Catalysis

From Citizendium, the Citizens' Compendium

Jump to: navigation, search

Main Article Talk Related Articles [?] Bibliography [?] External Links [?]

This is a draft article, under development and not meant to be cited; you can
help to improve it. These unapproved articles are subject to a disclaimer.
[edit intro]

Contents
[hide]

1 The catalysis mechanism

2 Types of catalysis and
examples
3 Promoters, inhibitors
and poisons
4 Applications
5 History

6 References

In chemistry and chemical engineering, catalysis is a process that uses an outside

substance (the catalyst) to accelerate the rate of a chemical reaction through an
uninterrupted and repeated cycle of elementary steps until the last step regenerates the
catalyst in its original form. The catalyst is usually present in relatively small amounts
and none of it is consumed in the process.[1] In the chemical process industries, catalytic
processes are of great economic importance with the petroleum industry being the largest
single user.
Many substances can act as catalysts, including: metals (in particular, transition metals),
chemical compounds (e.g., metal oxides, sulfides, nitrides), organometallic complexes,
and enzymes. Although a catalyst may be a gas, liquid or solid, most catalysts used in
industrial chemical reactions are heterogeneous (see below) and are in the form of porous
pellets. Since not all parts of a solid catalyst participate in the catalysis cycle, those parts
that do participate are referred to as active sites. A single porous pellet may have 1018
active catalytic sites.[1]
This article does not discuss enzymatic or biochemical catalysis (for information on those
types of catalysis, see the enzyme, biochemistry and organocatalysis articles).

(PD) Diagram: Milton Beychok

Fig. 1: The catalysis cycle and its elementary steps.

The catalysis mechanism

Figure 1 depicts the steps in a typical catalysis cycle. As depicted, the reactant molecules
A and B are reacted to yield a desired product P. The catalysis cycle starts with the
bonding of reactant molecules A and B to the catalyst. In the figure the catalyst is shown
as a small piece of solid (heterogeneous catalysis) to which A and B are adsorbed, but the
catalyst can also be a compound C dissolved in the reacting mixture (homogeneous
catalysis). In that case, A and B are temporarily chemically bound to C. A and B then
react, while bound to the catalyst C, to yield product P which is also bound to C. In the
last step, the catalyst C is regenerated by product P separating from it. By physical or
chemical separation methods the desired product P is removed from the mixture. The
regenerated catalyst C then begins the cycle again by bonding with two new reactant
molecules. [2]

(PD) Diagram: Milton Beychok

Fig. 2: Catalyst effect on a hypothetical chemical reaction.[3]

In chemistry, activation energy[4] is the energy that must be overcome in order for a
chemical reaction to occur. Activation energy may also be defined as the minimum
energy required to start a designated chemical reaction. It is denoted by Ea in units of
kilojoules per mole (kJ/mol). It may be thought of as the energy barrier that must be
overcome to start a chemical reaction. According to Arrhenius' theory the speed of
reaction depends exponentially (very steeply) on the height of the energy (also known as
transition) barrier. A small lowering of transition barrier can yield a drastic increase in
speed.
For a chemical reaction to proceed at a reasonable rate, there should exist an appreciable
number of reactant species (molecules, atoms, ions, etc.) with energy equal to or greater
than the activation energy of the reaction, which means that the temperature of the
reactants must be so high that enough of the reactant species have a thermal energy that is
sufficient to overcome the barrier. The higher the temperature, the more molecules (or
atoms, etc.) have this energy and will react, and the faster the reaction proceeds. That is,
reaction speed is strongly (in fact exponentially) dependent on temperature.[3] A catalyst
does not lower the activation energy for a reaction, instead it provides an alternative path
for the reaction that has a lower activation energy. The catalyst changes the chemical
kinetics of a reaction but not the chemical thermodynamics. The thermodynamic (Gibbs
free) energy of the reactants and products is not affected by the presence of the catalyst.
Figure 2 depicts how a catalyzed reaction follows a lower activation energy path than the
higher activation energy path followed by the same reaction when it is not catalyzed.
Overall, both the catalyzed path and the uncatalyzed path have the same change in Gibbs
free energy between the reactants and the reaction product.

