The manufacture of chemical manures
vJ^ hF>R 1 1^ G H Ptr '^f^ " -■ isJ, . jfT' 15'' dM^-fi i^/fM ig. -^ '^ •^'^'■^ '■M'^;mi^^'<^'^^ ^^ iaiii THE MANUFACTURE OF CHEMICAL MANURES THE MANUFACTURE OF CHEMICAL MANURES BY J. FRITSCH TRANSLATED FROM THE FRENCH, WITH NUMEROUS NOTES, BY DONALD GRANT WITH SIXTY-NINE ILLUSTRATIONS AND ONE HUNDRED AND EIGHT TABLES 1 , <> '. LONDON SCOTT, GREENWOOD & SON "THE OIL AND COLOUR TRADES JOURNAL" OFFICES 8 BROADWAY, LUDGATE, E.G. 1911 [The sole right of tratislation into English rests '.mth Scott, Greemvood &-■ Son] sk^^ r AGRIC> LIBRARY AUTHOR'S PREFACE. Notwithstanding the magnitude which the manufacture of Chemical Manures has assumed m France, no author has hitherto attempted to make it the subject of a special treatise in the French language. The author has endeavoured to fill this gap in spite of the difficulties inherent to the subject. From a technical point of view% French hterature supphes but little material for such a purpose. French chemists and works managers rarely write. They are tied down by pro- fessional secrecy, and when they do risk writing their prose is comphcated by an embarrassed reticence which deprives it of all practical interest. Foreign publications, German especially, are better equipped in this respect. In addition to numerous special treatises, annual reports on the progress of different industries are available, edited most often by retired practical . men or bv old works managers, knowing everything, calhng things by" their names, discussing the value of the new pro- cesses recommended or apphed, pointing out their merits and defects. • u i. u The numerous and valuable data which the author has thus collected have largely recompensed him for the ill-will which he encountered elsewhere. Certain constructors, it is true that they are not precisely at the head of mechanical progress, made a wry face. Others omitted to reply to our letters. This explains why French engineering firms are but little represented in this treatise. This explanation is due to the reader : it is for him to draw^ the moral. The author, however, hastens to add that he met with the best reception from specialists eminent by their know^- ledge and long experience, and obtained from them the most complete information. He here returns them his smcere thanks, as well as to the scientists who have aided him by their counsel and encouragement. The author makes no pretension of presenting a pertect treatise, yet he is confident that it will be useful to every one in any way connected with chemical manures. Paris, March, 1909. 256601 TRANSLATOK'S PREFACE. From a long experience as works uiana.s^er and chemist in the sulphuric acid and chemical manure trade, the translator has been able to add from his own knowled^/e acquired in actual practice numerous original practical notes to the Enghsh edition of M. Fritsch"s work, solely with the object of increasing the utihty of the treatise. It is to be hoped that the book which, independent of these notes, has unique merits of its own, will appeal in its Enghsh dress not only to manure manufacturers but to farmers themselves, as well as to agricultural students and all those who take an intelligent interest in the subject of agricultural chemistry. Common sense dictates that it is equally important for the student of agriculture to be able if need be to eti'ect the synthesis of a manure as to be able to carry out the analysis thereof. The student who can construct mentally a formula for a manure to yield, whether by dry mixing or wet mixing, certain pre- determined results on analysis, is more highly trained than he who can only use the faculties of destruction to resolve a manure into its constituent elements by slavishly following a treatise on agricultural chemical analysis, and that too often by methods which he would have to unlearn if he entered a manure factory, where he wrfiild have to analyse manures and raw materials against chemists of world-wide reputation. DONALD GRANT. May, V.ni. VI CONTENTS. CHAPTEE I. PHOSPHORIC ACID. PAGES Historv— Origin and distribution of phosphoric acid m nature— Properties of phosphorus-1. Physical properties-2. Chemical properties- Hvpophosphorous acid— Phosphorous acid— Phosphoric acid^Meta- phosphoric acid-Pvrophosphoric acid-Orthophosphoric acid- Monometallic orthophosphate-Dimetallic orthophosphate— In- metallic orthophosphate-Phosphate of lime-Monocalcic phosphate or acid phosphate of lime CaH,{PO,),-Dicalcic phosphate or monacid phosphate of lime-Tricalcic phosphate-Neutral phosphate of lime-Tribasic phosphate of lime Ca,(PO,),-Phosphates of ammonium and sodium— Basic phosphate of ammonium (MHJr.^ ^4 —Monacid phosphate of sodium (ordinary commercial phosphate ot soda Na.HPO, + 12H..O) — Monacid phosphate of ammonium and sodium— Monacid phosphate of ammonium -Monacid phosphate ot mac^nesium— Double phosphate of ammonium and magnesium NH^MgPO, + 6H2O— Phosphates of iron— The phospTaates of alumina i-id CHAPTEE II. PRINCIPAL PHOSPHATE DEPOSITS. I France :-Pas de Calais, Somme, Oise-1. Somme phosphate-2. Pas de Calais phosphates-3. Meuse and Ardennes phosphates--4. Cote d'Or phosphates-5. Cher phosphate— 6. Quercy phosphates (Lot and neighbouring departments)-?. Gard and Ardeche phosphates-8. ,Dr6me and Isere phosphates-9. Pyrenees or Arieges phosphates li. Belgium -.