the relatively scarce chlorine atoms or methyl radicals. But collision with a methane molecule could at most result only in the exchange of one methyl radical for another:

10. www.soran.edu.iq 10 The collision of a methyl radical with a chlorine molecule is, then, the important one. The methyl radical abstracts a chlorine atom, with one of the bonding electrons, to form a molecule of methyl chloride: The other product is a chlorine atom. This is step (3) in the mechanism.