In 1830 N. G. Sefström definitely proved the existence of a metallic element vanadium, which had been previously detected (in 1801) in certain lead ores by A. M. del Rio; subsequent elaborate researches by Sir Henry Roscoe showed many inaccuracies in the conclusions of earlier workers (for instance, the substance considered to be the pure element was in reality an oxide) and provided science with an admirable account of this element and its compounds. B. W. Gerland contributed to our knowledge of vanadyl salts and the vanadic acids. Chemically related to vanadium are the two elements tantalum and columbium or niobium. These elements occur in the minerals columbite and tantalite, and their compounds became known in the early part of the 19th century by the labours of C. Hatchett, A. G. Ekeberg, W. H. Wollaston and Berzelius. But the knowledge was very imperfect; neither was it much clarified by H. Rose, who regarded niobium oxide as the element. The subject was revived in 1866 by C. W. Blomstrand and J. C. Marignac, to whom is due the credit of first showing the true chemical relations of these elements. Subsequent researches by Sainte Claire Deville and L. J. Troost, and by A. G. Krüss and L. E. Nilson, and subsequently (1904) by Hall, rendered notable additions to our knowledge of these elements and their compounds. Tantalum has in recent years been turned to economic service, being employed, in the same manner as tungsten, for the production of the filaments employed in incandescent electric lighting.
In 1833 Thomas Graham, following the paths already traced out by E. D. Clarke, Gay Lussac and Stromeyer, published his masterly investigation of the various phosphoric acids and their salts, obtaining results subsequently employed by J. von Liebig in establishing the doctrine of the characterization and basicity of acids. Both phosphoric and phosphorous acids became known, although imperfectly, towards the end of the 18th century; phosphorous acid was first obtained pure by Davy in 1812, while pure phosphorous oxide, the anhydride of phosphorous acid, remained unknown until T. E. Thorpe’s investigation of the products of the slow combustion of phosphorus. Of other phosphorus compounds we may here notice Gengembre’s discovery of phosphuretted hydrogen (phosphine) in 1783, the analogy of which to ammonia was first pointed out by Davy and supported at a later date by H. Rose; liquid phosphuretted hydrogen was first obtained by Thénard in 1838; and hypophosphorous acid was discovered by Dulong in 1816. Of the halogen compounds of phosphorus, the trichloride was discovered by Gay Lussac and Thénard, while the pentachloride was obtained by Davy. The oxychloride, bromides, and other compounds were subsequently discovered; here we need only notice Moissan’s preparation of the trifluoride and Thorpe’s discovery of the pentafluoride, a compound of especial note, for it volatilizes unchanged, giving a vapour of normal density and so demonstrating the stability of a pentavalent phosphorus compound (the pentachloride and pentabromide dissociate into a molecule of the halogen element and phosphorus trichloride).
In 1840 C. F. Schönbein investigated ozone, a gas of peculiar odour (named from the Gr. ὄζειν, to smell) observed in 1785 by Martin van Marum to be formed by the action of a silent electric discharge on the oxygen of the air; he showed it to be an allotropic modification of oxygen, a view subsequently confirmed by Marignac, Andrews and Soret. In 1845 a further contribution to the study of allotropy was made by Anton Schrötter, who investigated the transformations of yellow and red phosphorus, phenomena previously noticed by Berzelius, the inventor Of the term “allotropy.” The preparation of crystalline boron in 1856 by Wöhler and Sainte Claire Deville showed that this element also existed in allotropic forms, amorphous boron having been obtained simultaneously and independently in 1809 by Gay Lussac and Davy. Before leaving this phase of inorganic chemistry, we may mention other historical examples of allotropy. Of great importance is the chemical identity of the diamond, graphite and charcoal, a fact demonstrated in part by Lavoisier in 1773, Smithson Tennant in 1706, and by Sir George Steuart-Mackenzie (1780–1848), who showed that equal weights of these three substances yielded the same weight of carbon dioxide on combustion. The allotropy of selenium was first investigated by Berzelius; and more fully in 1851 by J. W. Hittorf, who carefully investigated the effects produced by heat; crystalline selenium possesses a very striking property, viz. when exposed to the action of light its electric conductivity increases. Another element occurring in allotropic forms is sulphur, of which many forms have been described. E. Mitscherlich was an early worker in this field. A modification known as “black sulphur,” soluble in water, was announced by F. L. Knapp in 1848, and a colloidal modification was described by H. Debus. The dynamical equilibrium between rhombic, liquid and monosymmetric sulphur has been worked out by H. W. Bakhuis Roozeboom. The phenomenon of allotropy is not confined to the non-metals, for evidence has been advanced to show that allotropy is far commoner than hitherto supposed. Thus the researches of Carey Lea, E. A. Schneider and others, have proved the existence of “colloidal silver”; similar forms of the metals gold, copper, and of the platinum metals have been described. The allotropy of arsenic and antimony is also worthy of notice, but in the case of the first element the variation is essentially non-metallic, closely resembling that of phosphorus. The term allotropy has also been applied to inorganic compounds, identical in composition, but assuming different crystallographic forms. Mercuric oxide, sulphide and iodide; arsenic trioxide; titanium dioxide and silicon dioxide may be cited as examples.
The joint discovery in 1859 of the powerful method of spectrum analysis (see Spectroscopy) by G. R. Kirchhoff and R. W. Bunsen, and its application to the detection and the characterization of elements when in a state of incandescence, rapidly led to the discovery of many hitherto unknown elements. Within two years of the invention the authors announced the discovery of two metals, rubidium and caesium, closely allied to sodium, potassium and lithium in properties, in the mineral lepidolite and in the Dürkheim mineral water. In 1861 Sir William Crookes detected thallium (named from the Gr. θάλλος, a green bud, on account of a brilliant green line in its spectrum) in the selenious mud of the sulphuric acid manufacture; the chemical affinities of this element, on the one hand approximating to the metals of the alkalis, and on the other hand to lead, were mainly established by C. A. Lamy. Of other metals first detected by the spectroscope mention is to be made of indium, determined by F. Reich and H. T. Richter in 1863, and of gallium, detected in certain zinc blendes by Lecoq de Boisbaudran in 1875. The spectroscope has played an all-important part in the characterization of the elements, which, in combination with oxygen, constitute the group of substances collectively named the “rare earths.” The substances occur, in very minute quantity, in a large number of sparingly-distributed and comparatively rare minerals—euxenite, samarksite, cerite, yttrotantalite, &c. Scandinavian specimens of these minerals were examined by J. Gadolin, M. H. Klaproth, and especially by Berzelius; these chemists are to be regarded as the pioneers in this branch of descriptive chemistry. Since their day many chemists have entered the lists, new and powerful methods of research have been devised, and several new elements definitely characterized. Our knowledge on many points, however, is very chaotic; great uncertainty and conflict of evidence circulate around many of the “new elements” which have been announced, so much so that P. T. Cleve proposed to divide the “rare earth” metals into two groups, (1) “perfectly characterized”; (2) “not yet thoroughly characterized.” The literature of this subject is very large. The memorial address on J. C. G. de Marignac, a noted worker in this field, delivered by Cleve, a high authority on this subject, before the London Chemical Society (J.C.S. Trans., 1895, p. 468), and various papers in the same journal by Sir William Crookes, Bohuslav Brauner and others should be consulted for details.
In the separation of the constituents of the complex mixture of oxides obtained from the “rare earth” minerals, the methods