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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 www.gutenberg.org + + +Title: History of Phosphorus + +Author: Eduard Farber + +Release Date: September 20, 2010 [EBook #33766] + +Language: English + +Character set encoding: ISO-8859-1 + +*** START OF THIS PROJECT GUTENBERG EBOOK HISTORY OF PHOSPHORUS *** + + + + +Produced by Chris Curnow, Joseph Cooper, Louise Pattison +and the Online Distributed Proofreading Team at +https://www.pgdp.net + + + + + + +</pre> + + +<div class="tnote"> +<h3>Transcriber’s Notes</h3> + +<p>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.</p> + +<p>The front material, introduction and relevant index entries from +the Bulletin are included in each single-paper e-book.</p> + +<p><a href="#corrections_37">Corrections</a> to typographical errors are underlined +<ins class="mycorr" title="Original: like thsi">like this</ins>. Mouse over to view the original text.</p> + +</div> + + +<hr style="width: 65%;" /> + +<h1>SMITHSONIAN INSTITUTION<br /> +UNITED STATES NATIONAL MUSEUM<br /> +BULLETIN 240</h1> + +<div class="figright"> + <img src="images/i_002.png" alt="Smithsonian Press Logo" title="" /> +</div> + +<p class="right" style="clear:both;">SMITHSONIAN PRESS<br /></p> + +<p>MUSEUM OF HISTORY AND TECHNOLOGY</p> + +<p style="font-size: 2em; font-weight: bold;" class="smcap">Contributions<br /> +From the<br /> +Museum<br /> +of History and<br /> +Technology</p> + +<p style="font-size: 1.25em;"><em>Papers 34-44<br /> +On Science and Technology</em></p> + +<p>SMITHSONIAN INSTITUTION · WASHINGTON, D.C. 1966</p> + +<hr style="width: 65%;" /> + +<p class="center" style="font-size: 1.25em;"><em>Publications of the United States National Museum</em></p> + +<p>The scholarly and scientific publications of the United States National Museum +include two series, <cite>Proceedings of the United States National Museum</cite> and <cite>United States +National Museum Bulletin</cite>.</p> + +<p>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.</p> + +<p>The <cite>Proceedings</cite>, 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.</p> + +<p>In the <cite>Bulletin</cite> 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. <cite>Bulletins</cite> 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 <cite>Bulletin</cite> series under the heading <cite>Contributions from the United States +National Herbarium</cite>, and since 1959, in <cite>Bulletins</cite> titled “Contributions from the Museum +of History and Technology,” have been gathered shorter papers relating to the collections +and research of that Museum.</p> + +<p>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.</p> + +<p class="right"><span class="smcap">Frank A. Taylor</span><br /> +<em>Director, United States National Museum</em></p> + +<hr style="width: 65%;" /> +<p><span class="pagenum"><a name="Page_177" id="Page_177">[Pg 177]</a></span></p> + +<h1><a name="Paper_40" id="Paper_40"></a><span class="smcap">Contributions from<br /> +The Museum of History and Technology</span>:<br /> +<span class="smcap">Paper</span> 40<br /> +<br /><br /> +<span class="smcap">History of Phosphorus</span> +</h1> +<p><span class="rnum" style="font-size: larger;"> +<em>Eduard Farber</em></span><br /><br/></p> + +<p><span class="rnum">THE ELEMENT FROM ANIMALS AND PLANTS <a href="#Page_178">178</a></span><br /></p> +<p><span class="rnum">EARLY USES <a href="#Page_181">181</a></span><br /></p> +<p><span class="rnum">CHEMICAL CONSTITUTION OF PHOSPHORIC ACIDS <a href="#Page_182">182</a></span><br /></p> +<p><span class="rnum">PHOSPHATES AS PLANT NUTRIENTS <a href="#Page_185">185</a></span><br /></p> +<p><span class="rnum">FROM INORGANIC TO ORGANIC PHOSPHATES <a href="#Page_187">187</a></span><br /></p> +<p><span class="rnum">PHOSPHATIDES AND PHOSPHAGENS <a href="#Page_189">189</a></span><br /></p> +<p><span class="rnum">NUCLEIN AND NUCLEIC ACIDS <a href="#Page_192">192</a></span><br /></p> +<p><span class="rnum">PHOSPHATES IN BIOLOGICAL PROCESSES <a href="#Page_197">197</a></span><br /></p> +<p><span class="rnum">MEDICINES AND POISONS <a href="#Page_198">198</a></span><br /></p> + +<hr style="width: 65%;" /> +<p><span class="pagenum"><a name="Page_178" id="Page_178">[Pg 178]</a></span></p> + +<p> <span class="rnum"><em><big>Eduard Farber</big></em></span><br /></p> + +<h2><big>HISTORY OF PHOSPHORUS</big></h2> + +<div class="blockquotn"><p><i>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.</i></p> + +<p><i>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.</i></p> + +<p><span class="smcap">The Author</span>: <i>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.</i></p></div> + + +<p>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 <i>Phosphorus igneus</i>, Boyle’s <i>Icy Noctiluca</i>, 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.</p> + +<hr style="width: 65%;" /> + +<h3>The Element from Animals and Plants</h3> + +<p>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, <span class="pagenum"><a name="Page_179" id="Page_179">[Pg 179]</a></span>“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].”<a name="FNanchor_1_1" id="FNanchor_1_1"></a><a href="#Footnote_1_1" class="fnanchor">[1]</a></p> + +<p>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.<a name="FNanchor_2_2" id="FNanchor_2_2"></a><a href="#Footnote_2_2" class="fnanchor">[2]</a> 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).<a name="FNanchor_3_3" id="FNanchor_3_3"></a><a href="#Footnote_3_3" class="fnanchor">[3]</a> 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.<a name="FNanchor_4_4" id="FNanchor_4_4"></a><a href="#Footnote_4_4" class="fnanchor">[4]</a> 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.</p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i006.png" width="400" height="697" alt="Figure 1.—The alchemist discovers phosphorus. A painting +by Joseph Wright (1734-1779) of Derby, England." title="Figure 1." /> +<p class="caption">Figure 1.—<span class="smcap">The alchemist discovers phosphorus.</span> A painting +by Joseph Wright (1734-1779) of Derby, England.</p> +</div> + +<p>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.<a name="FNanchor_5_5" id="FNanchor_5_5"></a><a href="#Footnote_5_5" class="fnanchor">[5]</a> 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<span class="pagenum"><a name="Page_180" id="Page_180">[Pg 180]</a></span> 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.<a name="FNanchor_6_6" id="FNanchor_6_6"></a><a href="#Footnote_6_6" class="fnanchor">[6]</a></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i007.png" width="300" height="249" alt="Figure 2." title="Figure 2." /> +<p class="caption2">Figure 2.—<span class="smcap">Galley-oven</span>, 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 <span class="smcap">Anselme Payen</span>, <i>Précis de Chimie industrielle</i>, Paris, +1849; reproduced from <span class="smcap">Hugo Fleck</span>, <i>Die Fabrikation chemischer Produkte +aus thierischen Abfällen</i>, <a name="corr_40_1" id="corr_40_1"></a><ins class="mycorr" title="Original: Viewig">Vieweg</ins>, Braunschweig, 1862, page 80 of volume +2, 2nd group, of <span class="smcap">P. Bolley’s</span> <i>Handbuch der chemischen Technologie</i>.)</p> +</div> + +<p>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 <i>de novo</i>. 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.’”<a name="FNanchor_7_7" id="FNanchor_7_7"></a><a href="#Footnote_7_7" class="fnanchor">[7]</a></p> + +<p>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 +<i>sal microcosmicum</i>, 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.”