in the history of science. This paper was written in order to summarize these various means which led to the highly complex ways of present research.

The Element from Animals and Plants

It was a little late to search for the philosophers’ stone in 1669, yet it was in such a search that phosphorus was discovered. Wilhelm Homberg (1652-1715) described it in the following manner: Brand, “a man little known, of low birth, with a bizarre and mysterious nature in all he did, found this luminous matter while searching for something else. He was a glassmaker by profession, but he had abandoned it in order to be free for the pursuit of the philosophical stone with which he was engrossed. Having put it into his mind that the secret of the philosophical stone consisted in the preparation of urine, this man worked in all kinds of manners and for a very long time without finding anything. Finally, in the year 1669, after a strong distillation of urine, he found in the recipient a luminant matter that has since been called phosphorus. He showed it to some of his friends, among them Mister Kunkel [sic].”[1]

Neither the name nor the phenomenon were really new. Organic phosphorescent materials were known to Aristotle, and a lithophosphorus was the subject of a book published in 1640, based on a discovery made by a shoemaker, Vicenzo Casciarolo, on a mountain-side near Bologna in 1630.[2] Was the substance new which Brand showed to his friends? Johann Gottfried Leonhardi quotes a book of 1689 in which the author, Kletwich, claims that this phosphorus had already been known to Fernelius, the court physician of King Henri II of France (1154-1189).[3] To the same period belongs the “Ordinatio Alchid Bechil Saraceni philosophi,” in which Ferdinand Hoefer found a distillation of urine with clay and carbonaceous material described, and the resulting product named escarbuncle.[4] It would be worth looking for this source; although Bechil would still remain an entirely unsuccessful predecessor, it does seem strange that in all the distillations of arbitrary mixtures, the conditions should never before 1669 have been right for the formation and the observation of phosphorus.

Figure 1.—The alchemist discovers phosphorus. A painting by Joseph Wright (1734-1779) of Derby, England.

For Brand’s contemporaries at least, the discovery was new and exciting. The philosopher Gottfried Wilhelm von Leibniz (1646-1716) considered it important enough to devote some of his time (between his work as librarian in Hanover and Wolfenbüttel, his efforts to reunite the Protestant and the Catholic churches, and his duties as Privy Councellor in what we would call a Department of Justice) to a history of phosphorus. This friend of Huygens and Boyle tried to prove that Kunckel was not justified in claiming the discovery for himself.[5] Since then, it has been shown that Johann Kunckel (1630-1703) actually worked out the method which neither Brand nor his friend Kraft wanted to disclose. Boyle also developed a method independently, published it, and instructed Gottfried Hankwitz in the technique. Later on, Jean Hellot (1685-1765) gave a meticulous description of the details and a long survey of the literature.[6]

Figure 2.—Galley-oven, 1869. The picture is a cross section through the front of the oven showing one of the 36 retorts, the receivers for the distillate, and the space in the upper story used for evaporating the mixture of acid solution of calcium phosphate and coal. (According to Anselme Payen, Précis de Chimie industrielle, Paris, 1849; reproduced from Hugo Fleck, Die Fabrikation chemischer Produkte aus thierischen Abfällen, Vieweg, Braunschweig, 1862, page 80 of volume 2, 2nd group, of P. Bolley’s Handbuch der chemischen Technologie.)

To obtain phosphorus, a good proportion of coal (regarded as a type of phlogiston) was added to urine, previously thickened by evaporation and preferably after putrefaction, and the mixture was heated to the highest attainable temperature. It was obvious that phlogiston entered into the composition of the distillation product. The question remained whether this product was generated de novo. In his research of 1743 to 1746, Andreas Sigismund Marggraf (1709-1782) provided the answer. He found the new substance in edible plant seeds, and he concluded that it enters the human system through the plant food, to be excreted later in the urine. He did not convince all the chemists with his reasoning. In 1789, Macquer wrote: “There are some who, even at this time, hold that the phosphorical (‘phosphorische’) acid generates itself in the animals and who consider this to be the ‘animalistic acid.’”[7]

Although Marggraf was more advanced in his arguments than these chemists, yet he was a child of his time. The luminescent and combustible, almost wax-like substance impressed him greatly. “My thoughts about the unexpected generation of light and fire out of water, fine earth, and phlogiston I reserve to describe at a later time.” These thoughts went so far as to connect the new marvel with alchemical wonder tales. When Marggraf used the “essential salt of urine,” also called sal microcosmicum, and admixed silver chloride (“horny silver”) to it for the distillation of phosphorus, he expected “a partial conversion of silver by phlogiston and the added fine vitrifiable earth, but no trace of a more noble metal appeared.”[8]

Robert Boyle had already found that the burning of phosphorus produced an acid. He identified it by taste and by its influence on colored plant extracts serving as “indicators.” Hankwitz