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Mechanism of Catalysis

Catalysts work by changing the activation energy for a reaction, i.e., the minimum energy needed for the reaction to occur. This is accomplished by providing a new mechanism or reaction path through which the reaction can proceed. When the new reaction path has a lower activation energy, the reaction rate is increased and the reaction is said to be catalyzed.

If the activation energy for the new path is higher, the reaction rate is decreased and the reaction is said to be inhibited. Inhibitors can provide an interesting challenge to the chemist. For example, because oxygen is an inhibitor of free-radical reactions, many of which are important in the synthesis of polymers, such reactions must be performed in an oxygen-free environment, e.g., under a blanket of nitrogen gas.

In some reactions one of the reaction products is a catalyst for the reaction; this phenomenon is called self-catalysis or autocatalysis. An example is the reaction of permanganate ion with oxalic acid to form carbon dioxide and manganous ion, in which the manganous ion acts as an autocatalyst. Such reactions are potentially dangerous, since the reaction rate may increase to the point of explosion.

Some substances that are not themselves catalysts increase the activity of a catalyst when added with it to some reaction; such substances are called promoters. Alumina is a promoter for iron when it is used to catalyze the reaction of hydrogen and nitrogen to form ammonia. Substances that react with catalysts to reduce or eliminate their effect are called poisons.

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The Columbia Electronic Encyclopedia, 6th ed. Copyright © 2012, Columbia University Press. All rights reserved.

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