—Ciply phosphates— Liege phosphates. ^/I^- -^^§^^^,7, Lyme Regis coprolites-Cambridge coprolites-Suffolk coprolites. IV. Sweden and Norway :— Norwegian apatite. V. Germany, vi. Austria-Hungary :— Bohemian phosphates. VII. Russia. viii. Spain -.-Estremadura apatite. IX. North America -.-Canada- South Carolina-Land phosphate and river pliosphate— 1 loricla— Hard rock-Plate rock o? sheet rock-Soft phosphate-River pebbles —Land pebbles— Tennessee— Tennessee rock phosphate— Remarks on the actual condition of the phosphate industry m America. A. Africa :-Tunis and Algeria-Marly phosphates m i^odules-Phos- phatic limestones. XL Asia :-Phosphates of Oceania. (I-West India Islands :-Redonda Isles, Sombrero, Navassa, Aruba, Cura(^ao, Los Roques, Alta Vela, Rata. (H.) Islands of the Pacific Ocean .- Baker, Jarvis, Maiden, Fanning, Starbuck Howland, Phoenix^ Sidney ,Enderbury, Minerva, Aves, Lacepede, Flmt Browse (? Brown , Fluon, Chesterfield, Abrolhos, Mona, Cayman Chpperton Nauru Angaur, Makatea, etc. (I.) West India Islands:-!. Redonda vii viii CONTENTS. PAGES j)liosphate — 2. Sombrero phosphate — 3. Navassa phosphate — 4. Aruba phosphate — 5. Alta Vela phosphate — 6. Rata or Fernando Noronjo phosphate — 7. Monk's Island (Caribbean Sea) phospho guano — 8. Christmas Island phospho guano. (II.) Pacific Ocean Isles: — Baker Island guano — Jarvis guano — Fanning Island guano — Brown Island guano — Mejillones guano — Lacepede Island guano — Clipperton Island guano — Angaur Island phosphate — Makatea Isle phosphatic deposits — Distribution of phosphates in the different geological formations. (I.) Gneiss Epoch. (II.) Paleozoic (or primary) epoch — 1. Silurian formation — 2. Devonian formation — 3. Carbon- iferous formation. (HI.) Mesozoic or secondary epoch — 1. Trias for- mation— 2. .Jurassic formation — 3. Cretaceous — Cainozoic or Ter- tiary epoch — Eocene formation — Quaternary and recent epoch - 14-49 Geographical distribution of phosphate of lime and guano deposits and their chemical composition — Table ------- 50-59 CHAPTEE III. DRYING AND ENRICHMENT OF PHOSPHATES. Drying — Calcining the nodules — Two tests — Different methods of strengthening and utilizing poor quality phosphates : — 1. Dumonceau and Nicolas — 2. Simpson — 3. Brochon — 4. Winsinger — 5. O. lahne — 6. Martin — 7. Thonnar and Huxton — 8. Schucht — 9. Carr — 10. Glaser — 11. Petermann — 12. Hodgkins — Manufacture of precipitated phosphate by electrolysis - . _ . 60-66 CHAPTEE IV. HISTORICAL REVIEW OF SUPERPHOSPHATE MANUFACTURE. The manufacture of superphosphates from 1850 to 1870—1871 to 1880— 1880 to 1894—1895 to 1908 - 67-72 CHAPTEE V. - THEORY OF MANUFACTURE OF SOLUBLE PHOSPHATES. Effect of the impurities in phosphates on their behaviour in the process by which they are rendered soluble— Carbonates of lime and magnesia — Iodine — Calcium fluoride — Organic matter — Method of determin- ing the amount of acid to use in order to render the phosphate soluble 73-83 CHAPTEE VI. MANUFACTURE OF SUPERPHOSPHATE. 1. The grinding of the raw phosphate — 2. Dissolving the ground phos- phate in sulphuric acid — 3. Drying the superphosphate — 1. Grind- CONTENTS. ix PAGES. ing the raw phosphate — Crushers— Edge runners— Flatstoue mills — Ball mill — Pfeiffer's mill, with combined air separator—Jaw-breaker mills— Crac-king mills— Toothed roller mills— Disintegrators— Mills with percussion blades fitted in circular revolving boss — Elevators —Sieves— Filter press— Mixing of the phosphate with sulphuric acid — Evacuation of the toxic fumes ------ 81-110 CHAPTER VII. CRUSHING, SIFTING, DRYING, AND STORING OF SUPER- PHOSPHATE. RETROGRADATION. Emptying and shifting the superphosphate house or den — New methods- for the mechanical extraction of superphosphate from the " den " — AUegri's plant for shifting superphosphate from the "dens ' — Break- ing up and sifting or screening of superphosphate — Carr's disin- tegra:or— Cvlindrical crusher fitted with teeth — Cylindrical crusher,, with two rolls fitted with teeth— Artificial drying of superphosphate —Theoretical review of drying— Moller and Pfeiffer's drying machine — Heymann and Nitsch's process for drying superphosphates — Dr. Lorenz' process- Dr. Lutjens' successor — Superheated superphos- phates— Drying superphosphates in the cold — Drying of the super- phosphate by dusting and mixing in the Georges crusher-sifter — Storing (preservation) of superphosphate — Retrogradation (reaction) of phosphoric acid — Forestalling retrogradation by Schucht's method - - - - HM-i^i CHAPTER VIII. COMPOUND MANURES. Superphosphate of ammonia — Ammoniated superphosphate — Super- phosphate of ammonia and potash— Nitrophosphate— Tables for the ^ calculation of " superphosphate of ammonia "'- Dry mixings - 142-150 CHAPTER IX. THE MANUFACTURE OF PHOSPHORIC ACID, DOUBLE SUPER- PHOSPHATES AND VARIOUS PRODUCTS. Historical review — Manufacture of phosphoric acid — Manufacture of double supeiphosphate— Manufacture ot superphosphate of potas- sium and ammonium — Manufacture of sulpho-phosphates — Bisul- phate