The discovery of the elements. VII. Columbium ... - ACS Publications

THE DISCOVERY OF THE ELEMENTS. VII. COLUMBIUM, TANTALUM, AND VANADIUM* MARYELVIRA WEEKS.THEUNIVERSITY OR KANSAS. LAWRENCE, KANSAS

Although the metals columbium, tantalum, and vanadium were recognized very early i n the nineteenth century, the dificult task of preparing them in a pure state i s a n achievement of recent years. In 1801 the English chemist, Charles Hatchett, discovered a new element in a specimen of columbite which had a n interesting connection with the history of New England. I n the same year A. M . del Rio, a professor of mineralogy in Mexico, examined some "brown lead from Zimapan," and announced the discovery of a new metal, erythronium. I n the following year 'Berzelius' professor, A . G. Ekeberg, analyzed some tantalite from Finland and found in it a n element very similar to Hatchett's columbium. Although Dr. Wollaston belimed that columbium and tantalum are identical, Heinrich Rose and Marignac proved that they are two distinct elements. I n 1831 Sefsbom found in some soft iron from Eckersholm a metal, vanadium, which Wohler proved to be identical with del Rio's erythronium. . . . . . . I t i s impossible that he who h a once imbibed a taste for science can ever abandon it (1). ..a--; .#., ., Columbium The element columbium (niobium) was discovered in 1801 by the English chemist, Charles Hatchett, who was born in about 1765. As a young man in his thirties he was actively devoted to chemical research, and published in the Philosophical Transactions an analysis of lead molybdate from Carinthia and the results of some experiments on shell and bone (2),and in Nicholson's Journal an analysis of an earth from New South Wales called "Sydneia, or Terra Australis" (31). The discovery on which his fame rests was announced before the Royal Ed&%* Pohr Smilh Memorid CoNeclian Society on November 26, 1801, in a u";"m;'~Of P ~ ~ ~ ~ paper entitled, "Analysis of a Mineral c,,, H ~ ~ 1 7~0 5 ~~ ~ 8 4 E7 from North America containing a English chemist and manufacturer. Metal hitherto Unknown" (3). This Discoverer of columbium. Mast of his researches were in analytical and minmineral, now known as columbite, is eralogical "hemistry. a black rock found in New England, and the specimen Hatchett analyzed had an interesting history. * Illustrations by F. B. Dains, The University of Kansas, Lawrence, Kansas. 863

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writing to Wohler, expressed a similar opinion: "On my previous visit here in Karlsbad," said he, "I made the personal acquaintance of your king as Prince of Cumberland. He asked me if I knew a number of English chemists, and upon my replying that I knew Davy, Wollaston, Tennant, and Marcet, he shook his head and indicated that I had forgotten the foremost one, namely, Hatchett. He seemed greatly pleased that I also knew him, however did not want to believe that he had given up chemistry and SIRHANSSLOANE, 1660-1753 become a wagon-maker Founder of the British Museum. Physician, pharmacist, traveler, and collector of books, manuscripts, as his father's successor" coins, medals, gems, antiquities, and natural history (6). Hatchett retired to speamens. his estate at Roehampton, near London, anddied at Chelsea on February 10, 1847. He never succeeded in isolating columbium, and in fact the element eluded chemists for more than six decades. In 1864, however, C. W. Blomstrand reduced columbium chloride by heating it strongly in an atmosphere of hydrogen (48), and saw the shining steel-gray metal. In 1901 Henri Moissan pulverized some American columbite, mixed with it some sugar charcoal, compressed the mixture, and heated it from seven to eight minutes in his electric furnace, using a current of one thousand amperes under fifty volts. After volatilizing all the manganese and part of the iron and silicon, he obtained a melt containing columbium and tantalum comb'med with carbon. After preparing columbic acid by Marignac's method, he mixed eightytwo parts of it with eighteen of sugar carbon, moistened the mixture slightly with turpentine, and pressed it into the form of a cylmder, which he heated in his electric furnace, using six hundred amperes under fifty volts. A violent reaction tock place in accordance with the equation: CWr

+ 5C = 2Cb + 5C0.

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PHOTOMICROGRAPH OF COLUMBIUM Approximately 300X After cooling the mixture out of contact with the nitrogen of the air, he found a well-fused ingot with a metallic fracture (49). Moissan's columbium contained a small amount of combined carbon, and was so inert and refractory that he believed the element to be a non-metal resembling boron and silicon. In 1904 Clarence W. Balke (7), (18), in his dissertationforthedoctorate, determined the atomic weights of both columbium and tantalum, and two years later Werner von Boltou of the Siemens & Halske Company prepared a columbium regulus by an alumino-thermic method and purified i t by repeated melting in a vacuum electric furnace (17), (18). For twenty-three years this little specimen in Germany continued to be the only piece of pure columbium in the world, but in May, 1929, Dr. Balke exhibited before the American Chemical Society some highly polished sheets and rods of this rare metal. Because of its extreme whiteness and the beautiful polish

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William Thomas Brande (1788-1886). Davy's successor at the Royal Institution, was Charles Hatchett's son-in-law. The English edition of Brande's "Manual ofChemistry" was dedicated to Hatchett.

which it takes, there is every reason to believe that it will soon make its appearance in fashionable articles of jewelry (8). Tantalum Since minerals which contain columbium almost invariably contain also the close-ly related element, tantalum, i t is small wonder that chemists a t first confused the two elements. The discoverer of tantalum was the

