Overview of Catalysis & Catalyst

By: Doyouknow | Views: 6663 | Date: 23-Nov-2011

Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself.

Catalysis:

Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transformations. Catalysts that speed the reaction are called positive catalysts. Substances that slow a catalyst's effect in a chemical reaction are called inhibitors (or negative catalysts). Substances that increase the activity of catalysts are called promoters, and substances that deactivate catalysts are called catalytic poisons.

Catalytic reactions have a lower rate-limiting free energy of activation than the corresponding uncatalyzed reaction, resulting in higher reaction rate at the same temperature. However, the mechanistic explanation of catalysis is complex. Catalysts may affect the reaction environment favorably, or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds, or form specific intermediates that are not produced naturally, such as osmate esters in osmium tetroxide-catalyzed dihydroxylation of alkenes, or cause lysis of reagents to reactive forms, such as atomic hydrogen in catalytic hydrogenation.

Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the frequency of contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slowest step, and rates are limited by amount of catalyst and its "activity". In heterogeneous catalysis, the diffusion of reagents to the surface and diffusion of products from the surface can be rate determining. Analogous events associated with substrate binding and product dissociation apply to homogeneous catalysts.

Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by secondary processes. In heterogeneous catalysis, typical secondary processes include coking where the catalyst becomes covered by polymeric side products. Additionally, heterogeneous catalysts can dissolve into the solution in a solid–liquid system or evaporate in a solid–gas system.

General principles of catalysis:

Typical mechanism:


Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process regenerating the catalyst. The following is a typical reaction scheme, where C represents the catalyst, X and Y are reactants, and Z is the product of the reaction of X and Y:

Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so for the overall reaction:

X + Y → Z

As a catalyst is regenerated in a reaction, often only small amounts are needed to increase the rate of the reaction. In practice, however, catalysts are sometimes consumed in secondary processes.

As an example of this process, in 2008 Danish researchers first revealed the sequence of events when oxygen and hydrogen combine on the surface of titanium dioxide (TiO2, or titania) to produce water. With a time-lapse series of scanning tunneling microscopy images, they determined the molecules undergo adsorption, dissociation and diffusion before reacting. The intermediate reaction states were: HO2, H2O2, then H3O2 and the final reaction product (water molecule dimers), after which the water molecule desorbs from the catalyst surface.

Catalysis and reaction energetic:

Generic potential energy diagram showing the effect of a catalyst in a hypothetical exothermic chemical reaction X + Y to give Z. The presence of the catalyst opens a different reaction pathway (shown in red) with lower activation energy. The final result and the overall thermodynamics are the same.

Catalysts work by providing an (alternative) mechanism involving a different transition state and 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 reaction rate or selectivity, or enable the reaction at lower temperatures. This effect can be illustrated with a Boltzmann distribution and 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 because the rate of both the forward and the reverse reaction are both affected (see also thermodynamics). The fact that a catalyst does not change the equilibrium is a consequence of the second law of thermodynamics. Suppose there was such a catalyst that shifted equilibrium. Introducing the catalyst to the system would result in reaction to move to the new equilibrium, producing energy. Production of energy is a necessary result since reactions are spontaneous if and 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 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.

If a catalyst does change the equilibrium, then it must be consumed as the reaction proceeds, and thus it is also a reactant. Illustrative is the base-catalyzed hydrolysis of esters, where the produced carboxylic acid immediately reacts with the base catalyst and thus the reaction equilibrium is shifted towards hydrolysis.

The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is a mole per second. The productivity of a catalyst can be described by the turn over number (or TON) and the catalytic activity by the turn over frequency (TOF), 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.

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 transition state. It does not change the energy difference between starting materials and products (thermodynamic barrier), or the available energy (this is provided by the environment as heat or light).

