Phosphorus-From Discovery to Commodity
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Indian Journal of Chemical Technology Vol. 12, January 2005, pp. 108-122 Phosphorus-From discovery to commodity Jaime Wisniak* Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel 84105 Phosphorus is nearly the most widely and evenly distributed element on the surface of the earth, and probably the most subdivided. From a laboratory curiosity in the seventeeth century, it became recognized as a fundamental element of life and a large chemical commodity, improving agriculture and industry like very few other discoveries by men have done. Discovery of phosphorus nor the phenomenon was really new. Organic Mankind has been aware of luminiscent phosphorescent materials were known to Aristotle, phenomena for thousands of years; they are and a lithophosphorus was the subject of a book mentioned in different mythology and in the Bible. published in 1640, based on a discovery made by a Glowworms and fireflies, and the luminescent shoemaker, Vicenzo Casciarol, on Mons Padernus, organisms in sea water or on decaying fish and wood near Bologna in 16303. Casciarol claimed that the were long familiar sights and attracted the curiosity of stone was so heavy that he thought it contained a men. The Greeks called the planet Venus by the name heavy metal and that after it had been calcined in Phosphorus (morning star, from the Greek φϖζ = charcoal fire and cooled, it glowed in the darkness light + φερω = to bear), because it was visible before with a reddish light. The stone was called sunrise and after sundown. Venus took the name litheosphorus and also Bologna stone or lapis phosphorus in the morning and Hesperus in the bononiensis. Johann Gotfried Leonhardi (1746-1823) evening (hespera = afternoon, occident). Homer says: quotes a book of 1689 in which the author, Kletwich, "Phosphorus, the son of Heavens and Dawn leaves in claims that his phosphorus had already been known to the morning the Ocean river and by elevating its Jean Fernelius (1497-1558), the court physician of sacred forehead announces to the Earth the proximity King Henri II of France (1519-1559). In his book of the divine light, holds in his hand a torch and goes about the history of chemistry Ferdinand Hoefer flying before the chariot of Dawn". Pliny writes: "The (1811-1878) tells about finding in the publication fish on this account called the lamp fish rises to the “Ordinatio Alchid Bechil Saraceni Philosophi” the surface of the sea, and on calm nights gives a light description of a process in which urine was distilled with its fiery tongue, which puts out from his mouth" with clay and carbonaceous material, resulting in a 4 1a, and then "Glow worms shine like fires at night product named escarboucle . owing to the colour of their sides and loins, now A new variety of luminescent stones was giving a flash of light by opening their wings and now accidentally discovered in 1674 by Christian Adolph darkened by closing them"1b. Baldouin (1632-1682), at Grosshain, Saxony. It In the tenth century, Japanese used as decroative resulted from the strong ignition of the residue, material the luminescence of lacs that they prepared obtained by evaporating a solution of chalk in nitric from oyster shells. At the beginning of the eighteenth acid. Baldouin was a member of the Imperial century, appeared the first synthetic luminescent Academy of Sciences, and as such received the material in Europe, the stone of Bologna, also called cognomen Hermes. He therefore named his light sponge, and made of barium suphide. These preparation Phosphorus Hermeticus or, alternatively artificial products, which after exposure released the Magnes Luminaris because it attracted light like a absorbed light when placed in the dark arouse much magnet attracts iron particles. The name was changed excitement from the time of their discovery at the later to Baldwin's phosphorus. In 1675 Badouin beginning of the seventeenth century. issued a booklet describing this phosphor, but did not According to Farber2, neither the name phosphorus disclose the method of preparation5,6. The procedure ___________ was published first by Kunckel in his Laboratorium 7-9 *E-mail: [email protected] Chymicum . EDUCATOR 109 In the year 1669, phosphorus was accidentally that contributed many new facts to chemistry. He discovered in human urine as “a dark, unctuous, discovered mercury fulminate and nitric ester, and is daubing mass” by Hennig Brandt, a merchant and best known for his work on ruby glass and on alchemist of Hamburg, while searching for a liquid fulminate. In the third part of his book Laboratorium capable of transmuting silver into gold. Brandt was a Chymicum7 he gives an account of ruby glass and soldier in his youth, and it is said that later he became phosphorus, the two chemical