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A FOOTNOTE TO THE BICENTENARY CELEBRATIONS

By L. B. Hunt Johnson Matthey and Co Limited

Sir Humphry Davy was born in romantic nature and love of poetry, were all on December 17th 1778 and to celebrate the reviewed during the Symposium held during bicentenary of his birth the , December, but an important but less appreci- where he was Resident Professor from 1802 ated phase of his chemical investigations to 1813 and Honorary Professor for the fol- underlies one of the most significant applica- lowing ten years, organised a number of tions of platinum in modern industry. lectures and an exhibition illustrating his life Davy had excellent opportunities of secur- and work. ing platinum for his experiments. In 1807- Davy is probably best known to the year in which he first electrolysed fused for his isolation of and , and potash in a platinum spoon connected to the later the alkaline earth elements, by means of positive terminal of a battery-he was elected the then new methods of , one of the Joint Secretaries of the Royal and to the general public for his invention of Society (he had been elected a Fellow in 1803) the miner’s -the latter completed his colleague being . in only two weeks of intense investigation. Their association developed into a real friend- Many other aspects of Davy’s genius, his ship, and Davy was able to obtain his require- many decisive experiments, his remarkable ments from Wollaston, who had only recently series of lectures to crowded audiences at the succeeded in refining native platinum on a Royal Institution-to which he gave the scientific basis and in making malleable character it has ever since retained-and his platinum available commercially. In addition

Sir Humphry Davy 1778-1829 When Davy began his researches at the neudy founded Royal Institution the new ,field of had just opened, while the laws of chemical combination had yet to be firmly established. In the first of his six Bakerian Lectures to the Royal Society in 1806 he introduced a new concept into -the relation of electrical charge to chemical afinity, and much of his later work was in electro- chemistry, but in his rnajor researches on that led to the invention of the safety lamp he also discovered the phenomenon of heterogeneous over platinum From the portrait by Sir In the possession of the Royal Society.

Platinum Rev., 1979, 23, (l), 29-31 29 to their association in the Royal Society and that the elements might be arranged in Wollaston was among the managers of the the order of their natural resemblances; for Royal Institution, and in the Davy archives example preserved there a note gives his appreciation “Platinum is analogous to gold, silver and of Wollaston, describing him as palladium; and palladium is connected by distinct analogies with tin, , and “I think jealous and reserved in the earlier part manganese” of his life, but latterly he became far more agreeable and confiding and was a warm and But the most vital discovery concerning kind friend and a pleasant social companion” platinum arose during Davy’s classic re- In 1812 llavy published his “Elements of searches on flame arising from an appeal made Chemical Philosophy”, the first section com- to him after a disastrous explosion in a coal prising a remarkable summary of the history mine, followed by a number of other similar of chemistry. His comments on platinum explosions in the same area of Northumbria. later in the book are indicative: In a paper read to the Royal Society on January 1817 Davy described “the “Platinum is a most valuable ; as it is not 23, (z), oxidisable, nor fusible under common circum- discovery of a new and curious series of stances, and only with difficulty combinable phenomena”. with sulphur, and not acted upon by common , it is admirably adapted for the uses of “I was making experiments on the increase of the philosophical , and may be advan- the limits of the combustibility of gaseous tageously employed in all cases where gold is mixtures of coal gas and air by increase of applied, unless the use is connected with the temperature. For this purpose, I introduced colour or malleability of the metal” a small wire-gauze safe-lamp with some fine wire of platinum fixed abovc the flame, into a combustible mixture containing the maximum One other finding of importance in con- of coal gas, and when the inflammation had nection with platinum, made a few years later taken place in the wire-gauze cylinder, I threw in more coal gas, expecting that the heat than the major discovery about to be de- acquired by the mixed gas in passing through scribed, was the change in resistance of a the wire-gauze would prevent the excess from extinguishing the flame. The flame continued platinum wire with increasing temperature, for two or threc seconds after the coal gas was the basis of course of the modern resistance introduced; and when it was extinguished, that part of the wire of platinum which had been thermometer. In a paper given to the Royal hottest remained ignited, and continued so for Society in July 1821 on “Further Researches many minutes, and when it was removed into a dark room, it was evident that there was no on the Magnetic Phenomena Produced by flame in the cylinder. Electricity, with some new experiments on It was immediately obvious that this was the the properties of electrified bodies in their result which I had hoped to attain by other methods, and that the oxygene and coal gas in relation to conducting powers and tempera- contact with the wire combined without flame, ture” (I), Davy wrote and yet produced heat enough to preserve the wire ignited, and to keep up their own com- “The most remarkable general result that I bustion. I proved the truth of this conclusion obtained by these researches, and which I shall by making a similar mixture, heating a fine wire mention first, as it influences all the others, was, of platinum and introducing it into the mixture. that the conducting power of metallic bodies It immediately became ignited nearly to white- varied with the temperature, and was lower, in ness, as if it had been itself in actual combustion, some inverse ratio, as the temperature was and continued glowing for a long while, and higher. Thus a wire of platinum of I ‘220, and when it was extinguished, the inflammability three inches in length, when kept cool by oil dis- of the mixture was found entirely destroyed. charged the electricity of two batteries, or of A temperature much below ignition only was twenty double plates: but when suffered to be necessary for producing this curious phenom- heated by exposure in the air, it barely dis- enon, and the wire was repeatedly taking out charged one battery” and cooled in the atmosphere till it ceased to be visibly red; and yet when admitted again, Among his inspired forecasts were the con- it instantly became red hot . . . cepts that I have tried to produce these phenomena with various metals; but I have succeeded “Matter may ultimately be found to be the only with platinum and palladium; with same in essence, differing only in the arrange- copper, silver, iron, gold and zinc, the ment of its particles” effect is not produced.”

