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It is easy to understand a bimolecular reaction on the basis of collision theory.
But how can one account for a unimolecular reaction? If we assume that in such a reaction , the molecule A acquires the necessary activation energy for colliding with another molecule, then the reaction should obey second-order kinetics and not the first-order kinetics which is actually observed in several unimolecular gaseous reactions. A satisfactory theory of these reactions was proposed by F. A. Lindemann in 1922. (more…)