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Swedish chemist and mineralogist, Anders Gustaf Ekeberg. He was born a t Stockholm on January 16, 1767, the son of "Tose~hErik Ekeberg, -. a ship-builder in the service of the King. When he was ten years old he was sent to the school a t Kalmar, and two years later he went to Soderokra, where he boarded a t the home of the clergyman. It was there that he gained his first knowledge of Greek literature, a subject which gave him great pleasure throughout his life. When he was fourteen years old, he attended school a t Westervik and at Carlscrona and was an apt scholar both in science and in art. He graduated from the University of Upsala in 1788, presenting a thesis on "Oils Extracted from Seeds," and traveled, on salaly, through Germany. &

HENRIMOISSAN, 1852-1907 Professor of Chemistry at the &ole de Phnrmncie and a t the Sorbonne. The first to isolate fluorine and make a thorough study of its properties. With ' his electric furnace he prepared artificial diamonds and many rare metals. He brought about a revival of interest in inorganic chemical research.

Soon after his return to Upsala in 1790 he wrote a beautiful poem on the peace recently concluded between Sweden and Russia. In 1794, after publishing his first contribution to chemistry, he began his teaching career a t Upsala. Ekeberg suffered throughout his life from physical handicaps. A severe cold in childhood made him partially deaf for the rest of his life, and in 1801, when a flask exploded in his hand, he lost the sight of one eye (9). When he began to study chemistry, he already had a broad cultural background. He soon became deeply interested in the marvelous minerals

Swedish chemist, mineralogist, poet, and artist. Professor of Chemistry at Upsala when Berzelius was a student there. The discoverer of tantalum. He was one of the first chemists to

investigate yttria.

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to be found a t Ytterby and Fahlun, and made excellent analyses of a number of them. In 1802 he analyzed a specimen of tantalite from Kimito, Finland, and another mineral, yttrotantalite, from Ytterby, and found that both contained a hitherto unknown metal. Because it had been such a tantalizing task to trace it down, Ekeberg named it tantalum (32). In 1809 Dr. Wollaston analyzed both columbite and tantalite (10). His conclusion that columbium and tantalum are identical was accepted by chemists until 1846,when Heinrich Rose (a grandson of Valentine Rose the Elder and son of the Rose whom Klaproth educated) questioned it. Rose had made a thorough study of the columbites and tantalites from America and from Bodenmais, Bavaria, and had extracted from them two acids which he called uiobic (columbic) and pelopic - . acids. He found later, however, that the latter was not the acid of a new metal, as he had a t first supposed, but that it contained niobium (columbium) in a lower state of oxidation. Rose stated that niobic and hyponiobic acids are both different from tantalic acid (11). Although columbic and tantalic acids are extremelv dif6cult to seoarate. Marignac finally succeeded, not only Hermcn ROSE,1795-1864 in separating them, but also in showGerman analytical chemist and ing that columbium is both tri- and pharmacist. Son of Valentine Rose pentavalent, whereas tantalum always the Younger. H* comparative study of American columbite and Bavarian has a valence of five. The separation tantalite proved that columbium is based on the insolubility of potas- (niobium) and tantalum are two distinct metals. sium fluotantalate in comoarison with potassium fluo-oxycolumbate (12), (20). In the United States the element discovered by Hatchett is known as columbium, but in Europe most chemists prefer to use the name niobium which Heinrich Rose gave it. Ekeberg's later years were made less fruitful by continued illness. The few papers which he published contained the results of the analyses of minerals such as gadolinite, the topaz, and an ore of titanium. In his analysis of the mineral water of Medevi he was assisted by an obscure young student who was destined to bring great glory to the University of Upsala. The discovery of such a student as Berzelius was a far greater honor for Ekeberg than his disclosure of the rather rare element, tantalum. Berzelius warmly defended Ekeberg's claim to the discovery of this

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element. Tn the autumn of 1814 he wrote to Thomas Thomson objecting to an alteration which had been made in an English translation of one of his memoirs. Berzelius had used the word tantalum, and Thomson had evidently substituted the word columbium, whereupon Berzelius wrote, "Without wishmg to depreciate the merits of the celebrated Hatchett, i t is nevertheless necessary to observe that tantalum and its properties in the metallic as well as in its oxidized condition were not known a t all before Mr. Ekeberg." Berzelius went on to explain the differencesbetween Ekeberg's tantalum oxide and the columbium oxide prepared by Hatchett. Mr. Ekeberg received from a friend who had visited England [said he], a little portion of the columbic acid of Mr. Hatchett, and when the experiments of Mr. Wollaston came to his knowledge he examined that acid in a scrupulous manner. He recognized in it a large amount of tungstic acid which had given to the oxide its properties of reacting acid as well as those of combining with the alkalies and of coloring microcosmic salt. These observations of Mr. Ekeberg have gained still more weight by the discovery of a new fossil* that Mr. Gahn and I have just made near Fahlun, which fossil possesses the general properties of Mr. Hatchett's columbite, and in the analysis of which we have found oxide of tantalum combined with tungstic acid . . . . . Now, then [continued Berzelius], it is clear that the columbic acid of Mr. Hatchett, having been composed of oxide of tantalum and tungstic acid, which communicated to it a part of its specific properties, it is clear, I say, that Mr. Hatchett shares the discovery of tantalnm in almost the same manner as MM. Fourcroy and Vauquelin share with Mr. Tennant the honor of havifig discovered osmium ("Thomson's Svstem." Ed. IV. Vol. 1.. o. 200). and I sunoose that vou will not r&e to iendrr thgqamr jnsticr to'ihe work o/ ihe Swede i:keherg that vou ha\.e iust rrndrrrd to thc linrlirhman Trnnant * * ifo or the name of the metal [said ~&zelius],I do not think that the author of the discovery ought to count for much. For example you do not say menaccanite instead of titanium;t moreover Mr. Hatchett gave this name after the place where i t was thought the fossil had been found; now it is not good practice to name elementary substances in chemistry after the places where they have first been found; not to mention the fact that the place where columbite was found is still doubtfnl, in the same degree as i t is not certain that i t comes from America. The name tantalnm having none of these inconveniences and involving a beautiful meaning of a few properties of this particular metallic body, I have felt compelled to choose it by preference. The reason for the name tantalnm (derived from the story of Tantalus) is still more valid if one adds that metallic tantalum, reduced to the finest powder, is not attacked by any acid, not even by aqua regia, concentrated and boiling (13).

