The latter two equations constitute a chain
reaction, each one yielding a molecule of HBr and producing the reactant
atom for the other chain step. There also are reactions that either damp
down or reverse the chain process:
With these reactions and a certain amount of
algebra, one can arrive at the observed
rate expression in a straightforward though tedious manner. Although
the rate equation looks complicated, we can understand it in terms of
the HBr mechanism. For example, as [HBr] increases, its presence in the
denominator decreases the rate of reaction.
This happens because the chain-reversal reaction
sends more HBr back to H2 molecules and Br
atoms. At low HBr concentration, for which the ratio [HBr]/[Br2]
is small in comparison with the rate
constant k, the rate law simplifies to the 1�-order
expression that we saw previously:
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