CHAPTER VII
THE WORK OF EILHARDT MITSCHERLICH AND HIS DISCOVERY OF ISOMORPHISM.
During the height of the French Revolution, which caused the work of the Abbe Haüy to be suspended for a time, although he was fortunately not one of the many scientific victims of that terrible period, there was born, on the 7th of January 1794, in the village of Neuende, near Jever, in Oldenburg, the man who was destined to continue that work on its chemical side. Eilhardt Mitscherlich was the son of the village pastor, and nephew of the celebrated philologer, Prof. Mitscherlich of Göttingen. His uncle’s influence appears to have given young Mitscherlich a leaning towards philological studies, for during his later terms at the Gymnasium at Jever, where he received his early education, he devoted himself with great energy to the study of history and languages, for which he had a marked talent, under the able direction and kind solicitude of the head of the Gymnasium at that time, the historian Schlosser. He eventually specialised on the Persian language, and when Schlosser was promoted to Frankfort young Mitscherlich accompanied him, and there prosecuted these favourite studies until the year 1811, when he went to the university of Heidelberg.
For some time now he had cherished the hope of proceeding to Persia and conducting philological investigations on the spot, and in 1813, an opportunity presenting itself in the prospect of an embassy being despatched to Persia by Napoleon, he transferred himself to the university of Paris, with the object of obtaining permission from Napoleon to accompany the embassy. This visit to Paris must have been one of Mitscherlich’s most exciting and interesting experiences. For Napoleon had just returned from the disastrous Russian campaign of 1812, and was feverishly engaged in raising a new army wherewith to stem the great rise of the people which was now re-awakening patriotic spirit throughout the whole of Germany, and which threatened to sweep away, as it eventually did, the huge fabric of his central European Empire.
Indeed Mitscherlich appears to have been detained in Paris during the exciting years 1813 and 1814, and with the abdication of Napoleon on April 4th of that year, he was obliged to give up all idea of proceeding to Persia. He decided that the only way of accomplishing his purpose was to attempt to travel thither as a doctor of medicine. He therefore returned to his native Germany during the summer of 1814, and proceeded to Göttingen, which was then famous for its medical school. Here he worked hard at the preliminary science subjects necessary for the medical degree, while still continuing his philology to such serious purpose as to enable him to publish, in 1815, the first volume of a history of the Ghurides and Kara-Chitayens, entitled “Mirchondi historia Thaheridarum.” It is obvious from the sequel, however, that he very soon began to take much more than a merely passing interest in his scientific studies, and he eventually became so fascinated by them, and particularly chemistry, as to abandon altogether his cherished idea of a visit to Persia. Europe was now settling down after the stormy period of the hundred days which succeeded Napoleon’s escape from Elba, terminating in his final overthrow on June 18th, 1815, at Waterloo, and Mitscherlich was able to devote himself to the uninterrupted prosecution of the scientific work now opening before him. He had the inestimable advantage of bringing to it a culture and a literary mind of quite an unusually broad and original character; and if the fall of Napoleon brought with it the loss to the world of an accomplished philologist, it brought also an ample compensation in conferring upon it one of the most erudite and broad-minded of scientists.
In 1818 Mitscherlich went to Berlin, and worked hard at chemistry in the university laboratory under Link. It was about the close of this year or the beginning of 1819 that he commenced his first research, and it proved to be one which will ever be memorable in the annals both of chemistry and of crystallography. He had undertaken the investigation of the phosphates and arsenates, and his results confirmed the conclusions which had just been published by Berzelius, then the greatest chemist of the day, namely, that the anhydrides of phosphoric and arsenic acids each contain five equivalents of oxygen, while those of the lower phosphorous and arsenious acids contain only three. But while making preparations of the salts of these acids, which they form when combined with potash and ammonia, he observed a fact which had escaped Berzelius, namely, that the phosphates and arsenates of potassium and ammonium crystallise in similar forms, the crystals being so like each other, in fact, as to be indistinguishable on a merely cursory inspection.
Being unacquainted with crystallography, and perceiving the importance of the subject to the chemist, he acted in a very practical and sensible manner, which it is more than singular has not been universally imitated by all chemists since his time. He at once commenced the study of crystallography, seeing the impossibility of further real progress without a working knowledge of that subject. He was fortunate in finding in Gustav Rose, the Professor of Geology and Mineralogy at Berlin, not merely a teacher close at hand, but also eventually a life-long intimate friend. Mitscherlich worked so hard under Rose that he was very soon able to carry out the necessary crystal measurements with his newly prepared phosphates and arsenates. He first established the complete morphological similarity of the acid phosphates and arsenates of ammonium, those which have the composition NH4H2PO4 and NH4H2AsO4 and crystallise in primary tetragonal prisms terminated by the primary pyramid faces; and then he endeavoured to produce other salts of ammonia with other acids which should likewise give crystals of similar form. But he found this to be impossible, and that only the phosphates and arsenates of ammonia exhibited the same crystalline forms, composed of faces inclined at similar angles, which to Mitscherlich at this time appeared to be identical. He next tried the effect of combining phosphoric and arsenic acids with other bases, and he found that potassium gave salts which crystallised apparently exactly like the ammonium salts.
