The Project Gutenberg EBook of History of Phosphorus, by Eduard Farber

This eBook is for the use of anyone anywhere at no cost and with
almost no restrictions whatsoever.  You may copy it, give it away or
re-use it under the terms of the Project Gutenberg License included
with this eBook or online at

Title: History of Phosphorus

Author: Eduard Farber

Release Date: September 20, 2010 [EBook #33766]

Language: English

Character set encoding: ISO-8859-1


Produced by Chris Curnow, Joseph Cooper, Louise Pattison
and the Online Distributed Proofreading Team at

Transcriber’s Notes

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 to typographical errors are underlined like this. Mouse over to view the original text.


Smithsonian Press Logo



From the
of History and

Papers 34-44
On Science and Technology


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

[Pg 177]

Contributions from
The Museum of History and Technology
Paper 40

History of Phosphorus

Eduard Farber










[Pg 178]

 Eduard Farber


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, [Pg 179]“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.

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[Pg 180] 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.

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[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[Pg 181] 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.

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[Pg 182] 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]

Figure 4.

Figure 4.—Apparatus for converting white phosphorus into the red allotropic form, 1851. Redistilled phosphorus is heated in the glass or porcelain vessel (g) which is surrounded by a sandbath (e) and a metal bath (b). Vessel (j) is filled with mercury and water; together with valve (k), it serves as a safety device. The alcohol lamp (l) keeps the tube warm against clogging by solidified vapors. Because of hydrogen phosphides, the operation, carried out at 260° C., had to be watched very carefully. (According to Arthur Albright, 1851; reproduced from Hugo Fleck, Die Fabrikation chemischer Produkte ..., page 112.)

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[Pg 183] his manner of writing the formulas, each dot over the symbol for the element was to indicate an atom of oxygen; thus, he wrote:

... ::   .. ...      . .

 H3  P    H2 P   and  H P.[22]

Figure 5.

Figure 5.—Oven for the calcination of bones, about 1870. “The operation is carried out in a rather high oven, such as shown.... The fresh bones are thrown in at the top of the oven, B. First, fuel in chamber F is lighted, and a certain quantity of bones is burnt on the grid D. When these bones are burning well, the oven is gradually filled with bones, and the combustion maintains itself without addition of other fuel. A circular gallery, C, surrounds the bottom of the oven and carries the products of combustion into the chimney, H. The calcined bones are taken out at the lower opening, G, by removing the bars of grid B.” (Translation of the description from Figuier, Merveilles de l’industrie, volume 3, 1874, page 537.)

Figure 6.

Figure 6.—An advertisement with view of plant for manufacturing superphosphate about 1867. (From E. T. Freedley, Philadelphia and its Manufacturers in 1867, page 288.)

[Pg 184] Figure 7.

Figure 7.—Florida hard-rock phosphate mining. (From Carroll D. Wright, The Phosphate Industry of the United States, sixth special report of the Commissioner of Labor, Government Printing Office, Washington, 1893, plate facing page 43.)

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:

[Pg 185]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) · · ·
O3     phosphoric acid

(PHO) · ·
O2     phosphorus acid

(PH2O) ·
O      hypophosphorous acid.[24]

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 Théodore 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.

The other great advance in the use of phosphatic plant nutrients started with Liebig’s recommendation (1840) to treat bones with sulfuric acid for solubilization. This idea was not entirely new; since 1832, a production of a “superphosphate” from bones and sulfuric acid had been in progress at Prague. At[Pg 186] Rothamsted in 1842, John Bennet Lawes obtained a patent on the manufacture of superphosphate. Other manufactures in England followed and were successful, although James Muspratt (1793-1886) at Newton lost much time and “some thousands of pounds” on Liebig’s idea of a “mineral manure.”

Figure 8.

Figure 8.—Florida land-pebble phosphate mining. (From Carroll D. Wright, The Phosphate Industry of the United States ..., plate facing page 58.)

It was difficult enough to establish the efficacy of bones and artificially produced phosphates in promoting the growth of plants under special conditions of soils and climate; therefore, the question as to the action of phosphates in the growing plant was not even seriously formulated at that time. The beneficial effects were obvious enough to increase the use of phosphates as plant nutrients and to call for new sources of supply. Active developments of phosphate mining and treating started in South Carolina in 1867, and in Florida in 1888.[25]

In a reciprocal action, more phosphate application to soils stimulated increasing research on the conditions and reactions obtaining in the complex and varying compositions called soil. The findings of bacteriologists made it clear that physics and chemistry had to be amplified by biology for a real understanding of fertilizer effects. After 1900, for example, Julius Stoklasa (1857-1936) pointed out that bacterial action in soil solubilizes water-insoluble phosphates and makes them available to the plants.[26]

Figure 9.

Figure 9.—Florida river-pebble phosphate mining. (From Carroll D. Wright, The Phosphate Industry of the United States ..., plate facing page 64.)

The insight into the importance of phosphorus in organisms, especially since Liebig’s time, is reflected in the work of Friedrich Nietzsche (1844-1900). This “re-valuator of all values” who modestly said of himself: “I am dynamite!” once explained the human temperaments as caused by the inorganic salts they contain: [Pg 187]“The differences in temperament are perhaps caused more by the different distribution and quantities of the inorganic salts than by everything else. Bilious people have too little sodium sulfate, the melancholics are lacking in potassium sulfate and phosphate; too little calcium phosphate in the phlegmatics. Courageous natures have an excess of iron phosphate.” (See volume 12 of Nietzsche’s Works, edit. Naumann-Kröner, Leipzig, 1886.) In this strange association of inorganic salts with human temperaments, the role of iron phosphate as a producer of courage is particularly interesting. What would a modern philosopher conclude if he followed the development of insight into the composition and function of complex phosphate compounds in organisms?

From Inorganic to Organic Phosphates

By the middle of the 19th century, the source of phosphorus in natural phosphates and the chemistry of its oxidation products had been established. The main difficulty that had to be overcome was that these oxidation products existed in so many forms, not only several stages of oxidation, but, in addition, aggregations and condensations of the phosphoric acids. Once the fundamental chemistry of these acids was elucidated, the attention of chemists and physiologists turned to the task of finding the actual state in which phosphorus compounds were present in the organisms. It had been a great advance when it had been shown that plants need phosphates in their soil. This led to the next question concerning the materials in the body of the plant for which phosphates were being used and into which they were incorporated. Similarly, the knowledge that animals attain their phosphates from the digested plant food called, in the next step of scientific inquiry, for information on the nature of phosphates produced from this source.

The method used in this inquiry was to subject anatomically separated parts of the organisms to chemical separations. The means for such separations had to be more gentle than the strong heat and destructive chemicals that had been considered adequate up to then. The interpretation of the new results naturally relied on the general advance of chemistry, the development of new methods for isolating substances of little stability, of new concepts concerning the arrangements of atoms in the molecules, and of new apparatus to measure their rates of change.[Pg 188]

Patented Sept. 13, 1892.
Fig. 1.

