NAME:

MOHAMED HESHAM

SEC: 3 NO: 8

ENG: HAZEM

DR: EHSAN ABD

ELSALAM
 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.
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 tetra oxide-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. A Nanomaterial-based catalyst is
an example of a heterogeneous catalyst. 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
solidliquid system or evaporate in a solidgas system.

Background
The production of most industrially important chemicals involves
catalysis. Similarly, most biochemically significant processes are
catalyzed. Research into catalysis is a major field in applied
science and involves many areas of chemistry, notably in organ
metallic chemistry and materials science. Catalysis is relevant to
many aspects of environmental science, e.g. the catalytic converter
in automobiles and the dynamics of the ozone hole. Catalytic
reactions are preferred in environmentally friendly green chemistry
due to the reduced amount of waste generated as opposed to
stoichiometric reactions in which all reactants are consumed and
more side products are formed. The most common catalyst is the
hydrogen ion (H+). Many transition metals and transition metal
complexes are used in catalysis as well. Catalysts called enzymes
are important in biology.

A catalyst works by providing an alternative reaction pathway to

the reaction product. The rate of the reaction is increased as this
alternative route has lower activation energy than the reaction
route not mediated by the catalyst. The disproportionation of
hydrogen peroxide creates water and oxygen, as shown below.

2 H2O2 2 H2O + O2

This reaction is preferable in the sense that the reaction products

are more stable than the starting material, though the uncatalyzed
reaction is slow. In fact, the decomposition of hydrogen peroxide is
so slow that hydrogen peroxide solutions are commercially
available. This reaction is strongly affected by catalysts such as
manganese dioxide, or the enzyme peroxidase in organisms. Upon
the addition of a small amount of manganese dioxide, the
hydrogen peroxide reacts rapidly. This effect is readily seen by the
effervescence of oxygen. The manganese dioxide is not consumed
in the reaction, and thus may be recovered unchanged and re-used
indefinitely. Accordingly, manganese dioxide catalyses this
reaction.

*General principles of catalysis

1) 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:

X + C XC (1)

Y + XC XYC (2)

XYC CZ (3)

CZ C + Z (4)

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

X+YZ

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 titanium) 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.

2) Catalysis and reaction energetics

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).

3) 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, Nan 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 pre
activation 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.

1) 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. [Citation needed] 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.

2) 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.

3) Electro catalysts

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 nanoparticles 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.

4) Organo catalysis

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.

*Significance of catalysis

Estimates are that 90% of all commercially produced chemical products involve catalysts at some
stage in the process of their manufacture. In 2005, catalytic processes generated about $900 billion in
products worldwide. Catalysis is so pervasive that subareas are not readily classified. Some areas of
particular concentration are surveyed below.

1) Energy processing

Petroleum refining makes intensive use of catalysis for alkylation, catalytic cracking (breaking long-
chain hydrocarbons into smaller pieces), naphtha reforming and steam reforming (conversion of
hydrocarbons into synthesis gas). Even the exhaust from the burning of fossil fuels is treated via
catalysis: Catalytic converters, typically composed of platinum and rhodium, break down some of the
more harmful byproducts of automobile exhaust.

2 CO + 2 NO 2 CO2 + N2

With regard to synthetic fuels, an old but still important process is the Fischer-Tropsch synthesis of
hydrocarbons from synthesis gas, which itself is processed via water-gas shift reactions, catalyzed by
iron. Biodiesel and related biofuels require processing via both inorganic and biocatalysts.

Fuel cells rely on catalysts for both the anodic and cathodic reactions. Catalytic heaters generate
flameless heat from a supply of combustible fuel.

2) Bulk chemicals

Some of the largest-scale chemicals are produced via catalytic oxidation, often using oxygen.
Examples include nitric acid (from ammonia), sulfuric acid (from sulfur dioxide to sulfur trioxide by
the chamber process), terephthalic acid from p-xylene, and acrylonitrile from propane and ammonia.

Many other chemical products are generated by large-scale reduction, often via hydrogenation. The
largest-scale example is ammonia, which is prepared via the Haber process from nitrogen. Methanol is
prepared from carbon monoxide.

Bulk polymers derived from ethylene and propylene is often prepared via Ziegler-Natta catalysis.
Polyesters, polyamides, and isocyanates are derived via acid-base catalysis.
Most carbonization processes require metal catalysts; examples include the Monsanto acetic acid
process and hydroformylation.

