4.8 Catalysis

Learning Objectives

• To understand how catalysts increase the reaction rate and the selectivity of chemical reactions.

Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. A catalyst, therefore, does not appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. The catalyzed pathway has a lower E_a, but the net change in energy that results from the reaction (the difference between the energy of the reactants and the energy of the products) is not affected by the presence of a catalyst (Figure \(\PageIndex{1}\)). Nevertheless, because of its lower E_a, the reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature. Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount. In this section, we will examine the three major classes of catalysts: heterogeneous catalysts, homogeneous catalysts, and enzymes.

Figure \(\PageIndex{1}\): Lowering the Activation Energy of a Reaction by a Catalyst. This graph compares potential energy diagrams for a single-step reaction in the presence and absence of a catalyst. The only effect of the catalyst is to lower the activation energy of the reaction. The catalyst does not affect the energy of the reactants or products (and thus does not affect ΔE). (CC BY-NC-SA; anonymous)

The green line represents the uncatalyzed reaction. The purple line represent the catalyzed reaction .

A catalyst affects E_a, not ΔE.

Heterogeneous Catalysis

In heterogeneous catalysis, the catalyst is in a different phase from the reactants. At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way that a chemical bond in the reactant becomes weak and then breaks. Poisons are substances that bind irreversibly to catalysts, preventing reactants from adsorbing and thus reducing or destroying the catalyst’s efficiency.

An example of heterogeneous catalysis is the interaction of hydrogen gas with the surface of a metal, such as Ni, Pd, or Pt. As shown in part (a) in Figure \(\PageIndex{2}\), the hydrogen–hydrogen bonds break and produce individual adsorbed hydrogen atoms on the surface of the metal. Because the adsorbed atoms can move around on the surface, two hydrogen atoms can collide and form a molecule of hydrogen gas that can then leave the surface in the reverse process, called desorption. Adsorbed H atoms on a metal surface are substantially more reactive than a hydrogen molecule. Because the relatively strong H–H bond (dissociation energy = 432 kJ/mol) has already been broken, the energy barrier for most reactions of H₂ is substantially lower on the catalyst surface.

Figure \(\PageIndex{2}\): Hydrogenation of Ethylene on a Heterogeneous Catalyst. When a molecule of hydrogen adsorbs to the catalyst surface, the H–H bond breaks, and new M–H bonds are formed. The individual H atoms are more reactive than gaseous H₂. When a molecule of ethylene interacts with the catalyst surface, it reacts with the H atoms in a stepwise process to eventually produce ethane, which is released. (CC BY-NC-SA; anonymous)

Figure \(\PageIndex{2}\) shows a process called hydrogenation, in which hydrogen atoms are added to the double bond of an alkene, such as ethylene, to give a product that contains C–C single bonds, in this case ethane. Hydrogenation is used in the food industry to convert vegetable oils, which consist of long chains of alkenes, to more commercially valuable solid derivatives that contain alkyl chains. Hydrogenation of some of the double bonds in polyunsaturated vegetable oils, for example, produces margarine, a product with a melting point, texture, and other physical properties similar to those of butter.

Several important examples of industrial heterogeneous catalytic reactions are in Table \(\PageIndex{1}\). Although the mechanisms of these reactions are considerably more complex than the simple hydrogenation reaction described here, they all involve adsorption of the reactants onto a solid catalytic surface, chemical reaction of the adsorbed species (sometimes via a number of intermediate species), and finally desorption of the products from the surface.

Table \(\PageIndex{1}\): Some Commercially Important Reactions that Employ Heterogeneous Catalysts

Commercial Process	Catalyst	Initial Reaction	Final Commercial Product
contact process	V2O5 or Pt	2SO2 + O2 → 2SO3	H2SO4
Haber process	Fe, K2O, Al2O3	N2 + 3H2 → 2NH3	NH3
Ostwald process	Pt and Rh	4NH3 + 5O2 → 4NO + 6H2O	HNO3
water–gas shift reaction	Fe, Cr2O3, or Cu	CO + H2O → CO2 + H2	H2 for NH3, CH3OH, and other fuels
steam reforming	Ni	CH4 + H2O → CO + 3H2	H2
methanol synthesis	ZnO and Cr2O3	CO + 2H2 → CH3OH	CH3OH
Sohio process	bismuth phosphomolybdate	\(\mathrm{CH}_2\textrm{=CHCH}_3+\mathrm{NH_3}+\mathrm{\frac{3}{2}O_2}\rightarrow\mathrm{CH_2}\textrm{=CHCN}+\mathrm{3H_2O}\)	\(\underset{\textrm{acrylonitrile}}{\mathrm{CH_2}\textrm{=CHCN}}\)
catalytic hydrogenation	Ni, Pd, or Pt	RCH=CHR′ + H2 → RCH2—CH2R′	partially hydrogenated oils for margarine, and so forth