<a name="FNanchor_8_8" id="FNanchor_8_8"></a><a href="#Footnote_8_8" class="fnanchor">[8]</a></p> + +<p>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<a name="FNanchor_9_9" id="FNanchor_9_9"></a><a href="#Footnote_9_9" class="fnanchor">[9]</a> 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<span class="pagenum"><a name="Page_181" id="Page_181">[Pg 181]</a></span> point of +view, a point of view which they helped to create.</p> + +<p>The widespread interest in the burning of sulfur and of phosphorus, +naturally, caught Lavoisier’s attention. In his first volume of +<i>Opuscules Physiques et Chimiques</i> (1774), he devoted 20 pages to his +experiments on phosphorus. He amplified them a few years later<a name="FNanchor_10_10" id="FNanchor_10_10"></a><a href="#Footnote_10_10" class="fnanchor">[10]</a> when +he attributed the combustion to a combination of phosphorus with the +“eminently respirable” part of air. In the <i>Méthode de Nomenclature +Chimique</i> 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.<a name="FNanchor_11_11" id="FNanchor_11_11"></a><a href="#Footnote_11_11" class="fnanchor">[11]</a></p> + + +<hr style="width: 65%;" /> + +<h3>Early Uses</h3> + +<p>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.<a name="FNanchor_12_12" id="FNanchor_12_12"></a><a href="#Footnote_12_12" class="fnanchor">[12]</a> Robert Boyle had +the idea of using phosphorus as a light for underwater divers.<a name="FNanchor_13_13" id="FNanchor_13_13"></a><a href="#Footnote_13_13" class="fnanchor">[13]</a> A +century later, “instant lights” were sold, with molten phosphorus as the +“igniter,” but they proved cumbersome and unreliable.<a name="FNanchor_14_14" id="FNanchor_14_14"></a><a href="#Footnote_14_14" class="fnanchor">[14]</a> 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).<a name="FNanchor_15_15" id="FNanchor_15_15"></a><a href="#Footnote_15_15" class="fnanchor">[15]</a></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i010.png" width="300" height="252" alt="Figure 3." title="Figure 3." /> +<p class="caption2">Figure 3.—<span class="smcap">Distillation apparatus</span> (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 <span class="smcap">Hugo Fleck</span>, <i>Die +Fabrikation chemischer Produkte ...</i> page 90.)</p> +</div> + +<p>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.<a name="FNanchor_16_16" id="FNanchor_16_16"></a><a href="#Footnote_16_16" class="fnanchor">[16]</a> 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.<a name="FNanchor_17_17" id="FNanchor_17_17"></a><a href="#Footnote_17_17" class="fnanchor">[17]</a> However, in the growing<span class="pagenum"><a name="Page_182" id="Page_182">[Pg 182]</a></span> 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.<a name="FNanchor_18_18" id="FNanchor_18_18"></a><a href="#Footnote_18_18" class="fnanchor">[18]</a></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i011.png" width="300" height="297" alt="Figure 4." title="Figure 4." /> +<p class="caption2">Figure 4.—<span class="smcap">Apparatus for converting white phosphorus</span> 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 +<span class="smcap">Hugo Fleck</span>, <i>Die Fabrikation chemischer Produkte ...</i>, page 112.)</p> +</div> + +<hr style="width: 65%;" /> + +<h3>Chemical Constitution of Phosphoric Acids</h3> + +<p>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.”<a name="FNanchor_19_19" id="FNanchor_19_19"></a><a href="#Footnote_19_19" class="fnanchor">[19]</a> Actually, Gahn used at first hartshorn (<i>Cornu cervi +ustum</i>), 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 <i>sal microcosmicum</i> was an ammonia salt; instead, it +is “a tertiary neutral salt, consisting of <i>alkali minerali fixo</i> (i.e., +sodium), <i>alkali volatili</i>, and <i>acido phosphori</i>.”<a name="FNanchor_20_20" id="FNanchor_20_20"></a><a href="#Footnote_20_20" class="fnanchor">[20]</a></p> + +<p>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: <i>ortho</i>, <i>pyro</i>, and <i>meta</i>.</p> + +<p>Berzelius cited these acids as examples of compounds which are <span style="text-transform:lowercase;" class="smcap">ISOMERIC</span>. +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, <span style="text-transform:lowercase;" class="smcap">ISOMORPHISM</span>, 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.</p> + +<p>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.”<a name="FNanchor_21_21" id="FNanchor_21_21"></a><a href="#Footnote_21_21" class="fnanchor">[21]</a> 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<span class="pagenum"><a name="Page_183" id="Page_183">[Pg 183]</a></span> his manner of writing the formulas, each dot over the symbol +for the element was to indicate an atom of oxygen; thus, he wrote:</p> + +<p class="mono" style="margin-bottom:0px; margin-left: 20%;">... :: .. ... . .</p> +<p style="margin-top:0px; margin-left: 20%;"><span class="mono"> H<sup>3</sup> P H<sup>2</sup> P and H P.</span><a name="FNanchor_22_22" id="FNanchor_22_22"></a><a href="#Footnote_22_22" class="fnanchor">[22]</a></p> + +<div class="figcenter" style="width: 650px;"> + +<div class="figleft" style="width: 300px;"> +<img src="images/i013a.png" width="300" height="438" alt="Figure 5." title="Figure 5." /> +<p class="caption2">Figure 5.—<span class="smcap">Oven for the calcination of bones</span>, 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 <span class="smcap">Figuier</span>, <i>Merveilles de +l’industrie</i>, volume 3, 1874, page 537.)</p> +</div> + +<div class="figright" style="width: 300px;"> +<img src="images/i014.png" width="300" height="505" alt="Figure 6." title="Figure 6." /> +<p class="caption2">Figure 6.—<span class="smcap">An advertisement</span> with view of plant for +manufacturing superphosphate about 1867. (From <span class="smcap">E. T. Freedley</span>, +<i>Philadelphia and its Manufacturers in 1867</i>, page 288.)</p> +</div></div> + +<div class="figcenter" style="width: 600px;"> +<span class="pagenum"><a name="Page_184" id="Page_184">[Pg 184]</a></span> +<img src="images/i015.png" width="600" height="769" alt="Figure 7." title="Figure 7." /> +<p class="caption2">Figure 7.—<span class="smcap">Florida hard-rock phosphate mining.</span> (From +Carroll D. Wright, <i>The Phosphate Industry of the United States</i>, sixth +special report of the Commissioner of Labor, Government Printing Office, +Washington, 1893, plate facing page 43.)</p> +</div> + +<p>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:</p> + +<p style="margin-left:3em;"><span class="pagenum"><a name="Page_185" id="Page_185">[Pg 185]</a></span>2 P 3 aq. phosphoric acid</p> +<p style="margin-left:3em;">3 P 3 aq. pyrophosphoric acid</p> +<p style="margin-left:3em;">6 P 3 aq. metaphosphoric acid.</p> + +<p>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!<a name="FNanchor_23_23" id="FNanchor_23_23"></a><a href="#Footnote_23_23" class="fnanchor">[23]</a> +</p> + +<p>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.</p> + +<p>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:</p> + +<p style="margin-left:4em;">(PO) · · ·<br /> +<span style="margin-left:5em;">O<sup>3</sup> phosphoric acid</span><br /> +<span style="margin-left:2em;">H<sup>3</sup></span></p> + +<p style="margin-left:4em;">(PHO) · ·<br /> +<span style="margin-left:5em;">O<sup>2</sup> phosphorus acid</span><br /> +<span style="margin-left:2em;">H<sup>2</sup></span></p> + +<p style="margin-left:4em;">(PH<sup>2</sup>O) ·<br /> +<span style="margin-left:5em;">O hypophosphorous acid.<a name="FNanchor_24_24" id="FNanchor_24_24"></a><a href="#Footnote_24_24" class="fnanchor">[24]</a></span><br /> +<span style="margin-left:2em;">H</span></p> + + +<p>Further proof for these constitutions was sought in the study of the +esters formed when the acids react with alcohols.