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CATALYSIS

Catalysis is the increase in the rate of a chemical reaction due to the participation of an
additional substance called a catalyst. With a catalyst, reactions occur faster and with less
energy. Because catalysts are not consumed, they are recycled. Often only tiny amounts are
required.
Types:
Catalysts can be 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 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.

A heterogeneous catalyst has active sites, which are the atoms or crystal faces where the reaction
actually occurs. Depending on the mechanism, the active site may be either a planar exposed
metal surface, a crystal edge with imperfect metal valence or a complicated combination of the
two. Thus, not only 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 requires technically
challenging research. Thus, empirical research for finding out new metal combinations for
catalysis continues.

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 physically adsorbed, the reagents undergo chemisorption that results in
dissociation into adsorbed atomic species, 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
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(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. Supports prevent or
reduce agglomeration and sintering of the small catalyst particles, exposing more surface area,
thus catalysts have a higher specific activity (per gram) on a 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 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.

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 electrocatalyst is based upon nanoparticles of platinum that are
supported on slightly larger carbon particles. When in contact with one of the electrodesin a fuel
cell, this platinum increases the rate of oxygen reduction either to water, or to hydroxideor
hydrogen peroxide.

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 carboxylic acids, such as the formation of
methyl acetate from acetic acid and methanol. For inorganic chemists, homogeneous catalysis is
often synonymous with organometallic catalysts.

Activation Energy & Catalyst:


A substance that modifies the transition state to lower the activation energy is termed a catalyst; a
biological catalyst is termed an enzyme. It is important to note that a catalyst increases the rate of
reaction without being consumed by it. In addition, while the catalyst lowers the activation
energy, it does not change the energies of the original reactants or products. Rather, the reactant
energy and the product energy remain the same and only the activation energy is altered.
Theories of Catalysts:

The following theories are proposed to explain the mechanism of catalysis:

(i) Intermediate compound formulation theory:

According to this theory one of the reactants combines with catalyst to form intermediate
product, which carries out the reaction,

E.g.

where A and B are reactants, C is the catalyst and AC is the intermediate product.

(ii) Adsorption theory:

According to this theory, reactants are adsorbed on the surface of the catalyst and form a film.
Due to high concentration of the reactants on the film, reaction proceeds at a faster rate.
(iii) Modern adsorption theory:

According to this theory, reactants are adsorbed at the active centers i.e. free valencies etc. on the
solid surface and form activated complex which under strain forms new molecules and leaves the
surface. This explains, why the finely divided catalyst has greater activity.

(iv) Energy activation theory:

According to this theory, catalyst changes the value of activation energy which can be crossed by
the reactants easily and consequently products are formed.

Acidbase catalysis, acceleration of a chemical reaction by the addition of an acid or a base, the
acid or base itself not being consumed in the reaction. The catalytic reaction may be acid-specific
(acid catalysis), as in the case of decomposition of the sugar sucrose into glucose and fructose in
sulfuric acid; or base-specific (base catalysis), as in the addition of hydrogen cyanide to
aldehydes and ketones in the presence of sodium hydroxide. Many reactions are catalyzed by
both acids and bases.

The mechanism of acid- and base-catalyzed reactions is explained in terms of the Brnsted
Lowry concept of acids and bases as one in which there is an initial transfer of protons from an
acidic catalyst to the reactant or from the reactant to a basic catalyst. In terms of the Lewis theory
of acids and bases, the reaction entails sharing of an electron pair donated by a base catalyst or
accepted by an acid catalyst.

Acid catalysis is employed in a large number of industrial reactions, among them the conversion
of petroleum hydrocarbons to gasoline and related products. Such reactions include
decomposition of high-molecular-weight hydrocarbons (cracking) using aluminasilica catalysts
(BrnstedLowry acids), polymerization of unsaturated hydrocarbons using sulfuric acid or
hydrogen fluoride (BrnstedLowry acids), and isomerization of aliphatic hydrocarbons using
aluminum chloride (a Lewis acid).

Among industrial applications of base-catalyzed reactions is the reaction of diisocyanates with


polyfunctional alcohols in the presence of amines, used in the manufacture of polyurethane
foams.
For e.g.: Acid catalyzed reaction:

Enzyme catalysis is the increase in the rate of a chemical reaction by the active site of a protein.
The protein catalyst (enzyme) may be part of a multi-subunit complex, and/or may transiently or
permanently associate with a Cofactor (e.g. adenosine triphosphate). Catalysis of biochemical
reactions in the cell is vital due to the very low reaction rates of the uncatalysed reactions. A key
driver of protein evolution is the optimization of such catalytic activities via protein dynamics

The mechanism of enzyme catalysis is similar in principle to other types of chemical catalysis.
By providing an alternative reaction route the enzyme reduces the energy required to reach the
highest energy transition state of the reaction. The reduction of activation energy (Ea) increases
the amount of reactant molecules that achieve a sufficient level of energy, such that they reach
the activation energy and form the product. As with other catalysts, the enzyme is not consumed
during the reaction (as a substrate is) but is recycled such that a single enzyme performs many
rounds of catalysis.