D31.1 Heterogeneous Catalysts

A heterogeneous catalyst is present in a different phase from the reactants. Such catalysts are usually solids, and often function by furnishing an active surface upon which one or more steps in the reaction can occur.

A heterogeneous catalytic reaction has at least four steps in its reaction mechanism:

  1. Adsorption of the reactant(s) onto the surface of the catalyst
  2. Activation of the adsorbed reactant(s)
  3. Reaction of the adsorbed reactant(s)
  4. Diffusion of the product(s) from the surface into the gas or liquid phase (desorption)

Any one of these steps may be slow and thus may serve as the rate determining step. But the overall rate of the reaction is still faster than it would be without the catalyst. The figure below illustrates catalysis the reaction of an alkene with hydrogen on the surface of a nickel catalyst. The overall reaction is

\text{C}_2\text{H}_4\text{(g)} + \text{H}_2\text{(g)}\ {\overset{\text{Ni}}\longrightarrow}\ \text{C}_2\text{H}_6\text{(g)}

In this figure, four diagrams labeled a through d are shown. In each, a square array of green spheres forming a nickel surface is shown in perspective to provide a three-dimensional appearance. In a, the label “N i surface” is placed above with a line segment extending to the green spheres. At the lower left and upper right, pairs of white spheres bonded tougher together appear as well as white spheres on the green surface. Black arrows are drawn from each of the white spheres above the surface to the white sphere on the green surface. In b, the white spheres are still present on the green surface. Above the surface is a grayed-out structure labeled ethene with two C atoms and four H atoms. The label “Ethene” at the top of the diagram is connected to the greyed out structure with a line segment. Arrows indicating motion point down from this structure to a an ethene molecule with two central black spheres with a single bond indicated by a horizontal black rod between them. Above and below to the left and right, a total of four white spheres are connected to the black spheres with white rods. A line segment extends from this structure to the label, “Ethene adsorbed on surface; pi bond broken.” In c, the diagram is very similar to b except that the greyed out structure and labels are gone and one of the white spheres near the black and white structure in each pair on the green surface is greyed out. Arrows point from each greyed-out white sphere to each of the two black spheres. There is a label below that says, "H atoms migrate to C H 2". In d, only a single white sphere remains from each pair in the green surface. A curved arrow points from the middle of the green surface to a model above with two central black carbon-atom spheres with a single black rod indicating a single bond between them. Each of the black spheres has three small white spheres bonded as indicated by white rods between the black spheres and the small white spheres. The four bonds around each black sphere are evenly distributed about the black spheres.
Figure: Heterogeneous catalysis. There are four steps in the catalytic hydrogenation of ethene on a nickel surface. (Ni atoms on the surface are represented by green spheres.) (a) Hydrogen is adsorbed on the surface, breaking the H–H bonds and forming Ni–H bonds. (b) Ethene is adsorbed on the surface, breaking the π bond and forming Ni–C bonds. (c) H atoms diffuse across the surface and form new C–H bonds when they reach ethene molecules. (d) The saturated carbon atoms in C2H6 molecules can no longer bond to the surface so the ethane molecules escape from the surface.

The uncatalyzed C2H4(g) + H2(g) ⟶ C2H6(g) reaction would necessitate a transition state where the C=C π bond and the H-H σ bond are breaking while the two C-H σ bonds form. Such a transition state is so high in energy that without a catalyst, H2 is unreactive towards alkenes under most conditions.

Nickel is a catalyst often used in the hydrogenation of polyunsaturated fats and oils to produce saturated fats and oils. Other significant industrial processes that involve the use of heterogeneous catalysts include the preparation of sulfuric acid, the synthesis of ammonia from nitrogen and hydrogen, the oxidation of ammonia to nitric acid, and the synthesis of methanol. Heterogeneous catalysts are also used in the catalytic converters found on most gasoline-powered automobiles.

Exercise: Catalysis and Reaction Energy Diagram

Two diagrams of energy in kJ/mol versus reaction progress. Left diagram (a) has blue curve that starts at 6 kJ/mol, goes up to 42 kJ/mol and then goes down to 0 kJ/mol. Right curve starts at 6 kJ/mol, goes up to 29 kJ/mol, drops to 21 kJ/mol, goes up to 24 kJ/mol, and goes down to 0 kJ/mol.

One of the two reaction energy diagrams above corresponds to a reaction occurring without a catalyst, the other corresponds to a catalyzed reaction. Identify which diagram corresponds to the reaction occurring with a catalyst. In your notebook, explain why you chose that diagram and determine the activation energy for the catalyzed reaction.

Write in your notebook, then left-click here for an explanation.

A catalyst does not affect the energy of reactants or products, so those aspects of both diagrams are the same. There are two major differences between the graphs:

  1. Graph (b) has two transition states while graph (a) has one transition state;
  2. The highest energy transition state in graph (b) is significantly lower in energy than the transition state in graph (a).

These indicate the use of a catalyst in (b), as it is depicting a multi-step reaction with a lower activation energy.

There are two activation energies in (b).

  • Ea,1 is the difference between the energy of the starting reagents and the first transition state. In (b) the reactants are at 6 kJ/mol and the first transition state is at 29 kJ/mol, so Ea,1 is: 29 kJ/mol – 6 kJ/mol = 23 kJ/mol.
  • Ea,2 is the difference between the energy of the intermediates and the second transition state. In (b) the intermediates are at 21 kJ/mol and the second transition state is at 24 kJ/mol, so Ea,2 is 24 kJ/mol – 21 kJ/mol = 3 kJ/mol.

Exercise: Catalytic Mechanisms

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Chem 109 Fall 2023 Copyright © by Jia Zhou; John Moore; and Etienne Garand is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License, except where otherwise noted.