12.7 Catalysis

We have seen that the rate of many reactions can be accelerated by catalysts. A catalyst speeds up the rate of a reaction by lowering the activation energy; in addition, the catalyst is regenerated in the process. Several reactions that are thermodynamically favorable in the absence of a catalyst only occur at a reasonable rate when a catalyst is present. One such reaction is catalytic hydrogenation, the process by which hydrogen is added across an alkene C=C bond to afford the saturated alkane product. A comparison of the reaction coordinate diagrams (also known as energy diagrams) for catalyzed and uncatalyzed alkene hydrogenation is shown in [link] .

Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps, as depicted in the reaction diagrams shown in [link] . This lower activation energy results in an increase in rate as described by the Arrhenius equation. Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions . Consequently, the presence of a catalyst will permit a system to reach equilibrium more quickly, but it has no effect on the position of the equilibrium as reflected in the value of its equilibrium constant (see the later chapter on chemical equilibrium).

Using reaction diagrams to compare catalyzed reactions

The two reaction diagrams here represent the same reaction: one without a catalyst and one with a catalyst. Identify which diagram suggests the presence of a catalyst, and determine the activation energy for the catalyzed reaction:

Solution

A catalyst does not affect the energy of reactant or product, so those aspects of the diagrams can be ignored; they are, as we would expect, identical in that respect. There is, however, a noticeable difference in the transition state, which is distinctly lower in diagram (b) than it is in (a). This indicates the use of a catalyst in diagram (b). The activation energy is the difference between the energy of the starting reagents and the transition state—a maximum on the reaction coordinate diagram. The reagents are at 6 kJ and the transition state is at 20 kJ, so the activation energy can be calculated as follows:

$E_{\text{a}}=20\text{kJ}-6\text{kJ}=14\text{kJ}$

Check your learning

Determine which of the two diagrams here (both for the same reaction) involves a catalyst, and identify the activation energy for the catalyzed reaction:

Answer:

Diagram (b) is a catalyzed reaction with an activation energy of about 70 kJ.

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