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* A tantalite from Broddbo.

** See Part VIII of this series of articles. t See Part X I of this series of articles.

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In his reply to this letter on November 5, Thomson explained that he had known very little about Ekeberg's experiments and that his only reason for changing Berzelius' nomenclature had been to make the article more intelligible to English readers. He then added:

I regret that i t never has been in my power to make experiments on either of thesesubstances (columbite or tantalite). Ekeberg supplied me with a good many specimens, but the ship containing them and all my Swedishcollection, which I valued highly, was sunk in the Baltic, and all my property lost. Scottish chemist and editor. The first distinguished advocate of Dalton's atomic theory. Your fact about the new Author of a two-volume "Histom of Chemistrv" mineral like collumbite characterized bv its scientific ac&acv and beau(sic) is very interesting. 4 tiful literary st&. I shall insert what you have told me in the next number of my journal. It is all unknown here (14). On March 29, 1815, Dr. Marcet wrote to Berzelius: . . . . Dr. Wollaston made some time ago in my presence a little experimental inquiry on wolfram and tantalite and columbite, by which it appeared that Hatchett's columbite did not contain any tungsten, and that therefore he did not make the mistake you suspected he had made. If you are curious to have the details, I shall send them to you (15).

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After prolonged suffering with tuberculosis, Ekeberg died a t Upsala on February 11, 1813, a t the early age of forty-six years. In a letter to Dr. Marcet (16), Berzelins paid the following tribute to his gifted teacher: "Ekeberg has just died after a long, sad, hectic illness. He was one of the most lovable of men, he had sound knowledge, and an irresistible propensity for work. He was a good chemist and mineralogist, a happy poet and a very good artist."* Ekeberg had a kind, friendly, meny spirit

* "Ekeberg vimt de mourir aprLs une meladie hectipue longue et malheureuse. Cet hornme ktait des plus aimbtes; it possddait des connaissances solides et un penchant irrksistibk pour lc traaail. I1 &it bar chimiste et minkralogue, heurew po& et trLs bon peintre."

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that frequently soared above poverty and suffering, and his love of literature and art was a constant solace to him. Tantalum can be separated from columbium by recrystallization of the double~otassiumfluorides. In the commercial process the ore is fused with caustic soda. The insoluble sodium colnmbate, sodium tantalate, and iron tantalate are filtered off from the soluble sodium salts, and the iron is removed by treatment with hydrochloric acid. The columbic and tantalic acids are treated with hydrofluoric acid and enough potassium fluoride to convert the tantalum into the double fluoride, K8aF7, which is then rectystallized from water containing a little hydrofluoric acid (7). After Werner von Bolton of Charlottenburg succeeded in 1903 in refining the metal, it soon acquired a limited use as filaments (34). It was found, moreover, that surgical and dental instruments made from i t can be sterilized by heating or by immersion in acids without damage to the tantalum. Since, however, the price was almost prohibitive, Dr. Balke set to work in Chicago to make the metal 7,n a commercial scale. Using as his raw material a rich tantalum ore from the desolate Pilbarra region of western Australia, he finally succeeded in February, 1922, in preparing a tantalum ingot which was passed repeatedly through a rollmg mill to produce a flawless piece of sheet metal (8), (19). Tantalum is now made into spinnerets for the manufacture of rayon, into electrodes for the neon signs that give our Great White Ways a ruddier light, and into fine jewelry with iridescent colors. Its most interesting use, however, depends on its peculiar electrochemical behavior caused by the insolubility of its oxide in acid .,: solutions. When an alternating cury~. . ' rent is passed through a vessel conc.;,,,,, F..,,,, Frd,,,, c ~ ~ tainmg sulfuric acid, a bar of lead TANTALUM FOR WATCHCASES and a bar of tantalum (or of columbium), i t becomes a direct current (7), (19). Thus, because of the need for d i i c t current in radio reception, Ekeberg's tantalizing metal, in the form of radio rectifiers, "B" battery eliminators and trickle chargers, has li

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entered into the home life of thousands upon thousands of families. Vanadium In 1801, the year in which Hatchett discovered columbium, Andres Manuel del Rio, a professor of mineralogy in Mexico, examined a specimen of brown lead from Zimapan and concluded that it contained a new metal similar to chromium and uranium. Very little has been written concerning the personal life of del Rio. He was born in Spain in about 1769, studied a t Freiberg and a t Schemnitz, and finally became a professor in the School of Mines (Collegio de Mineria) in Mexico City, where he taught for twenty-five years (1795-1820) (2), (50).

