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By Professor A. J. B. Robertson
Department of Chemistry, Kings College, London
One hundred and forty years ago it was Berzelius proceeded to propose the exist-
possible for one man to prepare an annual ence of a new force which he called the
report on the progress of the whole of catalytic force and he called catalysis the
chemistry, and for many years this task was decomposition of bodies by this force. This
undertaken by the noted Swedish chemist is probably the first recognition of catalysis
J. J. Berzelius for the Stockholm Academy of as a wide-ranging natural phenomenon.
Sciences. In his report submitted in 1835 and Metallic catalysts had in fact been used in
published in 1836 Berzelius reviewed a num- the laboratory before 1800 by Joseph Priestley,
ber of earlier findings on chemical change in the discoverer of oxygen, and by the Dutch
both homogeneous and heterogeneous sys- chemist Martinus van Marum, both of whom
tems, and showed that these findings could be made observations on the dehydrogenation of
rationally co-ordinated by the introduction alcohol on metal catalysts. However, it seems
of the concept of catalysis. In a short paper likely that these investigators regarded the
summarising his ideas on catalysis as a new metal merely as a source of heat. In 1813,
force, he wrote (I): Louis Jacques Thenard discovered that
It is, then, proved that several simple or ammonia is decomposed into nitrogen and
compound bodies, soluble and insoluble, have hydrogen when passed over various red-hot
the property of exercising on other bodies an metals, and ten years later, with Pierre
action very different from chemical affinity.
By means of this action they produce, in these
Dulong, he found that the activity of iron,
bodies, decompositions of their elements and
different recombinations of these same elements
to which they remain indifferent.
copper, silver, gold, and platinum for de- Later he became Professor at the Conserva-
composing ammonia decreased in the order toire des A r t s et Metiers, and after winning a
given. This is one of the earliest recorded lottery, married the daughter of Dtsormes.
examples of a pattern of catalytic activity. That a chemical substance can speed up a
Thenard, the son of a peasant, after experi- chemical reaction without itself being chemic-
ence with Vauquelin in Paris as a laboratory ally changed became clear in a research on the
boy, became assistant and later Professor at decomposition of hydrogen peroxide, carried
the lkole Polytechnique. In 1857, then a peer, out by L. J. Thenard, who announced his
he became Chancellor of the University of discovery of this substance in 1818. Thenard
Paris. His collaborator Dulong was Professor had become interested in barium peroxide,
of Physics in the &ole Polytechnique, later probably because of the notable discovery by
becoming Director. He is, of course, famed Davy in 1807 of sodium and potassium, which
for the law of Dulong and Petit. He also he prepared by the electrolysis of their moist
proposed a hydrogen theory of acids in- hydroxides. Davys first Bakerian lecture in
dependently of Davy. 1806 On some Chemical Agencies of Elec-
Homogeneous catalytic processes have been tricity described work of such importance
used by mankind for some thousands of that the 3000 francs prize given by Napoleon I
years, for example in fermentation. Perhaps was awarded to him. Napoleon seems to have
the first attempt at a rational theory of catalysis been somewhat peeved that the prize went to
is the intermediate compound theory proposed an Englishman when a state of war existed
by Charles Bernard Desormes and Nicolas between England and France, and, noting the
Clement (2) for the homogeneous catalytic vital part the large Royal Institution voltaic
effect of nitrogen oxides in the lead chamber pile had played in the research, he ordered
process for the manufacture of sulphuric acid. two large voltaic piles to be built. Perhaps he
This particular process was later discussed adopted the type of argument we note even
more fully by Humphry Davy, and has now from some political circles, that two
received a huge amount of attention and voltaic piles will do twice as much useful work
discussion since these early times. as one, irrespective of who originates the
Clement studied science in Pans and ideas to be tried out with the piles. Thtnard
became assistant at the Ecole Polytechnique. probably investigated the alkaline earth
oxides with the initial aim of electrolysing safety-lamp. When additional coal gas was
them. T h e work he did on the reaction of introduced into the lamp, the flame went out
barium peroxide with nitric or hydrochloric but the platinum wire remained hot for many
acid led to the discovery of hydrogen peroxide. minutes. Davy immediately deduced that the
This he found to decompose when in contact oxygen and coal gas combined without flame
with many solids, some of which were not when in contact with the hot wire, thereby
chemically changed. He also found that the producing enough heat to keep the wire
action of metals in bringing about decomposi- incandescent. A hot platinum wire introduced
tion became more vigorous as the metal was into a mixture of coal gas and air immediately
reduced to a finer state of subdivision. became incandescent. Furthermore many
combustible vapours mixed with air were
Humphry Davys Classic Paper found by Davy to produce the same effect.
The first clear realisation that chemical Davy had discovered the phenomenon of
reaction between two gaseous reactants can heterogeneous catalytic oxidation.
occur on a metal surface without the metal Only platinum and palladium wires were
being chemically changed is found in a paper effective; wires of copper, silver, gold and
by Humphry Davy (3) published by the iron were ineffective. This is one of the
Royal Society in 1817. This describes the earliest recorded patterns of catalytic activity.
discovery of a new and curious series of In these researches Davy was assisted by
phenomena. During the researches which Faraday but it is unclear whether Faraday
led to the miners safety-lamp, Davy fixed a contributed to the development of the ideas
fine platinum wire above a coal-gas flame in a or acted mainly by carrying out Davys