SHperphosphate — Phosphatic peat ----- 151-1 6& APPENDIX. THK MANUFACrrRE OF PHOSPHORUS IN THE ELECTRIC FURNACE. Wing's process— Readman's patent— Harding's process— Gibb's furnace —Irvine's furnace— Duncan's patent— Parker's patent— Landis' method - 167-17^ X CONTENTS. CHAPTER X. PA.OBS MANUFACTURE OF BONE DUST AND OF BONE SUPER- PHOSPHATE (VITRIOLIZED BONES). Fertilizing value of bone — Storing, classifying, sorting and crushing bones — Storing — Classification of bones — 1. Kitchen bones — 2. Horse bones or knackers' bones — 3. Buried bones — 4. Bullocks' heads (sheep's heads)— 5. Scraps and waste — 6. Hornpiths — Boue picking — Bone crushing — 1. Slow-speed crusher — 2. Very quick-speed machine — Extraction of fat from bones — 1. Extraction of fat from bones by water — 2. Fat extraction from bones by steam — 3. Extrac- tion of fat from bones by benzine — Purification of bone fat — Bleach- ing of brown bone fat — Manufacture of bone dust — Classification of bone dust — 1. Normal bone dusts or bone dust No. 0 — 2. Bone dusts (without any other designation) — 3. Degelatinized boue dusts — 4. Mixed manure dusts — Meat dust (meat meal) — Adulteration — Manufacturing of bone superphosphates — Vitriolized bones — Vitriolated bones — Mixture of bone superphosphate (dissolved bones) and nitrogenous matter — Blood — Horn — Leather waste — Animal Charcoal — Bone ash — Manufacture of precipitated phosphate of lime ------------ 178-196 CHAPTER XI. MANUFACTURE OF BASIC SLAG. Origin of basic slag — The nature of basic slag — Tetraphosphate of calcium ^Solubility of basic slag — Crushing of basic slag — Remarks on the use of basic slag — Graphic illustrations of the manufacture of basic slag — Basic slag contracts — Sampling analysis - - - - 197-217 CHAPTER XII. NITROGENOUS MANURES. Nitrate of soda — Nitric acid — Chili nitrate of soda — The caliche terra salitrosa — 1. Open cast-iron pans — Paradas — 2. Cylindrical vertical pans — Maquinas — 3. Vessels heated by a closed tubular bundle (■? steam coil) — Storing and handling of nitrate — ProduC^ion of nitrate in 1907 — Ammoniacal salts — Manufacture of sulpbate of ammonia by distillation of gas liquor — Production of ammonia in the manufacture of coke — Recovery of auunouia from blast furnaces — Recovery of ammonia formed in gas producers — Siemens', Schilling's, Powson's, Wilson's and Mond's — Mond's process — 2. Bourgeois and Lencauchez's process — Manufacturing plant — Condensers — Stan- dard washer — Distilling plant - Naked tire stills— The English still — Mallet's still — Lunge's still — Feldmaun's still— Gruneberg and Blum's still — Manufacture of sulphate of ammonia from urine — Utilization of peat in the manufacture of ammoniacal salt — Recuperation of the ammonia — Gaillot and Brisset process — Muntz and Girard's process — Manufacture of sulphate of ammonia from peat by the Mond process — Crude ammonia from spent oxide - - 218-254 CONTENTS. xi CHAPTER XIII, PAGES MANUFACTURE OF MANURE FROISI ANIMAL WASTE. Preliminary remarks— Blood — Dried blood — Donard and Boulet's drying machine — Meat meal — Drying blood by lime — Commercial meat meal — Horn — Leather waste — Comparative value of different nitro- genous manures 255-267 CHAPTER XIV. RECOVERY OF NITROGEN FROM DISTILLERY SPENT WASH. MANUFACTURE OF CYANAMIDE AND OF NITRATE OF LIME. Utilization of distillery spent wash — General remarks — Recovery of nitrogen b}' Vasseux's process — Treatment of the spent wash by biological agents — Effront's methods — Treating spent wash by fermentation — The manufacture of cj'anamide and of nitrate of lime — Agricultural experiments with cyanamide — Rules for the use of cyanamide — Drawbacks in the use of nitrate of lime - - 268-277 CHAPTER XY. NITROGENIZED PHOSPHATIC MANURES. Peruvian guano — Its composition — Dissolved Peruvian guano — Other nitrogenized guanos — Bat guano — Hungarian bat guano — Eboli bat guano — Egyptian bat guano — Fish guano: historical review — The early manufacture of fish guano in Newfoundland and in Great Britain — Manufacture of fish guano in Norway — The fish guano industry in Britain - . . - 278-294 CHAPTER XVI. POTASSIC MANURES. :Stassfurt salts— Crude potash salts — 1. Carnallite — 2. Sylvine or sylvinite — 3. Kainit — 4. Schoenite — 5. Polyhalite — 6. Krugite — Dissolving the crude salts — Clarification — Crystallization — Clarifying — Treat- ment, of the mother liquor from the potassium chloride — Drying tlie chloride of potassium — Potassium sulphate — Double carbonate of potassium and magnesium — Double sulphate of potassium and magnesium — Other fertilizing salts — Commercial brands of potas- sium chloride (muriate of potash) — Manufacture of potash from felspar and other potassic minerals — Manufacture of potash from sunflower stalks in the Caucasus 295-315 xii CONTENTS. CHAPTEE XVII. PAGES TRANSFERENCE AND HANDLING OF RAW MATERIALS AND FINISHED PRODUCTS. Electric transhipment of phosphate and superphosphate in a manure factory — General arrangement of electrical conveying machinery in Pommersdorf chemical factory— General arrangement of electrical conveying machinery in Emmerich chemical manure factory — Electrical transhipment plant, St. Gobain's chemical factory, Boucau— Electrical transhipment plane in a German factorv— Cable transhipment system of Algerian phosphate factory - - "" - 316-332 INDEX 333.339, LIST OF TABLES. TABLE PAGE I. Showing percentage of phosphoric acid in various rocks - 2 II. Analyses of three different cypes of Sonime phosphates - 15 III. Analysis of average sample of a field of Orville phosphate dried in vacuo at 98° C, density at 16° C. 3-1307. (H. Lasne) ---]6 IV. Beauval phosphate deposit. Analysis made by Nantier at the date of discovery ......  