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[9] described methods for obtaining this acid, and Marggraf showed its chemical peculiarities. They did not necessarily establish phosphorus as a new element. To do that was not as important, at that time, as to conjecture on analogies with known substances. Underlying all its unique characteristics was the analogy of phosphorus with sulfur. Like sulfur, phosphorus can burn in two different ways, either slowly or more violently, and form two different acids. The analogy can, therefore, be extended to explain the results in both groups in the same way. In the process of burning, the combustible component is removed, and the acid originally combined with the combustible is set free. Whether the analogy should be pursued even further remained doubtful, although some suspicion lingered on for a while that phosphoric acid might actually be a modified sulfuric acid. Analogies and suspicions like these were needed to formulate new questions and stimulate new experiments. They are cited here for their important positive value in the historical development, and not for the purpose of showing how wrong these chemists were from our point of view, a point of view which they helped to create.
The widespread interest in the burning of sulfur and of phosphorus, naturally, caught Lavoisier’s attention. In his first volume of Opuscules Physiques et Chimiques (1774), he devoted 20 pages to his experiments on phosphorus. He amplified them a few years later[10] when he attributed the combustion to a combination of phosphorus with the “eminently respirable” part of air. In the Méthode de Nomenclature Chimique of 1787, the column of “undecomposed substances” lists sulfur as the “radical sulfurique,” and phosphorus, correspondingly, as the “radical phosphorique.” The acids are now shown to be compounds of the “undecomposed” radicals, the complete reversion of the previous concept of this relationship. A part of the old analogy remained as far as the acids are concerned: sulfuric acid corresponds to phosphoric; sulfurous acid to phosphorous acid with less oxygen than in the former.[11]
Early Uses
In the 18th century, phosphorus was a costly material. It was produced mostly for display and to satisfy curiosity. Guillaume François Rouelle (1703-1770) demonstrated the process in his lectures, and, as Macquer reports, he “very often” succeeded in making it.[12] Robert Boyle had the idea of using phosphorus as a light for underwater divers.[13] A century later, “instant lights” were sold, with molten phosphorus as the “igniter,” but they proved cumbersome and unreliable.[14] Because white phosphorus is highly poisonous, an active development of the use in matches occurred only after the conversion of the white modification into the red had been studied by Émile Kopp (1844), by Wilhelm Hittorf (1824-1914) and, in its practical application, by Anton Schrötter (1802-1875).[15]
Figure 3.—Distillation apparatus (1849) for refining crude phosphorus. The crude phosphorus is mixed with sand under hot water, cooled, drained, and filled into the retort. The outlet of the retort, at least 6 cm. in diameter, is partially immersed in the water contained in the bucket. A small dish, made from lead, with an iron handle, receives the distilled phosphorus. (From Hugo Fleck, Die Fabrikation chemischer Produkte ... page 90.)
The most exciting early use, however, was in medicine. It is not surprising that such a use was sought at that time. Any new material immediately became the hope of ailing mankind—and of striving inventors.[16] Phosphorus was prescribed, in liniments with fatty oils or as solution in alcohol and ether, for external and internal application. A certain Dr. Kramer found it efficient against epilepsy and melancholia (1730). A Professor Hartmann recommended it against cramps.[17] However, in the growing production of phosphorus for matches, the workers experienced the poisonous effects. In the plant of Black and Bell at Stratford, this was prevented by inhaling turpentine. Experiments on dogs were carried out to show that poisoning by phosphorus could be remedied through oil of turpentine.[18]