</p> + +<p>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.</p> + +<p>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.</p> + + + +<hr style="width: 65%;" /> +<h3>Phosphates as Plant Nutrients</h3> + + +<p>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.</p> + +<p>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.</p> + +<p>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<span class="pagenum"><a name="Page_186" id="Page_186">[Pg 186]</a></span> 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.”</p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i018.png" width="600" height="361" alt="Figure 8." title="Figure 8." /> +<p class="caption">Figure 8.—<span class="smcap">Florida land-pebble phosphate mining.</span> (From +Carroll D. Wright, <i>The Phosphate Industry of the United States ...</i>, +plate facing page 58.)</p> +</div> + +<p>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.<a name="FNanchor_25_25" id="FNanchor_25_25"></a><a href="#Footnote_25_25" class="fnanchor">[25]</a></p> + +<p>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.<a name="FNanchor_26_26" id="FNanchor_26_26"></a><a href="#Footnote_26_26" class="fnanchor">[26]</a></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i021.png" width="600" height="361" alt="Figure 9." title="Figure 9." /> +<p class="caption">Figure 9.—<span class="smcap">Florida river-pebble phosphate mining.</span> (From +Carroll D. Wright, <i>The Phosphate Industry of the United States ...</i>, +plate facing page 64.)</p> +</div> + +<p>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: <span class="pagenum"><a name="Page_187" id="Page_187">[Pg 187]</a></span>“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 <i>Nietzsche’s Works</i>, 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?</p> + + + +<hr style="width: 65%;" /> +<h3>From Inorganic to Organic Phosphates</h3> + + +<p>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.</p> + +<p>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.<span class="pagenum"><a name="Page_188" id="Page_188">[Pg 188]</a></span></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i025.png" width="400" height="600" alt="T. PARKER. +ELECTRICAL FURNACE. +Patented Sept. 13, 1892. +Fig. 1. + +Fig. 2. +Inventor Thomas Parker +By his attorneys Howson and Howson +Witnesses: George Baumann John Revell" title="Figure 10." /> +<p class="caption2">Figure 10.—<span class="smcap">Electric furnace for producing elemental +phosphorus</span>, 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:</p> +<blockquote> +<p>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.</p> + +<p>F is the furnace containing the charge to be treated. It has an +inlet-hopper at <i>a</i>, with slides AA, by which the charge can be admitted +without opening communication between the interior of the furnace and +the outer air.</p> + +<p>B is a screw conveyer by which the charge is pushed forward into the +furnace.</p> + +<p><i>c´c´</i> are the electrodes, consisting of blocks or cylinders or the like +of carbon fixed in metal socket-pieces <i>c c</i>, to which the +electric-circuit wires <i>d</i> from the <a name="corr_40_2" id="corr_40_2"></a><ins class="mycorr" title="Original: dynano">dynamo</ins> D are affixed. The current, +as aforesaid, may be either continuous or alternating. <i>c<sup>2</sup>c<sup>2</sup></i> 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 <i>c<sup>3</sup></i> (in contact with the socket-pieces <i>c</i>) and in the +furnace, as shown.</p> + +<p><i>g</i> is the outlet for the gas or vapor, <i>h</i> the slag-tap hole, and <i>x</i> +the opening for manipulating the charge, the said openings being closed +by clay or otherwise when the furnace is at work.</p> + +<p>I use coke or other form of carbon in the charge between the electrodes +<i>c´</i>, the said coke being in contact with the said electrodes, so that +complete incandescence is insured.</p> + +<p>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. <i>c´ c<sup>2</sup></i> 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.</p> +</blockquote></div> + +<p><span class="pagenum"><a name="Page_189" id="Page_189">[Pg 189]</a></span></p> + +<div class="figcenter" style="width: 650px;"> + +<div class="figleft" style="width: 300px;"> +<img src="images/i026.png" width="300" height="330" alt="Fig 254.—Trempage á la presse. +" title="Figure 11." /> +<p class="caption2">Figure 11.—<span class="smcap">Dipping of matchsticks</span> 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 <span class="smcap">Figuier</span>, <i>Merveilles de l’industrie</i>, volume 3, 1874, +page 575.)</p> +</div> + +<div class="figright" style="width: 300px;"> +<img src="images/i027.png" width="300" height="329" alt="Fig. 256.—Coupe du plateau á tremper les +allumettes chimiques dans la pâte de phosphore á chaud et au bain-marie." title="Figure 12." /> +<p class="caption2">Figure 12.—<span class="smcap">Pan for dipping matchsticks</span> 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 +<span class="smcap">Figuier</span>, volume 3, 1874, page 576.)</p> +</div> +</div> +<p style="clear: both;">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.</p> + + + +<hr style="width: 65%;" /> +<h3>Phosphatides and Phosphagens</h3> + + +<p>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.</p> +<p><span class="pagenum"><a name="Page_190" id="Page_190">[Pg 190]</a></span></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i028.png" width="400" height="785" alt="Alcoholic Fermentation" title="Figure 13." /> +<p class="caption2">Figure 13.—<span class="smcap">Survey of alcoholic fermentation</span>, 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 <i>Chemistry & Industry</i>, +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).”</p> +</div> + +<p style="clear:both;"><span class="pagenum"><a name="Page_191" id="Page_191">[Pg 191]</a></span> +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<a name="FNanchor_27_27" id="FNanchor_27_27"></a><a href="#Footnote_27_27" class="fnanchor">[27]</a> (1811-1876), because he obtained it from egg +yolk (in Greek, <i>lékidos</i>). 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, CH<sub>2</sub>.O.CH<sub>2</sub> and trimethylamine N(CH<sub>3</sub>)<sub>3</sub>.<a name="FNanchor_28_28" id="FNanchor_28_28"></a><a href="#Footnote_28_28" class="fnanchor">[28]</a> 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).</p> + +<table id="lecithin" summary="Structure of lecithin according to Strecker"> +<tr><td></td><td rowspan="3" style="font-size: 3em; vertical-align:top;">{</td><td>OH</td><td rowspan="3" style="font-size: 3em; vertical-align:top;">}</td><td> </td></tr> +<tr><td>N</td> <td>(CH<sub>3</sub>)<sub>3</sub></td> <td>Choline</td></tr> +<tr><td> </td> <td>C<sub>2</sub>H<sub>4</sub>O</td> <td></td></tr> +<tr><td> </td></tr> +</table> +<table id="lecithin2" summary="Structure of lecithin according to Strecker"> +<tr><td>C<sub>18</sub>H<sub>33</sub>O<sub>2</sub></td><td rowspan="3" style="font-size: 3em; vertical-align:top;">}</td><td style="text-align: right;">HO</td><td rowspan="3" style="font-size: 3em; vertical-align:top;">}</td></tr> +<tr><td></td><td></td><td>PO</td></tr> +<tr><td>C<sub>16</sub>H<sub>31</sub>O<sub>2</sub></td><td style="text-align: right;">C<sub>3</sub>H<sub>5</sub>O</td></tr> +<tr><td>Fatty Acids</td><td></td><td colspan="4">Glycerophosphate</td></tr> +<tr><td style="text-align: center;" colspan="5">'—————<sub>v</sub>————'</td></tr> +<tr><td style="text-align: center;" colspan="5">Lecithin</td></tr> +<tr><td style="text-align: center;" colspan="5">according to Strecker</td></tr> +</table> + +<p>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.