The energy diagram in Figure 2 illustrates several important points:[2]

The presence of the catalyst provides an alternative reaction path, which is

definitely more complex (see Figure 1) because it involves the catalyst, but
energetically much more favorable.
The activation energy of the catalyzed reaction is significantly smaller than that of
the uncatalyzed reaction. Given its exponential dependence on activation energy,
the rate of the catalyzed reaction is much higher.
Since the overall change in Gibbs free energy is the same for the catalyzed
reaction as for the uncatalyzed reaction, the reaction equilibrium constant (which
is a function of the Gibbs free energies of reactants and products only) is not
affected by the catalyst. As noted above, the catalyst does not change the chemical
thermodynamics of the reaction. Thus, if a reaction is thermodynamically
unfavorable, the catalyst cannot change that situation.

The term "turn over frequency" (TOF) is used quite commonly in the technical literature
to characterize the activity of catalysts. However, the definition of TOF in the literature is
not consistent and varies quite widely. For example, two of the definitions in the literature
are (the first is often used for homogeneous and the second for heterogeneous catalysis):

Moles of product formed per second per mole of catalyst[5]

Moles of reactants converted per second per active site.[2]

In both of the above definitions, the unit of time is sometimes designated as an hour
rather than a second.
Another catalytic activity term is the katal, an SI derived unit, which is used mostly in
biochemistry to characterize the activity of enzymes.[6]

Types of catalysis and examples

Catalysis can be categorized into two main types: heterogeneous and homogeneous. In
heterogeneous catalysis, the catalyst is in one phase[7] while the reactants and products are
in a different phase or, for some cases, two different phases. In homogeneous catalysis,
the catalyst is in the same phase as the reactants and the products.[8]
Heterogeneous catalysis[8][9][10]
Typical examples of heterogeneous catalysis involve a solid catalyst with the reactants as
either liquids or gases. Separation of the products from the catalyst is relatively easy.
However, the catalyst in heterogeneous catalysis is often less selective than in
homogeneous catalysis.
A few specific examples of heterogeneous catalysis are:[8][9][10]

The catalytic converters in automobiles convert exhaust gases such as carbon

monoxide (CO) and nitrogen oxides (NOx) into more harmless gases like carbon
dioxide (CO2) and nitrogen (N2). Metals (solids) like platinum (Pt), palladium
(Pd) and rhodium (Rh) are used as the catalyst. The metals are deposited as thin
layers onto a ceramic honeycomb. This maximizes the surface area and keeps the
amount of metal used to a minimum.

The large-scale industrial processes for manufacturing sulfuric acid (H2SO4)

involve using solid vanadium pentoxide (V2O5) as the catalyst to convert gaseous
sulfur dioxide (SO2) into gaseous sulfur trioxide (SO3).

The catalytic hydrogenation of liquid unsaturated hydrocarbons (alkenes) by

reacting them with gaseous hydrogen (H2) to produce liquid saturated
hydrocarbons (alkanes) uses metals like platinum (Pt) and palladium (Pd) as the
catalyst. This is an example of three-phase catalysis, the catalyst being a solid and
one of the reactants being a gas while another reactant and the product are liquids.

The Haber process N2+3H2 2NH3. The catalyst is porous iron prepared by
reducing magnetite, Fe3O4, with potassium hydroxide (KOH) added as a promoter
(see below).

Homogeneous catalysis[8][9][10]
Typical examples of homogeneous catalysis have the catalyst, reactant and products all
present as a gas or contained in a single liquid phase. Separation of the products from the
catalyst is relatively difficult. However, the catalyst in homogeneous catalysis is often
more selective than in heterogeneous catalysis.
A few examples of homogeneous catalysts are:[8][9][10]

The depletion of ozone (O3) in the ozone layer of the Earth's atmosphere by
chlorine free radicals (Cl) is a an example where everything is present in a gas
phase. The chlorine free radicals, derived from the slow breakdown of man-made
chlorofluorohydrocarbons (CFCs) like CCl2F2 released into the atmosphere, acts
both as a reactant and the catalyst in converting gaseous ozone to gaseous oxygen
(O2).

The production of an ester by reacting a carboxylic acid with an alcohol involves

the use of sulfuric acid as the catalyst and is an example where everything is
contained in a liquid phase. This reaction is known a Fischer esterification, named
after the German chemist Hermann Emil Fischer (1852 - 1919).