discoveries which he “an uncouth physician who knew not a word of considers to be the most important of the century. In a Latin”10. In spite of this deficiency he married a following publication (1680) Kunckel described the wealthy wife, but after her death he lost the inherited properties of phosphorus more fully but did not money. In an attempt to regain his list financial provide details about the method of its preparation. standing, he was lured by the spell of alchemy to He had first obtained phosphorus in the form of a search for gold. His experiments made in 1669 led to black soap, which glowed in spots and did not shine a white, waxy substance that glowed so enchantingly continuously. In his own words: "A little of this soap in the dark. When his alchemical experiments ground up in clear water and shaken about gives a revealed the light-giving element Brandt called it cold very pleasant light, and some of the particles which fire (kaltes feuer). Brandt kept secret his method of remain attached to the glass above the water flash and obtaining phosphorus, but the news of the amazing twinkle like little stars… This soap has the property discovery soon spread throughout Germany11. that gunpowder put with it and merely left in the Wilhelm Homberg (1652-1715) described Brandt's warmth of the sun, takes fire of its own accord…A discovery in the following manner: Brand, “a Man man can write on paper with it, and if he has a piece little known, of low birth, with a bizarre and only as large as the head of a small pin, he can make mysterious nature in all he did, found this luminous unbelievable light back and forth with it on the paper matter while searching for something else. He was a until the little grain is worn off and cannot be seen... I glassmaker by profession, but he had abandoned it in have something on still another subject; a thing which order to be free for the pursuit of the philosophical is so subtle that, if it is allowed to warm up on the stone with which he was engrossed. Having put it into bare hand, it forthwith inflames and gives a furious his mind that the secret of the philosophical stone fire. The residuum, which is left behind, shows an consisted in the preparation of urine, this man worked orange colour and flashes and shines like the in all kinds of manners and for a long time without Smegma". The last quoted passage appears to contain finding anything. Finally he found in the recopied a the earliest known reference to the red modification of 13 luminant matter that has since been called phosphorus . phosphorus. He showed it to some of his friends, After visiting with Brandt, Kunckel wrote among them Mister Kunkel”. Homberg considered immediately to his friend, Johann Daniel Krafft phosphorus to consist of phlogiston united with an (1624-1697), a commercial agent from Saxony acid so that during combustion the phlogiston Dresden. Krafft, without replying to Kunckel’s letter, escaped, and the acid remained as a residue12. left immediately for Hamburg and bought the secret Johann Kunckel (1630-1702), a contemporary of from Brandt for 200 (thalers) dollars, Brandt, was the son of an alchemist in the court of the Although Kunckel did not describe the method for Duke of Holstein. In his youth he studied pharmacy, the preparation of his phosphorus, it seems that he glass-making, and assaying; worked in the Dresden accomplished it, as did other chemists after him, by laboratory of John George II, Elector of Saxony; evaporating putrid urine to the consistency of a syrup, taught chemistry in the medical school at Wittenberg mixing it with sand or brick dust, and distilling at a and later managed the glass-works in Benlin high temperature from a fortified (coated with clay) belonging to Frederick William, the Elector of retort, the beak of which delivered under water in the Brandenburg. According to Weeks11 his last years receiver. The silicic acid of the sand or brick dust were spent at the service of King Charles XI of liberated phosphoric acid from the phosphates of the Sweden, who conferred on him the titles Baron von urine and this was reduced by the carbonaceous Löwenstern and Counselor of Metals. Kunkel was one material, which was present13. According to of the most competent chemists of the seventeenth Homberg, Kunckel’s process was essentially as century. He was an exceptionally able experimenter follows: Fresh urine was evaporated nearly to 110 INDIAN J. CHEM. TECHNOL., JANUARY 2005 dryness, after which the black residue was allowed to subsequently exhibited in Hamburg was Baldouin’s putrefy in a cellar for several months. This material phosphorus, a phosphorescent form of calcium nitrate was heated, gently at first and then strongly, with that had been prepared by distiling a solution of chalk twice its weight of sand, in a retort leading to a in nitric acid15.