It was there that he discovered a new metal which, because of the red ,. , I..,color that its salts acquire when SEFSTROM'S AUTOGRAPH ON T ~ E heated, he named erythronium (44). oa mRZELIUS. *ATISPI ON Upon further study, however, he de- THE BLOWPIPE cided that he was mistaken, and that the brown lead from Zimapan was merely a basic lead chromate containing 80.72% of lead oxide and 14.80'% of chromic acid (12). His paper therefore bore the modest title, "Discovery of Chromium in the Brown Lead of Zimapan" (21). In 1805 Collet-Descotils con!irmed del Rio's analysis, (ZZ), and for twenty-five years no more was heard of the new element, erythronium. According to PoggendorfS, del Rio left Mexico in 1820 because of a revolution there, and settled in Philadelphia. However, his paper (I) on the "Analysis of an Alloy of Gold and Rhodium from the Parting House a t Mexico" was published in the Annuls of Philosophy in October, 1825. The date of his death is not known with certainty, but PoggendoriT states that he died before 1849. In 1831 the Swedish chemist, Nils Gabriel Sefstrom, discovered a new element in iron from the Taberg mine in Smiland. Sefstrom was born on Juue2,1787, a t Ilsbo Socken, Norra Helsingland (2). He studied medicine, and received his medical degree a t the age of twenty-six years. After four years of practice in a hospital, he became a professor of chemistry

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and science a t the Caroline Institute of Medicine and Surgery, and from 1820 to 1839 he taught chemistry a t the newly erected School of Mines a t Stockholm (2). It was there that he made the remarkable discovery that Berzelius described so charmingly to Wohler in his letter of January 22, 1831: In regard to the sample which I am sending with this, I want to tell the following anecdote: In the far north there lived in olden times the goddess Vauadis, beautiful and lovable. One day some one knocked a t her door. The goddess remained comfortably seated and thought: let the person knock again; but there was no more knocking, and the one who had knocked went down the steps. The goddess was curious to see who it might be that was so indifferent to being admitted, sprang to the window, and looked a t the one who was going away. Alas! she said to herself, that's that fellow Wohler. Well, he surely deserved it; if he had been a little more concerned about it, he would have been admitted. The fellow does not look up to the window once in passing by. . . . . After a few days some one knocked again a t the door; but this time the knocking continued. The goddess finally came herself and opened the door. Sefstrom entered, and from this union vanadium was born. That is the name of the Gnnxrr.r. SeFsm.x new metal, whose former name suggesting Erian, meaning wool (whence Erianae was educated, lixi-1x4s Swedish physician and since Minervav taught human beings to spin chemist. Professorat the wool), has been rejected. The Herr Professor Caroline Institute of guessed correctly that the lead mineral from and Surgery Zimapan contains vanadium and not chromiun~. Sefstrijm himself proved with the little specihe discovered vanadium, men belonging to the professor that i t is vanaan element that proved to dium oxide. be with de' Ria's Vanadium [continued Berzelius] is a thing "erythronium." which is very hard t o find. It is related to everything with which it forms compounds in definite proportions, even with silica, so that only now have I been able to obtain it pure. I n Sefstrom's vanadium oxide which he brought with him are found phosphoric acid, silica, alumina, zirconia, and ferric oxide, of whose presence we had no suspicion, hut which we, because of ambiguous results, had to remove, one after another; so that in the three weeks which Sefstrom spent in working with me, we confined ourselves almost entirely to the task of finding these impurities and of thinking out ways of removing them. Sefstrom had to go home, but left me so much vanadium that I have been in no embarrassment over the continuance of the investigation. I shall send the Herr Professor some of it later, when I see about how much I can spare; but now in the midst of the research I need all I have (23).

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Berzelius then consoled Wohler for his failure to discover vanadium, saying it required more real genius to synthesize urea than to discover ten new elements. "I have mailed to PoggendoriT," he continued, "a little paper on vanadium by Sefstrom. I have also engaged Sefstrom to present it to the Academy so that his name alone may be linked with the discovery, which would not be the case if the first paper on it appeared under his and my name together. Thus it also becomes possible to announce the discovery sooner than if we had to wait for the conclusion of my research, which surely cannot be completed so quickly" (23). Two weeks later Wohler replied:

A thousand thanks, dear professor, for your kind letter with the beautiful story about the goddess Vanadis, which gave me great pleasure, although, frankly, it vexed me a little, though only a t first, to have made no visit to the beautiful one. Even if I had charmed her out of the lead mineral, I would have had only half the honor of discovery, because of the earlier results of del Rio on erythronium. But Sefstrom, because he succeeded by an entirely different method, keeps the honor unshared. As soon as I know the intimate relations of the metal, and you have sent me a little of it, I will analyze the lead mineral. . . . Anticipatory as it may seem [continued Wohler] yet, because of the slowness of the mails, it is time to ask whether, when I publish a notice of the mineral, I ought to give its earlier history, the supposed discovery by del Rio of a new metal in it, the refutation by Descotils? that Humboldt brouxht it with him, etc? I would not want in the least to take away from Sefstrom anything of h$ priority of discovery, especially since such indecision is repugnant in cases like this; on the other hand one must not expose one's self to the charge hy the public or especially by one's opponents that one through partisanship concealed earlier claims. In any case Humboldt shall be named, since he alone brought it with him, and with that the rest seems unavoidably linked. Do not laugh a t me because of my diplomatic question . . . . . (23). The keenness of Wohler's disappointment is more definitely expressed in his letter to Liebig of January 2, 1831, in which he writes:

. . . a t the moment I am interested only in the new Swedish metal, vanadium, discovered by Sefstrom, hut really by Berzelius. Ich war ein Esel not to have discovered it before in the brown lead ore from Zimapan, Mexico. I was engaged in analyzing it and had already found in it something new when, in consequence of hydrogen fluoride vapor, I became sick for several months (24). For a description of Sefstrom's method of isolating vanadium, it is necessary to quote again from the correspondence of Berzelius, this time from a letter to Dulong. On January 7, 1831, he wrote:

I must tell you of the discovery of a new metallic substance, of which this letter contains some preparations. . . . The discovery

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TABERG. SMALAND, SWEDEN Sefstrem discovered vanadium in iron from the Taberg mine.

was made by Mr. Sefstrom, director of the School of Mines a t Fahlun, who, wishing t o examine a kind of iron remarkable for its extreme softness, found in it, in extremely small quantity, a substance whose properties appear t o differ from those of bodies hitherto known, but the quantity of which was so infinitely small that too much expense would have been necessary in order to extract enough of it to permit of closer examination. This iron was t e e n from the Taberg mine in Smaland, which however contains only traces of the new body, hut Mr. Sefstrom, having found that the cast iron contained more of it than the wrought iron, concluded that the scoria formed during the conversion of the cast iron to malleable iron ought to contain larger quantities of it. This proved t o be true. Mr. Sefstrom extracted portions of i t which sufficed for studying it, and during his Christmas vacation came to see me, to finish with me the study of "the stranger (nouueau d4barqu8)" (25). Sefstrom's own account of the discovery is also of great interest.

It is several years [said he], since Rinmann, the manager of the mine, in order to discover easily whether an iron was brittle, gave a method which depends on the circumstance that such an iron, when attacked by muriatic (hydrochloric) acid, gives a black powder. Having occasionally treated in this manner an iron which was not brittle, and finally some iron from Eckersholm, I was greatly surprised to recognize in the latter the reaction of a brittle iron, although the iron from Taberg passes for the most flexible and tenacious that we have. I did not then have the leisure to investigate the nature of the black powder; but in April, 1830, I resumed my experiments t o see if it contained phosphorus or any other substance, which was for me not without importance.

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I dissolved a considerable quantity of iron in muriatic acid [continued Sefstrom] and I noticed that, while i t was dissolving, a few particles of iron, mainly those which deposit the black powder, dissolved more rapidly than the others, in such a m%y that there remained hollow veins in the midst of the iron bar. Upon examining this black powder, I found silica, iron, alumina, lime, copper, and, among other things, uranium. I could not discover in what condition this substance was, because the small quantity of powder did not exceed two decigrams, and, moreover, more than half of it was silica. After several experiments I saw that it was not chromium, and the comparative tests that I made proved t o me that it certainly was not. uranium. I had sought t o compare the highest degrees of oxidation, but I must remark that vanadium is found partly in the lower degree (26). In one of his letters Berzelius mentioned to Wohler an unfortunate accident: " . . . As Sefstrom came home t o Fahhm," said he, "to take up there the study of the vanadium alloy, a student spilled about one lot (ten grams) of dissolved vanadium oxide in such a way that none of it could be saved. Now he has nothing with which he can work, and must repeat the entire preparation process on the slag" (27). In May, 1830, a careful comparison of vanadium and uranium was made in Berzelius' laboratory. It was found that vanadium f o m s two series of compounds, the vanadic and the vanadous, but Berzelius and Sefstrom

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did not succeed in isolating the metal. Sefstrom died at Stockholm on November 30, 1845, a t the age of fifty-eight years. Wohler's researches (45) proved that he had been ~ r r e c in t believing that the ore del Rio bad analyzed in 1801 really contained vanadium instead of chromium (26). This mineral is now known as vanadinite, PhClv3Pbz(VO&. The final step in the discovery of vanadium was accomplished by the English chemist, Sir Henry Enfield Roscoe, who was born in London on January 7, 1833. When he was nine years old the family moved to LiverSIREDWARD (T. E.) THORPE, 1845-1925 pool. One of his first schoolmasters English chemist famous for his rereported that "Roscoe is a nice boy, search on the specific volumes of liquids but he looks about him too much, in relation to their chemical constitution, and for his work on the oxides of and does not know his irregular verbs" phosphorus and the compounds of va(36). His mother, who evidently nadium done in collaboration with Sir Henry Roscoe. Author of excellent did not object seriously to this habit textbooks of chemistry and of biagraof "lookina about." encourazed him phies and essays in historical chemistry. " to make chemical experiments at home and allowed him to transform one of the rooms into a laboratory. At the age of fifteen years the boy entered University College, London, where he studied under Thomas Graham and Alexander William Williamson. After graduating in 1853 with honors in chemistry, he went to Heidelberg to study quantitative analysis in the old monastery that had been transformed into a laboratory for Bunsen. After passing his doctor's examination summa cum l a d e , he collaborated with Bunsen in the famous researches on the chemical action of light. In the course of their long friendship Roscoe received from the great German master one hundred twenty-six letters, which he carefully preserved and finally presented in bound form to the Bunsen-Gesellschaft (38). When only twenty-four years old, Roscoe succeeded Frankland as professor of chemistry a t the University of Manchester. In the winter of 1862, when thousands of employees in the cotton-mills of Lancashire were thrown out of work because of the Civil War in America, Roscoe, in an effort to relieve the mental depression of the unemployed, instituted a series of popular "Science Lectures for the People." Roscoe, Tyndall, Huxley, and other noted scientists addressed large and appreciative audi-

