Catalysis
Catalysis is the increase in rate of a chemical reaction due to an added substance known as a catalyst. Catalysts are not consumed by the reaction and remain unchanged after the reaction. If the reaction is rapid and the catalyst is recycled quickly, a very small amount of catalyst often suffices; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst.
The rate increase occurs because the catalyst allows the reaction to occur by an alternative mechanism which may be much faster than the noncatalyzed mechanism. However the noncatalyzed mechanism does remain possible, so that the total rate can only increase in the presence of the catalyst and never decrease.
Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category.
Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture.
The term "catalyst" is derived from Greek wikt:καταλύω, kataluein, meaning "loosen" or "untie". The concept of catalysis was invented by chemist Elizabeth Fulhame, based on her novel work in oxidation-reduction experiments.
General principles
Example
An illustrative example is the effect of catalysts to speed the decomposition of hydrogen peroxide into water and oxygen:This reaction proceeds because the reaction products are more stable than the starting compound, but this decomposition is so slow that hydrogen peroxide solutions are commercially available. In the presence of a catalyst such as manganese dioxide, this reaction proceeds much more rapidly. This effect is readily seen by the effervescence of oxygen. The catalyst is not consumed in the reaction, and may be recovered unchanged and re-used indefinitely. Accordingly, manganese dioxide is said to catalyze this reaction. In living organisms, this reaction is catalyzed by enzymes such as catalase.
Another example is the effect of catalysts on air pollution and reducing the amount of carbon monoxide. Development of active and selective catalysts for the conversion of carbon monoxide into desirable products is one of the most important roles of catalysts. Using catalysts for the hydrogenation of carbon monoxide helps remove this toxic gas and produce useful materials.
Units
The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is quantified in moles per second. The productivity of a catalyst can be described by the turnover number and the catalytic activity by the turn over frequency, which is the TON per time unit. The biochemical equivalent is the enzyme unit. For more information on the efficiency of enzymatic catalysis, see the article on enzymes.Catalytic reaction mechanisms
In general, chemical reactions occur faster in the presence of a catalyst because the catalyst provides an alternative reaction mechanism having a lower activation energy than the noncatalyzed mechanism. In catalyzed mechanisms, the catalyst is regenerated.As a simple example occurring in the gas phase, the reaction can be catalyzed by adding nitric oxide. The reaction occurs in two steps:
The NO catalyst is regenerated. The overall rate is the rate of the slow step
An example of heterogeneous catalysis is the reaction of oxygen and hydrogen on the surface of titanium dioxide to produce water. Scanning tunneling microscopy showed that the molecules undergo adsorption and dissociation. The dissociated, surface-bound O and H atoms diffuse together. The intermediate reaction states are: HO, HO, then HO and the reaction product, after which the water molecule desorbs from the catalyst surface.
Reaction energetics
Catalysts enable pathways that differ from those of uncatalyzed reactions. These pathways have lower activation energy. Consequently, more molecular collisions have the energy needed to reach the transition state. Hence, catalysts can enable reactions that would otherwise be blocked or slowed by a kinetic barrier. The catalyst may increase the reaction rate or selectivity, or enable the reaction at lower temperatures. This effect can be illustrated with an energy profile diagram.In the catalyzed elementary reaction, catalysts do not change the extent of a reaction: they have no effect on the chemical equilibrium of a reaction. The ratio of the forward and the reverse reaction rates is unaffected. The second law of thermodynamics describes why a catalyst does not change the chemical equilibrium of a reaction. Suppose there was such a catalyst that shifted an equilibrium. Introducing the catalyst to the system would result in a reaction to move to the new equilibrium, producing energy. Production of energy is a necessary result since reactions are spontaneous only if Gibbs free energy is produced, and if there is no energy barrier, there is no need for a catalyst. Then, removing the catalyst would also result in a reaction, producing energy; i.e. the addition and its reverse process, removal, would both produce energy. Thus, a catalyst that could change the equilibrium would be a perpetual motion machine, a contradiction to the laws of thermodynamics. Thus, catalysts do not alter the equilibrium constant.
The catalyst stabilizes the transition state more than it stabilizes the starting material. It decreases the kinetic barrier by decreasing the difference in energy between starting material and the transition state. It does not change the energy difference between starting materials and products, or the available energy.
Related concepts
Some so-called catalysts are really precatalysts, which convert to catalysts in the reaction. For example, Wilkinson's catalyst RhCl loses one triphenylphosphine ligand before entering the true catalytic cycle. Precatalysts are easier to store but are easily activated in situ. Because of this preactivation step, many catalytic reactions involve an induction period.In cooperative catalysis, chemical species that improve catalytic activity are called cocatalysts or promoters.