Fig. 2.
Inventor Thomas Parker
By his attorneys Howson and Howson
Witnesses: George Baumann John Revell

Figure 10.—Electric furnace for producing elemental phosphorus, invented by Thomas Parker of Newbridge, England, and assigned to The Electric Construction Corporation of the same place. The drawing is part of United States patent 482,586 (September 13, 1892). The furnace was patented in England on October 29, 1889 (no. 17,060); in France on June 23, 1890 (no. 206,566); in Germany on June 17, 1890 (no. 55,700); and in Italy on October 23, 1890 (no. 431). The following explanation is cited from the U.S. patent:

Figure 1 [shown here] is a vertical section of the furnace, and Fig. 2 is a diagram to illustrate the means for regulating the electro-motive force or quantity of current across the furnace.

F is the furnace containing the charge to be treated. It has an inlet-hopper at a, with slides AA, by which the charge can be admitted without opening communication between the interior of the furnace and the outer air.

B is a screw conveyer by which the charge is pushed forward into the furnace.

c´c´ are the electrodes, consisting of blocks or cylinders or the like of carbon fixed in metal socket-pieces c c, to which the electric-circuit wires d from the dynamo D are affixed. The current, as aforesaid, may be either continuous or alternating. c2c2 are rods of metal or carbon, which are used to establish the electric circuit through the furnace, the said rods being inserted into holes in conductors c3 (in contact with the socket-pieces c) and in the furnace, as shown.

g is the outlet for the gas or vapor, h the slag-tap hole, and x the opening for manipulating the charge, the said openings being closed by clay or otherwise when the furnace is at work.

I use coke or other form of carbon in the charge between the electrodes , the said coke being in contact with the said electrodes, so that complete incandescence is insured.

A means for varying the electro-motive force or quantity of current across the furnace with the varying resistance of the charge is illustrated by the diagram, Fig. 2. c´ c2 indicate the electrodes in the furnace, as in Fig. 1, and D is the dynamo and T its terminals. E represents the exciting-circuit. R R are resistances, and R S is the resistance-switch, which is operated to put in more or less resistance at R as the resistance of the charge in the furnace lessens or increases. This switch may be automatically operated, and a suitable arrangement for the purpose is a current-regulator such as is described in the specification of English Letters Patent No. 14,504, of September 14, 1889, granted to William Henry Douglas and Thomas Hugh Parker.

[Pg 189]

Fig 254.—Trempage á la presse.

Figure 11.—Dipping of matchsticks in France, about 1870. The frame which holds the matches so that one end protrudes at the bottom, is lowered over a pan containing molten sulfur. The sulfur-covered matches are then dropped into a phosphorous paste. See figure 12. (From Figuier, Merveilles de l’industrie, volume 3, 1874, page 575.)

Fig. 256.—Coupe du plateau á tremper les
allumettes chimiques dans la pâte de phosphore á chaud et au bain-marie.

Figure 12.—Pan for dipping matchsticks into phosphorus paste, about 1870. The letters on the picture are: A, matches; B, water bath; C, frame; D, plate; E, phosphorus paste; F, oven. The phosphorus paste of Böttger, 1842, contained 10 phosphorus, 25 antimony sulfide, 12.5 manganese dioxide, 15 gelatin. According to Figuier (page 579), R. Wagner substituted lead dioxide for the manganese dioxide. (From Figuier, volume 3, 1874, page 576.)

In the system of chemistry, as it developed in the first half of the 19th century, the new development can be characterized as the turn from inorganic to organic phosphates, from the substance of minerals and strong chemical interactions to the components in which phosphate groups remained combined with carbon-containing substances.

Phosphatides and Phosphagens

The important phosphorus compounds in organisms are much more complex than the simple salts, to which Nietzsche attributed such influence on man’s character. Long before he wrote, it was known that phosphoric acid combines not only with inorganic bases to form salts, but with alcohols to form esters. In the middle of the 19th century, Théophile Juste Pelouze (1807-1867) extended this knowledge to an ester of glycerol. This proved to be significant in several respects. Glycerol had been shown by Michel Chevreul (1786-1889) as the substance in fats that is released in the process of soap boiling, when the fatty acids are converted into their salts. That it has the nature of an alcohol had been demonstrated by Marcellin Berthelot. Instead of one “alcoholic” hydroxyl group, OH, like ethanol (the alcohol of fermentation), or two hydroxyl groups (like ethylene glycol), glycerol contains three such groups. It was the only “natural” alcohol known at that time. That this alcohol would combine with phosphoric acid could be predicted, but that the ester, as obtained by Pelouze, still contained free acidic functions and formed a water-soluble barium salt was a new experience.

[Pg 190]

Alcoholic Fermentation

Figure 13.—Survey of alcoholic fermentation, 1951. The “well-known scheme of alcoholic fermentation” according to Albert Jan Kluyver (1888-1956), presented before the Society of Chemical Industry in the Royal Institution, March 7, 1951. In Chemistry & Industry, 1952, page 136 ff., Kluyver restates that “... the fermentation of one molecule of glucose is indissolubly connected with the formation of two molecules of adenosine triphosphate (ATP) out of two molecules of adenosine diphosphate (ADP).”

[Pg 191] Shortly after this experience had been gained, it became valuable for understanding the chemical nature of a new substance extracted from a natural organ. This substance was named lecithin by its discoverer, Nicolas Théodore Gobley[27] (1811-1876), because he obtained it from egg yolk (in Greek, lékidos). He used ether and alcohol for this extraction. Had he used water and mineral acid instead, he would not have found lecithin, but only its components. As Gobley and, slightly later, Oscar Liebreich (1839-1908), subjected lecithin to treatment with boiling water and acid, they separated it into three parts. One of them was the glycerophosphoric acid of Pelouze, the second was the well-known stearic acid of Chevreul, but the third was somewhat mysterious. This third substance was the same as one previously noticed when nerves had been subjected to an extraction by boiling water and acid and, therefore, called nerve-substance or neurine. Adolf Friedrich Strecker (1822-1871) established the identity of this neurine with a product he had extracted from bile and which went under the name of choline. Adolphe Wurtz (1817-1884) succeeded in synthesizing this substance from ethylene oxide, CH2.O.CH2 and trimethylamine N(CH3)3.[28] Thus, all three parts were identified, and Strecker put them together to construct a chemical formula for lecithin, glycerophosphoric acid combined with a fatty acid and with choline (a hydrate of neurine).

N (CH3)3 Choline
Fatty AcidsGlycerophosphate
according to Strecker

This formula was not quite correct. Richard Willstätter showed that an internal neutralization takes place between the amino group and the free acidic residue. This is expressed in his lecithin formula of 1918.

Lecithin (1918)

Lecithin (1918)

When the aim was to distill elementary phosphorus out of an organic material, it did not matter whether this was fresh or putrified. For obtaining lecithin out of egg yolk and similar materials, it was essential to use it in fresh condition. Otherwise, enzymes would have decomposed it. Through more recent work, four enzymes have been separated, which act specifically in decomposing lecithin. Enzyme A removes one fatty acid and leaves a complex residue, called lysolecithin, intact. Enzyme B attacks this residue and splits off the remaining fatty acid group from it, enzyme C liberates only the choline from lecithin, and enzyme D opens lecithin at the ester bond between glycerol and phosphoric acid. This is shown in the following diagram.