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ences each week for eleven consecutive winters, and the printed lectures were afterward sold for a penny all over the world (39). In his teaching Roscoe emphasized the need of liberal culture as a basis for technical training (28). In about 1865 he found that some of the copper veins of the Lower Keuper sandstone of the Trias in Cheshire contained vanadium (37) and that one of the lime precipitates from this ore contained about two per cent. of it. It was from this unpromising material that Roscoe and Sir Edward Thorpe laboriously prepared the pure vanadium compounds needed for a thorough study of the element. When Roscoe investigated these compounds he found that vanadium is a trivalent element of the phosphoms group. He also discovered that what ~ ~had taken ~ for the~ metal was reallv the mononitride, VN, and that most.of the vanadium pounds studied by the Swedish chemists had contained oxygen. On August 26, 1867, Roscoe wrote t o

879

chemist, mineralogist, and crystallographerwho demonstrated the isomorphism of sulfur and selenium crystals obtained from carbon bisulfide soiutions OF these elements, and showed that the ~ vanadates l are isomorphous i ~ with the phosphates. He also determined the crystal forms of many organic compounds, and wrote textbooks on crystallopraphy, metallurgy, and mineralogical and analytical chemistry.

Thorpe saying,

. . . I want you very much to stay with me till April to settle the vanadium and light matters and help me in London with my lectures. . . I have a t last found out about vanadium. The acid is VzOs like PzOs. The chloride VOC13 like POCl3 and the solid chlorides VOC12, VOC1, etc. This explains the isomorphism of the vanadate of lead and the corresponding phosphate and lots of other points. It becomes very interesting now . . . (40). On September 12 of the same year Roscoe wrote again to his assistant. Please ask Joseph [Heywood] to send me per book-post Pogg. Ann., vol. 98, in which volume is Rammelsberg's paper on the isomorphism of vanadates andphosphates. Thereisno doubt in my mind that vanadic acid is VzOs and i t will be exceedingly interesting to work out the vanadates which must all be explained as phosphates. The ordinary white NHa salt is NHaVOa (like NaP03) and is a meta-

~

880


MAY,1932

vanadate. The bi-vanadates can also be explained, but all need re-preparation and analysis. Did I tell you that we have now got V206, VzO4, V*03, VZOZ(I wish we had V also!), V202Cls, V202C14, V202C12,or VOCII, VOCI,, VOCI. At St. Andrews I saw Professor Heddle; he has a crystal half apatite and half vanadinite, and he threw out the suggestion long ago that vanadic acid is Vz06.. . (40). Five days later he sent Tborpe a detailed report of his experiments on the oxides of vanadium and said in conclusion, "The thing above all others necessary for us now is to get the metal" (40). Roscoe's first paper on the subject was the Bakerian Lecture read before the Royal Society on December 19, 1867. On February 14, 1868, with Sir Edward Thorpe as his assistant, he gave a demonstration lecture a t the Royal Institution in which he proved that the lemon-colored chloride to which Berzelius had assigned the formula VC13 actually contains oxygen. When the audience saw him pass the vapor from a few grams of this chloride, together with pure hydrogen gas, over red-hot carbon, and watched him test the resulting gas for carbon dioxide by passing i t into clear baryta water, it was convinced that Berzelius' formula must be incorrect. Roscoe proved by analysis that the lemon-colored chloride is an oxychloride now known as vanadyl chloride, VOCZ (12), (29). When he began his researches on vanadium, its compounds were listed a t f 35 per ounce, and the metal itself was unknown. After all attempts a t direct reduction of the oxides had failed, Roscoe attempted to reduce vanadium &chloride, VC12, with hydrbgen. Rigorous exclusion of oxygen and moisture was necessary, and, since vhadium metal reacts violently with glass and porcelain, the chloride was placed in platinum boats inside a porcelain tube. The tube itself could not be made of platinum because of the porosity of that metal a t red heat. When he heated the tube, hydrochloric acid gas came off in "torrents," and continued to be evolved in decreasing quantity for from forty to eighty hours. When it finally ceased to come off, the tube was cooled and the boat was found t o contain "a light whitish grey-colored powder, perfectly free from chlorine." When Roscoe examined this powder under the microscope, he found that it reflected light powerfully and that it consisted of "a brilliant shining crystalline metallic mass possessing a bright silverwhite lustre." Roscoe's paper announcing the isolation of metallic vanadium was read before the Royal Society on June 16,1869 (33). While studying a t Heidelberg, S u Edward Thorpe read in a French periodical on popular science that the Copley Medal had been awarded to Sir Henry E. Roscoe. His letter of congratulation brought the following reply: In the first place let me thank you for your letter and congratulations upon the great French discovery! Many of these Parisian