</p> + +<div class="figcenter" style="width: 300px;"> +<img src="images/lecithin_1918.png" width="300" height="178" alt="Lecithin (1918)" title="" /> +<p class="caption">Lecithin (1918)</p> +</div> + +<p>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.</p> + +<table id="lecithin3" summary="Enzymatic Splitting of Lecithins"> +<tr><th colspan="3"><span class="smcap">Enzymatic Splitting of Lecithins</span></th></tr> +<tr><td><span class="smcap">Enzyme</span></td><td><span class="smcap">Substrate</span></td><td><span class="smcap">Products</span></td></tr> +<tr><td style="text-align:center;">A</td><td>Lecithin</td><td>Lysolecithin and fatty acids.</td></tr> +<tr><td style="text-align:center;">B</td><td>Lysolecithin</td><td>Glycero-phospho-choline and fatty acids.</td></tr> +<tr><td style="text-align:center;">C</td><td>Lecithin</td><td>Phosphatidic acid and choline.</td></tr> +<tr><td style="text-align:center;">D</td><td>Lecithin</td><td>Phosphoryl choline and diglyceride.</td></tr> +</table> + +<p>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 H<sub>2</sub>NCH<sub>2</sub>CH<sub>2</sub>OH is found +instead of the choline of lecithin. The variations include the alcohol, +to which the fatty acids and choline phosphate are attached, <a name="corr_40_3" id="corr_40_3"></a><ins class="mycorr" title="Original: For">for</ins> +example, glycerol can be replaced by the so-called meat-sugar, inositol, +which has six hydroxyl groups in its hexagon-shaped molecule +<span class="pagenum"><a name="Page_192" id="Page_192">[Pg 192]</a></span>C<sub>6</sub>H<sub>6</sub>(OH)<sub>6</sub>.</p> + +<div class="figleft" style="width: 300px;"> +<img src="images/i032.png" width="300" height="401" alt="Figure 14." title="figure 14." /> +<p class="caption2">Figure 14.—<span class="smcap">Eduard Buchner</span> (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).</p> +</div> + +<p>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.<a name="FNanchor_29_29" id="FNanchor_29_29"></a><a href="#Footnote_29_29" class="fnanchor">[29]</a> 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....”<a name="FNanchor_30_30" id="FNanchor_30_30"></a><a href="#Footnote_30_30" class="fnanchor">[30]</a> But <a name="corr_40_4" id="corr_40_4"></a> +<ins class="mycorr" title="Original: phosphatide soccur">phosphatides occur</ins> 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.<a name="FNanchor_31_31" id="FNanchor_31_31"></a><a href="#Footnote_31_31" class="fnanchor">[31]</a></p> + +<p>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.</p> + +<div class="figcenter" style="width: 350px;"> +<div class="figleft" style="width: 150px;"> +<img src="images/creatine_phosphate.png" width="150" height="152" alt="Creatine Phosphate" title="" /> +<span class="caption">Creatine Phosphate</span> +</div> +<div class="figright" style="width: 150px;"> +<img src="images/arginine_phosphate.png" width="150" height="279" alt="Arginine Phosphate" title="" /> +<span class="caption">Arginine phosphate</span> +</div> +</div> + +<hr style="width: 65%;" /> +<h3>Nuclein and Nucleic Acids</h3> + + +<p>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<span class="pagenum"><a name="Page_193" id="Page_193">[Pg 193]</a></span> 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.<a name="FNanchor_32_32" id="FNanchor_32_32"></a><a href="#Footnote_32_32" class="fnanchor">[32]</a> 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.</p> + +<p>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.</p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i035a.png" width="300" height="331" alt="Figure 15." title="Figure 15." /> +<p class="caption2">Figure 15.—<span class="smcap">Albrecht Kossel</span> (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. (<i>Photo courtesy National Library of Medicine, +Washington, D.C.</i>)</p> +</div> + +<p>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:</p> +<div style="margin-left:4em;"> +<p>Phosphoric acid—Carbohydrate—Guanine</p> +<p>Phosphoric acid—Carbohydrate—Cytosine</p> +<p>Phosphoric acid—Carbohydrate—Thymine</p> +<p>Phosphoric acid—Carbohydrate—Adenine</p> +</div> + +<p>Of the four basic components on the right, thymine occurs in the +<a name="corr_40_5" id="corr_40_5"></a><ins class="mycorr" title="Original: nucleidic">nucleic</ins> +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</p> + +<pre> + NH<sub>2</sub> + / + C=O + \ + NH<sub>2</sub> +</pre> + +<p>is involved, and they form pairs of oxidized and reduced states: +<span class="pagenum"><a name="Page_194" id="Page_194">[Pg 194]</a></span></p> + +<table id="purine" summary="Purine & Pyrimidine"> +<tr><td><span class="smcap">Purine</span></td><td style="text-align: right;"><span class="smcap">Pyrimidine</span></td></tr> +<tr><td style="text-align: right;">(reduced) Adenine</td><td> + </td><td>(oxidized) Thymine</td></tr> +<tr><td style="text-align: right;">(oxidized) Guanine</td><td> + </td><td>(reduced) Cytosine</td></tr> +</table> + +<div class="figcenter" style="width: 300px;"> +<img src="images/pyrimidine.png" width="188" height="149" alt="Pyrimidine" title="" /> +<p class="caption">Pyrimidine</p> +</div> + +<div class="figcenter" style="width: 550px;"> +<div class="figleft" style="width: 249px;"> +<img src="images/purine.png" width="249" height="226" alt="Purine" title="" /> +<p class="caption">Purine</p> +</div> +<div class="figright" style="width: 220px;"> +<img src="images/adenine.png" width="220" height="203" alt="Adenine" title="" /> +<p class="caption">Adenine</p> +</div> +</div> +<p style="clear:both;"> </p> + +<div class="figcenter" style="width: 680px;"> +<div class="figleft" style="width: 248px;"> +<img src="images/guanine.png" width="248" height="223" alt="Guanine" title="" /> +<p class="caption">Guanine</p> +</div> +<div class="figright" style="width: 161px;"> +<img src="images/uracil.png" width="161" height="198" alt="Uracil" title="" /> +<p class="caption">Uracil</p> +</div> +</div> +<div><img src="images/cytosine.png" width="210" height="201" alt="Cytosine" title="" /></div> +<p class="caption">Cytosine</p> + +<p style="clear:both;" class="center">The carbohydrate is ribose or deoxyribose.</p> + +<div class="figcenter" style="width: 400px;"> +<div class="figleft" style="width: 179px;"> +<img src="images/arabinose.png" width="179" height="239" alt="Arabinose" title="" /> +<p class="caption">Arabinose</p> +</div> +<div class="figright" style="width: 166px;"> +<img src="images/l-ribose.png" width="166" height="232" alt="L-Ribose" title="" /> +<p class="caption"><span class="smcap">l</span>-Ribose</p> +</div> +</div> +<p style="clear:both;" class="center">Fischer and Piloty, 1891</p> + +<div class="figcenter" style="width: 415px;"> +<img src="images/deoxyribose.png" width="415" height="145" alt="Deoxyribose" title="" /> +<p class="caption">Deoxyribose</p> +</div> + +<p>The exact position of phosphoric acid was established after long work +and verified by synthesis.<a name="FNanchor_33_33" id="FNanchor_33_33"></a><a href="#Footnote_33_33" class="fnanchor">[33]</a></p> + +<p>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,<a name="FNanchor_34_34" id="FNanchor_34_34"></a><a href="#Footnote_34_34" class="fnanchor">[34]</a> 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.</p> + +<div class="figcenter" style="width: 400px;"> +<img src="images/i037.png" width="400" height="206" alt="Adenosine Triphosphate: Adenine, D-Ribose, Phosphoric +acid" title="" /> +</div> + +<p>This change of ATP was considered to be the main source of energy in +muscle contraction by Otto Meyerhof.