WHAT YOU KNOW ABOUT CATALYSTS A
substance that affects the rate of reaction but
emerges from the process unchanged.
HOW ELSE CAN IT BE DEFINED?
◦ Promotes a more efficient molecular path or
mechanism.
◦ Changes only the rate of reaction and does not
affect the equilibrium.
Catalysts are the workhorses of chemical
transformations in the industry. Catalysts are
indispensable in
◦ Production of transportation fuels in one of the
approximately 440 oil refineries all over the world
◦ Production of bulk and fine chemicals in all
branches of chemical industry
◦ Prevention of pollution by avoiding formation of
waste (unwanted byproducts)
◦ Abatement of pollution in end-of-pipe solutions
(automotive and industrial exhaust)
A catalyst offers an alternative, energetically
favorable mechanism to the noncatalytic
reaction
Occurrence,
study and use
of catalysts
and catalytic
processes.
Catalytic
reaction is a
cyclic event.
Ref: Concepts of Modern Catalysis and Kinetics
by: I. Chorkendorff and J.W. Niemantsverdriet
Potential Energy Diagram comparing non catalytic and
catalytic reaction
The catalyst offers an alternative path for the
reaction.
The activation energy of the catalytic reaction
is significantly smaller.
The overall change in free energy for the
catalytic reaction equals that of the
uncatalyzed reaction.
The catalyst accelarates both the forward and
the reverse reaction to the same extent.
If the bonding between reactants and catalyst
is too weak.
If bond between the catalyst and one species
is too strong, the first will be mostly occupied
by the latter.
If product P is strongly bound to the catalyst
for separation to occur, then it poisons the
catalyst.
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, nanoparticles,
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
Catalysts can be either heterogeneous or
homogeneous, depending on whether a
catalyst exists in the same phase as the
substrate
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.
The total surface area of solid has an
important effect on the reaction rate.
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.
In homogeneous catalysis, both the catalyst
and the reactants are in the same phase.
◦ Example: Ozone reaction with chlorine atoms
Industry uses a multitude of homogenous
catalysts in all kinds of reactions to produce
chemicals. The catalytic carbonylation of
methanol to acetic acid
Enzymes are nature’s catalysts.
For the moment it is sufficient to consider an
enzyme as a large protein, the structure of
which results in a very shape-specific active
site.
◦ Example: Enzyme catalase catalyzes the
decomposition of hydrogen peroxide into water and
oxygen
In heterogeneous
catalysis, solids
catalyze reactions
of molecules in
gas or solution.
Heterogeneous
catalysts are the
workhorses of the
chemical and
petrochemical
industry.
Example: Cleaning automotive exhaust by
catalytic reaction.
Reaction Mechanism
To accelerate reactions under relatively
milder conditions
Green Chemistry
◦ To eliminate the need for toxic reactants
◦ To minimize the production of waste or undesired
by-products
Atom Economy
ethylene
epoxide
Microscopic
(subnanometer):
spectroscopy,
computational chemistry,
kinetics, mechanism
mesoscopic (1-10
nanometer): catalyst
preparation,
characterization,
mechanistic investigation
(transport),
Shaped catalyst (mm to
cm): porosity, strength,
attrition resistance
Macroscopic level (reactors -
cm to m): mass/heat transport,
catalyst activity, sensitivity,
mechanical strength.
Activation and breaking of a chemical bond inside
a molecule: picosecond regime,
completion of an entire reaction cycle from
complexation between catalyst and reactants
through separation from the product:
microseconds for the fastest enzymatic reactions to
minutes for complicated reactions on surfaces.
On the mesoscopic level, diffusion in and outside
pores, and through shaped catalyst particles may
take between seconds and minutes, and the
residence times of molecules inside entire reactors
may be from seconds to, effectively, infinity if the
reactants end up in unwanted byproducts such as
coke, which stay on the catalyst.