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wonders have after all turned out myths-and this last is, I believe, no exception-the expression "Medaille de Copley" is, so far as I am aware, the French (and bad French, too!) for the "Bakerian Lecture." I am, however, none the less obliged to you for your good wishes on this occasion, and for all the valuable help which in many ways you gave me (41). Roscoe's textbooks of chemistry were unusually successful, passed through edition after edition, and were translated into Russian, Italian, Hungarian, Polish, Swedish, modern Greek, Japanese, Urdu, Profcswr ifChrmistry at tlw i.nirers!ty of \IanIcelandic, Bengali, Turkish, cherttr. Cullnbor tor wtth hun.;m it! rcsrarclles in h t l l o r of excrlltnt tcrthooksand -~ , Malavalam, and Tamil. ohotochcm~~trv. treatises an pure and applied chemistry. His autobiography (42) was written with great charm, and the "Treatise on Chemistry" by Roscoe and Schorlemmer is familiar to all chemists. Sir Henry's last years were spent on his beautiful estate at Woodcote in southern England. Here Lady Roscoe took endless pleasure in the cultivation of flowers and flowering shrubs and in entertaining her husband's distinguished guests. "My father," said Miss Roscoe, "delighted to bring foreigners, and the more heterogeneous they were the more he was pleased. I remember one luncheon party of late years, consisting of a Chinamau, a Japanese, a Czech, a German, and our three selves, and the Occidentals were much the quietest of the party" (43). After enjoying a serene old age, Sir Henry E. Roscoe died suddenly on December 18, 1915, during an attack of angina pectoris. In 1927 J. W. Marden and M. N. Rich of the research st& of the Westinghouse Lamp Company obtained metallic vanadium 99.9% pure by heating a mixture of vanadic oxide, metallic calcium, and calcium chloride in an electric furnace for an hour at a temperature of about 1400° Fahren?