VII. Analyses of various phosphates in the Meuse, Ardennes, etc., districts. (Delattre) ------ 19 VIII. Analysis of Ardennes nodules. (Maret and Delattre) - 20 gB£;\ IX. Analyses of Auxois phosphates. (Delattre) - - - - 21 X. Analysis of Quercy phosphates 22 XI. Analyses of Ciply phosphates --..__ 24 XII. Analyses of Liege phosphates --.--. 24 XIII. Analyses of Lyme Regis coprolites. (Thompson Herapath) 25 XIV. Analysis of Cambridge coprolites ----- 26 XV. Analysis of Suffolk coprolites ------ 25 XVI. Analyses of fossil bones from Sutton bone bed - - - 26 XVII. Analyses of Suffolk, etc., coprolites ----- 26 XVIII. Analysis of Norwegian apatit (crystals) - - - - 27 XIX. Analysis of Bohemian phosphates ----- 27 XX. Analysis of Russian phosphorite nodules - . -  - - - 31 * XXIII. Analysis of a fine sample of hard rock phosphate - - 32 XXIV. Analyses of hard rock phosphate from Blue River Co. - 33 .\XV. Analysis of land pebble phosphate ----- 35 XXVI. Analysis of Tennessee rock phosphate - - . - 35 XXVII. Complete analysis of au Algerian phosphate - - - 38 XXVIII. Analyses of two samples  XX A. Analysis of Sombrero phosphate. (Voelcker) -  Vela phosphate ----- 41 XXXII. Analysis of Monk's Island phosphate - - - - 41 XKXIII. Analysis of Baker Island guano 43 XXXIV. Analysis of Jarvis Island guano ------ 44 XXXV. Analyses of Fanning I^iland guano ----- 44 XXXVI. Analyses of Brown Island guano ----- 44 XXXVII. Analyses of Lacepede Island guano 45 XXXVIII. and XXXIX. Analyses of Mejillones guano - - - 46-7 XL. Analysis of Clipperton Island guano 47 XLa. Geographical distribution of phosphate of lime and guano deposits and their chemical composition XLI. Amount and strength of acid required to dissolve various phosphates --------- XLII. Results of experiments with ordinary superphosphate and superphosphate dried at different temperatures on Ligouro oats --------- XLIII. Showing changes in composition which Tennessee super- phosphates undergo in four and a half months from date of making --..---. XLIV. Showing for a succession of years the increase in hay from one application of basic slag to a poor meadow XLV. Number of cwt. required in a 5 ton mixing, or of tons in a 100 ton mixing of a superphosphate ot a given strength in P«0.:, to produce a manure of a given strength in P^g - - - XLVI. Showing in cwt. the amount of sulphate of ammonia of different strengths that must be contained in a 5 ton heap to get a manure containing from 1'850 up to 5 per cent nitrogen .---.- XLVII. Showing the analysis of  as supplied to manure factories L. Analysis of bone dust from fat extracted bones - LI. Analyses of new and used and spent bone char. (Pierre) LII. Showing the composition of five samples bone ash. (Voelcker)  phosphate of lime found in basic slag --------- ^04 LVI. Analyses of hexagonal crystals found in basic slag - - 204 LVII. Analyses of black needles, magnetic and non-magnetic, found in basic slag ------- LVIII. Analyses of blue crystals found in basic slag. - - LIX. Solubility of basic slag in water saturated with carbonic acid - -. ..---.- LX. Showing the results of Jensch's researches on basic slag LXI. Effect of composition of basic slag on facility of grinding - LXII. Showing the influence of the ratio of the peroxide of iron to protoxide on the ease of grinding of basic slag - - 213 129 1.37 141 146 149-50 156 173 174 174 185 192 206 206 209 210 213 LIST OF TABLES. xv TABLE PAf^ LXIII. Analysis of blue and bi'own crystals in basic slag - - 216- LXIV. Showing composition of caliche ------ 220 LXV. Analysis of Ciiilian nitrate of soda 221 LXVI. Analysis of better quality nitrate of soda. - - - 221 LXVII. Analyses of a double nitrate of potash and soda - - - 222 LXVIII. Analyses of gas liquor from coals of different origin - - 226 LXIX. Analysis of British gas liquor ------ 226- LXX. LXXII. Table for conversion of nitrogen per cent into ammonia per cent and vice versa ------- 254 LXXIII. Analyses of bullocks, calves, sheep, and pigs' blood - - 256- LXXIV. Composition of meat meal - 262 LXXV. Showing agricultural value of nitrogenous manures (nitrate 100) - ^6T LXXVI. Showing comparative agricultural money value of nitro- genous manure in francs per kilogram - - - 267 LXXVII. Showing value and amount of manure from spent wash from 1 ton molasses .-_-.-- 270 LXXVIII. Analyses of cyanamide 27S LXXIX. Analyses of Peruvian guano 280- LXXX, Analyses of Peruvian guano _.---_ 280 LXXXI. Analyses of Peruvian guano 281 LXXXII. Analyses of Peruvian guano ------ 281 LXXXIII. Analyses of guano from middle bed of Peruvian guano deposits ---------- 283' LXXXIV. Analysis* of Peruvian guano nodules (lower bed) - - - 283. LXXXV. Analyses of different cargoes of Peruvian guano - - - 284 LXXXVI. Analysis of bat guano :287 LXXXVII. Analysis of Hungarian bat guano 28T LXXXVIII. Analysis of Egyptian bat guano 288 LXXXIX. Analysis of Eboli bat guano 288. XC. Analysis of Brittany lisli guano ------ 291. XCI. Analyses of Norwegian fish ^uano . . - . - 293. XCII. Showing the composition of nitrogenous manures - - 294 XCIII. Potash content of various plants 295- XCIV. Analysis of first borehole sample of Stassfurt potash salts - 297 XCV. Analysis of carnallite 298 XCYI. Analysis of sylvinite (pure) 298 XCVII. Analysis of sylvine as it comes from the mine - - - 299 XCVIII. Showing analysis of kainit. (Reichardt) - - - - 299 XCIX. Analysis of polyhalite 30O C. Analysis of krugite. (Mercker) 301 CI. Analysis of crystals from potash salt crystallizers - - 303 CII. Analysis of mother liquor from clarification of potash salts 304 CIII. Analysis of mother liquor from potassium chloride - - 305- svi LIST OF TABLES. TABLE • PAGE CIV. Analysis of schoenite. (Mercker) 307 CV. Analysis of sludge from clarification of potash salts - - 308 CVI. GomiDositiou of Stassfurt potash salts ----- 309 CVII. Chlorine content of crude potash salts ... - 311 •CVIII. Effect of soluble mineral salts on grain crops - . - 313 CHAPTER I. PHOSPHORIC ACID. History. — The discovery of phosphorus is due to the alchemists. In 1669, Brandt, a Hamburg merchant, searching for the philo- sopher's stone in human urine, discovered an interesting substance which he called yhosphorus, i.e. a body luminous in the dark. All the phosphori known up to then — and there was quite a series of them — to become luminous had to be previously exposed to sun- light, and yet their luminosity soon vanished, whilst the new body emitted a glow of its own accord, and preserved that property permanently. It was, therefore, termed pJiosj^horus. Brandt kept his process secret. But, in his turn, Kunkel, a Beilin chemist, soon discovered phosphorus. In 1688, Albinus extracted phos- phorus from mustard seed and cress seed. Thus within a few years phosphorus was found in both the animal and vegetable kingdoms without, however, anyone dreaming of its connexion with inorganic nature. According to the cosmic theories of the times this sub- stance was held to be the product of other bodies, or even the result of spontaneous generation under the influence of ill -defined vital forces. The scientists of the time had not yet distinguished the chemical elements, the very simple theory of which was destined in the future to furnish the very basis of the science of these bodies. It is interesting, however, to observe that free phosphorus was prepared and examined for seventy years without its compound with oxygen, phosphoric acid, from which it had been isolated and to which it so easily reverts, being known. Phosphoric acid was not discovered till 1743, by Margraff, who ascertained its exact nature and succeeded in re-converting it into phosphorus by calcining it with charcoal. In 1769, Gahn, a Swedish chemist, found this acid in bones, and a few years later Scheele, his countryman, published a process by which phosphorus could be extracted from bones, which is still used in its main features.^ Ten years after the discovery of phosphoric acid in bones, and more than 100 years after the first preparation of phosphorus, Gahn found this body in the mineral kingdom also, viz. in lead phosphate (pyromorphite) ; Vauquelin and Klaproth soon afterwards found, phosphoric acid in apatite, that beautiful mineral, met with in large masses, the com- 1 Scheele was by birth a Prussian. See Scheele's " Chemical Essays," Scott, Greenwood and Son. 1 CHEMICAL MANURES. position of which is analogous with the earthy parts of bone. Such are, briefiy summarized, the chief historical facts regarding the discovery of phosphorus and phosphoric acid in the three kingdoms of nature. Since then chemists have continued their investigations ; they have searched for this substance everywhere, and they have found it more and more as analytical methods have been improved. Its presence in urine and in bones led to its presence in all the fluids and organs of man and animals being suspected, and very soon it was found to be so. It was found in all plants and in all their organs. It was thenceforth recognized that the phosphorus contained in the body of animals was of vegetable origin. But from whence do plants derive this substance ? The answer to that question was sought for a long time. Even up to the middle of the eighteenth century, when scientists like Saussure (1740-1799) and others were led by simple logic to look for phosphoric acid in the soil, agronomists persisted in regarding it as a derivative of other substances, because very little of it was found in the soil, and this little might very well be brought on to the land by farmyard ■dung. However, improved analytical methods were bound gradu- a,lly to elicit the truth. Origin and Distribution of PhospJioric Acid in Nature. — If it be interesting for the farmer and the chemist to follow the migrations of an air-bell, and the curious phenomena under the influence of which the molecule of nitrogen becomes successively ammonia or nitric acid, then vegetable organism, then finally muscular fibre, it is none the less instructive to follow the migrations of the molecule of phosphorus. Let us endeavour to grasp these migrations, and to trace them, starting from the point of origin of phosphoric acid, i.e. the presence of this body in the primitive and crystalline rocks. The analysis of the primitive rocks, and of the metalliferous veins which they contain, proves that phosphoric acid is almost always one of their constituent elements. ^ Associated with lime, the 1 The two men of science who studied the question most profoundly were Forchammer of Copenhagen and Stockhardt of Germany. The latter found phosphoric acid in several rocks in which it was believed to be absent. The I)ercentages of phosphoric found in different rocks are as follows : — TABLE L— PERCENTAGE OF PHOSPHORIC ACID IN VARIOUS ROCKS. Rock. Per cent. Rock. Per cent. Feldspar (Rochsbourg ) . 1-70 Melaphyre (Plauen) 0-38 Gneiss (Gerlusdorf) 0-7S Syenit (Plauen). 0-18 Granulet (Penig) 0-()8 Gneiss (Tharandt) 0-2-5 Grauit (Hellsdorf) 0-.58 Felsite (Tharandt) 0-21 (Burgstaldt) 0-08 Limestone (Schweindorf) O-ol Basalt (Tharandt) MO 1 PHOSPHOEIC ACID. 3 oxides of iron, manganese, lead and copper, this body constantly reveals its presence to the expert chemist who makes a special search for it. Its proportions are most often very minute, but that matters little, as plants have a marvellous faculty of freeing from the soil the principles necessary to their development. And let us remark with Bobierre, "how everything hangs on a chain, to explain to us the distribution of phosphoric acid in our crops. Let us go back, in imagination, to the origin of things, to those great natural phenomena, all the traditions in regard to which are in ac- cordance with what geology reveals to us of these gigantic phases. The igneous rocks contain phosphoric acid. The disintegration of these rocks under the combined influence of Vv^ater, air, temperature, and carbonic acid, soon favours the physical divisions of the rock masses. Vegetation develops, vivacious, luxuriant, immense, ac- cumulating at the same time both carbon from the atmosphere — which it is to return as coal to far-off generations — and phosphates which its organs, immersed in a virgin soil, assimilate to abandon one day in a fine state of division on the surface of the soil. And as an energetic, active, incessant medium of this providential dis- tribution, the animal world supervened with its powerful capacity of condensation of principles, rich in phosphorus and in nitrogen. Thus it is that vegetation supplies phosphates clothed in a new dress for the alimentary needs of new individuals. The molecule of phos- phoric acid is no longer the inert crystalline portion of the igneous rock, it is no longer the mineral framew^ork of the plant, it is the osseous substance of the animal, it is both its skeleton and its flesh, its nervous fibre, and its entire being. Our ideas of the organism and of phosphorus are inseparable the one from the other." The beds of the different geological periods all contain fossils, more or less rich in phosphoric acid. The Cambrian yields Licjulides and Dis- cenides, forerunners of the Brachmpods, whose calcareous shells were comparatively rich in phosphoric acid. At a later period vertebrae appear ; first, the Silurian fish, then the saurians of the Carbonifer- ous and Permian, and finally, the birds (Jurassic) and mammals (Trias), the skeletons of which form the principal elements of the accumulation of phosphoric acid. Thus the soil of all formations may contain phosphates, but they are not found in large quantity except in certain formations and under peculiarly favourable circum- stances, which we vaguely perceive, but of which it is impossible to give a really satisfactory explanation. The solution of phosphoric acid by rain water, charged with carbonic acid, traversing the superficial layer of soil covered with vegetation and thus rich in humus, its entrainment into the subsoil, and its accumulation in the subjacent rock, the chemical affinity of which favours its combii.ation — such seems to be the genesis of phosphate deposits. I leeting hme, oxides of iron, and alumina the phosphoric acid solu- 4 CHEMICAL MANUEES. tions form phosphates of Hme, kon, and alumina. On the phosphate beds so formed new layers of phosphates were deposited as soon as- the carbonic acid acting as the phosphoric acid solvent had set free sedimentary phosphates. When the solution percolated into hollows it formed pockets. The carbonated water could even con- vert already formed phosphate into a special form, for example that of vitreous statfelite. Nodules w^ere formed when the rock to which the phosphoric acid was combined was deficient in consistency, or had lost it, for example owing to the upheaval of the deposit, the different portions of which were washed and removed by water, thus rounding the fragments. Nodules may a^ain be formed by the fixation of phosphoric acid round a centre, for example around grains of sand swimming in the solution on the impulse of a crystal! growing in an appropriate solution, or organisms or even bells of gas rising in the solution drawing to it particles of the same nature as itself. Finally, another hypothesis of the formation of nodules is that where precipitated phosphate of lime had been gradually re- united into compact nuclei by water through the intervention of" pebbles of silex. Apatite was the first phosphate formed by the crystallization of the incandescent rocky magma. Its crystaUine form is hexagonal. As it cooled slowly, the mass of liquid apatite formed crystals of different sizes, from capillary needles, scarcely visible, up to 12 in. in length. Their interior always assumes a. lamellar structure. Apatite is found massive, w^ith this crystalline structure, or even compact and massive when it is embedded in basalts. But compact massive apatite always comes from crystalline apatite. Pseudo-apatite is disintegrated apatite. All these forms of phosphate, from the crystalline form to the amorphous, from isolated nodules to rock phosphate, go back to an identical origin. Sum- ming up, phosphorus existed in the beginning of things in the primitive rocks. It has become more assimilable in virtue of its- distribution in sedimentary and transported soils; vegetables have absorbed it, then they have given it up to the animals, which have condensed and accumulated it in numerous points of the globe. Let us note, with Buckland, that it is astonishing that the human race should, for so many centuries, have remained ignorant of the fact that a considerable portion of the surface of the globe was formed by the debris of the animals w^hich inhabited the ancient seas. There exists, according to the same author, vast plains and enormous mountains which are merely, so to speak, the charnel houses of preceding generations, in which the petrified debris of extinct animals and vegetables are piled up to form marvellous monuments. These monuments attest the work of life and death during incalcul- able periods. Cuvier, appreciating these curious natural phenomena, declared that the sight of such a spectacle as that of the debris of life forming almost all the soil on which our feet tread was so- PHOSPHORIC ACID. 5 terrible as to render it difficult for him to retain his imagination on the causes which have produced such great effects. These etfects, so terrifying to the genius of Cuvier, are really only the result of one and the same cause — an efficient cause, which is confirmed under the most diverse conditions, and in all latitudes, with a wonderful unity of design. Only the Sovereign Master of Life and Death could accomplish such wonders. Let us now try to find the amount of phosphoric acid in different media — phosphoric acid in the soil, in plants and animals. About the time when British agro- nomists 1 were exploring the deposits of phosphate of lime of Estra- madura, it was discovered, in Surrey, that the use of ground bones, and other bodies rich in phosphoric acid, produced no beneficial re- sult when applied to soils, fertile enough in themselves, the subsoil of which belonged to certain deposits of the lower and upper Green- sand. This led to the supposition that phosphate of lime, which is one of the fertilizing constituents of ground bones, is naturally pre- sent in these soils in sufficient proportion. Mr. J. C. Nesbit, an expert chemist, immediately collected the soils and rocks of these districts so as to ascertain the cause of their fertility. Amongst others, he received from Farnham samples of a fertile marl, situated on the property of Mr. J. M. Paine. A rapid examination showed the presence, in this marl, of an unusual amount of phosphoric acid, and in November, 1847, he informed Mr. Paine of this discovery.^ From this marl 28 per cent of phosphoric acid, corresponding to 60-67 of phosphate of lime, was extracted. The general mass of the marl contained 2 to 3 per cent of phosphoric acid, equal to 4-33 to 6-5 per cent of phosphate. It will be seen that in presence of such a proportion of phosphoric acid the application of phosphatic manures was quite superfluous. 2But Mr. Paine himself, in conjunction with Professor Way, the then chemist of the Royal Agricultural Society of England, in 1848 published the results of their then combined elaborate researches on the phosphoric strata of the chalk formation in a paper in the " Journal of the Royal Agricultural Society of Eng- land," Vol. IX, Part I, pp. 56-84. The reader is referred to this memoir : suffice it to mention here that the marl contains nodules much richer in phosphate of lime than the marl in which they are diffused. — Tp. 6 CHEMICAL MAXUEES. makes 30 tons of that acid per hectare or 12 tons per acre. The ditfiision of phosphoric acid in arable land responds, moreover, to a providential law, that element being as indispensable to plant life as to animal life. In the absence of phosphoric acid, none of our cultivated plants can pass through all the phases of vegetation ; the seed may germinate, produce leaves, stem, branches, but these organs remain attenuated, lingering, till the plant dies prematurely without bearino; flowers or fruit. Co ren winder made researches to follow up phosphorus in plants. Analyses of