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The Early History of

By Professor A. J. B. Robertson Department of , King’s 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 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 , 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 on 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 is decomposed into and “It is, then, proved that several simple or compound bodies, soluble and insoluble, have when passed over various red-hot the property of exercising on other bodies an , and ten years later, with Pierre action very different from chemical affinity. Dulong, he found that the activity of , By means of this action they produce, in these bodies, decompositions of their elements and different recombinations of these same elements to which they remain indifferent.”

Louis Jacques Th6nard 1777-1857 Born at Nogent-sur-Seine, The‘nnrd cane to Yoris at the age of 17 during the Reign of Terror to study pharmacy. His keenness brought him to the notice of Vauquelin and Fourcroy, both of whom ad- vanced his career. In 1804 he replaced Vuuquelin in the chair of chemistry at the CoEl?ge de France while in 1810 he was appointed Professor at the &ole Polytechnique and succeeded Fourcroy in the Academie des Sciences. In 182.5 Charles X crented him Baron. From the portrait in the Wellcome Institute of the History of Medicine

Platinum Metals Rev., 1975, 19, (2), 64-69 64 1778-1829 Davy tau(5ht himself by reading Lavoisier’s “Traite Elementaire de Chimie” and began his career at the newly formed Pneumatic Institute at Rristol. In 1801 he toas ofercd a post at the Royd Institution by Count Rumford, and it was here that he carried out most of his brilliant experimental work andgave his famous lectures. In 1812 he was knighted by the Prince Regent and he wus elected President of the Royal Society in 1820. From the portrait by Sir Thomas Lawrence in the posses- sion of the Royal Society

copper, , gold, and for de- Later he became Professor at the Conserva- composing ammonia decreased in the order toire des Arts 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 can speed up a Thenard, the son of a peasant, after experi- 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 , 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 , which for the law of Dulong and Petit. He also he prepared by the electrolysis of their moist proposed a hydrogen theory of in- . Davy’s 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 voltaic effect of nitrogen in the lead chamber pile had played in the research, he ordered process for the manufacture of sulphuric . 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

Platinum Metals Rev., 1975, 19, (2), 65 The opening page of the manu- srript of Sir Humphry Dauy’s paper read to the Royal Society on Junuary 23rd. 1817, “Some new experiments and ohservations on the combination of gaseous mixtures, with an account of a method for keeping a continued light in mixtures of inflammable and air tuithoutflame”. The paper goes on: “I had intended to expose jine platinum wires to oqgen and olrJant and to oxygen and hydrogen during their slow cornbination under different circumstances, when I zuas acci- dentally led to the knowledge oj’ the fact, and at the same time to ihe dixooery of a ncw and curious series of phenonoena.” Duvy had discovered heterogeneolts

oxides with the initial aim of electrolysing safety-lamp. When additional coal gas was them. The 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 , 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 Davy’s 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 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 Davy’s

Platinum Metals Rev., 1975, 19, (2), 66 instructions. The two-man team which made and Thenard (6) in Paris, who discovered that these discoveries about palladium and could also act at must have been one of the strongest in the ordinary temperatures whereas , , whole . , silver and gold acted catalytically In order to initiate catalytic oxidation the only at higher temperatures. Their note wires used by Davy needed to be hot, but in actually appeared in the Annales de Chimie et 1820 (4), Profcssor of de Physique before Dobereiner’s paper because Chemistry at Cork in Ireland, formerly his discovery was communicated privately by Assistant: at the Royal Institution, and cousin Liebig to Dulong and Thenard. of Humphry Davy, prepared a finely-divided Dobereiner’s work had, however, been platinum catalyst of such high activity that it communicated from Paris to Faraday in a acted at room temperature. When this letter of September 16th, 1823, from J. N. P. catalyst was dropped on to any porous Hachette and within a few days Faraday substance moistened with alcohol, oxidation had proceeded to repeat the experiment and occurred so rapidly that the catalyst became confirm the findings. In a brief note (7) red hot. signed merely “M. F.” he wrote “it was communicated to me by M. Hachette and Dobereiner’s Experiment having verified it I think every chemist will J. W. Dobereiner (5), Professor of be glad to hear its nature”. Chemistry at Jena and formulator of the law of triads, reduced a catalyst prepared by the Faraday’s Review procedure Edmund Davy had described and Dulong and Thenard in a later paper (8) obtained a spongy platinum which brought reported that the ability to bring about gaseous about the combination of hydrogen and combination is a general property of suffi- oxygen at room temperature and quickly ciently-heated solids, while Faraday (9), in a became red hot as a result. This remarkable very good review of early work on hetero- discovery was rapidly followed up by Dulong geneous catalysis, drew attention to the merits

