Catalysts and Catalysis

GROUP 5
What are Catalysis?
Catalysis is the process of increasing the rate of a chemical reaction
by adding a substance known as catalyst, which is not consumed in
the catalyzed reaction and can continue to act repeatedly. Because
of this, only very small amounts of catalyst are required to alter the
reaction rate in principle.
In general, chemical reactions occur faster in the presence of a
catalyst because the catalyst provides an alternative reaction
mechanism with a lower activation energy than a non-catalyzed
mechanism.
The catalysis has no effect on the direction of the reaction. The
direction can be controlled by adding or removing water (Le
Chatelier principle)
Catalysts have no effect on the equilibrium constant and on the
equilibrium composition. These are substances that speed up a
reaction but which are not consumed by it and do not appear in the
net reaction. Also, catalysts affect forward and reverse rates equally.
It can be used to speed up a reversible reaction such as ester
formation or its reverse, ester hydrolysis.
Catalysis may be classified as either homogeneous and
heterogeneous.
Homogeneous catalyst is one whose molecules are dispersed in the
same phase as the reactant’s molecules.
Heterogeneous catalyst in one whose molecules are not in the
same phase as the reactant’s which are typically gases or liquids that
are absorbed onto the surface of the solid catalyst.
Enzymes and other biocatalyst are often considered as third
category.
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.
Catalysis is relevant to many aspects of environmental science. (ex.
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 wasted generated.
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 a lower activation energy than the reaction
route not mediated by the catalyst.
Catalysts called enzymes are important in biology.
History
Anything that increases the rate of a process
is a “catalyst”, a term derived from Greek
καταλύειν, meaning “to annul” or “to untie”
or “to pick up”.
The concept of catalysis was invented by
chemist Elizabeth Fulhame and described in a
1794 book, based on her novel work in
oxidation-reduction experiments.
the first chemical reaction in organic
chemistry that utilized a catalyst was studied
in 1811 by Gottlieb Kirchoff who discovered
the acid-catalyzed of starch to glucose.
The term catalysis was later used by Jöns Jacob Berzelius in 1835 to
describe the reactions that are accelerated by substances that
remain unchanged after the reaction.
Fulhame, who predated Berzelius, did work with water as opposed
to metals in her reduction experiments.
Other 18th century chemists who corked in catalysis were Eilhard
Mitscherlich who referred to it as contact processes, and Johann
Wolfgang Döbereiner who spoke of contact action. He developed
Döbereiner’s lamp, a lighter based on hydrogen and platinum
sponge, which became a commercial success in the 1820s that lives
on today.
Humphry Davy discovered the use of platinum in catalysis.
In the 1880s, Wilhelm Ostwald at Leipzig University started a
systematic inverstigation into reactions that were catalyzed by the
presence of acids and bases, and found that chemical reactions
occur at finite rates that these rates can be used to determine the
strengths of acids and bases. For this works, he was awarded the
1909 Novel Prize in Chemistry.
Vladimir Ipatieff performed some of the earliest industrial scake
reactions, including the discovery and commercialization of
oligomerization and the development of catalysts for hydrogenation.
Materials
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. (zeolites,
alumina, graphitic carbon)
Transition metals are often used to catalyze redox reactions
(oxidation, hydrogenation). Examples are nickel such as Raney nickel
for hydrogenation and vanadium oxide for oxidation of sulfur oxide
into sulfur trioxide by contact process.
Some so-called catalysts are really precatalysts. They convert to
catalysts in the reaction. Also, they are easier to store but are easily
activated.
Types of Catalysts
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.
The catalytic affect arises from disruption of the reactant molecules
brought about by their interaction with the surface of the catalyst.
A heterogeneous catalyst has active sites, which are atoms or
crystal faces where the reaction actually occurs.
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 higher specific activity on a
support.
Homogeneous Catalysis
As the name implies, homogeneous catalysts are present in the
same phase (gas or liquid solution) as the reactants. Homogeneous
catalysts generally enter directly into the chemical reaction by
forming a new compound or complex with reactant, but are released
in their initial form after the reaction is complete, so that they do not
appear in the net equation.
Acid-Base Catalysis
Many reactions are catalyzed by the presence of an acid or a base; in many cases,
both acids and bases will catalyze the same reaction. As one might expect, the
mechanism involves the addition or removal of proton, changing the reactant into
more kinetically liable form.
The most well-known acid-catalyzed reaction is the hydrolysis or formation of an
ester – a reaction that most students encounter.
Organocatalysis
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 higher loading than transition metal
based catalysts, but these catalysts are usually commercially available in bulk,
helping to reduce costs.
In early 2000s, these organocatalysts were considered “new generation” and
are competitive to traditional metal(-ion)-containing catalysts.
Photocatalysts
Photocatalysts is the phenomenon where the catalyst can receive
light such as visible light, be promoted to an excited state, and then
undergo intersystem crossing with the starting material, returning to
ground state without being consumed. The excited state of the
starting marterial will then undergo reactions it ordinarily could not
if directly illuminated.
Singlet oxyen is usually produced by photocatalysis.
Photocatalysts are also the main ingredient in dye-sensitized solar
cells.
Enzymes and Biocatalysts
Enzymes or biocatalyst are the natural proteins
produced in tiny quantities by all living organisms
and functioning as highly selective biochemical
catalysts in converting one molecule into
another.
Enzymes are essential to life because they
speed up metabolic reactions to a very great
extent, but do not undergo any change in
themselves

Enzymes and Biocatalysts
In the industry they are used for
degrading oil spills and wastes into
harmless compounds, in cleaning fat
(food) stains, and in fermentation
processes to make alcoholic
beverages.
Nanocatalysts
- Nanocatalysis is a rapidly growing field which involves the use of
nanomaterials as catalysts for a variety of homogeneous and
heterogeneous catalysis applications.
- Nanomaterial-based catalysts are usually heterogeneous
catalysts broken up into metal nanoparticles in order to speed up the
catalytic process
Mechanisms of reaction
on surfaces
Dissociative Adsorption
The simplest heterogeneous process is chemisorption followed by
bond-breaking. The most common and thoroughly studied of these
is the dissociation of hydrogen which takes place on the surface of
most transition metals.