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Transcriber's Note.

This is Paper 40 from the Smithsonian Institution United States National Museum Bulletin 240, comprising Papers 34-44, which will also be available as a complete e-book.

The front material, introduction and relevant index entries from the Bulletin are included in each single-paper e-book.

Corrections are listed at the end of the e-book.

SMITHSONIAN INSTITUTION

UNITED STATES NATIONAL MUSEUM

BULLETIN 240

SMITHSONIAN PRESS

MUSEUM OF HISTORY AND TECHNOLOGY

CONTRIBUTIONS FROM THE MUSEUM OF HISTORY AND TECHNOLOGY

_Papers 34-44_ _On Science and Technology_

SMITHSONIAN INSTITUTION . WASHINGTON, D.C. 1966

_Publications of the United States National Museum_

The scholarly and scientific publications of the United States National Museum include two series, _Proceedings of the United States National Museum_ and _United States National Museum Bulletin_.

In these series, the Museum publishes original articles and monographs dealing with the collections and work of its constituent museums--The Museum of Natural History and the Museum of History and Technology--setting forth newly acquired facts in the fields of anthropology, biology, history, geology, and technology. Copies of each publication are distributed to libraries, to cultural and scientific organizations, and to specialists and others interested in the different subjects.

The _Proceedings_, begun in 1878, are intended for the publication, in separate form, of shorter papers from the Museum of Natural History. These are gathered in volumes, octavo in size, with the publication date of each paper recorded in the table of contents of the volume.

In the _Bulletin_ series, the first of which was issued in 1875, appear longer, separate publications consisting of monographs (occasionally in several parts) and volumes in which are collected works on related subjects. _Bulletins_ are either octavo or quarto in size, depending on the needs of the presentation. Since 1902 papers relating to the botanical collections of the Museum of Natural History have been published in the _Bulletin_ series under the heading _Contributions from the United States National Herbarium_, and since 1959, in _Bulletins_ titled "Contributions from the Museum of History and Technology," have been gathered shorter papers relating to the collections and research of that Museum.

The present collection of Contributions, Papers 34-44, comprises Bulletin 240. Each of these papers has been previously published in separate form. The year of publication is shown on the last page of each paper.

FRANK A. TAYLOR _Director, United States National Museum_

CONTRIBUTIONS FROM THE MUSEUM OF HISTORY AND TECHNOLOGY: PAPER 40

HISTORY OF PHOSPHORUS

_Eduard Farber_

THE ELEMENT FROM ANIMALS AND PLANTS 178

EARLY USES 181

CHEMICAL CONSTITUTION OF PHOSPHORIC ACIDS 182

PHOSPHATES AS PLANT NUTRIENTS 185

FROM INORGANIC TO ORGANIC PHOSPHATES 187

PHOSPHATIDES AND PHOSPHAGENS 189

NUCLEIN AND NUCLEIC ACIDS 192

PHOSPHATES IN BIOLOGICAL PROCESSES 197

MEDICINES AND POISONS 198

_Eduard Farber_

HISTORY OF PHOSPHORUS

_The "cold light" produced by phosphorus caused it to be considered a miraculous chemical for a long time after its discovery, about 1669. During the intervening three centuries numerous other chemical miracles have been found, yet phosphorus retains a special aura of universal importance in chemistry. Many investigators have occupied themselves with this element and its diverse chemical compounds. Further enlightenment and insight into the ways of nature can be expected from these efforts._

_Not only is the story of phosphorus a major drama in the history of chemistry; it also illustrates, in a spectacular example, the growth of this science through the discovery of connections between apparently unrelated phenomena, and the continuous interplay between basic science and the search for practical usage._

THE AUTHOR: _Eduard Farber is a research professor at American University, Washington, D.C., and has been associated with the Smithsonian Institution as a consultant in chemistry._

When phosphorus was discovered, nearly three centuries ago, it was considered a miraculous thing. The only event that provoked a similar emotion was the discovery of radium more than two centuries later. The excitement about the _Phosphorus igneus_, Boyle's _Icy Noctiluca_, was slowly replaced by, or converted into, chemical research. Yet, if we would allow room for emotion in research, we could still be excited about the wondrous substance that chemical and biological work continues to reveal as vitally important. It is a fundamental plant nutrient, an essential part in nerve and brain substance, a decisive factor in muscle action and cell growth, and also a component in fast-acting, powerful poisons. The importance of phosphorus was gradually recognized and the means by which this took place are characteristic and similar to other developments 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.

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 Wolfenbuettel, 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]

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 _Methode 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 Francois 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 Emile Kopp (1844), by Wilhelm Hittorf (1824-1914) and, in its practical application, by Anton Schroetter (1802-1875).[15]

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]

Chemical Constitution of Phosphoric Acids

In a long article on phosphorus, Edmond Willm wrote in 1876: "For a century, urine was the only source from which phosphorus was obtained. After Gahn, in 1769, recognized the presence of phosphoric acid in bones, Scheele indicated the procedure for making phosphorus from them."[19] Actually, Gahn used at first hartshorn (_Cornu cervi ustum_), and Scheele doubted, until he checked it himself, that his esteemed friend was right. A few years later, Scheele corrected Gahn's assumption that the _sal microcosmicum_ was an ammonia salt; instead, it is "a tertiary neutral salt, consisting of _alkali minerali fixo_ (i.e., sodium), _alkali volatili_, and _acido phosphori_."[20]

In the years after 1770, phosphorus was discovered in bones and many other parts of various animals. Treatment with sulfuric acid decomposed these materials into a solid residue and dissolved phosphoric acid. Many salts of this acid were produced in crystalline form. Heat resistance had been considered one of the outstanding characteristics of phosphoric acid. Now, however, in the processes of drying and heating certain phosphates, it became clear that three kinds of phosphoric acids could be produced: _ortho_, _pyro_, and _meta_.

