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Reactions of Radicals
Introduction
Homolytic bond cleavage leads to the formation
of radicals (also called free radicals).
Radicals are highly reactive, short-lived species.
Single-barbed arrows are used to show the movement of
single electrons.
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Production of Radicals
Homolysis of relatively weak bonds such as O-O or X-X
bonds can occur with addition of energy in the form of
heat or light.
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Reactions of Radicals
Radicals tend to react in ways that lead to pairing of
their unpaired electron.
Hydrogen abstraction is one way a halogen radical can react to
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Reaction
Example
This reaction below is highly exothermic since Ho is a large and negative.
Ho is not dependant on the mechanism; only the initial and final states of the
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radical.
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X=F, Cl, or Br
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be seen.
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Chain propagation
A chlorine radical reacts with a molecule of methane to generate
a methyl radical.
propagation cycles.
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Chain termination
Occasionally the reactive radical intermediates are quenched by reaction
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Activation Energies
When using enthalpy values (Ho) the term for the
difference in energy between starting material and the
transition state is the energy of activation (Eact).
Recall when free energy of activation (Go) values are used this
difference is G.
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Iodinination has a prohibitively high value for Eact of the first step and
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be most rapid.
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Selectivity of Bromine
Bromine is much less reactive but more selective than
chlorine in radical halogenation.
Fluorine shows almost no discrimination in replacement of hydrogens
because it is so reactive.
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Radical Halogenation
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Markovnikov addition.
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The 2o radical abstracts a hydrogen atom from HBr. This leads to the
product and regenerates a bromine atom. Then repetitions of
steps 3 and 4 lead to a chain reaction.
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Chain Termination
The radical at the end of the growing polymer chain can also abstract
a hydrogen atom from itself by what is calledback biting. This leads
to chain branching.
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