-

~

-

~

-

-

~~~~

882


MAY,1932

heit. When the resulting mass was cooled and stirred into cold water. beads of pure metallic vanadium separated out (35). The principal use of this metal is for removing air bubbles from steel in order t o prevent the formation of blow-boles in the finished castings. The vanadium combines with both the oxygen and nitrogen of the bubbles, forming oxides and nitrides that float with the slag and are skimmed off. The small amount of vanadium, ranging from 0.05 to 0.5%, remaining in the steel profoundly alters its properties, greatly increasing its toughness. elasticity, and tensile strength. , Thus themetal that Sefstrom and Berzelius named for the ancient Swedish goddess of beauty has come to play an important utilitarian rBle in the construction of locomotive frames, driving axles, and large shaftings for electrical machinery. Literature Cited ( I ) DELRIO, ''Analysis of an Alloy of Gold and Rhodium from the Parting House at Mexico," Annals of Phil. [2], 10,256 (Od., 1825). ( 2 ) PoccENnoRFa, "Biosraphisch-Literarisches Handw6rterbuch zur Geschichte der exakten Wissenschaften," 5 vols., Verlag Chemie, Leipzig, 1863-1926. Articles on Hatchett, del Rio, and Sefstr6m. "Outline of the Properties and Habitudes of the Metallic Substance (3) HATCHETT, lately discovered by Charles Hatchett, Esq., and by him denominated Columbium." Nicholson's 1. 121. .. 1. 3 2 4 (Tan... 1802): . . Crell's Ann.. 37. 197-201. 25770, 352-64 (1802). (.4.) "New Metal Columbium." Nicholson's 3.. . 14.. 181 (Tune. .- . 1806). ( 5 ) THOMSON, "History of Chemistry." Vol. 2, p l b u m and Bentley, London, 1831, p. 231. ''Briefwecb~elzwischen J. Berzelius und F. W6hler." Vol. 2, Verlag (6) WALLACH, von Wilhelm Engelmann, Leipzig, 1901, p. 544. (7) BALKE,"Metals of the Tungsten and Tantalum Groups," Ind. Eng. Chem., 21, 1002-7 (Nov., 1929); BALKEAND EDGARF. SMITH,"Observations an Columbium," J. Am. Chem. Soc., 30, 1637-68 (Nov., 1908); BALKE,"The Atomic Weight of Tantalum," I. Am. Chem. Soc., 32, 1127-33 (Oct., 1910). (8) "American Chemical Industries. Fansteel Products Co., Inc.," I& Eng. Chem., 22, 1409-12 (Dec., 1930). (9) "Biographical Account of Mr. Ekeberg, Assistant Professor of Chemistry a t Upsla," Annals fo, Phil. [I], 4, 241-3 (Oct., 1814); Kongl. Vetenskaps Academiens Handlingar, 1813, p. 276. "On the Identity of Columbium and Tantalum," Nicholson's J., 25, (10) WOLLASTON, 23-8 (Jan., 1810). (11) ROSE,H.. "On a New Metal, Pelopium, Contained in the Bavarian Tantalite," Phil. Mag. [3], 29, 409-16 (Nov., 1846); Obituary of H. Rose, J. Chem. SOL., 17, 43740 (Proc. of Mar. 31, 1864). "Histoire de la Chimie," Vol. 2, Baudry e t Cie, Paris, 1891, pp. 341-5. (I?) JAGNAUX, (13) %DEnBAUM, "Jac Berzelius Bref," Vol. 3, part 6 , Almqvist and Wiksells, Upsala. 1912-1914, pp. 18-20. (14) Ibid., Vol. 3, part 6, p. 25. (15) Ibid., Vol. 1, part 3, p. 123. (16) Ihid., Vol. 1, part 3, p. 40.

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T H E DISCOVERY OF THE ELEMENTS.

VII

883

GILBS,"Obse~ationson Niobium, Tantalum, and Titanium," Chem. News, 95, "Das Niob, seine Darstellung 1-3,37-9 (Jan. 4 and Jan. 25. 1907); VON BOLTON, und Seine Eigenschaften," Z. Elektrochem., 13, 145-9 (Apr., 1907). "Rare Metals," Fansteel Products Co., N. Chicago, 1929, pp. 7-22. BALKE,"The Production and Uses of Ductile Tantalum," Chem. Met. E7q.. 27, 1271-3 (Dec. 27, 1922). MAR~GNAC, "Recherches sur les Combinaisons du Niobium," Ann. chim. phys. [4], 8, 5 7 5 (May, 1866); "Recherches sur les Combinaisons du Tantale," Ann. chim. pkys. [4], 9, 249-76 (Nov., 1866). DEL RIO. ''Discovery of Chromium in the Brown Lead of Zimirpan," Gilb. Ann., 71, 7. COLLET-DESCOTILS, ''Analy~ede la mine b m e de plomb de Zimapan, dans le royaume du Mexique, envoyhe par M. Humboldt, et dans laquelle M. del Rio dit avoir dCcouvert un nauveau mhtal," Ann. chim. phys. [I], 53,268-71 (1805). WALLACH, "Briefwech~elzwischen J. Berzelius und F. Wbhler." ref. (6), Vol. 1, p. 336. Letter of Feb. 6, 1831. "ZUT Erimemng an Friedrich Wahler," Ber., 15, 3170 (Dec., VON HOFMANN, AND EMILIEWOHLER. ''Justus Liehig's und Friedrich Wbhler's 1882); HOFMANN Briefwechsel," Vol. 1, F. Vieweg und Sohn, Braunschweig, 1888, pp. 38-9. "Jac S~DERBAU M , Berzelius Bref," ref. (13), Vol. 2, part 4, pp. 98-9. SEFSTROM, "Sur le Vanadium, metal nouveau, trouvh dans du fer en banes de Eckersholm, forge qui tire sa mine de Taberg dans le Sm&laud," Ann. chim, phys., 46, 1 0 5 1 1 (1831). WALLACH. "Briefwechsel zwischen 1.Berzelius und F. WOhler," ref. (6). . . Vol. 1. pp. 340-1. S c ~ u s r s nAND SHIPLEV."Britain's Heritape - of Science." Constable and Co.. London, 1917, pp. 149-50. ROSCOE,"On Vanadium, One of the ~ r i v a i e n Group t of Elements." Phil. Mag. + 141, 35, 307-14 (Apr., 1868). "Alchemv in Old New En~land." - . -1.CHEM.EDUC..8,2094 (Oct., 1931): . . NEWELL. "Colonial Chemistry. I. New England," ibid., 2, 1 6 1 4 (Mar., 1925). HATCHETT. "An Analvsis of the Earthy Substance from New South Wales, called Sydneia, or Terra Australis," .?richolson's J.,2, 72-80 (May, 1798). EKEBERG. "Of the Proverties of the Earth Yttria, compared with those of Glucine: uf I'ossils, in which thc first of these 1:artlts is cuntainrd; and of thr I)i,rwc ry of a new Subsrancc of a nletallic Nature (I'antaliom,,'' .Vir/inlson's I . 3,251-5 (LJrr 1802). Roscoe, "Researches on Vanadium. Part 11." Phil. Mag. [4], 39, 1 4 6 5 0 (Feb., 1870). FANSTEEL PRODUCTS CO., INC., "Metallic Tantalum," J. &EM. EDUC.,2, 1168-9 (Dec., 1925); VON BOLTON, "Das Tantal, seine Darstellung und seine Eigenschaften," Z. Elektrochem., 11, 45-51 (Jan. 20, 1905). "Vanadium New Member of World's Metal Family," J. C ~ E ME. ~ u c . 4, , 686 (May, 1927); MARDEN AND RICH, "Vanadium," Ind. Eng. Chem., 19, 786-8 (July, 1927). THOEPE,"The Right Honourable Sir Henry Enfield Roscoe," Longmans, Green and Co.. London, 1916, p. 18. Ibid., p. 123. Ibid.,p. 26. IM.,pp. 3&9. Ibid.. pp. 12530.

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(33) (34)

(35)

(36) (37) (38) (39) (40)

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(41) THORPE,"The Right Honourable Sir Henry Enfield Roscoe," ref. (36), p. 129. (42) ROSCOE."The Life and Experiences of Sir Henry Enfield Roscoe," Macmillan, London, 1906. 420 pp. (43) THORPE,"The Right Honourable Sir Henry Enfield Roscoe," ref. (36), pp. 199-200. Cilb. Ann., 18, 118 (1804). (44) HIJMBOLDT, (45) WOHLER,Pogg. Ann., 21,49 (1831). (46) C. A. BROWNE,"Some Relations of Early Chemistry in America to Medicine," J. CHEW.Eouc., 3, 268-70 (Mar., 1926). (47) WATERS,"A Sketch of the Life of John Winthrap the Younger. Founder of Ipswich. Massachusetts, in 1633." printed for the Ipswich Historical Sac., 1899, P. 76. Poem oq,Winthrop by B. Tompsan. (48) BLomsmm, "Uber die Siiuren der Tantalgruppe-Mineralien:' J. prakt. Chem., 97, 37-50 (Heft 1, 1866); Oefversigt af Akad. Fdrh.. 21, 541 (1864). (49) Morssm, "Nouvean traitement de la niobite; prbparation et propribtb de la fonte de niobium." Compt. rend., 133, 20-5 (July, 1901). (50) DBLRIO, "Elementos de Orictognosia." "Bl6meus d'Orictognosie ou de la connoissance des Fossiles, dispos6s suivant k s primipes de Werner, A l'usage du CollPge royal des mines du Mexique," Imprimerie de Zuniga et Ontiveros, Mexico City, 1795. Review in Ann. chim. phys. [I], 21, 2 2 1 4 (Feb., 1797).

The discovery of the elements. VII. Columbium ... - ACS Publications

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