<a name="FNanchor_35_35" id="FNanchor_35_35"></a><a href="#Footnote_35_35" class="fnanchor">[35]</a> 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.</p> + +<p>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.<span class="pagenum"><a name="Page_195" id="Page_195">[Pg 195]</a></span></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i038.png" width="300" height="268" alt="Figure 16." title="Figure 16." /> +<p class="caption2">Figure 16.—<span class="smcap">Otto Meyerhof</span> (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. (<i>Photo courtesy +National Library of Medicine, Washington, D.C.</i>)</p> +</div> + +<div class="figcenter" style="width: 660px;"> +<div class="figleft" style="width: 300px;"> +<img src="images/i039a.png" width="300" height="359" alt="Figure 17." title="Figure 17." /> +</div> +<div class="figright" style="width: 300px;"> +<img src="images/i039b.png" width="300" height="358" alt="Figure 17." title="Figure 17." /> +</div> +<div class="figcenter" style="width: 600px; clear:both;"> +<p class="caption2">Figure 17.—<span class="smcap">Arthur Harden</span> (1865-1940), left, <span class="smcap">and Hans A. +S. von Euler-Chelpin</span> (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.</p> +</div> +</div> + +<p><span class="pagenum"><a name="Page_196" id="Page_196">[Pg 196]</a></span></p> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i040.png" width="300" height="413" alt="Figure 18." title="Figure 18." /> +<p class="caption2">Figure 18.—<span class="smcap">George de Hevesy</span> (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).</p> +</div> + +<div class="figcenter" style="width: 650px;"> +<div class="figleft" style="width: 300px;"> +<img src="images/i041a.png" width="300" height="400" alt="Figure 19." title="Figure 19." /> +</div> +<div class="figright" style="width: 285px;"> +<img src="images/i041b.png" width="285" height="400" alt="Figure 19." title="Figure 19." /> +</div> +<div class="figcenter" style="width: 600px; clear:both;"> +<p class="caption2">Figure 19.—<span class="smcap">Carl F. Cori</span> (b. 1896) <span class="smcap">and his wife, Gerty T. +Cori</span> (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. (<i>Photo +courtesy National Library of Medicine, Washington, D.C.</i>)</p> +</div> +</div> + +<p><span class="pagenum"><a name="Page_197" id="Page_197">[Pg 197]</a></span> +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.</p> + +<p>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.</p> + + + +<hr style="width: 65%;" /> +<h3>Phosphates in Biological Processes</h3> + + +<p>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?</p> + +<p>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.</p> + +<p>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.<a name="FNanchor_36_36" id="FNanchor_36_36"></a><a href="#Footnote_36_36" class="fnanchor">[36]</a> 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:</p> + +<div class="figcenter" style="width: 400px;"> +<img src="images/i043b.png" width="400" height="355" alt="Coenzyme I" title="" /> +</div> + + +<div class="figcenter" style="width: 650px;"> +<div class="figleft" style="width: 300px;"> +<img src="images/i043a.png" width="300" height="382" alt="Figure 20." title="Figure 20." /> +<p class="caption2">Figure 20.—<span class="smcap">Fritz A. Lipmann</span> (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.</p> +</div> +<p><span class="pagenum"><a name="Page_198" id="Page_198">[Pg 198]</a></span></p> +<div class="figright" style="width: 300px;"> +<img src="images/i044.png" width="300" height="419" alt="Figure 21." title="Figure 21." /> +<p class="caption2">Figure 21.—<span class="smcap">Alexander R. Todd</span> (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.</p> +</div> +</div> + +<p style="clear:both;">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.</p> + +<p>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 B<sub>1</sub>. +Others of the B vitamins contain phosphate groups, for example those of +the B<sub>2</sub> and B<sub>6</sub> group, and in B<sub>12</sub>, one lonely phosphate forms a +bridge in the large molecule that contains one atom of cobalt: +C<sub>63</sub>H<sub>90</sub>N<sub>14</sub>O<sub>14</sub>PCo. The formation of vitamin A from carotine +occurs under the influence of ATP.</p> + +<p>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.</p> + +<p>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.<a name="FNanchor_37_37" id="FNanchor_37_37"></a><a href="#Footnote_37_37" class="fnanchor">[37]</a></p> + +<p>In his research on the radioactive isotope P<sup>32</sup>, 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.”<a name="FNanchor_38_38" id="FNanchor_38_38"></a><a href="#Footnote_38_38" class="fnanchor">[38]</a> 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.</p> + + + +<hr style="width: 65%;" /> +<h3>Medicines and Poisons</h3> + + +<p>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<span class="pagenum"><a name="Page_199" id="Page_199">[Pg 199]</a></span> 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.<a name="FNanchor_39_39" id="FNanchor_39_39"></a><a href="#Footnote_39_39" class="fnanchor">[39]</a> Yeast itself is +considered to be a valuable food additive.</p> + +<p>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.”<a name="FNanchor_40_40" id="FNanchor_40_40"></a><a href="#Footnote_40_40" class="fnanchor">[40]</a> +Diisopropyl fluorophosphate has since become a potential agent for +chemical warfare. It inactivates an enzyme which controls the +transmission of nerve impulses to muscle, <a name="corr_40_6" id="corr_40_6"></a><ins class="mycorr" title="Original: acetylcholin">acetylcholine</ins> esterase.</p> + +<p>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,<a name="FNanchor_41_41" id="FNanchor_41_41"></a><a href="#Footnote_41_41" class="fnanchor">[41]</a> 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.<a name="FNanchor_42_42" id="FNanchor_42_42"></a><a href="#Footnote_42_42" class="fnanchor">[42]</a></p> + +<div class="figleft"> +<span class="pagenum"><a name="Page_200" id="Page_200">[Pg 200]</a></span> +<img src="images/dipterex.png" width="250" height="149" alt="Bayer's L 13/59 (Dipterex)" title="" /> +</div> +<p><br /><br />Bayer's L 13/59<br />(Dipterex)</p> +<p style="clear:both;"> </p> +<div class="figleft"> +<img src="images/schradan.png" width="300" height="159" alt="Octamethylpyrophosphoramide: Schradan" title="" /> +</div> +<p><br /><br />Schradan<br />Octamethylpyrophosphoramide</p> + +<div class="figcenter" style="width: 650px; clear:both;"> +<div class="figleft" style="width: 300px;"> +<img src="images/i048a.png" width="300" height="381" alt="Figure 22." title="Figure 22." /> +</div> +<div class="figright" style="width: 303px;"> +<img src="images/i048b.png" width="303" height="381" alt="Figure 22." title="Figure 22." /> +</div> +<div class="figcenter" style="width: 600px; clear:both;"> +<p class="caption2">Figure 22.—<span class="smcap">Arthur Kornberg</span> (b. 1918) <span class="smcap">and Severo Ochoa</span> +(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, P<sup>32</sup>. The synthetic polyribonucleotides were +found to resemble the natural substances in all essentials.</p> +</div> +</div> + +<div class="figcenter" style="width: 600px;"> +<img src="images/i049a.png" width="300" height="328" alt="Figure 23." title="Figure 23." /> +<p class="caption2">Figure 23.—<span class="smcap">Melvin Calvin</span> (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.</p> +</div> + +<p>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 <a name="corr_40_7" id="corr_40_7"></a><ins class="mycorr" title="Comma inserted">Hevesy,</ins> 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.