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Nov. 4, 1869]
NATURE
21

year. It was in 1830 that he was appointed Professor of Chemistry at the Andersonian University, Glasgow; and it is said that his mother, who was on her deathbed, lived to hear the glad tidings of his appointment. He was now more favourably circumstanced for experimental labours, and we find that the seven years spent at the Andersonian University were years of great activity.

In 1837 he was appointed Professor of Chemistry in the London University, now called University College, London, and he occupied that chair with great distinction till the year 1855, when he succeeded Sir John Herschel as Master of the Mint, which appointment may be considered an acknowledgment on the part of the Government of his scientific services and of his high character.

His numerous discoveries have been much quoted. Some of their theoretical bearings claim a brief notice here.

His investigation of the phosphates is remarkable in many ways. It was known that solutions of phosphoricacid in water vary in their properties; and chemists were satisfied with giving a name to the changes without investigating their nature. These solutions contained phosphoric acid and water, and were assumed to have like composition. They were accordingly called isomeric. Graham observed that they differ from one another in the proportion of water combined with the acid, and constitute in reality different compounds.

He knew that water combines with acids as other bases do, and he showed that the various compounds of phosphoric acid and water constitute distinct salts, each of which admits of its hydrogen being replaced by other metals without disturbance of what we should now call the type. Thus, to use our present notation, the three hydrates PO₄H₃, P₂O₇H₄, PO₄H₄, correspond to the following proportions of acid:—

Graham observed that the hydrate PO₄H₄ is constituted like a salt, inasmuch as its hydrogen can be replaced atom for atom by other metals, like sodium, potassium, &c., forming such compounds as PO₄NaH₂, PO₄Na₃H, &c.

In order to appreciate duly the powers of mind of the author of this admirable research, we ought to compare his methods of reasoning with those generally prevalent among contemporary chemists, and on the other hand with the methods of to-day. One would fancy that Graham had been acquainted with the modern doctrines of types and of polybasic acids, so clearly does he describe the chemical changes in matter-of-fact language, and so consistently does he classify the compounds by their analogies. At that early period we find Graham considering hydrogen, in various salts, as a basylous metal; an idea which (in spite of its undeniable truth) some chemists of the present day have not fully realised.

Amongst minor chemical researches may be mentioned a series of experiments on the slow oxidation of phosphorus by atmospheric air. He discovered that this process (and the faint light which accompanies it) is arrested by the presence in the air of a trace of oletiant gas, 1/456 of the volume of the air being sufficient for the purpose. Still smaller proportions of some other vapours were found capable of producing this same effect; spirits of turpentine being particularly remarkable, as less than a quarter of a thousandth of its vapour with air was found sufficient to prevent the slow oxidation of phosphorus.

On another occasion Graham investigated phosphuretted hydrogen, and made some remarkable observationsconcerning the conditions of the formation of the spontaneously inflammable gas. One of these deserves especial notice in connection with the action of oletiant gas, and in preventing the oxidation of phosphorus. He found that phosphuretted hydrogen is rendered spontaneously inflammable by the admixture of a very small proportion of an oxide of nitrogen, probably nitrous acid.

One of the most obscure classes of combinations are those which water forms with various salts. These bodies are characterised by the chief peculiarities which belong to definite chemical compounds; but chemists are as yet unable to explain them.

Water so combined is called water of crystallisation, and is said to be physically, not chemically, combined. A very convenient way of getting rid of a difficulty, by passing it on to our neighbours.

Graham examined the proportion of such water of crystallisation in a considerable number of salts, and he moreover examined the properties which it has when so combined. He found that some of the water in an important class of sulphates is held far more firmly than the remainder, and with force equal to that with which water is held in various chemical compounds. He showed that such firmly combined water can be replaced by salts in a definite chemical proportion. In fact, he got fairly hold of the subject by chemical methods, and laid the foundation for an explanation of it.

He discovered and examined compounds of alcohol with salts, and derived from them valuable evidence of the analogy between alcohol and water.

Thomas Graham (from a recent Photograph)

On a later occasion he made a series of important experiments upon the transformation of alcohol into ether and water, by the action of hydric sulphate. Liebig had endeavoured to explain the formation of ether in this process, by representing it as due to the decomposition at a high temperature of a compound of ether previously formed at a lower temperature; such decomposition being due to the increased tension of the vapour of ether at the higher temperature.

Graham justly argued that if the decomposition were due to the tension of ether vapour, it would not take place, and ether would not be formed, if the tension were not allowed to exert itself. He heated the materials in a closed tube, and proved that ether was formed, although the tension of its vapour was counteracted by the pressure thus obtained.

The line of research which occupied most of his attention, and in which his results were perhaps the most important, was that of diffusion; and it would be difficult to over-estimate the importance to molecular chemistry of his measurements, of the relative velocities of these