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Instant Notes in Inorganic Chemistry

Instant Notes in Inorganic Chemistry

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Published by: Gabriel Flores on Mar 22, 2012
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Key Notes

Introduction

Catalysts speed up reactions, and provide selectivity for the desired
product. Homogeneous catalysts (often organometallic compounds)
act in the same phase as the reactions, heterogeneous catalysts (often
transition metals on an oxide support) in another phase.

Dihydrogen chemistry

Heterogeneous catalysts are used in the production of synthesis gas
(H2-CO) and from it methanol, for ammonia synthesis and for large-
scale hydrogenation. Organometallic catalysts provide more
selectivity for specialized hydrogenation reactions.

Oxidation reactions

Heterogeneous oxidation catalysts are used in the production of
H2SO4 and HNO3 and for the selective oxidation of hydrocarbons.

Alkene polymerization

Alkene polymerization is performed by Ti compounds (Ziegler-Natta
catalysts) and by organometallic compounds of early transition
metals.

Gasoline and
automobile catalysts

Petroleum products undergo catalytic hydrodesulfurization and re-
forming processes. Catalysts in automobile exhaust systems convert
pollutants (hydrocarbons, CO, NO) to CO2 and N2.

Related topics

Stability and reactivity (B3)
Inorganic reactions and
synthesis (B6)

Organometallic compounds
(H10)
Industrial chemistry: bulk
inorganic chemicals (J4)

Introduction

A catalyst is a substance that speeds up a chemical reaction but is not itself consumed. Catalysts do not alter the
thermodynamics of a reaction or the position of equilibrium, but act by providing an alternative pathway of lower activation
energy. A high proportion of industrial chemical processes, inorganic and organic, use catalysts. They allow many
reactions to be performed at lower temperatures than without a catalyst, and also provide selectivity in producing a
specific product in reactions where several products are feasible thermodynamically. Enzymes (which often contain
metallic elements; see Topic J3) are uniquely selective biological catalysts.
A catalyst present in the same phase as the reactants (generally liquid) is called homogeneous, one in a different
phase is heterogeneous. Most heterogeneous catalysts are solids, and act by adsorption of gaseous or liquid
reactants on a surface. Homogeneous catalysts are specific molecules, often organometallic compounds, that can be
tailored in a more specific way to give a required product than is possible with heterogeneous catalysts. On the other
hand, it is generally harder to separate the products from homogeneous catalysts. Another difference is that

heterogeneous catalysis is usually performed at higher temperatures than homogeneous catalysis. Metallic elements used
as heterogeneous catalysts are often in the form of small particles on a support such as Al2O3 or SiO2. This provides a
high surface area for the active catalyst, and reduces the tendency for sintering (i.e. coalescence into larger particles)
at the operating temperature.
A catalytically active substance must be able to bind the reactant molecules and release the products. For example,
hydrogenation with a metallic Ni catalyst proceeds via adsorbed hydrogen atoms formed by dissociation of H2 on the
metal surface (1). Transition metals and their compounds are effective catalysts because of their ability to coordinate
molecules and to change oxidation state (see Topic H1). An appropriate degree of reactivity is often provided by
elements from groups 9 and 10, either in metallic form or as organometallic compounds. More reactive elements (e.g.
early transition metals) are more likely to bind reactants irreversibly, less reactive ones (e.g. Au) not to bind them at
all.

Dihydrogen chemistry

H2 is mostly produced by steam re-forming of hydrocarbons. The simplest reaction is

In this endothermic reaction, the equilibrium is driven to the right by using elevated temperatures (900°C). The usual
catalyst is Ni supported on Al2O3. The H2-CO mixture is known as synthesis gas or syngas, and may be used directly
for further reactions, the most important being methanol synthesis:

A Cu-ZnO-Al2O3 catalyst is used, which is less active than ones involving metals in earlier groups, so that the C-O bond
is not broken. Methanol is an important stage in further synthesis; see, for example, the Monsanto acetic acid process
catalyzed by Rh compounds (Topic H10).
Another important reaction for synthesizing useful organic compounds is hydroformylation:

Homogeneous catalysts based on cobalt carbonyl compounds were previously used, but have been largely replaced by
the Union-Carbide process with [(Ph3P)2Rh(CO)Cl] as the catalyst.
Two major uses of H2 are for ammonia synthesis and the hydrogenation of unsaturated vegetable oils to make
margarine. The former reaction (see Topic F5) is exothermic and the equilibrium constant therefore decreases with
temperature. In the Haber process a potassium-promoted iron catalyst is used, this relatively reactive metal being
necessary to adsorb and dissociate the very stable N2 molecule at moderate temperatures (400°C). The yield of NH3 is
improved by working at high pressure. Large-scale catalytic hydrogenation of alkenes is normally carried out with a
Ni-SiO2 catalyst. More selective hydrogenation for specialized purposes (e.g. pharmaceuticals where specific isomers

270SECTION J—ENVIRONMENTAL, BIOLOGICAL AND INDUSTRIAL ASPECTS

are required) is possible with homogeneous catalysts; for example, Wilkinson’s catalyst (2), which undergoes oxidative
addition of H2 under mild conditions (see Topic H9).

Oxidation reactions

Catalytic oxidation steps are involved in the manufacture of the major industrial chemicals sulfuric and nitric acid. HNO3
manufacture starts with ammonia, which is oxidized to NO (see Topic F5). A very active Pt-Rh catalyst is used, the
contact time being minimized to avoid forming the thermodynamically more favorable products N2 and N2O. To make
H2SO4 it is necessary to oxidize SO2 to SO3 (see Topic F8). The catalyst is vanadium pentoxide, V2O5. Oxides of
transition and post-transition metals are also used for selective oxidation of hydrocarbons; for example, from
alkenes to carbonyl compounds and acid anhydrides, which are used for polymer manufacture. The action of these
catalysts appears to depend on the ability of the metallic element to change oxidation state and coordination number.
Oxygen is transferred to the adsorbed reactant molecules from the catalyst surface, which is then reoxidized in another
step.

Alkene polymerization

Domestic and industrial plastics are mostly formed by polymerizing alkenes:

The reaction is exothermic and can be initiated by free radicals (often from peroxo compounds), but organometallic
catalysts give more controllable results. Most widely used are Ziegler-Natta catalysts made by mixing Al2Et6 (where
Et is the ethyl group) with TiCl4. Solid TiCl3 is formed and catalysis occurs at surface Ti-Et groups, to which alkene
molecules coordinate and undergo insertion into the Ti-R bond (see Topic H10). An advantage of these catalysts is that
they may form stereoregular polymers where all the R groups in -C(R)H-CH2- have the same stereochemical
configuration. This gives stronger materials with higher melting points than the random stereochemistry resulting from
radical polymerization.

A new generation of catalysts is based on cyclopentadienyl compounds of early transition metals such as 3, which in
the presence of aluminoxane (MeAlO)n forms the active species [(η5

−C5H5)2ZrCH3]+
.

J5—INDUSTRIAL CHEMISTRY: CATALYSTS271

Gasoline and automobile catalysts

Natural petroleum contains organic sulfur compounds, which must be removed before further processing, as they block
active sites in some catalysts and so act as poisons. When burnt they also give the environmental pollutant SO2 (see
Topic J6). Hydrodesulfurization is the reaction in which organic sulfur is converted to H2S, which is easily removed.
Catalysts based on mixed Co-Mo sulfides are used. Subsequent processing of petroleum involves catalytic cracking
and re-forming in which long-chain hydrocarbons are reduced to shorter ones, together with isomerization processes
giving a more desirable mixture of compounds. Bifunctional catalysts for these reactions contain metals such as Pt
that are active for hydrogenation, and zeolites (see Topic D5) as acid catalysts providing H+

to give carbocations that

readily isomerize.

Catalysts for automobile exhaust systems are designed to remove environmental pollutants such as unburned
hydrocarbons, CO formed from incomplete combustion and oxides of nitrogen. Three-way catalysts are based on Pt
and Rh together with various additives that together perform a complex series of reactions, including removal of
hydrocarbons by oxidation and steam re-forming (see above), and

Their operation depends on the absence of poisons such as lead compounds, and on a fuel injection system that provides
an almost perfect stoichiometric ratio of fuel and oxygen to the engine: this is achieved by a feedback system using a
sensor that monitors the O2 content of the exhaust gases, based on an electrochemical cell using the ionic conductor
ZrO2 as a solid electrolyte (see Topic D7).

272SECTION J—ENVIRONMENTAL, BIOLOGICAL AND INDUSTRIAL ASPECTS

Section J—Environmental, biological and industrial aspects

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