Platinum Metals Rev., 1979, 23, (1) 30 Thus did Davy discover the phenomenon , at a heat below redness; but if beat into thin laminae, it occasions its combustion of heterogeneous catalytic oxidation, and at the heat of boiling mercury, and, when in although he obtained the same result with the form of the thinnest foil, at usual tempera- tures. I cooled the spongy platinum to 3” of ether, alcohol and other vapours it was left Fahr., and still it inflamed hydrogen nearly of to others to carry further the study of this the same temperature, issuing from a tube cooled by and ice. profoundly important effect. , I thought that common radiant heat or light, his cousin and one-time assistant in the Royal might be necessary to the effect; but the cooled Institution and later Professor of Chemistry metal and the gases acted with the same phenomena in darkness. at Cork, went on to prepare finely divided It may be supposed that the spongy platinum platinum catalysts that were active at room absorbs hydrogen, or that it contains ; temperature (3) while - but neither of these hypotheses will apply to the fact that I first observed, of the ignition of sometimes described as Davy’s greatest dis- fine wires in different mixtures of inflammable covery and his major contribution to science- gases and air, at temperatures so far below ignition. who was assisting Humphry Davy in the A probable explanation of the phenomenon, experiments just described, went on much may, I think, be founded upon the electro- later to the study of catalysis, having been chemical hypothesis which I laid before the Royal Society in 1806; and which has been mystified by the peculiar reaction of platinum since adopted and explained, according to their with the oxygen and hydrogen produced in own ideas, by different philosophers.” his experiments on the electrolytic decompo- Immediately after the publication of this sition of water (4). second edition Davy became ill and exhausted, Davy himself gave little further attention and after four years of wandering in Europe to the phenomenon and made only one passing he died in at the early age of 50 on reference to it in a somewhat obscure place. May 29, 1829. In 1818 he had published a book “On the A century and a half later some of the Safety Lamp . . . with Some Researches on questions raised by Davy’s discovery have Flame”, but in 1825 he was moved to publish still not been satisfactorily answered despite a second edition because his experience, as he intensive research, especially during the past wrote in the preface twenty-five years or so. Ignorance of the finer points of reaction mechanism has not, “having shewn that the precautions which it was intended to describe either are not known however, proved to be a hindrance to the or are not attended to, I have thought it might large-scale usage of catalysed reactions assist the cause of humanity to advertise the book a second time” (5) depending upon platinum or its allied metals in modern chemical industry. This edition contained several appendices, and in Appendix No. 2 he returned to the References subject and to the later work of Dobereiner I Humphry Davy, Phil. Trans. Roy. SOC.,1821, with finely divided platinum such as Edmund 111,425 Davy had used (6) and of Dulong and 2 Humphry Davy, Phil. Trans. Roy. SOC.,1817, 1073 77 Thenard, who had shown that palladium and 3 Edmund Davy, Phil. Trans. Roy. SOC.,1820, iridium could behave catalytically at room 1x0, 108 Michael Faraday, Phil. Trans. Roy. SOC., temperature while nickel, cobalt, rhodium, 4 1834, I24>55 silver and gold were active only at higher 5 Humphry Davy, “On the Safety Lamp for temperatures (7). Davy continued : Preventing Explosives in Mines, Houses Lighted by Gas, Spirit Warehouses, or Maga- zines in Ships etc., with Some Researches on “It is probable that the rationale of all these Flame”, Appendix pp processes is of the same kind. Whenever any 1825, 2, 148-151 chemical operation is produced by an increase 6 J. W. Dobereiner, Ann. Chin?. Phys., 1823, 24, of temperature, whatever occasions an accumu- 91 lation of heat, must tend to give greater facility 7 P. L. Dulong and L. J. Thenard, Ann. Chim. to the process; a very thick wire of platinum Phys., 1823,23,440; see also A. J. B. Robertson, does not act upon a mixture of oxygen and Platinum Metals Rev., 1975, 19, (2), 64

Platinum Metals Rev., 1979, 23, (1) 31