He then discovered that not only do the acid phosphates and arsenates of potassium and ammonium, H2KPO4, H2(NH4)PO4, H2KAsO4, and H2(NH4)AsO4 crystallise in similar tetragonal forms, but also that the four neutral di-metallic salts of the type HK2PO4 crystallise similarly to each other.
He came, therefore, to the conclusion that there do exist bodies of dissimilar chemical composition having the same crystalline form, but that these substances are of similar constitution, in which one element, or group of elements, may be exchanged for another which appears to act analogously, such as arsenic for phosphorus and the ammonium group (although its true nature was not then determined) for potassium. He observed that certain minerals also appeared to conform to this rule, such as the rhombohedral carbonates of the alkaline earths, calcite CaCO3, dolomite CaMg(CO3)2, chalybite FeCO3, and dialogite MnCO3; and the orthorhombic sulphates of barium (barytes, BaSO4), strontium (celestite, SrSO4), and lead (anglesite, PbSO4). Wollaston, who, in the year 1809, had invented the reflecting goniometer, and thereby placed a much more powerful weapon of research in the hands of crystallographers, had already, in 1812, shown this to be a fact as regards the orthorhombic carbonates (witherite, strontianite, and cerussite) and sulphates (barytes, celestite, and anglesite) of barium, strontium, and lead, as the result of the first exact angular measurements made with his new instrument; but his observations had been almost ignored until Mitscherlich reinstated them by his confirmatory results.
While working under the direction of Rose, Mitscherlich had become acquainted with the work of Haüy, whose ideas were being very much discussed about this time, Haüy himself taking a very strong part in the discussion, being particularly firm on the principle that every substance of definite chemical composition is characterised by its own specific crystalline form. Such a principle appeared to be flatly contradicted by these first surprising results of Mitscherlich, and it naturally appeared desirable to the latter largely to extend his observations to other salts of different groups. It was for this reason that he had examined the orthorhombic sulphates of barium, strontium, and lead, and the rhombohedral carbonates of calcium, magnesium, iron, and manganese, with the result already stated that the members of each of these groups of salts were found to exhibit the same crystalline form, a fact as regards the former group of sulphates which had already been pointed out not only by Wollaston but by von Fuchs (who appears to have ignored the work of Wollaston) in 1815, but had been explained by him in a totally unsatisfactory manner. Moreover, about the same time the vitriols, the sulphates of zinc, iron, and copper, had been investigated by Beudant, who had shown that under certain conditions mixed crystals of these salts could be obtained; but Beudant omitted to analyse his salts, and thus missed discovering the all-important fact that the vitriols contain water of crystallisation, and in different amounts under normal conditions. Green vitriol, the sulphate of ferrous iron, crystallises usually with seven molecules of water of crystallisation, as does also white vitriol, zinc sulphate; but blue vitriol, copper sulphate, crystallises with only five molecules of water under ordinary atmospheric conditions of temperature and pressure. Moreover, copper sulphate forms crystals which belong to the triclinic system, while the sulphates of zinc and iron are dimorphous, the common form of zinc sulphate, ZnSO4.7H2O, being rhombic, like Epsom salts, the sulphate of magnesia which also crystallises with seven molecules of water, MgSO4.7H2O, while that of ferrous sulphate, FeSO4.7H2O, is monoclinic, facts which still further complicate the crystallography of this group and which were quite unknown to Beudant and were unobserved by him. But Beudant showed that the addition of fifteen per cent. of ferrous sulphate to zinc sulphate, or nine per cent. to copper sulphate, caused either zinc or copper sulphate to crystallise in the same monoclinic form as ferrous sulphate. He also showed that all three vitriols will crystallise in mixed crystals with magnesium or nickel sulphates, the ordinary form of the latter salt, NiSO4.7H2O, being rhombic like that of Epsom salts.
The idea that two chemically distinct substances not crystallising in the cubic system, where the high symmetry determines identity of form, can occur in crystals of the same form, was most determinedly combated by Haüy, and the lack of chemical analyses in Beudant’s work, and the altogether incorrect “vicarious” explanation given by von Fuchs, gave Haüy very grave cause for suspicion of the new ideas. The previous observations of Rome de l’Isle in 1772, Le Blanc in 1784, Vauquelin in 1797, and of Gay-Lussac in 1816, that the various alums, potash alum, ammonia alum, and iron alum, will grow together in mixed crystals or in overgrowths of one crystal on another, when a crystal of any one of them is hung up in the solution of any other, does not affect the question, as the alums crystallise in the cubic system, the angles of the highly symmetric forms of which are absolutely identical by virtue of the symmetry itself.