</p> + +<p>Some impression of the continuing growth in this field<a name="FNanchor_43_43" id="FNanchor_43_43"></a><a href="#Footnote_43_43" class="fnanchor">[43]</a> can be gained +from the following data.</p> + +<p class="center"><span class="smcap">Phosphate Rock</span><br /> +annually “sold or used by producer” in the United States in million long +tons (2,240 lbs.)</p> + +<table id="table1" summary="Year, Million Long Tons"> +<tr><td> 1880 </td><td> 0.2</td></tr> +<tr><td> 1890</td><td> 0.5</td></tr> +<tr><td> 1900</td><td> 1.5</td></tr> +<tr><td> 1910</td><td> 2.655</td></tr> +<tr><td> 1920</td><td> 4.104</td></tr> +<tr><td> 1930</td><td> 3.926</td></tr> +<tr><td> 1940</td><td> 4.003</td></tr> +<tr><td> 1945</td><td> 5.807</td></tr> +<tr><td> 1950</td><td> 11.114</td></tr> +<tr><td> 1955</td><td> 12.265</td></tr> +<tr><td> 1955</td><td> (world: about 56)</td></tr> +<tr><td> 1960</td><td> 17.202</td></tr> +<tr><td> 1962</td><td> 19.060</td></tr> +</table> + +<p class="center">Sources: U.S. Bureau of the Census. <i>Historical Statistics of the United +States 1789-1945</i> (1949); <i>Statistical Abstract of the United States.</i></p> + +<p class="center"><span class="smcap">Elemental Phosphorus</span><br /> +annually produced in the United States in short tons (2,000 lbs.)</p> + +<table id="table2" summary="Year, Short Tons"> +<tr><td>1939 </td><td>43,000</td></tr> +<tr><td>1944</td><td>85,679</td></tr> +<tr><td>1950</td><td>153,233</td></tr> +<tr><td>1956</td><td>312,200</td></tr> +<tr><td>1958</td><td>335,750</td></tr> +<tr><td>1959</td><td>366,350</td></tr> +<tr><td>1960</td><td>409,096</td></tr> +<tr><td>1961</td><td>430,617</td></tr> +<tr><td>1962</td><td>451,970</td></tr> +</table> + +<p class="center">Source: U.S. Department of Commerce.</p> + + + +<hr style="width: 65%;" /> +<div class="footnotes"> +<h3>FOOTNOTES:</h3> + +<div class="footnote"><p><a name="Footnote_1_1" id="Footnote_1_1"></a><a href="#FNanchor_1_1"><span class="label">[1]</span></a> <span class="smcap">Wilhelm Homberg</span>, <i>Mémoires Académie, 1666-1699</i> (Paris, +1730), vol. 10, under date of April 30, 1692, pp. 57-61.</p></div> + +<div class="footnote"><p><a name="Footnote_2_2" id="Footnote_2_2"></a><a href="#FNanchor_2_2"><span class="label">[2]</span></a> <span class="smcap">Fortunio Licetus</span>, <i>Lithiophosphorus sive de lapide +Bononiensi</i> (Venice, 1640).</p></div> + +<div class="footnote"><p><a name="Footnote_3_3" id="Footnote_3_3"></a><a href="#FNanchor_3_3"><span class="label">[3]</span></a> Cited in <span class="smcap">Peter Joseph Macquer</span> <i>Chymisches Wörterbuch</i>, 2nd +ed. (Leipzig: Weidmann, 1789), vol. 4, p. 508, footnote “c” as “Kletwich +(de phosph. liqu. et solid. 1689, Thes. II).”</p></div> + +<div class="footnote"><p><a name="Footnote_4_4" id="Footnote_4_4"></a><a href="#FNanchor_4_4"><span class="label">[4]</span></a> <span class="smcap">Ferdinand Hoefer</span>, <i>Histoire de la Chimie</i> (Paris, 1843), +vol. 1, p. 339.</p></div> + +<div class="footnote"><p><a name="Footnote_5_5" id="Footnote_5_5"></a><a href="#FNanchor_5_5"><span class="label">[5]</span></a> <span class="smcap">G. W. von Leibniz</span>, <i>Mémoires Académie</i> (Paris, 1682); +<i>Akademie der Wissenschaften, Miscellanea Berolinensia</i> (Berlin, 1710), +vol. 1, p. 91.</p></div> + +<div class="footnote"><p><a name="Footnote_6_6" id="Footnote_6_6"></a><a href="#FNanchor_6_6"><span class="label">[6]</span></a> <span class="smcap">Jean Hellot</span>, <i>Mémoires Académie 1737</i> (Paris, 1766), under +date of November 13, 1737, pp. 342-378.</p></div> + +<div class="footnote"><p><a name="Footnote_7_7" id="Footnote_7_7"></a><a href="#FNanchor_7_7"><span class="label">[7]</span></a> <span class="smcap">Macquer</span>, op. cit. (footnote 3), p. 551.</p></div> + +<div class="footnote"><p><a name="Footnote_8_8" id="Footnote_8_8"></a><a href="#FNanchor_8_8"><span class="label">[8]</span></a> <span class="smcap">A. S. Marggraf</span>, <i>Akademie der Wissenschaften, Miscellanea +Berolinensia</i> (Berlin, 1743), vol. 7, 342 ff.; see also <span class="smcap">Wilhelm Ostwald</span> +<i>Klassiker der Exakten Naturwissenschaften</i> (Leipzig: Engelmann, 1913), +no. 187.</p></div> + +<div class="footnote"><p><a name="Footnote_9_9" id="Footnote_9_9"></a><a href="#FNanchor_9_9"><span class="label">[9]</span></a> <span class="smcap">G. Hanckewitz</span>, [Hankwitz], <i>Philosophical Transactions of +the Royal Society of London</i>, 1724-1734, abridged (London, 1809), vol. +7, pp. 596-602.</p></div> + +<div class="footnote"><p><a name="Footnote_10_10" id="Footnote_10_10"></a><a href="#FNanchor_10_10"><span class="label">[10]</span></a> <span class="smcap">Antoine Laurent Lavoisier</span>, “Sur la Combustion du Phosphore +de Kunckel, Et sur la nature de l’acide qui resulte de cette +Combustion,” <i>Mémoires Académie 1777</i>, (Paris, 1780), pp. 65-78.</p></div> + +<div class="footnote"><p><a name="Footnote_11_11" id="Footnote_11_11"></a><a href="#FNanchor_11_11"><span class="label">[11]</span></a> <span class="smcap">Guyton de Morveau</span> and others, <i>Méthode de Nomenclature +Chimique</i>, Proposée par MM. de Morveau, Lavoisier, Bertholet, & de +Fourcroy (Paris, 1787), plate 9.</p></div> + +<div class="footnote"><p><a name="Footnote_12_12" id="Footnote_12_12"></a><a href="#FNanchor_12_12"><span class="label">[12]</span></a> <span class="smcap">Macquer</span>, op. cit. (footnote 3), p. 513.</p></div> + +<div class="footnote"><p><a name="Footnote_13_13" id="Footnote_13_13"></a><a href="#FNanchor_13_13"><span class="label">[13]</span></a> <span class="smcap">Marie Boas</span>, <i>Robert Boyle and Seventeenth Century +Chemistry</i> (New York: Cambridge University Press, 1958), p. 226; see +also <span class="smcap">Wyndham Miles</span>, “The History of Dr. Brand’s Phosphorus Elementarus,” +<i>Armed Forces Chemical Journal</i> (November-December 1958), p. 25.</p></div> + +<div class="footnote"><p><a name="Footnote_14_14" id="Footnote_14_14"></a><a href="#FNanchor_14_14"><span class="label">[14]</span></a> <span class="smcap">Archibald Clow</span> and <span class="smcap">Nan L. Clow</span>, <i>The Chemical Revolution</i> +(London: Batchworth Press, 1952), p. 451.</p></div> + +<div class="footnote"><p><a name="Footnote_15_15" id="Footnote_15_15"></a><a href="#FNanchor_15_15"><span class="label">[15]</span></a> <span class="smcap">Émile Kopp</span>, <i>Comptes-rendus hebdomadaires des Séances de +l’Académie des Sciences, Paris</i> (1844), vol. 18, p. 871; <span class="smcap">Wilhelm +Hittorf</span>, <i>Annalen der Chemie und Pharmazie</i>, suppl. to vol. 4, p. 37; +<span class="smcap">Anton Schrötter</span>, <i>Annales de Chimie et de Physique</i>, series 3, vol. 24 +(1848), p. 406; see also Schrötter’s report on “Phosphor und Zündwaaren” +in <span class="smcap">A. W. von Hofmann</span>, <i>Bericht über die Entwicklung der Chemischen +Industrie</i> (Braunschweig: Vieweg, 1875), pp. 219-246.</p></div> + +<div class="footnote"><p><a name="Footnote_16_16" id="Footnote_16_16"></a><a href="#FNanchor_16_16"><span class="label">[16]</span></a> <span class="smcap">R. Glauber</span>, <i>Furni Novi Philosphici</i> (Amsterdam, 1649), +vol. 2, pp. 12 ff.</p></div> + +<div class="footnote"><p><a name="Footnote_17_17" id="Footnote_17_17"></a><a href="#FNanchor_17_17"><span class="label">[17]</span></a> <span class="smcap">Hermann Schelenz</span>, <i>Geschichte der Pharmazie</i> (Berlin: +Springer, 1904), p. 598.</p></div> + +<div class="footnote"><p><a name="Footnote_18_18" id="Footnote_18_18"></a><a href="#FNanchor_18_18"><span class="label">[18]</span></a> <span class="smcap">J. Personne</span>, <i>Comptes-rendus ...</i>, Paris (1869), vol. 68, +pp. 543-546.