Promoters, inhibitors and poisons

Promoters are substances, small amounts of which can increase the activity of a catalyst.
For example, the activity of the iron (Fe) catalyst used in the Haber process for ammonia
synthesis is increased by the addition of a small amount of potassium (K) as a promoter.
Small amounts of some substances can reduce the the activity a catalyst. If the reduction
in activity is reversible, the substances are called inhibitors. If the reduction in activity is
irreversible, the substances are called poisons.[11]
Inhibitors are sometimes used to increase the selectivity of a catalyst by retarding
undesirable reactions. For example, the conversion of acetylene (C2H2) to ethylene (C2H4)
by catalytic hydrogenation uses palladium as the catalyst and lead acetate
(Pb(CH3COO)2) as the inhibitor. Without the partial deactivation of the catalyst by the
inhibitor, the ethylene produced would be further hydrogenated to undesirable ethane.
As an example of the precautions taken to avoid catalyst poisoning, the expensive
platinum (Pt) and rhenium (Re) catalyst in the catalytic reforming process for producing
high-quality gasoline in petroleum refineries is subject to irreversible deactivation by
sulfur, nitrogen and arsenic compounds. Because of that, the petroleum naphtha
feedstocks to catalytic reformers are always processed for removal of such compounds
prior to being fed to the reformers.

Applications
Petroleum refining

Fluid catalytic cracking: Breaking large hydrocarbon molecules into smaller ones
Catalytic reforming: Reforming molecules to produce high quality gasoline
component
Hydrodesulfurization: Removing sulfur compounds from refinery intermediate
products
Hydrocracking: Breaking large hydrocarbon molecules into smaller ones
Alkylation: Converting isobutane and butylenes into a high-quality gasoline
component
Isomerization: Converting pentane into a high-quality gasoline component
Claus process: Convering gaseous hydrogen sulfide into elemental sulfur

Chemicals and petrochemicals

Steam reforming for hydrogen production

Haber process for ammonia production
Styrene and Butadiene synthesis for use in producing synthetic rubber
Contact process for production of sulfuric acid
Ostwald process for production of nitric acid
Methanol synthesis
Various processes for producing many different plastics and synthetic fabrics

Other

Catalytic converters for mitigating automobile exhaust emissions

Fischer-Tropsch and Coal gasification processes for producing synthetic fuel
gases and liquid fuels
Various processes for producing many different medicines

History
Catalysts had been used in the laboratory before 1800 by Joseph Priestly in England and
by the Dutch chemist Martinus van Marum, both of whom made observations on the
dehyrogenation of alcohol with metal catalysts. However, it seems that both of them
regarded the metal merely as a source of heat.
These are some of the chemists whose work during the 1800's led to the development of
the modern catalyst technology:[12][13]

In 1806, the French chemists Charles Bernard Dsormes and his son-in-law
Nicolas Clment made perhaps the first attempt to propose a theory of catalysis
based on the catalytic effect of nitrogen oxides in the lead chamber process for the
manufacture of sulfuric acid.[14]

In 1813, the French chemist Louis Jacques Thnard discovered that ammonia is
entirely decomposed into nitrogen and hydrogen when passed over various redhot metals.

In 1817, Sir Humphrey Davy, an English chemist, published a paper about his
work with flameless oxidation of coal gas in the presence of preheated, hot
platinum wires. That paper contained perhaps the first clear realization that
chemical reaction between two gaseous reactants can occur on a metal surface
without the metal being chemically changed.[15]

In 1820, Edmund Davy, a chemistry professor at Cork in Ireland and a cousin of

Sir Humphrey Davy, prepared a finally divided platinum catalyst which had such
high activity that it acted at room temperature without any preheating.

In 1823, Johann Wolfgang Dbereiner, a chemistry professor at the University of

Jena in Germany demonstrated that hydrogen and atmospheric air ignited
spontaneously in the presence of a platinum sponge.[16][17] He then applied his
work to construct a fire stick (or Feuerzeug in German) which was a fire lighter
based on hydrogen and a catalyst of platinum sponge that became a commercial
success in the 1820s.

In 1836, the Swedish chemist Jns Jakob Berzelius coined the term catalysis to
describe the effect that reactions are accelerated by substances that remain
unchanged after the reaction.[18][19]

In 1838, C.F. Kuhlmann of France first oxidized ammonia using a platinum

catalyst to produce nitrogen oxides which he then absorbed in water to produce
nitric acid. However, his process was not then commercialized because ammonia
was too expensive at that time compared to the Chile saltpetre (potassium nitrate)
being used at that time to produce nitric acid.