Typical catalytic materials:

The chemical nature of catalysts is as diverse as catalysis itself, although some generalizations can be made. Proton acids are probably the most widely used catalysts, especially for the many reactions involving water, including hydrolysis and its reverse. Multifunctional solids often are catalytically active, e.g. zeolites, alumina, higher-order oxides, graphitic carbon, nano particles, nanodots, and facets of bulk materials. Transition metals are often used to catalyze redox reactions (oxidation, hydrogenation). Examples are nickel, such as Raney nickel for hydrogenation, and vanadium(V) oxide for oxidation of sulfur dioxide into sulfur trioxide. Many catalytic processes, especially those used in organic synthesis, require so called "late transition metals", which include palladium, platinum, gold, ruthenium, rhodium, and iridium.

Some so-called catalysts are really precatalysts. Precatalysts convert to catalysts in the reaction. For example, Wilkinson's catalyst RhCl (PPh3)3 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.

Chemical species that improve catalytic activity are called co-catalysts (co catalysts) or promoters in cooperative catalysis.

Types of catalysis:

Catalysts can be either heterogeneous or homogeneous, depending on whether a catalyst exists in the same phase as the substrate. Biocatalysts (enzymes) are often seen as a separate group.

Heterogeneous catalysts:

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. Diverse mechanisms for reactions on surfaces are known, depending on how the adsorption takes place (Langmuir-Hinshelwood, Eley-Rideal, and Mars-van Krevelen). The total surface area of 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.


For example, in the Haber process, finely divided iron serves as a catalyst for the synthesis of ammonia from nitrogen and hydrogen. The reacting gases adsorb onto "active sites" on the iron particles. Once adsorbed, the bonds within the reacting molecules are weakened, and new bonds between the resulting fragments form in part due to their close proximity. In this way the particularly strong triple bond in nitrogen is weakened and the hydrogen and nitrogen atoms combine faster than would be the case in the gas phase, so the rate of reaction increases. Another place where a heterogeneous catalyst is applied is in the contact process (oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid).

Heterogeneous catalysts are typically “supported,” which means that the catalyst is dispersed on a second material that enhances the

effectiveness or minimizes their cost. 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 are porous materials with a high surface area, most commonly alumina or various kinds of activated carbon. Specialized supports include silicon dioxide, titanium dioxide, calcium carbonate, and barium sulfate.

Homogeneous catalysts:

Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles invoked in heterogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a solvent with the substrates. One example of homogeneous catalysis involves the influence of H+ on the esterification of esters, e.g. methyl acetate from acetic acid and methanol. For inorganic chemists, homogeneous catalysis is often synonymous with organometallic catalysts. 


Electrocatalysts:

In the context of electrochemistry, specifically in fuel cell engineering, various metal-containing catalysts are used to enhance the rates of the half reactions that comprise the fuel cell. One common type of fuel cell electro catalyst is based upon nano particles of platinum that are supported on slightly larger carbon particles. When in contact with one of the electrodes in a fuel cell, this platinum increases the rate of oxygen reduction to water, either to hydroxide or hydrogen peroxide.


Organocatalysis:


Whereas transition metals sometimes attract most of the attention in the study of catalysis, small organic molecules without metals can also exhibit catalytic properties, as is apparent from the fact that many enzymes lack transition metals. Typically, organic catalysts require a higher loading (amount of catalyst per unit amount of reactant, expressed in mol% amount of substance) than transition metal (-ion)-based catalysts, but these catalysts are usually commercially available in bulk, helping to reduce costs. In the early 2000s, these organocatalysts were considered "new generation" and are competitive to traditional metal (-ion)-containing catalysts. Organocatalysts are supposed to operate akin to metal-free enzymes utilizing, e.g., non-covalent interactions such as hydrogen bonding. The discipline organocatalysis is divided in the application of covalent (e.g., proline, DMAP) and non-covalent (e.g., thiourea organocatalysis) organocatalysts referring to the preferred catalyst-substrate binding and interaction, respectively.

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Comments
Marty Samson  |  23-Feb-2012 07:35:06 IST
Another perpetual motion machine.

What do you think of this one?

http://www.scienceforums.net/topic/54128-continuous-frictioned-motion-machine/
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