</p></div> + +<div class="footnote"><p><a name="Footnote_19_19" id="Footnote_19_19"></a><a href="#FNanchor_19_19"><span class="label">[19]</span></a> <span class="smcap">A. Wurtz</span>, <i>Dictionnaire de Chimie</i> (Paris, 1876), vol. 2, +part 2, p. 951.</p></div> + +<div class="footnote"><p><a name="Footnote_20_20" id="Footnote_20_20"></a><a href="#FNanchor_20_20"><span class="label">[20]</span></a> <span class="smcap">Karl W. Scheele</span>, <i>Nachgelassene Briefe und +Aufzeichnungen</i>, edit. A. E. Nordenskiöld (Stockholm: Norstedt, 1892), +pp. 38, 144.</p></div> + +<div class="footnote"><p><a name="Footnote_21_21" id="Footnote_21_21"></a><a href="#FNanchor_21_21"><span class="label">[21]</span></a> <span class="smcap">J. J. Berzelius</span>, <i>Lehrbuch</i>, transl. F. Wöhler (Dresden, +1827), vol. 3, part 1, p. 96.</p></div> + +<div class="footnote"><p><a name="Footnote_22_22" id="Footnote_22_22"></a><a href="#FNanchor_22_22"><span class="label">[22]</span></a> <span class="smcap">Thomas Graham</span>, <i>Philosophical Transactions of the Royal +Society of London</i> (1833), pp. 253-284.</p></div> + +<div class="footnote"><p><a name="Footnote_23_23" id="Footnote_23_23"></a><a href="#FNanchor_23_23"><span class="label">[23]</span></a> <span class="smcap">Justus Liebig’s</span> <i>Annalen der Pharmacie</i> (1838), vol. 26, +p. 113 ff.</p></div> + +<div class="footnote"><p><a name="Footnote_24_24" id="Footnote_24_24"></a><a href="#FNanchor_24_24"><span class="label">[24]</span></a> <span class="smcap">A. Wurtz</span>, <i>Annales de Chimie et de Physique</i>, series 3, +vol. 16 (1846), p. 190.</p></div> + +<div class="footnote"><p><a name="Footnote_25_25" id="Footnote_25_25"></a><a href="#FNanchor_25_25"><span class="label">[25]</span></a> <span class="smcap">Carroll D. Wright</span>, <i>The Phosphate Industry in the United +States</i>, sixth special report of the Commissioner of Labor (Washington, +1893).</p></div> + +<div class="footnote"><p><a name="Footnote_26_26" id="Footnote_26_26"></a><a href="#FNanchor_26_26"><span class="label">[26]</span></a> <span class="smcap">J. Stoklasa</span>, <i>Biochemischer Kreislauf des Phosphat-Ions im +Boden, Centralblatt für Bakteriologie ...</i> (Jena: Fischer, March 22, +1911), vol. 29, nos. 15-19.</p></div> + +<div class="footnote"><p><a name="Footnote_27_27" id="Footnote_27_27"></a><a href="#FNanchor_27_27"><span class="label">[27]</span></a> <span class="smcap">N. T. Gobley</span>, <i>Comptes-rendus</i> ..., Paris (1845), vol. 21, +p. 718.</p></div> + +<div class="footnote"><p><a name="Footnote_28_28" id="Footnote_28_28"></a><a href="#FNanchor_28_28"><span class="label">[28]</span></a> <span class="smcap">A. Wurtz</span>, <i>Comptes-rendus</i> ..., Paris (1868), vol. 66, p. +772.</p></div> + +<div class="footnote"><p><a name="Footnote_29_29" id="Footnote_29_29"></a><a href="#FNanchor_29_29"><span class="label">[29]</span></a> <span class="smcap">L. Thudichum</span>, <i>Die chemische Constitution des Gehirns des +Menschen und der Tiere</i> (1901); see also <span class="smcap">H. Wittcoff</span>, <span class="smcap">The Phosphatides</span> +(New York: Reinhold, 1951).</p></div> + +<div class="footnote"><p><a name="Footnote_30_30" id="Footnote_30_30"></a><a href="#FNanchor_30_30"><span class="label">[30]</span></a> <span class="smcap">William Crookes</span>, <i>British Association for the Advancement +of Science, Reports</i> (1887), sec. B, p. 573.</p></div> + +<div class="footnote"><p><a name="Footnote_31_31" id="Footnote_31_31"></a><a href="#FNanchor_31_31"><span class="label">[31]</span></a> <span class="smcap">J. E. Courtois</span> and <span class="smcap">A. Lino</span>, <i>Progress in the Chemistry of +Organic Natural Products</i>, edit. L. Zechmeister (Vienna: Springer +Verlag, 1961), vol. 19, p. 316-373.</p></div> + +<div class="footnote"><p><a name="Footnote_32_32" id="Footnote_32_32"></a><a href="#FNanchor_32_32"><span class="label">[32]</span></a> <span class="smcap">A. Wurt</span>, <i>Dictionnaire de Chimie</i>, supp. part 2, [n.d.] p. +1087; <span class="smcap">A. Kossel</span>, <i>Zeitschrift für physiologische Chemie</i>, series 3 +(1879), p. 284.</p></div> + +<div class="footnote"><p><a name="Footnote_33_33" id="Footnote_33_33"></a><a href="#FNanchor_33_33"><span class="label">[33]</span></a> <span class="smcap">Alexander Todd</span>, <i>Les Prix Nobel en 1957</i> (Stockholm).</p></div> + +<div class="footnote"><p><a name="Footnote_34_34" id="Footnote_34_34"></a><a href="#FNanchor_34_34"><span class="label">[34]</span></a> <span class="smcap">Hans von Euler-Chelpin</span>, <i>Les Prix Nobel en 1929</i> +(Stockholm).</p></div> + +<div class="footnote"><p><a name="Footnote_35_35" id="Footnote_35_35"></a><a href="#FNanchor_35_35"><span class="label">[35]</span></a> <span class="smcap">O. Meyerhof</span> and <span class="smcap">E. Lundsgaard</span>, <i>Naturwissenschaften</i> +(Berlin, 1930), vol. 18, pp. 330, 787.</p></div> + +<div class="footnote"><p><a name="Footnote_36_36" id="Footnote_36_36"></a><a href="#FNanchor_36_36"><span class="label">[36]</span></a> <span class="smcap">K. Lohmann</span>, <i>Naturwissenschaften</i> (Berlin, 1929), vol. 17, +p. 624; <span class="smcap">C. H. Fiske</span> and <span class="smcap">Y. Subbarow</span>, <i>Science</i> (Washington, 1929), vol. +70, p. 381 f.</p></div> + +<div class="footnote"><p><a name="Footnote_37_37" id="Footnote_37_37"></a><a href="#FNanchor_37_37"><span class="label">[37]</span></a> <span class="smcap">J. Brachet</span>, <i>Scientia, Revista di Scienza</i> (1960), vol. +95, p. 119.</p></div> + +<div class="footnote"><p><a name="Footnote_38_38" id="Footnote_38_38"></a><a href="#FNanchor_38_38"><span class="label">[38]</span></a> <span class="smcap">George de Hevesy</span>, <i>Les Prix Nobel en 1940</i> (Stockholm). +See also <span class="smcap">Eduard Farber</span>, <i>Nobel Prize Winners in Chemistry</i>, 2nd ed. (New +York: Schuman, 1963), p. 179.</p></div> + +<div class="footnote"><p><a name="Footnote_39_39" id="Footnote_39_39"></a><a href="#FNanchor_39_39"><span class="label">[39]</span></a> <a name="corr_40_8" id="corr_40_8"></a><ins class="mycorr" title="Original: See.">See,</ins> e.g., <i>Chemical Week</i>, vol. 77 (September 3, 1955), +p. 79 f.; <span class="smcap">J. Bolle</span>, <i>Chimie et Industrie</i> (1960), vol. 83, p. 252.</p></div> + +<div class="footnote"><p><a name="Footnote_40_40" id="Footnote_40_40"></a><a href="#FNanchor_40_40"><span class="label">[40]</span></a> <span class="smcap">W. Lange</span>, <i>Berichte der Deutschen Chemischen Gesellschaft</i> +(Berlin, 1929), vol. 62, p. 793; vol. 65 (1932), p. 1598.</p></div> + +<div class="footnote"><p><a name="Footnote_41_41" id="Footnote_41_41"></a><a href="#FNanchor_41_41"><span class="label">[41]</span></a> <span class="smcap">Gerhard Schrader</span>, U.S. patent 2,336,302 of 1943 (priority +in Germany, 1938); <span class="smcap">S. A. Hall</span> and <span class="smcap">M. Jacobson</span>, <i>Industrial and +Engineering Chemistry</i> (1943), vol. 40, p. 694.</p></div> + +<div class="footnote"><p><a name="Footnote_42_42" id="Footnote_42_42"></a><a href="#FNanchor_42_42"><span class="label">[42]</span></a> <span class="smcap">A. M. Mattsen</span> and others, <i>Journal of Agriculture and Food +Chemistry</i> (1955), vol. 3, p. 319.</p></div> + +<div class="footnote"><p><a name="Footnote_43_43" id="Footnote_43_43"></a><a href="#FNanchor_43_43"><span class="label">[43]</span></a> <span class="smcap">John B. Van Wazer</span>, <cite>Phosphorus and its Compounds</cite>, 2 vols. +(vol. 1, <cite>Chemistry</cite>; vol. 2 <cite>Technology, Biological Functions and +Applications</cite>), New York: Interscience, 1958, 1961.