In the 1880s, Wilhelm Ostwald at Leipzig University in Germany 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.

In 1894 Ostwald gave the first modern definition:[20] Catalysis is the acceleration
of a chemical reaction, which proceeds slowly, by the presence of a foreign
substance. For his work on catalysis, Ostwald was awarded the 1909 Nobel Prize
in Chemistry.[21]

From these early beginnings, large industries have arisen and a vast body of scientific
information has been accumulated. The economic contribution from catalysis is as
remarkable as the phenomenon itself. Four sectors of the worlds economy are petroleum,
energy production, chemicals production, and the food industry; and they are all critically
dependent on the use of catalysts. Estimates are that catalysis contributes to greater than
35% of global GDP; the biggest part of this contribution comes from the generation of
high energy fuels which depend on the use of small amounts of catalysts in the worlds
petroleum refineries.[22]

References
1. 1.0 1.1 Commission on Physical Sciences, Mathematics, and Applications
(CPSMA), National Academies (1992). Catalysis Looks to the Future. National
Academies Press. ISBN 0-309-04584-3. Available online at Executive Summary
2. 2.0 2.1 2.2 I. Chorkendorff and J. W. Niemantsverdriet (2007). Concepts of Modern
Catalysts and Kinetics, 2nd Edition. Wiley-VCH. ISBN 3-527-31672-8.
3. 3.0 3.1 The Effect of Catalysts on Reaction Rates From a website provided by Jim
Clarke, retired Head of Chemistry and then Head of Science at Truro School in
Cornwall, United Kingdom.
4. A term introduced in 1889 by the Swedish scientist Svante Arrhenius
5. Hideo Kurosawa and Akio Yamamoto (2003). Fundamentals of Molecular
Catalysis, 1st Edition. Elsevier Science. ISBN 0-444-50921-6.
6. R. Dybkaer (2001). Unit "katal" for Catalytic Activity (IUPAC Technical
Report). Pure Appl. Chem. 73 (6): 927-931.
7. If a boundary exists between the catalyst and the reaction system (i.e., the
reactants and the products), then the system has two phases. In this context, a
phase is different from the most familiar states of matter: solid, liquids and gases.
For example, if a liquid catalyst and a liquid reaction system were mutually
insoluble, a boundary would exist between the catalyst and the reaction system.

That would constitute two phases in the context of catalysis whereas it would be
considered as being one state of matter, namely a liquid.
8. 8.0 8.1 8.2 8.3 8.4 Types of Catalysis From a website provided by Jim Clarke, retired
Head of Chemistry and then Head of Science at Truro School in Cornwall, United
Kingdom.
9. 9.0 9.1 9.2 9.3 Chemistry Explained Chemistry Encyclopedia
10. 10.0 10.1 10.2 10.3 Catalyst Lecture 12 Faculty of Chemistry, Silesian University of
Technology, Poland
11. Lecture Notes From the website of the University of Texas Southwestern
Medical Center
12. The Early History of Catalysis A.J B. Robertson, Chemistry Department, Kings
College, London.
13. Johann Wolfgang Dbereiner's Feuerzeug George P. Kaufmann, Chemistry
Department, California State University, Fresno, California.
14. C. B. Dsormes and N. Clment (1806), Annals Chim. 59 (329)
15. H. Davy (1817), Phil. Trans. Roy. Soc. 107 (77)
16. J. W. Dbereiner (1823), Ann. Phys. 74 (269)
17. J. W. Dbereiner (1823), Ann. Chim. 24 (91)
18. J. J. Berzelius, Some Ideas on a New Force which Acts in Organic Compounds,
Annales chimie physiques, 1836, vol. 61, 146151. Translated in Henry M.
Leicester and Herbert S. Klickstein, A Source Book in Chemistry 1400-1900
(1952), p. 267. Google books
19. Keith J. Laidler and John H. Meiser (1982). Physical Chemistry, 1st Edition.
Benjamin-Cummings Publishing, p.423. ISBN 0-8053-5682-7.
20. W. Ostwald, Zeitschrift fr physikalische Chemie, volume 15, pages 705-706
(1894)
21. M.W. Roberts (2000). Birth of the catalytic concept (1800-1900). Catalysis
Letters 67 (1): 14.
22. What is Catalysis or Catalysis, So what? From the website of the North
American Catalysis Society.