roots, stem, and fruit proved that phosphorus exists in nascent organs w^here it contri- butes to organization. It diminishes proportionally in the root ; thus the root of beet-root does not contain phosphorus after the maturity of the seed. It is to be found in the seed. Corenwinder found that in the pollen of flowers there is a considerable amount of organic phosphorus recovered as phosphoric acid in the ash of these minute organisms. In this respect pollen is analogous with the seminal fluid. Saussure and, later, Garreau, Professor of Botany at Lille, pointed out that the leaves of a tree give, on estivation, ashes more rich in phosphorus than at any other epoch of vegetation. If now we gradually ascend to the examination of animals, we find that their bones, their muscles, their nervous and cerebral substance, the fluids of their organism, blood, milk, urine, seminal fluid, are always and everywhere permeated with phosphorus. Intimately associated with organic substances, phos- phorus abounds in the cerebral mass and the nervous system. One may almost say that it is organized. Combined with oxygen and lime it forms one of the important elements of the skeleton. Dis- solved by the animal fluids, it is unceasingly carried from one point to the other of the individual, and if its total amount remains fixed, for a given animal, its molecule nevertheless displaced by solvent or vital actions is excreted, then replaced by a new molecule, brought by the digestive system. To remove phosphoric acid and lime from the diet and try to nourish an animal on purely nitrogen- ous principles is to attempt its life. The animal in this respect behaves like the plant (Bobierre). According to Elie de Beaumont, a human skeleton weighs, on an average, 4*6 kg., say 10 lb., and assuming that human bones contain 53 -04 per cent of phosphate of lime, a skeleton ought to con- PHOSPHORIC ACID. 7 tain 2-440 kg., say 5^ lb. But a human body weighs, on an aver- age, 75 kg., say 165 lb. ; deducting the weight of the skeleton there remains 70 kg., say 154 lb. of soft parts, which on incineration yield, like ox-beef, 1*5 per cent of ash entirely composed of phosphate of soda, potash or lime, and alkaline chlorides. The amount of phos- phoric acid which they contain may be taken as equal to an amount of phosphate of lime equal to 80 per cent of the weight of the ash, or to 1-5 per cent of the weight of the soft parts multiplied by 0-8, say 840 grm. These 840 grm. added to the 2-440 kg. contained in bones, give a total of 3-28 kg. of phosphate of lime, say 1-439 kg. of phosphoric acid or 639 grm. of pure phosphorus. These figures show the importance of the role which phosphoric acid plays in the support of the globe. They ought to teach us also to use, with wise fore- sight, the stores of phosphoric acid with which bygone ages have endowed us, because, whatever may be the importance of the deposits now knowm and exploited, and even of those w^hich may be discovered in the future, they are far from being inexhaustible ; besides the danger of dispersion of phosphoric acid by default of restitution to the soil actuahy exists, more threatening for a future less distant than that of the dispersion of nitrogen and potash. Properties of Phosphorus — (1) Physical Properties. — Phosphorus obtained by Scheele's method, i.e. by the distillation of phosphate of hme and charcoal, is a colourless yellow translucent body. It is found in commerce mainly as sticks. At the ordinary temperature it is soft like w^ax, brittle in the cold. It has the odour of garlic. Its density varies bet^veen 1-82 and 1-84. It is insoluble in water and in alcohol, very soluble in essential oils, ether, benzol, carbon disulphide, sulphur chloride, and phosphorus chloride.^ Phosphorus melts at a temperature of 44 -z" C. and forms a colourless, oily liquid ; if melted phosphorus be rapidly cooled it is converted into a black mass w^ith a metallic appearance ; if, on the contrary, the molten mass be still further heated — up to a temperature of 250-260° C. — it is converted into a red modification w^hich, at 280° C, reverts to the ordinary form. Phosphorus is highly poisonous. The absorption of a few centigrammes suffices to produce the death of a man by ^ The solution of phosphorus in carbon disulphide was used by the Irish Fenians to burn the farms of their countrymen who were refractory to the Land L i'rigue. This solution evaporates spontaneously and leaves phosphorus in a state of extreme division. The phosphorus then inflames spontaneously. If wooden objects be coated with a solution of Fenian fire nothing can prevent a confiagra- tion. The solution of phosphorus in carbon disulphide, mixed with sulphur chloride, can be preserved well in close vessels but inflames with violence if a few drops of ammonia are allowed to fall thereon. This is the Lorraine tire of Nickles of 1869. Care must be taken to work in the open air on small quan- tities and to pour the ammonia by aid of a long tube. The new Lorraine tire of P. Guyot, 1871, is a solution of phosphorus in carbon disulphide to which sulphur bromide has been added. It inflames in 1 or 2 minutes after ammonia has been added. 8 CHEMICAL MANURES. 