Johann Wolfgang Dobereiner 1780-1849 Born the son of a Bavarian coachman, Ddbereiner was apprrnticed to a pharmacist and practised as an assistant in Karlsruhe, Bayreuth and Stras- bourg. He attended lectures on chemistry, - ogy and philosophy and in 1810 was proposed for an Extraordinary Professorship in chemistry ut the University of Jena. Herr he also berame a chemical assistant to Goethe. He intwested himself in the rejning of some South American native platinum, und after learning of Edmund Davy’s experiments on the power of platinum to promote the oxidation of alcohol he showed that platznum sponge would ignite a stream of hydrogen

Platinum Metals Rev., 1975, 19, (2), 67 of their experiments. He wrote (paragraph reaction between hydrogen and oxygen. He 611): also found, when working with mixtures of “In the two excellent papers by MM. DULONG hydrogen, monoxide and , and TH~~NARD,these philosophers show that that selective catalytic oxidation on platinum elevation of temperature favours the action, but is possible. does not alter its character, Sir HUMPHRY DAVY’Sincandescent platina wire being the Henry had studied under Joseph Black in same phenomenon with D~BEREINW’Sspongy Edinburgh and had also worked with the platina. They show that all metals have this noted Scottish chemist Thomas Thomson. power in a greater or smaller degree, and that it is even possessed by such bodies as charcoal, Later he directed his father’s chemical works. pumice, porcelain, glass, rock crystal, etc., He is famed for Henry’s law concerning when their temperatures are raised; and that gaseous solubilities. another of DAVY’Seffects, in which oxygen and hydrogen had combined slowly together at a heat below ignition, was really dependent upon Fusinieri’s Theory the property of the heated glass, which it has in common with the bodies named above.” The first attempt to give a detailed theoreti- cal discussion of heterogeneous catalytic Later in the paper Faraday wrote (para- oxidation on platinum was made by the Italian graph 618): physician Ambrogio Fusinieri (12) in a paper “The effect is evidently produced by most, published in 1824. He discussed the effects if not all, bodies, weakly perhaps by many discovered by Dobereiner and others. He of them, but rising to a high degree in platina. DULONGand TH~NARDhave very philosophic- also explained in more detail his own experi- ally extended our knowledge of the property mental observations (first expounded in a to its possession by all the metals, and by note) and remarked that these would dispel all earths, glass, stones, etc. (611.); and every idea of its being a known and recognised electric confusion and doubt, writing : action is in this way removed.” “Ora espongo in pih dettaglio le mie osser- This last sentence in effect rejects a some- vazione che dissipano ogni confusione ed ogni dubbio; ed altre ancora ve ne soggiungo di pih what vague suggestion made by Dulong and recenti.” Thenard that the power of solids to bring about reactions of gases is electrical in origin, Fusinieri contended, in opposition to Day, although, as Faraday noted, Dulong and that in fact the of on plati- Thenard expressed themselves with great num occurs with flame, which may be caution on the theory of the effect. obscured by light from the platinum, or may Additional significant experimental dis- be invisible. He further contended that during coveries concerning heterogeneous catalytic the oxidation of ether “ laminae” of oxidation were made by William Henry (IO), the combustible substance could be seen with who used as a catalyst either platinum sponge the naked eye, the laminae running over the or moulded balls made of china clay and platinum surface and then disappearing by spongy platinum. These catalytic balls were burning. Fusinieri thought that the ether first described by Dobereiner, to whom forming the laminae was solidified, although Henry refers. The two papers by Dobereiner he noted a relation between the appearance and Henry were the first to describe the use and disappearance of the laminae and capillary of a supported platinum catalyst. Dobereiner’s action of . According to Fusinieri, the contributions to catalysis have been reviewed platinum catalyst acted like a candle wick with in more detail by McDonald (11). Henry the laminae burning like candle wax. As an found that prevented the surface explanation of the formation and burning of combination of a mixture of hydrogen and the concrete laminae, which Fusinieri thought with oxygen, and carbon he saw, he proposed the concept of “native monoxide slightly slowed down the surface caloric” (Faraday’s translation).

