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Chain reactions

Many gas-phase reactions and liquid-phase polymerization


reactions are chain reactions.

reaction intermediate  intermediate  intermediate

chain carriers

radical chain reaction

radicals
The rate laws of chain reactions
consider the pyrolysis, or thermal decomposition in the
absence of air, of acetaldehyde.

v  k CH 3CHO 
3/2
CH3CHO(g) → CH4(g) + CO(g)

The Rice–Herzfeld mechanism for this reaction is as


follows (the dot signifies an unpaired electron and marks a
radical):
the net rate of change of the intermediates (·CH3 and
CH3CO·) may be set equal to zero:

The sum of the two equations is


The steady-state concentration of ·CH3 radicals is

It follows that the rate of formation of CH4 is


In many cases, a chain reaction leads to a complicated rate
law. An example is the hydrogen–bromine reaction:

The following mechanism has been proposed to account


for this rate law
The net rates of formation of the two intermediates are

The steady-state concentrations of the intermediates are


obtained by solving these two simultaneous equations and
are
When we substitute these concentrations into the
expression for d[HBr]/dt, we obtain