The discovery of red phosphorus - ACS Publications


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The Discovery of Red Phosphorus (1847) by Anton von Schrotter (1802-1875) MORITZ KOHN

New York City

(Translated by Ralph E. Oesfier, Uniwersity of Cincinnati)

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CIENTIFIC chemistry in Vienna is about 100 years old. It hegan when Schrotter was called to the Vienna Polytechnikum in 1843. To him is due the discovery of red phosphorus, an accomplishment of equal significance to the scientific and technical worlds. He presented his findings before the Vienna Academy of Sciences on December 9,1847. Schrotter is the acknowledged discoverer of red phosphorus, even though others had doubtless had this substance in their hands. It was well known that a red by-product sometimes appears when phosphorus is burned; i t had also been noted that sticks of the element acquire a red coating when they are exposed to the light. Berzelius' stated that phosphorns occurs in two auotropic modifications. The first, the familiar yellow phosphorus, fumes in the air. When exposed to sunlight, i t is transformed to the red form that does not oxidize or fume when in contact with air. When distilled, the red modification reverts to the yellow form. Kopp2 in this same year reported that acidic by-products are formed during the preparation of ethyl iodide, together with "a solid, pulverulent residue, whose color is dark red. This material, if thoroughly washed, is insipid, odorless, has little attraction for the oxygen of the air, and is nothing but phosphorus in its red modification."' However, numerous other chemists of the time regarded the red substance as a lower oxide of phosphorus. This question was decisively settled by Schriitter's work. The Vienna Academy inaugurated (1850) its series of Memoirs with his fruitful paper, "A new allotropic state of phosphorus." It is the first paper (pp. 1to 12) of the first volume of this important record of r e ~ e a r c h . ~He found that sunlight changes yellow into red phosphorus, even when moisture and atmospheric oxygen are rigidly excluded. The red product was separated from the residual yellow phosphorus by treatment with carbon disulfide. Red phosphorus was also prepared from the yellow variety by heating i t to about 250°C. in an inert gas. Heating to higher temperatures reconverted the red modification to the yellow one. Industrial chemists quickly became interested in this new material. Arthur Alhright erected, near Birmingham, a small plant to carry out Schrotter's procedure on an industrial scale. He obtained his patent in 185L6 1 Benzs~ms, Yahresbericht, 23, 51 (1844).

"mil Kopp (1817-1875) was a well-known teacher of industrial chemistry. He succeeded A. P. Bolley in the chair of chemical technology at the Zurich Polytechnikum. His successor was G. Lunge. a KOPP,Compt. rend., 18, 872 (1844). See also Scmik~en,I. prekt. Chem. (I), 51, 155 (1850); Compt. rend., 31, 138 (1850).

Schrotter had pointed out that red phosphorns might be valuable in the match industry. Future developments substantiated this astute prediction. Swedish (safety) matches ignite only when scratched against a rough surface that contains nonpoisonous red phosphorus. The head of the ordinary old-style match contains toxic yellow phosphorus and lights when drawn across any rough surface. The decided difference in cost was a distinct handicap to the widespread introduction and use of the safety match. However, various enlightened governments, for reasons of public safety and health, outlawed the use of yellow phosphorus in matches. The natural consequence was a great expansion of the safety match industry.= The Montyon Prize was awarded to Schrotter by the Paris Academy in 1856. This honor was designed to acknowledge the services of those who had made notable contribution to industrial-hygienic conditions. At the announcement of the award the Academy emphasized the high scientific value of Schrotter's work. In 1875, a t a ceremonious meeting of the Vienna Academy, the renowned Joseph Stefan, professor of physics in the University of Vienna, eulogized his recently deceased colleague, Schrotter: "The Vienna Academy of Sciences may regard the award of the Montyon Prize for its first memoir as an omen that its activity from that time forward would be dedicated to the increase of science and therefore also to the benefit of mankind." Anton Schrotter was horn on November 26, 1802, a t Olmiitz. His father was an apothecary. He hegan his university studies in medicine, but later switched to natural science (chemistry and physics). I n 1830 he received an appointment in the Technical Institute a t Graz; in 1843 he was called to the Polytechnical Institute in Vienna. After 25 years of outstanding service in this school, he was appointed (1868) director of the Mint.' His worthy academic successor was Heinrich Hlasiwetz. Busts of Schrotter and Hlasiwetz still stand in the old lecture hall of the Vienna Polytechnikum.

(Continued on wgege 554) MUSPRATT,"Theoretical, Practical and Analytical Chemistry in Use in Art and Trade," Glasgow, London, New York, 1860, Vol. 2, p. 686. "nother Austrian chemist, Karl Auer von Welsbach, was the discoverer of still another method of producing fire by friction. He obtained a patent in 1905 for the preparation of pyrophoric alloys (cerium steel). Many prominent scientists have been Master of the Mint. No less a personage than Isaac Newton filled this post. In 1854, when the celebrated astronomer and physicist John Herschel retired, his successor at the London Mint was the chemist, Thomas Graham. Pelouze was Master of the Mint in Paris. After his death (1868) the world-renowned chemist, J. B. Dulvas took over this responsible position. J. S. Stas occup~eda hke post in Brussels.

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Anton von Schrotter, the Discoverer of Red Phosphorus (See page 522)

DISCOVERY OF RED PHOSPHORUS (1847) BY ANTON VON SCHROTTER (1802-1875) (Conlinued from Nge 522) Ill health forced Schrotter to retire in 1874. In 1875 A. W. Hofmann compiled a comprehensive report on the development of the chemical industrie~.~He enlisted the aid of friends and colleagues, each an expert in his particular field. Schrotter contributed the chapter on "Phosphorus and Matches." This was his last effort; he died on April 15, 1875. Deserved honors came to Schrotter both from his native country and from abroad. On May 14, 1847, he and 32 other prominent Austrian scientists were Bericht iiber die Entwickelung der chemisehen Industrie wahrend dcs letzten Jahrzehnts im Verein mit Freunden uhd Fachgenossen, erstattet yon Dr. A. W. Hofmann. Rrunswick, 187.5-77,

elected to the newly created Academy of Sciences. From 1850 he was the General Secretary of this body, the most eminent Austrian scientific corporation. Honorary doctorates were conferred on him by various universities; learned societies were proud to elect him to membership. I n 1873, the German Chemical Society conferred honorary membership on him, together with such notables as E. Frankland (London); R. Fresenius (Wiesbaden) ; J. S. Stas (Brussels) ; A. Williamson (London); A. Wurtz (Paris); N. Zinin (St. Petersburg). Emperor Franz Joseph raised him to the nobility in 1857, with the formal title: Schrotter, Ritter van Kristelli.