Enzymatic Splitting of Lecithins
ALecithinLysolecithin and fatty acids.
BLysolecithinGlycero-phospho-choline and fatty acids.
CLecithinPhosphatidic acid and choline.
DLecithinPhosphoryl choline and diglyceride.

Several fatty acids can be present in lecithin from various sources: palmitic and oleic acid, besides the stearic acid which at first had been thought the only one involved. In another group of extracts from brain or nerve tissue, amino-ethanol H2NCH2CH2OH is found instead of the choline of lecithin. The variations include the alcohol, to which the fatty acids and choline phosphate are attached, for example, glycerol can be replaced by the so-called meat-sugar, inositol, which has six hydroxyl groups in its hexagon-shaped molecule [Pg 192]C6H6(OH)6.

Figure 14.

Figure 14.—Eduard Buchner (1860-1917) received the Nobel Prize in Chemistry for his discovery of cell-free fermentation, the first step in finding the role of phosphate in fermentations (1907).

The generally similar behavior of these phosphate-and fat-containing substances was emphasized by Ludwig Thudichum (1829-1901). He coined the name phosphatides for this group of substances from seeds and nerves.[29] His work on the phosphates in brain substance aroused particular interest. When William Crookes drew his highly imaginative picture of an “evolution” of the chemical elements, he put into it “phosphorus for the brain, salt for the sea, clay for the solid earth....”[30] But phosphatides occur in many places of organisms, in bacteria, in leaves and roots of plants, in fat and tissues of animals. And where phosphatides are found, there are also enzymes that specifically act on them. They are called phosphatases to imply that they split the phosphatides. In addition, enzymes are present, which transfer phosphate groups from one compound to another. They are more abundant in seeds of high fat content than in the more starch-containing seeds, but even potatoes and orange juice have phosphatases.[31]

Thus, from phosphatides, phosphoric acid is generated, and they could also be called phosphagens. Since 1926, however, the name phosphagens has been reserved for a group of organic substances that release their phosphoric acid very readily. The link between phosphorus and carbon is provided by oxygen in the phosphatides, by nitrogen in the phosphagens. In vertebrates, the basis for the phosphoric acid is creatine, whereas invertebrates have arginine instead.

Creatine Phosphate Creatine Phosphate
Arginine Phosphate Arginine phosphate

Nuclein and Nucleic Acids

All parts of an organism are essential for life. Only with this in mind does it make sense to say that the most important part of the cell is its nucleus. From the nuclei of cells in pus and in salmon sperm, Johann Friedrich Miescher (1811-1887) obtained a peculiar kind of substance, which he named nuclein (1868). Its phosphate content was easily discovered, but to find the exact proportions and the nature of the other components required special methods of separation from phosphatides and other proteins. It was difficult to develop such methods at a time when little was known about the properties, and particularly[Pg 193] the stability, of a nuclein. For preparing nuclein from yeast cells, Felix Hoppe-Seyler (1825-1895) described the following details: Yeast is dispersed in water to extract soluble materials, like salts or sugars. After a few hours, the insoluble material is separated, washed once more with water, and then extracted with a very dilute solution of sodium hydroxide. The slightly alkaline solution, freed from insoluble residues, is slowly added to a weak hydrochloric acid. A precipitate forms which is separated by filtration, washed with dilute acid, then with cold alcohol, and finally extracted by boiling alcohol. The dried residue is the nuclein.[32] It contains six percent phosphorus. A little more washing with water, a slightly longer treatment with acid or alcohol gives products of lower phosphorus content. Many experimental variations were necessary to establish the procedure that leads to purification without alteration of the natural substance.

This was also true for the methods of chemical degradation, carried out in order to find the components of nucleins in their highest state of natural complexity. It was learned for example, that the special kind of carbohydrate present in nucleins was very susceptible to change under the conditions of hydrolysis by acids. Phoebus Aaron Theodor Levine (1869-1940), therefore, used the digestion by a living organism. With E. S. London, he introduced a solution of nucleic acid into, e.g., the gastrointestinal segment of a dog through a gastric fistula and withdrew the product of digestion through an intestinal fistula. Fortunately, the products obtained in such degradations were not new in themselves. The carbohydrate in this nucleic acid proved to be identical with D-ribose, which Emil Fischer had artificially made from arabinose and named ribose to indicate this relationship (1891). The nitrogenous products of the degradation were identical with substances previously prepared in the long study of uric acid. In the course of this study, Emil Fischer established uric acid and a number of its derivatives as having the elementary skeleton of what he called “pure uric acid,” abbreviated to purine. Out of Adolf Baeyer’s work on barbituric acid came the knowledge of pyrimidine and its derivatives.

Figure 15.

Figure 15.—Albrecht Kossel (1853-1927) received the Nobel Prize in Medicine and Physiology in 1910 for his work on nucleic substances, which contain a high proportion of phosphorus. The chemical bonds of this phosphorus in the molecules of nucleic substances were determined in later work. (Photo courtesy National Library of Medicine, Washington, D.C.)

From these findings, together with what Oswald Schmiedeberg (1838-1921) had established concerning the presence of four phosphate groups in the molecule (1899), Robert Feulgen (1884-1955) constructed the following scheme of a nucleic acid. Feulgen’s formula of 1918 is:

Phosphoric acid—Carbohydrate—Guanine

Phosphoric acid—Carbohydrate—Cytosine

Phosphoric acid—Carbohydrate—Thymine

Phosphoric acid—Carbohydrate—Adenine

Of the four basic components on the right, thymine occurs in the nucleic acid from the thymus gland. Yeast contains uracil instead. The difference between these two bases is one methyl group: thymine is a 5-methyluracil. In all of these basic substances, the structure of urea


is involved, and they form pairs of oxidized and reduced states: [Pg 194]

(reduced) Adenine + (oxidized) Thymine
(oxidized) Guanine + (reduced) Cytosine













The carbohydrate is ribose or deoxyribose.





Fischer and Piloty, 1891



The exact position of phosphoric acid was established after long work and verified by synthesis.[33]

A compound of adenine, ribose, and phosphoric acid was found in yeast, blood, and in skeletal muscle of mammals. From 100 grams of such muscle, 0.35-0.40 grams of this compound were isolated. If the muscle is at rest, the compound contains three molecules of phosphoric acid, linked through oxygen atoms. It was named adenosine triphosphate or adenyltriphosphoric acid,[34] usually abbreviated by the symbol ATP. It releases one phosphoric acid group very easily and goes over in the diphosphate, ADP, but it can also lose 2 P-groups as pyrophosphoric acid and leave the monophosphate, AMP.

Adenosine Triphosphate: Adenine, D-Ribose, Phosphoric

This change of ATP was considered to be the main source of energy in muscle contraction by Otto Meyerhof.[35] The corresponding derivatives of guanine, cytosine, and uracil were also found, and they are active in the temporary transfer of phosphoric acid groups in biological processes.

Thus, the study of organic phosphates progressed from the comparatively simple esters connected with fatty substances of organisms to the proteins and the nuclear substances of the cell. The proportional amount of phosphorus in the former was larger than in the latter; the actual importance and function in the life of organisms, however, is not measured by the quantity but determined by the special nature of the compounds.[Pg 195]

Figure 16.