Platinum Metals Rev., 1975, 19, (2), 68 Faraday in his momentous paper of 1834 (9), new process of manufacture of an important which proposed the idea (increasingly sup- chemical substance. The process was first ported since the researches of Langmuir) of worked to make fuming sulphuric acid by simultaneous of both reactants on Messel in 1875. Very little is known about the a platinum surface, reviewed Fusinieri’s views inventor, despite a search of local records at some length, but he confessed that he could made by E. Cook (14)~except that he was the not form a distinct idea of the concept of son of a tailor and was born in Milk Street, native caloric, and remarked that his knowl- Bristol. edge of the language in which the Fusinieri The first to use platinum as a catalyst for memoir is written was imperfect. Faraday ammonia oxidation was C. F. Kuhlmann who during his European tour with Davy and reported his results to the Scientific Society of Lady Davy, in which he acted as scientific Lille, France, in 1838. An account of early assistant and unofficial valet, had learnt developments with platinum catalysts for the Italian, but the Fusinieri paper of 1824 uses ammonia oxidation process for Italian which is as out-dated as Chaucerian manufacture has been given by L. B. Hunt English, and sentences in which “calorico (IS). nativo” appears have been said to be totally From these small beginnings vast industries incomprehensible (13). It is not surprising based on catalysis have arisen and a huge that Faraday was unable to form a distinct quantity of scientific information has been idea of what Fusinieri meant by “calorico accumulated. Despite numerous theoretical nativo.” discussions catalytic action is still to some extent a mystery-indeed it is notable that The Beginnings of large-scale processes are based on catalysts Industrial Catalysis which from a theoretical point of view can The industrial possibilities of heterogeneous hardly be described. Catalysis a century and catalytic oxidation were appreciated as early a half after Davy’s discovery still remains a as 1831 by Peregrine Phillips, Junior, who in challenge to the chemist. that year took out a British Patent (No. 6096) for “Certain Improvements in Manufacturing References Sulphuric Acid commonly called Oil of I (J. J.)* Berzelius, Annls. Chim. Phys., 1836, 146 Vitriol.” The specification states : 61, 2 (Cl B:)* DPsormes and (N.)* Climent, Annls. “The first improvement then, namely, the Chim., 1806, 59, 329 instantaneous union of sulphurous acid with 3 H. Davy, Phil. Trans. Roy. SOC.,1817, 107~77 the oxygen of the atmosphere, I effect by 4 E. Davy, Phil. Trans. Roy. SOC.,1820,110, 108 drawing them in proper proportions by the 5 (J. W.)* DCibereiner, Annls. Chim. Phys., 1823, action of an air pump or other mechanical 24>91 means thro’ an ignited tube or tubes of platina, 6 (P. L.)* Dulong and (L. J.)* Thknard, Annls. porcelain, or any other material not acted on Chim. Phys., 1823,23,440 when heated by the sulphurous acid gas. In the 7 M. F(araday), Quart. J. Science. 1823, 16, 179 said tube or tubes I place fine platina wire or 8 (I?. L.)* Dulong and (L. J.)* Thinard, Annls. platina in any finely-divided state, and I heat Chim. Phys., 1823,24, 380 them to a strong yellow heat, and by preference 9 M. Faraday, Phil. Trans. Roy. SOC.,1834,124, in the chamber of a reverberatory furnace; and 55 I do affirm that sulphurous acid gas being made 10 W. Henry, Phil. Mag., 1825, 65, 269; Phil, to pass with a sufficient supply of atmospheric Trans. Roy. SOC.,1824, r14, 266 air through tubes as described, properly heated 11 D. McDonald, Platinum Metals Rev., 1965, 9, and managed, will be instantly converted into 136 sulphuric acid gas, which will be rapidly 12 A. Fusinieri, Giurnali di Fisica, 1824,7, 371 absorbed as soon as it comes into contact with 13 M. Farinelli, A. L. B. Gale and A. J. B. .” Robertson, Annals Sci., r974,31, 19 14 (Sir) E. Cook, Nature, 1926, 117,419 This far-sighted patent has made Phillips 15 L. B. Hunt, Platinum Metals Rev., ~958,2,129 one of the inventors who have devised a really * Initials are not given in the original paper

Platinum Metals Rev., 1975, 19, (2), 69