In tandem catalysis two or more different catalysts are coupled in a one-pot reaction.
In autocatalysis, the catalyst is a product of the overall reaction, in contrast to all other types of catalysis considered in this article. The simplest example of autocatalysis is a reaction of type A + B → 2 B, in one or in several steps. The overall reaction is just A → B, so that B is a product. But since B is also a reactant, it may be present in the rate equation and affect the reaction rate. As the reaction proceeds, the concentration of B increases and can accelerate the reaction as a catalyst. In effect, the reaction accelerates itself or is autocatalyzed. An example is the hydrolysis of an ester such as aspirin to a carboxylic acid and an alcohol. In the absence of added acid catalysts, the carboxylic acid product catalyzes the hydrolysis.
Switchable catalysis refers to a type of catalysis where the catalyst can be toggled between different ground states possessing distinct reactivity, typically by applying an external stimulus. This ability to reversibly switch the catalyst allows for spatiotemporal control over catalytic activity and selectivity. The external stimuli used to switch the catalyst can include changes in temperature, pH, light, electric fields, or the addition of chemical agents.
A true catalyst can work in tandem with a sacrificial catalyst. The true catalyst is consumed in the elementary reaction and turned into a deactivated form.
The sacrificial catalyst regenerates the true catalyst for another cycle. The sacrificial catalyst is consumed in the reaction, and as such, it is not really a catalyst, but a reagent. For example, osmium tetroxide is a good reagent for dihydroxylation, but it is highly toxic and expensive. In Upjohn dihydroxylation, the sacrificial catalyst N-methylmorpholine N-oxide regenerates OsO4, and only catalytic quantities of OsO4 are needed.
Classification
Catalysis may be classified as either homogeneous or heterogeneous. A homogeneous catalysis is one whose components are dispersed in the same phase as the reactant's molecules. A heterogeneous catalysis is one where the reaction components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Similar mechanistic principles apply to heterogeneous, homogeneous, and biocatalysis.Heterogeneous catalysis
Heterogeneous catalysts act in a different phase than the reactants. Most heterogeneous catalysts are solids that act on substrates in a liquid or gaseous reaction mixture. Important heterogeneous catalysts include zeolites, alumina, higher-order oxides, graphitic carbon, transition metal oxides, metals such as Raney nickel for hydrogenation, and vanadium oxide for oxidation of sulfur dioxide into sulfur trioxide by the contact process.Diverse mechanisms for reactions on surfaces are known, depending on how the adsorption takes place. The total surface area of a solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger the surface area for a given mass of particles.
A heterogeneous catalyst has active sites, which are the atoms or crystal faces where the substrate actually binds. Active sites are atoms but are often described as a facet of a solid. Most of the volume but also most of the surface of a heterogeneous catalyst may be catalytically inactive. Finding out the nature of the active site is technically challenging.
For example, the catalyst for the Haber process for the synthesis of ammonia from nitrogen and hydrogen is often described as iron. But detailed studies and many optimizations have led to catalysts that are mixtures of iron-potassium-calcium-aluminum-oxide. The reacting gases adsorb onto active sites on the iron particles. Once physically adsorbed, the reagents partially or wholly dissociate and form new bonds. In this way the particularly strong triple bond in nitrogen is broken, which would be extremely uncommon in the gas phase due to its high activation energy. Thus, the activation energy of the overall reaction is lowered, and the rate of reaction increases. Another place where a heterogeneous catalyst is applied is in the oxidation of sulfur dioxide on vanadium oxide for the production of sulfuric acid. Many heterogeneous catalysts are in fact nanomaterials.
Heterogeneous catalysts are typically "supported", which means that the catalyst is dispersed on a second material that enhances the effectiveness or minimizes its cost. Supports prevent or minimize agglomeration and sintering of small catalyst particles, exposing more surface area, thus catalysts have a higher specific activity on support. Sometimes the support is merely a surface on which the catalyst is spread to increase the surface area. More often, the support and the catalyst interact, affecting the catalytic reaction. Supports can also be used in nanoparticle synthesis by providing sites for individual molecules of catalyst to chemically bind. Supports are porous materials with a high surface area, most commonly alumina, zeolites, or various kinds of activated carbon. Specialized supports include silicon dioxide, titanium dioxide, calcium carbonate, and barium sulfate.