Figure 16.—Otto Meyerhof (1884-1951) received one-half of the Nobel Prize in Medicine and Physiology in 1922 for his discovery of the metabolism of lactic acid in muscle, which involves the action of phosphates, especially adenosine duophosphates. (Photo courtesy National Library of Medicine, Washington, D.C.)

Figure 17.
Figure 17.

Figure 17.—Arthur Harden (1865-1940), left, and Hans A. S. von Euler-Chelpin (b. 1875), right, shared the Nobel Prize in Chemistry in 1929. Harden received it for his research in fermentation, which showed the influence of phosphate, particularly the formation of a hexose diphosphate. Euler-Chelpin received his award for his research in fermentation. He found coenzyme A which is a nucleotide containing phosphoric acid.

[Pg 196]

Figure 18.

Figure 18.—George de Hevesy (b. 1885) received the Nobel Prize in Chemistry in 1943 for his research with isotopic tracer elements, particularly radiophosphorus of weight 32 (ordinary phosphorus is 31).

Figure 19.
Figure 19.

Figure 19.—Carl F. Cori (b. 1896) and his wife, Gerty T. Cori (1896-1957) received part of the Nobel Prize in Medicine and Physiology in 1947 for their study on glycogen conversion. In the course of this study, they identified glucose 1-phosphate, now usually referred to as “Cori ester,” and its function in the glycogen cycle. (Photo courtesy National Library of Medicine, Washington, D.C.)

[Pg 197] The study of this function is the newest phase in the history of phosphorus and represents the culmination of the previous efforts. This newest phase developed out of an accidental discovery concerning one of the oldest organic-chemical industries, the production of alcohol by the fermentative action of yeast on sugar. A transition of carbohydrates through phosphate compounds to the end products of the fermentation process was found, and it gradually proved to be a kind of model for a host of biological processes.

Specific phosphates were thus found to be indispensable for life. In reverse, the wrong kind of phosphates can destroy life. As a result, an important part of the new phase in phosphorus history consisted in the study—and use—of antibiotic phosphorus compounds.

Phosphates in Biological Processes

The first indication that phosphorus is important for life came from the experience that plants take it up from the substances in the soil. They incorporate it in their body substance. What makes phosphorus so important that they cannot grow without it? The next insight was that animals acquire it from their plant food. It is then found in bones, in fat and nerve tissue, in all cells and particularly in the cell nuclei. What are its functions there?

The answers to such questions were developed from the study of a long-known process, the conversion of carbohydrates into carbon dioxide and alcohol by yeast. It started with Eduard Buchner’s discovery of 1890, that fermentation is produced by a preparation from yeast in which all living cells have been removed. When yeast is dead-ground and pressed out, the juice still has the ability to produce fermentation.

It is strange, but in many ways characteristic for the process of science, that the “riddle” of phosphorus in life was solved by first eliminating life. In such “lifeless” fermentations, Arthur Harden found that the conversion of sugar begins with the formation of a hexose phosphate (1904). The “ferment” of yeast, called zymase, proved to be a composite of several enzymes. Hans von Euler-Chelpin isolated one part of zymase, which remains active even after heating its solution to the boiling point. From 1 kilogram of yeast, he obtained 20 milligrams of this heat-stable enzyme, which he called cozymase and identified as a nucleotide composed of a purine, a sugar, and phosphoric acid.[36] In the years between the two World Wars, zymase was further resolved into more enzymes, one of them the coenzyme I, which was shown to be ADP connected with another molecule of ribose attached to the amide of nicotinic acid, or diphosphopyridine nucleotide:

Coenzyme I
Figure 20.

Figure 20.—Fritz A. Lipmann (b. 1899) shared with Hans Adolf Krebs the Nobel Prize in Medicine and Physiology in 1953 for his work on coenzyme A. He discovered acetyl phosphate as the substance in bacteria, which transfers phosphate to adenylic acid.

[Pg 198]

Figure 21.

Figure 21.—Alexander R. Todd (b. 1907) received the Nobel Prize in Chemistry in 1957 for his research on nucleotides. He determined the position of the phosphate groups in the molecule and confirmed it by synthesis of dinucleotide phosphates.

Its function is connected with the transfer of hydrogen between intermediates formed through phosphate-transferring enzymes. Fermentation proceeds by a cascade of processes, in which phosphate groups swing back and forth, and equilibria between ATP with ADP play a major role.

Many of the enzymes are closely related to vitamins. Thus, cocarboxylase A, which takes part in the separation of carbon dioxide from an intermediate fermentation product, is the phosphate of vitamin B1. Others of the B vitamins contain phosphate groups, for example those of the B2 and B6 group, and in B12, one lonely phosphate forms a bridge in the large molecule that contains one atom of cobalt: C63H90N14O14PCo. The formation of vitamin A from carotine occurs under the influence of ATP.

The first stages in fermentation are like those in respiration, which ends with carbon dioxide and water. These two are the materials for the reverse process in photosynthesis. When light is absorbed by the chlorophyll of green plants, one of the initial reactions is a transfer of hydrogen from water to a triphosphopyridine nucleotide, which later acts to reduce the carbon dioxide. Under the influence of ATP, phosphoglyceric acid is synthesized and further built up by way of carbohydrate phosphates to hexose sugars and finally to starch. In many starchy fruits, a small proportion of phosphate remains attached to the end product.

The synthesis of proteins is under the control of deoxyribonucleic acid or ribonucleic acid, abbreviated by the symbols DNA and RNA. The genes in the nucleus are parts of a giant DNA molecule. RNA is a universal constituent of all living cells. Where protein synthesis is intense, the content in RNA is high. Thus, the spinning glands of silkworms are extraordinarily rich in RNA.[37]

In his research on the radioactive isotope P32, George de Hevesy gained some insight into the surprising mobility of phosphates in organisms: “A phosphate radical taken up with the food may first participate in the phosphorylation of glucose in the intestinal mucose, soon afterwards pass into the circulation as free phosphate, enter a red corpuscle, become incorporated with an adenosine triphosphoric-acid molecule, participate in a glycolytic process going on in the corpuscle, return to circulation, penetrate into the liver cells, participate in the formation of a phosphatide molecule, after a short interval enter the circulation in this form, penetrate into the spleen, and leave this organ after some time as a constituent of a lymphocyte. We may meet the phosphate radical again as a constituent of the plasma, from which it may find its way into the skeleton.”[38] Much has been added in the last 30 years to complete this picture in many details and to extend it to other biochemical processes, including even the changes of the pigments in the retina in the visual process, or in the conversion of chemical energy to light by bacteria and insects.

Medicines and Poisons

In the delicate balance of these processes, disturbances may occur which can be remedied by specific phosphate-containing medicines. Thus, adenosine phosphate has been recommended in cases of angina[Pg 199] pectoris and marketed under trade names like sarkolyt, or in compounds named angiolysine. A considerable number of physiologically active organic phosphates can be found in the patent literature.[39] Yeast itself is considered to be a valuable food additive.