3) Fine chemicals

Many fine chemicals are prepared via catalysis; methods include those of heavy industry as well as
more specialized processes that would be prohibitively expensive on a large scale. Examples include
olefin metathesis using Grubbs' catalyst, the Heck reaction, and Friedel-Crafts reactions. Because
most bioactive compounds are chiral, many pharmaceuticals are produced by enantioselective
catalysis (catalytic asymmetric synthesis).

4) Food processing

One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) of
fats using nickel catalyst to produce margarine. Many other foodstuffs are prepared via biocatalysis
(see below).

5) Biology

In nature, enzymes are catalysts in metabolism and catabolism. Most biocatalysts are protein-based,
i.e. enzymes, but other classes of bimolecular also exhibit catalytic properties including ribozymes,
and synthetic deoxyribozymes.

Biocatalysts can be thought of as intermediate between homogenous and heterogeneous catalysts,

although strictly speaking soluble enzymes are homogeneous catalysts and membrane-bound enzymes
are heterogeneous. Several factors affect the activity of enzymes (and other catalysts) including
temperature, pH, and concentration of enzyme, substrate, and products. A particularly important
reagent in enzymatic reactions is water, which is the product of many bond-forming reactions and a
reactant in many bond-breaking processes.
Enzymes are employed to prepare many commodity chemicals including high-fructose corn syrup and
acryl amide.

6) In the environment

Catalysis impacts the environment by increasing the efficiency of industrial processes, but catalysis
also plays a direct role in the environment. A notable example is the catalytic role of chlorine free
radicals in the breakdown of ozone. These radicals are formed by the action of ultraviolet radiation on
chlorofluorocarbons (CFCs).

Cl + O3 ClO + O2

ClO + O Cl + O2

*History

In a general sense, anything that increases the rate of a process is a "catalyst", a term
derived from Greek , meaning "to annul," or "to untie," or "to pick up." The
phrase catalyzed processes was coined by Jns Jakob Berzelius in 1836[14] to describe
reactions that are accelerated by substances that remain unchanged after the reaction.
Other early chemists involved in catalysis were Alexander Mitscherlich who referred to
contact processes and Johann Wolfgang Dbereiner who spoke of contact action and whose
lighter based on hydrogen and a platinum sponge became a huge commercial success in the
1820s. Humphry Davy discovered the use of platinum in catalysis. In the 1880s, Wilhelm
Ostwald at Leipzig University started a systematic investigation into reactions that were
catalyzed by the presence of acids and bases, and found that chemical reactions occur at
finite rates and that these rates can be used to determine the strengths of acids and bases.
For this work, Ostwald was awarded the 1909 Nobel Prize in Chemistry.
*Inhibitors, poisons and promoters

Substances that reduce the action of catalysts are called catalyst inhibitors if reversible, and
catalyst poisons if irreversible. Promoters are substances that increase the catalytic activity,
even though they are not catalysts by themselves.

Inhibitors are sometimes referred to as "negative catalysts" since they decrease the reaction
rate. However the term inhibitor is preferred since they do not work by introducing a
reaction path with higher activation energy; this would not reduce the rate since the
reaction would continue to occur by the non-catalyzed path. Instead they act either by
deactivating catalysts, or by removing reaction intermediates such as free radicals.

The inhibitor may modify selectivity in addition to rate. For instance, in the reduction of
ethyne to ethene, the catalyst is palladium (Pd) partly "poisoned" with lead (II) acetate (Pb
(CH3COO) 2). Without the deactivation of the catalyst, the ethene produced will be further
reduced to ethane.

The inhibitor can produce this effect by e.g. selectively poisoning only certain types of active
sites. Another mechanism is the modification of surface geometry. For instance, in
hydrogenation operations, large planes of metal surface function as sites of hydrogenolysis
catalysis while sites catalyzing hydrogenation of unsaturated are smaller. Thus, a poison
that covers surface randomly will tend to reduce the number of uncontaminated large planes
but leave proportionally smaller sites free, thus changing the hydrogenation vs.
hydrogenolysis selectivity. Many other mechanisms are also possible.

Promoters can cover up surface to prevent production of a mat of coke, or even actively
remove such material (e.g. rhenium on platinum in plat forming). They can aid the
dispersion of the catalytic material or bind to reagents.