</p></div> +</div> + +<hr style="width: 25%;" /> + +<p class="center"><small>U.S. GOVERNMENT PRINTING OFFICE: 1965</small></p> + +<p class="center"><small>For sale by the Superintendent of Documents, U.S. Government Printing +Office Washington, D.C. 20402—Price 25 cents</small></p> + + +<hr style="width: 65%;" /> + +<h3>INDEX</h3> + +<p>Aristotle, <a href="#Page_179">179</a><br /><br /></p> + + +<p>Baeyer, Adolf, <a href="#Page_193">193</a></p> + +<p>Bechil, Achild, <a href="#Page_179">179</a></p> + +<p>Berthelot, Marcellin, <a href="#Page_189">189</a></p> + +<p>Berzelius, Jöns Jakob, <a href="#Page_182">182</a></p> + +<p>Black and Bell, plant at Stratford, <a href="#Page_182">182</a></p> + +<p>Boussingault, Jean Baptiste, <a href="#Page_185">185</a></p> + +<p>Boyle, Robert, <a href="#Page_178">178</a>, <a href="#Page_179">179</a></p> + +<p>Brand, H., <a href="#Page_178">178</a>, <a href="#Page_179">179</a></p> + +<p>Buchner, Hans, <a href="#Page_197">197</a>, <a href="#Page_200">200</a><br /><br /></p> + + +<p>Calvin, Melvin, <a href="#Page_200">200</a></p> + +<p>Casciarolo, Vicenzo, <a href="#Page_179">179</a></p> + +<p>Chevreul, Michel, <a href="#Page_189">189</a></p> + +<p>Cori, Carl F., <a href="#Page_200">200</a></p> + +<p>Cori, Gerti T., <a href="#Page_200">200</a></p> + +<p>Crookes, William, <a href="#Page_192">192</a><br /><br /></p> + + +<p>Davy, Sir Humphry, <a href="#Page_185">185</a></p> + +<p>De Hevesy, George, <a href="#Page_198">198</a>, <a href="#Page_200">200</a></p> + +<p>De la Vega, Garcilaso, <a href="#Page_185">185</a></p> + +<p>De Saussure, Théodore, <a href="#Page_185">185</a><br /><br /></p> + + +<p>Euler-Chelpin, Hans von, <a href="#Page_197">197</a>, <a href="#Page_200">200</a><br /><br /></p> + + +<p>Fernelius, Jean, <a href="#Page_179">179</a></p> + +<p>Feulgen, Robert, <a href="#Page_193">193</a></p> + +<p>Fischer, Emil, <a href="#Page_193">193</a><br /><br /></p> + + +<p><a name="corr_40_9" id="corr_40_9"></a><ins class="mycorr" title="Original: Gähn">Gahn</ins>, Johann Gottlieb, <a href="#Page_182">182</a></p> + +<p>Gay-Lussac, Joseph Louis, <a href="#Page_182">182</a></p> + +<p>Gobley, Nicolas Théodore, <a href="#Page_191">191</a></p> + +<p>Graham, Thomas, <a href="#Page_182">182</a>, <a href="#Page_183">183</a>, <a href="#Page_185">185</a><br /><br /></p> + + +<p>Hankwitz, Gottfried, <a href="#Page_180">180</a></p> + +<p>Harden, Arthur, <a href="#Page_197">197</a>, <a href="#Page_200">200</a></p> + +<p>Hartmann, Immanuel Peter, <a href="#Page_181">181</a></p> + +<p>Hellot, Jean, <a href="#Page_180">180</a></p> + +<p>Henry II, King of France, <a href="#Page_179">179</a></p> + +<p>Hittorf, Wilhelm, <a href="#Page_181">181</a></p> + +<p>Hoefer, Ferdinand, <a href="#Page_179">179</a></p> + +<p>Holmberg, Wilhelm, <a href="#Page_178">178</a></p> + +<p>Hoppe-Seyler, Felix, <a href="#Page_193">193</a></p> + +<p>Humboldt, Alexander von, <a href="#Page_185">185</a></p> + +<p>Huygens, Christiaan, <a href="#Page_179">179</a><br /><br /></p> + + +<p>Incas, <a href="#Page_185">185</a><br /><br /></p> + + +<p>Kletwich, Johann Christopher, <a href="#Page_179">179</a></p> + +<p>Koppe, Émile, <a href="#Page_181">181</a></p> + +<p>Kornberg, Arthur, <a href="#Page_200">200</a></p> + +<p>Kossel, Albrecht, <a href="#Page_200">200</a></p> + +<p>Kraft, Johann Daniel, <a href="#Page_179">179</a></p> + +<p>Kramer, Dr. ——, <a href="#Page_181">181</a></p> + +<p>Kunckel, Johann, <a href="#Page_179">179</a><br /><br /></p> + + +<p>Lange, W., <a href="#Page_199">199</a></p> + +<p>Lavoisier, Antoine Laurent, <a href="#Page_181">181</a>, <a href="#Page_185">185</a></p> + +<p>Laws, John Bennet, <a href="#Page_186">186</a></p> + +<p>Leibnitz, Gottfried Wilhelm von, <a href="#Page_179">179</a></p> + +<p>Lennox, Charles, third Duke of Richmond, <a href="#Page_185">185</a></p> + +<p>Leonhardi, Johann Gottfried, <a href="#Page_179">179</a></p> + +<p>Levine, Phoebus Aaron Theodor, <a href="#Page_193">193</a></p> + +<p>Liebig, Justus, <a href="#Page_183">183</a>, <a href="#Page_185">185</a>, <a href="#Page_186">186</a></p> + +<p>Liebreich, Oscar, <a href="#Page_191">191</a></p> + +<p>Lipmann, Fritz, <a href="#Page_200">200</a></p> + +<p>London, E. S., <a href="#Page_193">193</a><br /><br /></p> + + +<p>Macquer, Peter Joseph, <a href="#Page_180">180</a></p> + +<p>Marggraf, Andreas Sigismund, <a href="#Page_180">180</a></p> + +<p>Meyerhof, Otto, <a href="#Page_194">194</a>, <a href="#Page_200">200</a></p> + +<p>Miescher, Johann Friedrich, <a href="#Page_192">192</a></p> + +<p>Muspratt, James, <a href="#Page_186">186</a><br /><br /></p> + + +<p>Nietzsche, Friedrich, <a href="#Page_186">186</a>, <a href="#Page_187">187</a>, <a href="#Page_189">189</a><br /><br /></p> + + +<p>Ochoa, Severo, <a href="#Page_200">200</a><br /><br /></p> + + +<p>Pelouze, Théophile Juste, <a href="#Page_189">189</a><br /><br /></p> + + +<p>Rouelle, Guillaume François, <a href="#Page_181">181</a><br /><br /></p> + + +<p>Scheele, Karl W., <a href="#Page_182">182</a></p> + +<p>Schmiedeberg, Oswald, <a href="#Page_193">193</a></p> + +<p>Schrader, Gerhard, <a href="#Page_199">199</a></p> + +<p>Schrötter, Anton, <a href="#Page_181">181</a></p> + +<p>Stoklasa, Julius, <a href="#Page_186">186</a></p> + +<p>Strecker, Adolf Friedrich, <a href="#Page_191">191</a><br /><br /></p> + + +<p>Thudichum, Ludwig, <a href="#Page_192">192</a></p> + +<p>Todd, Lord Alexander, <a href="#Page_200">200</a><br /><br /></p> + + +<p>Willm, Edmond, <a href="#Page_182">182</a></p> + +<p>Willstätter, Richard, <a href="#Page_191">191</a></p> + +<p>Wurtz, Adolphe, <a href="#Page_185">185</a>, <a href="#Page_191">191</a><br /><br /></p> + + +<div class="tnote"> +<h3><a name="corrections_37" id="corrections_37"></a>Transcriber’s Notes</h3> + + +<p>The following typographical errors have been corrected:</p> + +<p class="hang4">Page <a href="#corr_40_1">180</a> “<i>Abfällen</i>, Vieweg, Braunschweig,” - had “Viewig”.</p> + +<p class="hang4">Page <a href="#corr_40_2">188</a> “wires <i>d</i> from the dynamo D” - had “dynano”.</p> + +<p class="hang4">Page <a href="#corr_40_3">191</a> “phosphate are attached, for example,” - had “attached, For”.</p> + +<p class="hang4">Page <a href="#corr_40_4">192</a> “But phosphatides occur” - had “phosphatide soccur”.</p> + +<p class="hang4">Page <a href="#corr_40_5">193</a> “the nucleic acid from the thymus” - had “nucleidic”.</p> + +<p class="hang4">Page <a href="#corr_40_6">199</a> “acetylcholine esterase.” - had “acetylcholin”.</p> + +<p class="hang4">Page <a href="#corr_40_7">200</a> “George de Hevesy, Carl F. Cori,” - comma added after Hevesy.</p> + +<p class="hang4">Footnote <a href="#corr_40_8">39</a>: “See, e.g., <i>Chemical Week</i>, vol. 77” - had “See. e.g.”</p> + +<p class="hang4"><a href="#corr_40_9">Index Entry</a>: “Gahn, Johann Gottlieb, 182” - had “Gähn”</p> + +<p>The spelling of “Bertholet” [Claude Louis Berthollet] is as given on the +original title page of the work referenced in this paper.</p> + +<p>Inconsistent hyphenation of chemical names has been retained.</p> +</div> + + + + + + + + +<pre> + + + + + +End of the Project Gutenberg EBook of History of Phosphorus, by Eduard Farber + +*** END OF THIS PROJECT GUTENBERG EBOOK HISTORY OF PHOSPHORUS *** + +***** This file should be named 33766-h.htm or 33766-h.zip ***** +This and all associated files of various formats will be found in: + https://www.gutenberg.org/3/3/7/6/33766/ + +Produced by Chris Curnow, Joseph Cooper, Louise Pattison +and the Online Distributed Proofreading Team at +https://www.pgdp.net + + +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. 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