On the other hand, there are phosphate compounds that act as poisons. One group of such compounds was discovered in 1929 by W. Lange, who wrote: “Of interest is the strong action of mono-fluorophosphate esters on the human body—the effect is produced by very small quantities.”[40] Diisopropyl fluorophosphate has since become a potential agent for chemical warfare. It inactivates an enzyme which controls the transmission of nerve impulses to muscle, acetylcholine esterase.

Organic esters of phosphoric acids are used as insecticides. The hexa-ethylester of tetraphosphoric acid, prepared by Gerhard Schrader by heating triethylphosphate with phosphorus oxychloride,[41] actually contains tetraethylpyrophosphate (TEPP) among others. Bayer’s Dipterex, the dimethyl ester of 2,2,2-trichloro-1-hydroxyethyl-phosphonate, has been modified to dimethyl-2,2-dichlorovinyl-phosphate and is especially active against the oriental fruit fly.[42]

[Pg 200] Bayer's L 13/59 (Dipterex)

Bayer's L 13/59


Octamethylpyrophosphoramide: Schradan


Figure 22.
Figure 22.

Figure 22.—Arthur Kornberg (b. 1918) and Severo Ochoa (b. 1905) shared the Nobel Prize in Medicine and Physiology in 1959. Kornberg received it for research on the biological synthesis of deoxyribonucleic acid. In particular, he found that four triphosphate components and a small amount of the end product as a “template” had to be present for the enzymatic synthesis. Ochoa received his share of the prize for research in ribonucleic acid and deoxyribonucleic acid. In particular, Ochoa synthesized polyribonucleotides and used the radioactive isotope, P32. The synthetic polyribonucleotides were found to resemble the natural substances in all essentials.

Figure 23.

Figure 23.—Melvin Calvin (b. 1911) received the Nobel Prize in Chemistry in 1961 for his research in photosynthesis, in which he specified the function of phosphoglyceric acid as an intermediate in the synthesis of carbohydrates from carbon dioxide and water by green plants.

The story of phosphorus, which began 300 years ago, has acquired new importance in this century. Many scientists have contributed to it: 13 of them have received Nobel Prizes for work directly bearing on the chemical and biological importance of phosphorus compounds. In chronological order, they are: Eduard Buchner, Albrecht Kossel, Otto Meyerhof, Arthur Harden, Hans von Euler-Chelpin, George de Hevesy, Carl F. Cori, Gerty T. Cori, Fritz Lipmann, Lord Alexander Todd, Arthur Kornberg, Severo Ochoa, and Melvin Calvin. The developers of industrial production and commercial utilization of phosphate compounds have had other rewards.

Some impression of the continuing growth in this field[43] can be gained from the following data.

Phosphate Rock
annually “sold or used by producer” in the United States in million long tons (2,240 lbs.)

1880      0.2
1890 0.5
1900 1.5
1910 2.655
1920 4.104
1930 3.926
1940 4.003
1945 5.807
1950 11.114
1955 12.265
1955 (world: about 56)
1960 17.202
1962 19.060

Sources: U.S. Bureau of the Census. Historical Statistics of the United States 1789-1945 (1949); Statistical Abstract of the United States.

Elemental Phosphorus
annually produced in the United States in short tons (2,000 lbs.)

1939     43,000

Source: U.S. Department of Commerce.


[1] Wilhelm Homberg, Mémoires Académie, 1666-1699 (Paris, 1730), vol. 10, under date of April 30, 1692, pp. 57-61.

[2] Fortunio Licetus, Lithiophosphorus sive de lapide Bononiensi (Venice, 1640).

[3] Cited in Peter Joseph Macquer Chymisches Wörterbuch, 2nd ed. (Leipzig: Weidmann, 1789), vol. 4, p. 508, footnote “c” as “Kletwich (de phosph. liqu. et solid. 1689, Thes. II).”

[4] Ferdinand Hoefer, Histoire de la Chimie (Paris, 1843), vol. 1, p. 339.

[5] G. W. von Leibniz, Mémoires Académie (Paris, 1682); Akademie der Wissenschaften, Miscellanea Berolinensia (Berlin, 1710), vol. 1, p. 91.

[6] Jean Hellot, Mémoires Académie 1737 (Paris, 1766), under date of November 13, 1737, pp. 342-378.

[7] Macquer, op. cit. (footnote 3), p. 551.

[8] A. S. Marggraf, Akademie der Wissenschaften, Miscellanea Berolinensia (Berlin, 1743), vol. 7, 342 ff.; see also Wilhelm Ostwald Klassiker der Exakten Naturwissenschaften (Leipzig: Engelmann, 1913), no. 187.

[9] G. Hanckewitz, [Hankwitz], Philosophical Transactions of the Royal Society of London, 1724-1734, abridged (London, 1809), vol. 7, pp. 596-602.

[10] Antoine Laurent Lavoisier, “Sur la Combustion du Phosphore de Kunckel, Et sur la nature de l’acide qui resulte de cette Combustion,” Mémoires Académie 1777, (Paris, 1780), pp. 65-78.

[11] Guyton de Morveau and others, Méthode de Nomenclature Chimique, Proposée par MM. de Morveau, Lavoisier, Bertholet, & de Fourcroy (Paris, 1787), plate 9.

[12] Macquer, op. cit. (footnote 3), p. 513.

[13] Marie Boas, Robert Boyle and Seventeenth Century Chemistry (New York: Cambridge University Press, 1958), p. 226; see also Wyndham Miles, “The History of Dr. Brand’s Phosphorus Elementarus,” Armed Forces Chemical Journal (November-December 1958), p. 25.

[14] Archibald Clow and Nan L. Clow, The Chemical Revolution (London: Batchworth Press, 1952), p. 451.

[15] Émile Kopp, Comptes-rendus hebdomadaires des Séances de l’Académie des Sciences, Paris (1844), vol. 18, p. 871; Wilhelm Hittorf, Annalen der Chemie und Pharmazie, suppl. to vol. 4, p. 37; Anton Schrötter, Annales de Chimie et de Physique, series 3, vol. 24 (1848), p. 406; see also Schrötter’s report on “Phosphor und Zündwaaren” in A. W. von Hofmann, Bericht über die Entwicklung der Chemischen Industrie (Braunschweig: Vieweg, 1875), pp. 219-246.

[16] R. Glauber, Furni Novi Philosphici (Amsterdam, 1649), vol. 2, pp. 12 ff.

[17] Hermann Schelenz, Geschichte der Pharmazie (Berlin: Springer, 1904), p. 598.

[18] J. Personne, Comptes-rendus ..., Paris (1869), vol. 68, pp. 543-546.

[19] A. Wurtz, Dictionnaire de Chimie (Paris, 1876), vol. 2, part 2, p. 951.

[20] Karl W. Scheele, Nachgelassene Briefe und Aufzeichnungen, edit. A. E. Nordenskiöld (Stockholm: Norstedt, 1892), pp. 38, 144.

[21] J. J. Berzelius, Lehrbuch, transl. F. Wöhler (Dresden, 1827), vol. 3, part 1, p. 96.

[22] Thomas Graham, Philosophical Transactions of the Royal Society of London (1833), pp. 253-284.

[23] Justus Liebig’s Annalen der Pharmacie (1838), vol. 26, p. 113 ff.

[24] A. Wurtz, Annales de Chimie et de Physique, series 3, vol. 16 (1846), p. 190.

[25] Carroll D. Wright, The Phosphate Industry in the United States, sixth special report of the Commissioner of Labor (Washington, 1893).

[26] J. Stoklasa, Biochemischer Kreislauf des Phosphat-Ions im Boden, Centralblatt für Bakteriologie ... (Jena: Fischer, March 22, 1911), vol. 29, nos. 15-19.

[27] N. T. Gobley, Comptes-rendus ..., Paris (1845), vol. 21, p. 718.

[28] A. Wurtz, Comptes-rendus ..., Paris (1868), vol. 66, p. 772.

[29] L. Thudichum, Die chemische Constitution des Gehirns des Menschen und der Tiere (1901); see also H. Wittcoff, The Phosphatides (New York: Reinhold, 1951).

[30] William Crookes, British Association for the Advancement of Science, Reports (1887), sec. B, p. 573.

[31] J. E. Courtois and A. Lino, Progress in the Chemistry of Organic Natural Products, edit. L. Zechmeister (Vienna: Springer Verlag, 1961), vol. 19, p. 316-373.

[32] A. Wurt, Dictionnaire de Chimie, supp. part 2, [n.d.] p. 1087; A. Kossel, Zeitschrift für physiologische Chemie, series 3 (1879), p. 284.

[33] Alexander Todd, Les Prix Nobel en 1957 (Stockholm).

[34] Hans von Euler-Chelpin, Les Prix Nobel en 1929 (Stockholm).

[35] O. Meyerhof and E. Lundsgaard, Naturwissenschaften (Berlin, 1930), vol. 18, pp. 330, 787.

[36] K. Lohmann, Naturwissenschaften (Berlin, 1929), vol. 17, p. 624; C. H. Fiske and Y. Subbarow, Science (Washington, 1929), vol. 70, p. 381 f.

[37] J. Brachet, Scientia, Revista di Scienza (1960), vol. 95, p. 119.

[38] George de Hevesy, Les Prix Nobel en 1940 (Stockholm). See also Eduard Farber, Nobel Prize Winners in Chemistry, 2nd ed. (New York: Schuman, 1963), p. 179.

[39] See, e.g., Chemical Week, vol. 77 (September 3, 1955), p. 79 f.; J. Bolle, Chimie et Industrie (1960), vol. 83, p. 252.

[40] W. Lange, Berichte der Deutschen Chemischen Gesellschaft (Berlin, 1929), vol. 62, p. 793; vol. 65 (1932), p. 1598.

[41] Gerhard Schrader, U.S. patent 2,336,302 of 1943 (priority in Germany, 1938); S. A. Hall and M. Jacobson, Industrial and Engineering Chemistry (1943), vol. 40, p. 694.

[42] A. M. Mattsen and others, Journal of Agriculture and Food Chemistry (1955), vol. 3, p. 319.

[43] John B. Van Wazer, Phosphorus and its Compounds, 2 vols. (vol. 1, Chemistry; vol. 2 Technology, Biological Functions and Applications), New York: Interscience, 1958, 1961.


For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402—Price 25 cents


Aristotle, 179

Baeyer, Adolf, 193

Bechil, Achild, 179

Berthelot, Marcellin, 189

Berzelius, Jöns Jakob, 182

Black and Bell, plant at Stratford, 182

Boussingault, Jean Baptiste, 185

Boyle, Robert, 178, 179

Brand, H., 178, 179

Buchner, Hans, 197, 200

Calvin, Melvin, 200

Casciarolo, Vicenzo, 179

Chevreul, Michel, 189

Cori, Carl F., 200

Cori, Gerti T., 200

Crookes, William, 192

Davy, Sir Humphry, 185

De Hevesy, George, 198, 200

De la Vega, Garcilaso, 185

De Saussure, Théodore, 185

Euler-Chelpin, Hans von, 197, 200

Fernelius, Jean, 179

Feulgen, Robert, 193

Fischer, Emil, 193

Gahn, Johann Gottlieb, 182

Gay-Lussac, Joseph Louis, 182

Gobley, Nicolas Théodore, 191

Graham, Thomas, 182, 183, 185

Hankwitz, Gottfried, 180

Harden, Arthur, 197, 200

Hartmann, Immanuel Peter, 181

Hellot, Jean, 180

Henry II, King of France, 179

Hittorf, Wilhelm, 181

Hoefer, Ferdinand, 179

Holmberg, Wilhelm, 178

Hoppe-Seyler, Felix, 193

Humboldt, Alexander von, 185

Huygens, Christiaan, 179

Incas, 185

Kletwich, Johann Christopher, 179

Koppe, Émile, 181

Kornberg, Arthur, 200

Kossel, Albrecht, 200

Kraft, Johann Daniel, 179

Kramer, Dr. ——, 181

Kunckel, Johann, 179

Lange, W., 199

Lavoisier, Antoine Laurent, 181, 185

Laws, John Bennet, 186

Leibnitz, Gottfried Wilhelm von, 179

Lennox, Charles, third Duke of Richmond, 185

Leonhardi, Johann Gottfried, 179

Levine, Phoebus Aaron Theodor, 193

Liebig, Justus, 183, 185, 186

Liebreich, Oscar, 191

Lipmann, Fritz, 200

London, E. S., 193

Macquer, Peter Joseph, 180

Marggraf, Andreas Sigismund, 180

Meyerhof, Otto, 194, 200

Miescher, Johann Friedrich, 192

Muspratt, James, 186

Nietzsche, Friedrich, 186, 187, 189

Ochoa, Severo, 200

Pelouze, Théophile Juste, 189

Rouelle, Guillaume François, 181

Scheele, Karl W., 182

Schmiedeberg, Oswald, 193

Schrader, Gerhard, 199

Schrötter, Anton, 181

Stoklasa, Julius, 186

Strecker, Adolf Friedrich, 191

Thudichum, Ludwig, 192

Todd, Lord Alexander, 200

Willm, Edmond, 182

Willstätter, Richard, 191

Wurtz, Adolphe, 185, 191

Transcriber’s Notes

The following typographical errors have been corrected:

Page 180Abfällen, Vieweg, Braunschweig,” - had “Viewig”.

Page 188 “wires d from the dynamo D” - had “dynano”.

Page 191 “phosphate are attached, for example,” - had “attached, For”.

Page 192 “But phosphatides occur” - had “phosphatide soccur”.

Page 193 “the nucleic acid from the thymus” - had “nucleidic”.

Page 199 “acetylcholine esterase.” - had “acetylcholin”.

Page 200 “George de Hevesy, Carl F. Cori,” - comma added after Hevesy.

Footnote 39: “See, e.g., Chemical Week, vol. 77” - had “See. e.g.”

Index Entry: “Gahn, Johann Gottlieb, 182” - had “Gähn”

The spelling of “Bertholet” [Claude Louis Berthollet] is as given on the original title page of the work referenced in this paper.

Inconsistent hyphenation of chemical names has been retained.

End of the Project Gutenberg EBook of History of Phosphorus, by Eduard Farber


***** This file should be named 33766-h.htm or *****
This and all associated files of various formats will be found in:

Produced by Chris Curnow, Joseph Cooper, Louise Pattison
and the Online Distributed Proofreading Team at

Updated editions will replace the previous one--the old editions
will be renamed.

Creating the works from public domain print editions means that no
one owns a United States copyright in these works, so the Foundation
(and you!) can copy and distribute it in the United States without
permission and without paying copyright royalties.  Special rules,
set forth in the General Terms of Use part of this license, apply to
copying and distributing Project Gutenberg-tm electronic works to
protect the PROJECT GUTENBERG-tm concept and trademark.  Project
Gutenberg is a registered trademark, and may not be used if you
charge for the eBooks, unless you receive specific permission.  If you
do not charge anything for copies of this eBook, complying with the
rules is very easy.  You may use this eBook for nearly any purpose
such as creation of derivative works, reports, performances and
research.  They may be modified and printed and given away--you may do
practically ANYTHING with public domain eBooks.  Redistribution is
subject to the trademark license, especially commercial



To protect the Project Gutenberg-tm mission of promoting the free
distribution of electronic works, by using or distributing this work
(or any other work associated in any way with the phrase "Project
Gutenberg"), you agree to comply with all the terms of the Full Project
Gutenberg-tm License (available with this file or online at

Section 1.  General Terms of Use and Redistributing Project Gutenberg-tm
electronic works

1.A.  By reading or using any part of this Project Gutenberg-tm
electronic work, you indicate that you have read, understand, agree to
and accept all the terms of this license and intellectual property
(trademark/copyright) agreement.  If you do not agree to abide by all
the terms of this agreement, you must cease using and return or destroy
all copies of Project Gutenberg-tm electronic works in your possession.
If you paid a fee for obtaining a copy of or access to a Project
Gutenberg-tm electronic work and you do not agree to be bound by the
terms of this agreement, you may obtain a refund from the person or
entity to whom you paid the fee as set forth in paragraph 1.E.8.

1.B.  "Project Gutenberg" is a registered trademark.  It may only be
used on or associated in any way with an electronic work by people who
agree to be bound by the terms of this agreement.  There are a few
things that you can do with most Project Gutenberg-tm electronic works
even without complying with the full terms of this agreement.  See
paragraph 1.C below.  There are a lot of things you can do with Project
Gutenberg-tm electronic works if you follow the terms of this agreement
and help preserve free future access to Project Gutenberg-tm electronic
works.  See paragraph 1.E below.

1.C.  The Project Gutenberg Literary Archive Foundation ("the Foundation"
or PGLAF), owns a compilation copyright in the collection of Project
Gutenberg-tm electronic works.  Nearly all the individual works in the
collection are in the public domain in the United States.  If an
individual work is in the public domain in the United States and you are
located in the United States, we do not claim a right to prevent you from
copying, distributing, performing, displaying or creating derivative
works based on the work as long as all references to Project Gutenberg
are removed.  Of course, we hope that you will support the Project
Gutenberg-tm mission of promoting free access to electronic works by
freely sharing Project Gutenberg-tm works in compliance with the terms of
this agreement for keeping the Project Gutenberg-tm name associated with
the work.  You can easily comply with the terms of this agreement by
keeping this work in the same format with its attached full Project
Gutenberg-tm License when you share it without charge with others.

1.D.  The copyright laws of the place where you are located also govern
what you can do with this work.  Copyright laws in most countries are in
a constant state of change.  If you are outside the United States, check
the laws of your country in addition to the terms of this agreement
before downloading, copying, displaying, performing, distributing or
creating derivative works based on this work or any other Project
Gutenberg-tm work.  The Foundation makes no representations concerning
the copyright status of any work in any country outside the United

1.E.  Unless you have removed all references to Project Gutenberg:

1.E.1.  The following sentence, with active links to, or other immediate
access to, the full Project Gutenberg-tm License must appear prominently
whenever any copy of a Project Gutenberg-tm work (any work on which the
phrase "Project Gutenberg" appears, or with which the phrase "Project
Gutenberg" is associated) is accessed, displayed, performed, viewed,
copied or distributed:

This eBook is for the use of anyone anywhere at no cost and with
almost no restrictions whatsoever.  You may copy it, give it away or
re-use it under the terms of the Project Gutenberg License included
with this eBook or online at

1.E.2.  If an individual Project Gutenberg-tm electronic work is derived
from the public domain (does not contain a notice indicating that it is
posted with permission of the copyright holder), the work can be copied
and distributed to anyone in the United States without paying any fees
or charges.  If you are redistributing or providing access to a work
with the phrase "Project Gutenberg" associated with or appearing on the
work, you must comply either with the requirements of paragraphs 1.E.1
through 1.E.7 or obtain permission for the use of the work and the
Project Gutenberg-tm trademark as set forth in paragraphs 1.E.8 or

1.E.3.  If an individual Project Gutenberg-tm electronic work is posted
with the permission of the copyright holder, your use and distribution
must comply with both paragraphs 1.E.1 through 1.E.7 and any additional
terms imposed by the copyright holder.  Additional terms will be linked
to the Project Gutenberg-tm License for all works posted with the
permission of the copyright holder found at the beginning of this work.

1.E.4.  Do not unlink or detach or remove the full Project Gutenberg-tm
License terms from this work, or any files containing a part of this
work or any other work associated with Project Gutenberg-tm.

1.E.5.  Do not copy, display, perform, distribute or redistribute this
electronic work, or any part of this electronic work, without
prominently displaying the sentence set forth in paragraph 1.E.1 with
active links or immediate access to the full terms of the Project
Gutenberg-tm License.

1.E.6.  You may convert to and distribute this work in any binary,
compressed, marked up, nonproprietary or proprietary form, including any
word processing or hypertext form.  However, if you provide access to or
distribute copies of a Project Gutenberg-tm work in a format other than
"Plain Vanilla ASCII" or other format used in the official version
posted on the official Project Gutenberg-tm web site (,
you must, at no additional cost, fee or expense to the user, provide a
copy, a means of exporting a copy, or a means of obtaining a copy upon
request, of the work in its original "Plain Vanilla ASCII" or other
form.  Any alternate format must include the full Project Gutenberg-tm
License as specified in paragraph 1.E.1.

1.E.7.  Do not charge a fee for access to, viewing, displaying,
performing, copying or distributing any Project Gutenberg-tm works
unless you comply with paragraph 1.E.8 or 1.E.9.

1.E.8.  You may charge a reasonable fee for copies of or providing
access to or distributing Project Gutenberg-tm electronic works provided

- You pay a royalty fee of 20% of the gross profits you derive from
     the use of Project Gutenberg-tm works calculated using the method
     you already use to calculate your applicable taxes.  The fee is
     owed to the owner of the Project Gutenberg-tm trademark, but he
     has agreed to donate royalties under this paragraph to the
     Project Gutenberg Literary Archive Foundation.  Royalty payments
     must be paid within 60 days following each date on which you
     prepare (or are legally required to prepare) your periodic tax
     returns.  Royalty payments should be clearly marked as such and
     sent to the Project Gutenberg Literary Archive Foundation at the
     address specified in Section 4, "Information about donations to
     the Project Gutenberg Literary Archive Foundation."

- You provide a full refund of any money paid by a user who notifies
     you in writing (or by e-mail) within 30 days of receipt that s/he
     does not agree to the terms of the full Project Gutenberg-tm
     License.  You must require such a user to return or
     destroy all copies of the works possessed in a physical medium
     and discontinue all use of and all access to other copies of
     Project Gutenberg-tm works.

- You provide, in accordance with paragraph 1.F.3, a full refund of any
     money paid for a work or a replacement copy, if a defect in the
     electronic work is discovered and reported to you within 90 days
     of receipt of the work.

- You comply with all other terms of this agreement for free
     distribution of Project Gutenberg-tm works.

1.E.9.  If you wish to charge a fee or distribute a Project Gutenberg-tm
electronic work or group of works on different terms than are set
forth in this agreement, you must obtain permission in writing from
both the Project Gutenberg Literary Archive Foundation and Michael
Hart, the owner of the Project Gutenberg-tm trademark.  Contact the
Foundation as set forth in Section 3 below.


1.F.1.  Project Gutenberg volunteers and employees expend considerable
effort to identify, do copyright research on, transcribe and proofread
public domain works in creating the Project Gutenberg-tm
collection.  Despite these efforts, Project Gutenberg-tm electronic
works, and the medium on which they may be stored, may contain
"Defects," such as, but not limited to, incomplete, inaccurate or
corrupt data, transcription errors, a copyright or other intellectual
property infringement, a defective or damaged disk or other medium, a
computer virus, or computer codes that damage or cannot be read by
your equipment.

of Replacement or Refund" described in paragraph 1.F.3, the Project
Gutenberg Literary Archive Foundation, the owner of the Project
Gutenberg-tm trademark, and any other party distributing a Project
Gutenberg-tm electronic work under this agreement, disclaim all
liability to you for damages, costs and expenses, including legal

defect in this electronic work within 90 days of receiving it, you can
receive a refund of the money (if any) you paid for it by sending a
written explanation to the person you received the work from.  If you
received the work on a physical medium, you must return the medium with
your written explanation.  The person or entity that provided you with
the defective work may elect to provide a replacement copy in lieu of a
refund.  If you received the work electronically, the person or entity
providing it to you may choose to give you a second opportunity to
receive the work electronically in lieu of a refund.  If the second copy
is also defective, you may demand a refund in writing without further
opportunities to fix the problem.

1.F.4.  Except for the limited right of replacement or refund set forth
in paragraph 1.F.3, this work is provided to you 'AS-IS' WITH NO OTHER

1.F.5.  Some states do not allow disclaimers of certain implied
warranties or the exclusion or limitation of certain types of damages.
If any disclaimer or limitation set forth in this agreement violates the
law of the state applicable to this agreement, the agreement shall be
interpreted to make the maximum disclaimer or limitation permitted by
the applicable state law.  The invalidity or unenforceability of any
provision of this agreement shall not void the remaining provisions.

1.F.6.  INDEMNITY - You agree to indemnify and hold the Foundation, the
trademark owner, any agent or employee of the Foundation, anyone
providing copies of Project Gutenberg-tm electronic works in accordance
with this agreement, and any volunteers associated with the production,
promotion and distribution of Project Gutenberg-tm electronic works,
harmless from all liability, costs and expenses, including legal fees,
that arise directly or indirectly from any of the following which you do
or cause to occur: (a) distribution of this or any Project Gutenberg-tm
work, (b) alteration, modification, or additions or deletions to any
Project Gutenberg-tm work, and (c) any Defect you cause.

Section  2.  Information about the Mission of Project Gutenberg-tm

Project Gutenberg-tm is synonymous with the free distribution of
electronic works in formats readable by the widest variety of computers
including obsolete, old, middle-aged and new computers.  It exists
because of the efforts of hundreds of volunteers and donations from
people in all walks of life.

Volunteers and financial support to provide volunteers with the
assistance they need are critical to reaching Project Gutenberg-tm's
goals and ensuring that the Project Gutenberg-tm collection will
remain freely available for generations to come.  In 2001, the Project
Gutenberg Literary Archive Foundation was created to provide a secure
and permanent future for Project Gutenberg-tm and future generations.
To learn more about the Project Gutenberg Literary Archive Foundation
and how your efforts and donations can help, see Sections 3 and 4
and the Foundation web page at

Section 3.  Information about the Project Gutenberg Literary Archive

The Project Gutenberg Literary Archive Foundation is a non profit
501(c)(3) educational corporation organized under the laws of the
state of Mississippi and granted tax exempt status by the Internal
Revenue Service.  The Foundation's EIN or federal tax identification
number is 64-6221541.  Its 501(c)(3) letter is posted at  Contributions to the Project Gutenberg
Literary Archive Foundation are tax deductible to the full extent
permitted by U.S. federal laws and your state's laws.

The Foundation's principal office is located at 4557 Melan Dr. S.
Fairbanks, AK, 99712., but its volunteers and employees are scattered
throughout numerous locations.  Its business office is located at
809 North 1500 West, Salt Lake City, UT 84116, (801) 596-1887, email  Email contact links and up to date contact
information can be found at the Foundation's web site and official
page at

For additional contact information:
     Dr. Gregory B. Newby
     Chief Executive and Director

Section 4.  Information about Donations to the Project Gutenberg
Literary Archive Foundation

Project Gutenberg-tm depends upon and cannot survive without wide
spread public support and donations to carry out its mission of
increasing the number of public domain and licensed works that can be
freely distributed in machine readable form accessible by the widest
array of equipment including outdated equipment.  Many small donations
($1 to $5,000) are particularly important to maintaining tax exempt
status with the IRS.

The Foundation is committed to complying with the laws regulating
charities and charitable donations in all 50 states of the United
States.  Compliance requirements are not uniform and it takes a
considerable effort, much paperwork and many fees to meet and keep up
with these requirements.  We do not solicit donations in locations
where we have not received written confirmation of compliance.  To
SEND DONATIONS or determine the status of compliance for any
particular state visit

While we cannot and do not solicit contributions from states where we
have not met the solicitation requirements, we know of no prohibition
against accepting unsolicited donations from donors in such states who
approach us with offers to donate.

International donations are gratefully accepted, but we cannot make
any statements concerning tax treatment of donations received from
outside the United States.  U.S. laws alone swamp our small staff.

Please check the Project Gutenberg Web pages for current donation
methods and addresses.  Donations are accepted in a number of other
ways including including checks, online payments and credit card
donations.  To donate, please visit:

Section 5.  General Information About Project Gutenberg-tm electronic

Professor Michael S. Hart was the originator of the Project Gutenberg-tm
concept of a library of electronic works that could be freely shared
with anyone.  For thirty years, he produced and distributed Project
Gutenberg-tm eBooks with only a loose network of volunteer support.

Project Gutenberg-tm eBooks are often created from several printed
editions, all of which are confirmed as Public Domain in the U.S.
unless a copyright notice is included.  Thus, we do not necessarily
keep eBooks in compliance with any particular paper edition.

Most people start at our Web site which has the main PG search facility:

This Web site includes information about Project Gutenberg-tm,
including how to make donations to the Project Gutenberg Literary
Archive Foundation, how to help produce our new eBooks, and how to
subscribe to our email newsletter to hear about new eBooks.