Berzelius cited these acids as examples of compounds which are ISOMERIC. This word was intended to designate compounds which contain the same number of atoms of the same elements but combined in different manners, thereby explaining their different chemical properties and crystal forms. It was in 1830 that Berzelius propounded this companion of the concept, ISOMORPHISM, which was to collect all cases of equal crystal form in compounds in which equal numbers of atoms of different elements are put together in the same manner. Together, the two concepts of isomerism and isomorphism seemed to cover all the known exceptions from the simplest assumption as to specificity and chemical composition.

However, only a few years later Thomas Graham (1805-1869) proved that the three phosphoric acids are not isomeric. He used the proportion of 2 P to 5 O in the oxide which Berzelius had thought justified at least until "an example of the contrary could be sufficiently established."[21] Refining the techniques of Gay-Lussac (1816) and several other investigators, Graham characterized the three phosphoric acids as "a terphosphate, a biphosphate, and phosphate of water." Actually, this was the wrong terminology for what he meant and formulated as trihydrate, bihydrate, and monohydrate of phosphorus oxide. In his manner of writing the formulas, each dot over the symbol for the element was to indicate an atom of oxygen; thus, he wrote:

... :: .. ... . . H^{3} P H^{2} P and H P.[22]

Graham had come to this understanding of the phosphoric acids through his previous studies of "Alcoates, definite compounds of Salts and Alcohol analogous to the Hydrates" (1831). Liebig started from analogies he saw with certain organic acids when he formulated the phosphoric acids with a constant proportion of water (aq.) and varying proportions of "phosphoric acid" (P) as follows:

2 P 3 aq. phosphoric acid 3 P 3 aq. pyrophosphoric acid 6 P 3 aq. metaphosphoric acid.

Salts are formed when a "basis," i.e., a metal oxide, replaces water. When potassium-acid sulfate is neutralized by sodium base, the acid-salt divides into Glauber's salt and potassium sulfate, which proves the acid-salt to be a mixture of the neutral salt with its acid. Sodium-acid phosphate behaves quite differently. After neutralization by a potassium "base" (hydroxide), the salt does not split up; a uniform sodium-potassium phosphate is obtained. Therefore, phosphoric acid is truly three-basic![23]

This result has later been confirmed, but the analogy by means of which it had been obtained was very weak, in certain parts quite wrong.

The acids from the two lower oxides of phosphorus were also considered as three-basic. Adolphe Wurtz (1817-1884) formulated them in 1846, according to the theory of chemical types:

(PO)... O^{3} phosphoric acid H^{3}

(PHO).. O^{2} phosphorus acid H^{2}

(PH^{2}O). O hypophosphorous acid.[24] H

Further proof for these constitutions was sought in the study of the esters formed when the acids react with alcohols.

Among the analogies and generalizations by which the research on phosphoric acid was supported, and to the results of which it contributed a full share, was the new theory of acids. Not oxygen, Lavoisier's general acidifier, but reactive hydrogen determines the character of acids. In this brief survey, it seems sufficient just to mention this connection without describing it in detail.

The study of phosphoric acids led to important new concepts in theoretical chemistry. The finding of polybasicity was extended to other acids and formed the model that helped to recognize the polyfunctionality in other compounds, like alcohols and amines. The hydrogen theory of acids was fundamental for further advance. In another dimension, it is particularly interesting to see that large-scale applications followed almost immediately and directly from the new theoretical insight. The first and foremost of these applications was in agriculture.

Phosphates as Plant Nutrients

One hundred years after the discovery of "cold light," the presence of phosphorus in plants and animals was ascertained, and its form was established as a compound of phosphoric acid. This knowledge had little practical effect until the "nature" of the acid, in its various forms, was explained through the work of Thomas Graham. From it, there started a considerable technical development.

At about that time (1833), the Duke of Richmond proved that the fertilizing value of bones resided not in the gelatin, nor in the calcium, but in the phosphoric acid. Thus, he confirmed what Theodore de Saussure had said in 1804, that "we have no reason to believe" that plants can exist without phosphorus. Unknowingly at first, the farmer had supplied this element by means of the organic fertilizers he used: manure, excrements, bones, and horns. Now, with the value of phosphorus known, a search began for mineral phosphates to be applied as fertilizers. Jean Baptiste Boussingault (1802-1887), an agricultural chemist in Lyons, traveled to Peru to see the guano deposits. Garcilaso de la Vega (ca. 1540 to ca. 1616) noted in his history of Peru (1604) that guano was used by the Incas as a fertilizer. Two hundred years later, Alexander von Humboldt revived this knowledge, and Humphry Davy wrote about the benefits of guano to the soil. Yet, the application of this fertilizer developed only slowly, until Justus Liebig sang its praise. Imports into England rose and far exceeded those into France where, between 1857 and 1867, about 50,000 tons were annually received.