Homogeneous Catalysis

In homogeneous catalysis, the catalyst is in the same phase as the reactant(s). The number of collisions between reactants and catalyst is at a maximum because the catalyst is uniformly dispersed throughout the reaction mixture. Many homogeneous catalysts in industry are transition metal compounds (Table \(\PageIndex{2}\)), but recovering these expensive catalysts from solution has been a major challenge. As an added barrier to their widespread commercial use, many homogeneous catalysts can be used only at relatively low temperatures, and even then they tend to decompose slowly in solution. Despite these problems, a number of commercially viable processes have been developed in recent years. High-density polyethylene and polypropylene are produced by homogeneous catalysis.

Table \(\PageIndex{2}\): Some Commercially Important Reactions that Employ Homogeneous Catalysts

Commercial Process	Catalyst	Reactants	Final Product
Union Carbide	[Rh(CO)2I2]^−	CO + CH3OH	CH3CO2H
hydroperoxide process	Mo(VI) complexes	CH3CH=CH2 + R–O–O–H
hydroformylation	Rh/PR3 complexes	RCH=CH2 + CO + H2	RCH2CH2CHO
adiponitrile process	Ni/PR3complexes	2HCN + CH2=CHCH=CH2	NCCH2CH2CH2CH2CN used to synthesize nylon
olefin polymerization	(RC5H5)2ZrCl2	CH2=CH2	–(CH2CH2–)n: high-density polyethylene

Enzymes

Enzymes, catalysts that occur naturally in living organisms, are almost all protein molecules with typical molecular masses of 20,000–100,000 amu. Some are homogeneous catalysts that react in aqueous solution within a cellular compartment of an organism. Others are heterogeneous catalysts embedded within the membranes that separate cells and cellular compartments from their surroundings. The reactant in an enzyme-catalyzed reaction is called a substrate.

Because enzymes can increase reaction rates by enormous factors (up to 10¹⁷ times the uncatalyzed rate) and tend to be very specific, typically producing only a single product in quantitative yield, they are the focus of active research. At the same time, enzymes are usually expensive to obtain, they often cease functioning at temperatures greater than 37 °C, have limited stability in solution, and have such high specificity that they are confined to turning one particular set of reactants into one particular product. This means that separate processes using different enzymes must be developed for chemically similar reactions, which is time-consuming and expensive. Thus far, enzymes have found only limited industrial applications, although they are used as ingredients in laundry detergents, contact lens cleaners, and meat tenderizers. The enzymes in these applications tend to be proteases, which are able to cleave the amide bonds that hold amino acids together in proteins. Meat tenderizers, for example, contain a protease called papain, which is isolated from papaya juice. It cleaves some of the long, fibrous protein molecules that make inexpensive cuts of beef tough, producing a piece of meat that is more tender. Some insects, like the bombadier beetle, carry an enzyme capable of catalyzing the decomposition of hydrogen peroxide to water (Figure \(\PageIndex{3}\)).

Figure \(\PageIndex{3}\): A Catalytic Defense Mechanism. The scalding, foul-smelling spray emitted by this bombardier beetle is produced by the catalytic decomposition of \(\ce{H2O2}\).

Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction by binding to a specific portion of an enzyme and thus slowing or preventing a reaction from occurring. Irreversible inhibitors are therefore the equivalent of poisons in heterogeneous catalysis. One of the oldest and most widely used commercial enzyme inhibitors is aspirin, which selectively inhibits one of the enzymes involved in the synthesis of molecules that trigger inflammation. The design and synthesis of related molecules that are more effective, more selective, and less toxic than aspirin are important objectives of biomedical research.

Summary

Catalysts participate in a chemical reaction and increase its rate. They do not appear in the reaction’s net equation and are not consumed during the reaction. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Enzymes are biological catalysts that produce large increases in reaction rates and tend to be specific for certain reactants and products. The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction.