'> ^ss^m Digitized by tine Internet Arcinive in 2010 witin funding from University of Britisii Columbia Library http://www.archive.org/details/phosphatesofameOOwyat Tin-: niospiiATES of America. WHERE AND HOAV Tm¥^(Mll; IIQW T1IEY ARE MINED; AND AVHAT THEY COST. WITH I^RA-CTIC^L TREATISES ON THE MANUFACTURE OF SULPHURIC ACID, ACID PHOSPHATE, PHOS- PHORIC ACID, AND CONCENTRATED SUPERPHOSPHATES, AND SELECTED METHODS OF CHEMICAL ANALYSIS. BY FRANCIS WYATT,ph. D. THIRD EDITION. THE SCIENTIFIC PUBLISIIIXG CO., 27 Park Place, New York. 1892, THIS BOOK IS Dedicated to my Friend RICHARD P. ROTH WELL Editor of The Engineering and Mining Journal, AS AN HUMBLE TRIBUTE OF MY ESTEEM AND HIGH CONSIDERATION. P E E F A (.' E rrilE self-explanatory title of this book enables nie to dispense with a lengthy introduction, nor, if I were to write one, could I add anything to what I have endeavored to say in its pages. It embodies many facts, figures and suggestions resulting from long observation and an extremely varied practical experience ; and while these are designed for the exclusive use of specialists, I trust that, taken altogether, it will ])rove highly profitable read- ing to all those numerous classes directly or indirectly interested in the production, manufacture, sale and consumption of com- mercial fertilizers. I have endeavored to couch it in common, every-day language, and have avoided as far as possible all unnecessary chemical for- muhT and technical terms. In a word, my aim and ambition have been to make it intelligible and useful to the ordinary careful reader, and if I have partially succeeded in this, I shall be more than repaid for the labor it has cost me. The Author. Laboratory of Ivdi'striai, Chemistry, 12 Park Place, New York. P E E FACE TO THE SECOND EDITION. TT is seldom that any book, much less a scientific treatise, passes into its second, edition Avithin a week after the publication of the first. That it has been found necessary to bring out a second edition of "The Phosphates of America'' thus soon is evidence of the deep interest that is now being taken in phosphate mining and the manufacture and use of superphosphates for agricultural purposes by the people of this countrj' and Europe. Indeed, so great has been tlie demand for the book, that it has been impossible to fill all the orders received. The Publishers take this opportunity to express their gratification that this work has been so much appreciated. The Publishers. New Youk, December IH'Jl, PREFACE TO THE THIRD EDITION. 'T'HE second edition of this book has followed the first into the hands of the public with a rapidity unprecedented in technical literature. Its favorable reception by all classes of readers has forcibly demonstrated that there was a vacant space for it upon every bookshelf, and the publishers again express their sincere pleasure, not only at having foreseen the necessity, but at having been able to so satisfactorily supply it. The Publishers. New York, December 1891. THE PHOSPHATES OF AMERICA. CHAPTER I. INTRODUCTORY— GENERALITIES. The theory of scientific agriculture is based upon a complete knowledge of the nature of soils, plants, animals and manures, and it is evident that until these elements are thoroughly understood no attempts at improvement or plans for increased production can possibly be successful. Is it not curiously illustrative of the gen- eral ignorance that very few people know anything of the earth they tread or the soil they cultivate, in what way it was formed, or of what it is composed? How, then, can they imagine the mighty inundations and the terrible upheavals? How conceive anything of that gigantic disemboweling of the earth-monster, and of the awful torrents of burning lavas which it lias vomited forth? Can they realize that our tallest mountains, even those which from their height are covered with perpetual snow, were once submerged in rolling seas? or that the rocks and cliffs we meet with in our plains are nothing more than agglomerated masses of organisms that swarmed the waters? This is a seductive topic ; one that might readily carry us far beyond the scope of this small work ; and one that, feeling as we do how utterly impotent we should prove in any attempt to do it justice, we would rather not touch upon at all. Remembering, however, that we are not writing solely for the scientific or technical, and that we design to interest the general reader, we are bold enough to alteni])t a brief summary of acfjuired facts in order to make subse(iiient arguments more forcible and clear. We believe it to be generally admitted by our geological teachers 10 The Phosphates of America. that when ottr glohe was launched into space it was a liquid some- what similar to molten glass, and therefore presented a vastly dif- ferent appearance to that with which we are acquainted. When this mass began to cool, it probably resembled an immense glass ball, the solidified sides of which were uplifted by the bubbling of the intensely hot liquid mass within. These solid projections formed our mountains, and, passing from the transparent to the opaque, they gradually assumed the crystalline form. AYhat is known as the earth's crust must have resulted from an extraordinarily for- cible action consequent upon the fall of temperature. Certain vapors were condensed into acid bodies, and these acids, attacking the alkaline crust, combined with its most powerful bases to form various salts. Some of these salts — such as sulphate of lime or gypsum — were deposited, while others, principally the chlorides, remained in solution and formed the seas. The neutralization of the stronger and more corrosive acids permitted the weaker car- bonic acid to develop its activity, and it is this acid which has con- tinued to ])lay the most important part in nature in our own times. Held in solution by the running waters, it attacked and dissolved the various bases which existed in such large quantities in the moun- tains, and deposited them in the form of carbonates in the valleys. The pi-ocess of saturation, or neutralization, being entirely accom- plished, chemical equilibrium may be said to have become estab- lished ; the period of great geological catastrophes, therefore, came to an end, and the temperature of the earth gradually sank below the boiling-point. A few volcanic disturbances continued, it is true, to occasionally convulse it ; there was the upheaval, splitting asunder and comjilete overthrow of mountains, the drying up and the division of seas, and the formation of lakes of both fresh and salt Avater, but they became more and more rare as the temperature continued to cool. The rocks with which we are all acquainted and Avhich have grown out of these continuous and still-continuing changes may be roughly divided into three groups : First, Sandstoxes. Second, Limestoxes. Third, Granite or Gneiss. And it is their decomposition, under the combined influence of the atmosphere and water, during a long period, that has ulti- mately produced fertile soils containing silicates of aluminum, The Phosphates of America. 11 potassium, sodium, magnesium, iron ; phosphates, sulphates and chlorides. The soil at first resulting from this gradual decomposition formed very thin layers, in which only the lower orders of })lants found sufficient food to fructif}', deriving from the air and the rain their carbon, hydrogen, oxygen and nitrogen. In the natural process of death and decay, these fresh elements of fertility, in vari- ous states of combination, were transferred by thejilantsto the soil, which was thus enabled to afford nourishment to a higher vegetation. It is the oreneral custom to class arable lands according to the nature of their predominating constituents, and thus we allude to soils as sandy, clayey and limey. Sandy soils are distinguished by their extreme porosity, and are frequently in such a line state of division that in the dry season the least wind will displace and scatter them in all directions. In such cases they are naturally sterile ; but when they are sufficiently moist, they facilitate and encourage the growth of an immense variety of plants of the lower order, Avhich, by their eventual decomposition or putrefaction, form considerable deposits of that valuable substance called humus. Such soils are more propitious than any others for the develop- ment of jtlants with very delicate or fine roots, such as barley, rye, oats, lucern, lupins, lentils and potatoes ; but they require constant attention, and a large and regular quantity of manui-e, because their porosity permits them to absorb such an abundance of oxygen that all their organic matter ife rapidly burnt up. Clayey soils are heavy and compact, and when they contain more than fifty per cent, of pure clay are onerous to work, and un])rofitable to cultivate. It has, however, fortunately been dis- covered that the addition to them of so small a quantity as two per cent, of burnt lime suffices to so entirely change their nature and consistency, by transforming the silicate of alumina into a ]»orous silicate and aluminate of lime, that it is now an easy matter in districts where lime is cheap and plentiful to overcome this diffi- culty. In hot countries or in windy regions or in districts where the subsoil is of a very permeable character, good clay lands offer great advantages, and although they periodically require the api)li- cation of large quantities of reconstituents, they possess the faculty of retaining all the precious elements supplied to them, and of storing them up for the use of successive crops. When they contain a proportion of about ten i)er cent, of carbonate of lime, or chalk, 12 The, Phosphates of America. they are the best of all soils for the extensive growth of such important plants as wheat, corn, clover, hemp, peas and beans, and of such trees as the chestnut and the oak. Limey, or purely calcareous, are even lighter than sandy soils, and when, as is sometimes the case, they are very white and dry they are absolutely barren. Such as thej^e are, however, rarely encountered, for we generally find them mixed with a sufficiency of clay to give them some degree of consistency and render them available for ordinary pur- poses. Few soils are entirely devoid of lime, owing to the fact that all rocks contain it in greater or lesser proi)ortion, and because it is transported in immense quantities by waters, in the form of bi- carbonate, and deposited. If it were otherwise, or if, in the absence of lime, other alkaline substances were not forthcoming, the acid principles secreted by all plants could not be saturated, and the inevitable result would be decomposition and death. In its pure form, however, lime is such an extremely strong base that it is in- compatible with life, and hence it never exists in the soil unless it be combined either with carbonic or silicic or sometimes with sul- phuric and nitric acids. It Avill be thus seen that the study of geology, even if only elementary, enables the agriculturist to more accurately gauge the natural resources of his land, and will teach him how to adapt his ideas upon drainage, irrigation and ploughing to the surrounding circumstances of soil and climate. It will also prepare his mind for the teachings of chemistry ; that science which has done more than any other to improve the general condition of mankind, and which will enable him to ob- tain the maximum returns from the soil and from plants. If production is to be cheap it must be rapid and plenteous, yet, as we all know, the progress of unaided nature is slow and method- ical, and so chemistry, by investigating the laws Avhich govern the development of all living things and by carefully observing the facts acquired by the practical experience of centuries, has found the means by which the farmer may assist and hasten the natural processes. The work is, of course, still far from complete, but we are at least faniiliar with the elements essential to plant-growth. We know how these elements are distributed, what jxjrtion of them is or should be contained in our soils, and Avhat soils are most ])ro- l)itious for diiferent kinds of plants. Sixty years ago the science of agriculture was in its infancy- The PhosjjJiates of America. 13 Our grandfathers could not understand why hands once so fertile and productive should show signs of approaching exhaustion. The light only came to us after we had studied how out-door plants live, whence they obtain their food, of what elements that food is composed and how it is conveyed and absorbed into their organ- isms. In point of fact, we have discovered that the manner of life in plants is A'ery similar to the manner of life in animals and man. They require certain foods in stated j)roportions which i)ass through the process of digestion, they must breathe a certain atmosphere, and they are subject to the influences of heat and cold, light and darkness. The tissues of their bodies, like ours, are composed of carbon, hydrogen, oxygen, nitrogen and certain mineral acids and bases, such as phosphoric and sulphuric acids, lime potash, magnesia and iron. Since, therefore, it is admittedly necessary for man to con- stantly absorb a siifticiency of these elements in the form of food, it follows that similar food is required by plants for similar pur- poses. Having determined the elementary composition of plants, inves- tigators directed their attention to the analysis of soils, in order to establish comi)arisons between virgin or uncultivated lands and old varieties which had long been tributaries to every kind of culture. It Avas found that in the former there is an abundance of most of the dominating mineral ingredients discovered in 2)lant organ- isms, whereas in the latter they either exist only in minute propor- tions or are lacking altogether. This marked a most important stage in our progress. Argument is no longer necessary to prove that if agriculture is to continue to be the basis of national Avealth and prosperity, means must be found of restoring to our soils the chief elements yearly taken away from them by the crops. These chief elements have been shown to be nitrogen, phosphoric acid, and i>otash, and that they play the most important parts in the functions of vegetation, and are the most liable to exhaustion, is ])roved by the following figures, borrowed from an address delivered by Prof. II. "W. Wiley at the Buf- falo meeting of the American Association for the Advancement of Science. According to this careful and painstaking chemist, the estimated mean annual values of some of the agricultural products of the United States closely approach the following figures : 14 The Plioi'pUahs of America. Wheat 450,000,000 bushels, valued at $440,000,000 Maize 1,900,000,000 " " 627,000,000 Oats 600,000,000 " " 168,000,000 Barley 60,000,000 " " 33,000,000 Rye 25,000,000 " " 14,000,000 Buckwheat 13,000,000 " . " 7,280,000 Potatoes 200,000,000 " " 100,000,000 Butter, milk and cheese " 380,000,000 Fruits " 100,000,000 Eice 98,000,000 lbs. at 5 cts, " 4,900,000 Vegetables '« 50,000,000 Tobacco 483,000,000 lbs. at 9 cts. " 42,000,000 Cotton 6,500,000 bales (480 lbs.) " 250,000,000 Wool 300,000,000 lbs. at 15 cts. " 45,000,000 Hay 45,000,000 tons at |8 " 360,000,000 Miscellaneous, including flax, fl.ax-seed, hemp, grass- seed, garden seeds, wines, nursery jjroducts, etc., valued at 408,945,000 The mean percentage of ash or mineral matter contained in the most imjiortant of these products is as follows : WOieat 2.06 Maize 1 . 55 Oats 3.18 Barley 2.89 Rye 2.09 Buckwheat 1.37 Rice 0.39 Potatoes 3.77 Hay 7.24 Cotton stalks 3.10 Straw of wheat 5.37 rye 4.79 " barley 4.80 oats 4.70 " buckwheat 6.15 Stalks of maize 4.87 The approximate quantities of mineral matters taken from the- soil by a single crojj of the cei'eals would thus be : GRAIN. Wt. in lbs. % Ash. Wi. Ash in lbs. Wheat 27,000,000,000 2.06 556,200,000 Maize 106,400,000,000 1.55 1,649,200,000 Oats 19,200,000,000 3.18 610,560,000 Barley 2,880,000,000 2.89 83,232,000 Rye 1,400,000,000 2.09 29,260,000 Buckwheat 650,000,000 1.37 8,905,000 Total 2,937,357,000 STRAW. Wt. in lbs. % Ash. Wt. Ash in lbs. Wheat 45,378,000,000 5.37 2,436,798,600 Maize 212,800,000,000 4.87 10,363,360,000 Oats 32,000,000,000 4.70 1,504,000,000 The Fhosjjhates of America. 15 %rt. in lbs. % Ash. Wt. Ash in lbs. Barley 4,800,000,000 4.80 230,400,000 Rye 2,333,000,000 4.79 111,750,700 Buckwheat 1,083,000,000 6. 15 66,604,500 Total 14,712,913,800 The total weight of ash in the whole cereal production of the country is therefore — In grain 2,937,357,000 pounds In straw 14,712,913,800 Total 17,650,270,800 " Since it is our intention to limit the scope of this work to phos- phates, we may neglect all other constituents of the above amounts of ash, and confine our attention to the QUANTITY OF PHOSPHORIC ACID YEARLY REMOVED FROM THE SOIL IX THE UNITED STATES. Wt. Ash in lbs. Wheat 556,200,000 Maize 1,649,200,000 Oats 610,560,000 Barley 83.232,000 Rye 29,260,000 Buckwheat 8,905,000 Total 1,189,376,195 STRAW. % Phos- Wt. Phosphoric Wt. Ash in lbs. ' phoric Acid. Acid in lbs. Wheat 2,436,798,600 4.81 117,210,012 Maize 10,363.860,000 12.66 1,312.001,376 Oats 1,504,000,000 4.69 70,537,600 Barley 230,400,000 4.48 10,321,920 Rye 111,750,700 6.46 7,219,095 Buckwheat 66,604,500 11.89 7,919,275 Total 1,525,209,278 Total weight of the phosphoric acid in grain 1,189,376,195 Grand total, pounds 2,714,585,473 The acreage under cultivation for the production of the above cereals is estimated officially as follows : % Phos- phoric Acid. Wt. Phosphoric Acid in Iba. 46.98 261,302,760 45.00 742,140,000 23.02 140,550,912 32.82 27,316,742 46.93 13,731,718 48.67 4,334,063 IG The Phos2)hates of America. Wheat 40,000,000 acres Maize 7-^,000, 000 Oats 23,000,000 Barley 2,500,000 Rye 1,800,000 Buckwheat 900,000 Total 143,200,000 The quantity of phosphoric acid per acre is therefore, for the whole cereal crojj : 2,714,585,473 -f- 143,200,000 = 19.0 pounds. For the hay crop a similar estimate may be made of the quan- tities of plant food removed. The mean percentage of ash in the grasses of the United States is 7.97 ; for timothy it is 5.88 ; for clover it is 6.83. The mean content of ash may consequently be taken at 6.89 per cent. The total weight of hay j^roduced, multiplied by this number, gives 6,201,000,000 pounds as the total weight of ash in the hay crop of the United States. For the ash of timothy the percentage of phosphoric acid is 8.42 ; for red clover, 6.74. The mean percentage of phosphoric acid in the ash of timothy and clover is, therefore, 7.56. The total weight of phosphoric acid in the hay crop there- fore is 6,201,000,000 X "^'^^ = 468,795,600 pounds. 100 The number of acres harvested in the United States is about 37,500,000, and the quantity of phosphoric acid removed per acre is consequently 468,795,600 ^ 37,500,000 = 12.5 pounds. The PhospJtates of America. 17 CHAPTER II. PHOSPHATES AND THEIR ASSIMILABILITY. Ix the spring-time phosphates are found in noteworthy quanti- ties in young organs of plants, especially in the leaves, but the quantity gradually diminishes as the plant approaches maturity, until when the blossoms appear the phosphates are found to have entirely quitted the leaves and accumulated in the seeds. This is the cause of that peculiar effect, which has long puzzled farmers, that fodder cut and brought in after the period of niaturit]i proves to be much less nourishing to the cattle than that cut before this period has arrived. It is worthy of note that in every instance this displacement of the })hosphates is accompanied by an equal displacement of the nitrogen, and all those who have made successive anal3'ses of grains in different stages of maturity, must have been struck by the regu- lar parallel manner in which the quantities of both have progres- sively augmented. Mr. Corenwinder, alluding to this migration of j^hosphorus in vegetables, remarks : "It has long been known that young buds are rich in nitrog- enous matters, which are always accompanied by a relatively considerable portion of phosphorus, and there is no doubt that these two elements are united in the vegetable kingdom according to some mode of combination which is yet a mystery." And Mr. Boussingault, writing upon the same subject, says : " We perceive a certain constant relation between the projjor- tions of nitrogen and phosphoric acid contained in foods, those being richest in the latter element which contain most nitrogen. This would appear to indicate that in the vegetable organization phosphates particularly cling to the nitrogenous principles, and that they follow the latter into the organization of animals." The absolute necessity for the presence of phosphoric acid in the soil needs no further discussion. It is admitted on all hands that in its absence, vegetation, even when abundantly supplied with nitrogen and all other necessary elements, must come to a standstill. 18 Tlie P1ios2Jliates of America. The form in which it is assimilated is that of jihosphate, pro- duced hy the combination of the acid with various bases. Enor- mous deposits of phosphate, chiefly of phosphate of lime, have been and doubtless will continue to be discovered in every quar- ter of the globe ; and as, besides being so essential to plant life, it is the principal constituent of bones, we have here another proof that if by some extraordinary phenomenon its source were suddenly cut off or exhausted, all vegetable and animal life would cease. So far back as the year 1698 a celebrated French engineer (Vauban), writing in the JJhne Moyaly said : " We have for a long time past been universally complaining of the falling off in the quantity and quality of our crops ; our fai-ms are no longer giving us the returns we were accustomed to ; yet few persons are taking the pains to examine into the causes of this diminution, which will become more and more formidable unless proper remedies are discovered and applied." This was a warning note, but it was not until after the com- mencement of the present century that the English farmers began to use crushed bones as a manure, and even then they did so in blind ignorance of the principles to which they owed their virtues, as is clearly shown by an article published by one of the scientific pajjers of that day (1830), in which the writer says : " We need take into no account the earthy matters or phosphate of lime contained in the bones, because as it is indestructible and insoluble it cannot serve as a manure, even though it is placed in a damp soil with a combination of circumstances analytically stronger than any of the processes known to organic chemistry." A subsequent writer upon the same subject declares that "bones, after having undergone a certain process of natural fer- mentation, contain no more than two per cent, of gelatine^ and as they derive their fertilizing power from this substance only, they may be considered as having no value as manure." That such opinions as these should have prevailed only fifty years ago seems to us all the more preposterous because of the gigantic strides which we have made since then and because of the singular fact that even the Chinese were better informed than our grandfathers, inasmuch as they knew that the fertilizer was a mineral principle, and for many centuries have used burnt bones as manures. Despite the unflagging researches of the best men of the time, The PJiospJiates of America. 19 it was not until the year 1843 that the Duke of Richmond, after an exhaustive series of experiments upon the soil Avith both fresh and degelatinized bones, came to the conclusion that they owed their value not to gelatine or fatty matters, but to thei7- larc/e per- centage of phosphoric acid/ The spark thus emitted soon spread into a flame, and conclusive experiments shortly after published by the illustrious Boussingault set all uncertainty at rest forever Numerous species of vegetables were jjlanted in burnt sand, which was ascertained by analyses to contain no trace of phos- phoric acid. It was, however, made rich in every other element of fertility. iVo development of these jykoits took p)lace until phosphate of lime had been added to the sand, but after this addi- tion their (jrowth became flourishing ! Meanwhile large workable dejjosits of mineral phosphates were already known to exist, they having been almost simultaneously discovered in their respective countries by Buckland in England Berthier in France, and Holmes in America; and in the course of a lecture delivered to the British Association in 1845, Professor Henslow, describing the Suffolk coprolites, suggested the immense value of their application to agriculture. From this time may be dated the development of phosphate-mining as an industry, the pursuit of which has proved so remunerative to capital and labor. The mode of occurrence of the best known deposits of phosphate of lime may well be termed eccentric. They have been found in rocks of all ages and of nearly every texture. Sometimes they are very pure, sometimes their combinations are extremely variable. Here they are found in veins, there in pockets, and here again in stratified layers or beds in connection with fossilized debris of all kinds deposited by the ancient seas. Apart from the deposits of the American continent, England, France, Germany, Belgium, Spain, Portugal, Norway, Russia and the West Indies, all have workable and more or less productive i)ho8phate mines, some idea of which may be gathered from the following analyses: The Phospliates of America. :::^ OS o l-T T-l o 2 S •aaNio'iva « o in »C CO *-" (aoyuaAY) o o C9 « o LO 00 1-1 Cl o w NTitnaa ■*^ "^ o ^> O o o o p CO Cl o o o •aoxvMj o o t- c? ■^ i- l- c; O LJ 'SKKOS « ^ CO 1.1 '^ ■^ o o rH tH O 00 C £~ o in o o C5 -* I- Cl o t- •saxnoHdOO -* o t o o •^ NvissnH o CI CO Tt' CO TH TH o CO s g t- 50 •<+ CO o 2 2 •saxixvdv ^ CO CO CO Cl AVAHOJJ o o C7 LO IC o « O 05 ' -t o 1-1 CO CO p- -- CO LT ^ O CO •saxnoHdOO OJ -* 00 05 c 1— aoaiaaKVO « CO l- -r CO c T-H c O 00 O LO ^ ^ o o o lo-g 00 O LO •ONvno o r- c I- saNoniixan o T-l CO CO Cl CO •pauiuiaaj apun snou'BA. Tt* o ec o t- o 1" GO r- iO c 't OC' 2 2? •saxNaaHY e? ^ •^ i- o ci I -* o o CI Ci c: •^ t •MYKHao o{ C^ Cl -* m o t CO § u i^ t" c> ^ LI U5 S ir Cl 2 £: I- o CO o n ^ * lu •YOOYMnO o T-l 05 o t- rt o 2 c: d o CO CO iC += CO C^ o -^ o IS o S <^5 ^ O ifi »-~ o o c CO o Cl £■ *-- l-l o r- o o c? CO IC ec Cl i* <= -1^ Cl o o O CO CO CO C5 o o ic ,_ o C5 O lO i- o i;c C: •^ c 00 i-i o •YSSYAYK L"; Tt^" CO CO C7 Tf 00 .^^— »- CO O 05 O CO •asanonxaod c o «r oc C: ec CO S ^ CO O Ift c to CO c c cs any CO oi t- CO ^ i-I J? w CO o o BSIMYdS CO -^ o t- T- 01 ■4-3 65.87 per cent, of tribasic phosphate of lime. It appears to have been forgotten, overlooked, or ignored, by the opponents of these phosphates that the phosphoric acid in the soil invariably exists in the form of phosjjhates of iron and alumina. The so-called experts had 2)robably not then learned what they are now compelled to admit, that although some difficulty may attend their decomposition in the factory or their transformation into chemical fertilizers, these phosphates are extremely valuable in the raw state — if very finely ground — as a direct manure. Nor is this a matter of any personal opinion or prejudice, for as we and others have frequently shown, the iron and alumina in the soils exercise an immediate transforming action upon the phosphate of lime introduced into them in both natural and artificial forms. Any one can demonstrate this transformation by adding eitlier peroxide of iron or alumina, or both, to a solution of lime 2)hos- phates in water charged with carbonic-acid gas (ordinary car- 22 The Phosphates of America. ■bonated water at high pressure), -when in a very t^hort time all phosphoric acid will have disappeared from the solution and will he found in the deposit as phosphate of iron and alumina. If the chemists alluded to had confined their statements to the fact that i)hosphates of iron and alumina were not advantageous materials for the manure manufacturer, they would have been per- fectly correct ; hut they took on themselves a vast responsibility when they declared them to be useless as fertilizers, for of all questions, that as to the form in which phosphoric acid offers the best all-round advantage to the 2>ractical farmer is the most subtle and most delicate. If we accept the generally-admitted and rational theory that no element can i)enetrate into the interior of a plant unless it be in so- lution, it naturally follows that preference will be invariably given to those commercial phosj^hates which are most readily subject to dissociation ; and this will entirely dejjend upon two conditions : (a) Their own degree of aggregation. {h) The nature and comj30sition of the soil in which they are employed. The first thing to be obtained is undoubtedly a fineness of pulverization which will so divide the molecules as to render them easily decomposable by the natural action of the elements con- tained in the ground. Here we touch at once the real source of our difficulty, for in the matter of pulverization only partial suc- cess has so far been achieved by any sufficiently cheap mechanical means, and we are not very much further forward now than we were in 1857, when Liebig recognized the difliculty and proposed, in order to solve it, to chemically perform the disintegration by manufacturing superphosphates. From the standpoint of disintegration this method of Liebig's has been entirely satisfactory, and has enabled agriculture lo rap- idly obtain results from the use of phosphoric acid which would otherwise have been impossible. From a chemical point of view, however, the whole theory fails. We have seen that superphos- phates are only soluble in Avater so long as the sulphuric acid with which they have been manufactured retains its ascendency, and that when they reach the soil, especially where carbonates are in abundance, the sulphuric acid is at once overpowered, and the phos- phoric acid, instead of remaining combined Avith one molecule of lime and two molecules of water, at once undergoes revei-sion. To put it plainly, the issue revolves upon a matter of time and of The Phosjjhates of America. 23 money. The farmer buys a ton of raw phosphates, ground as finely as possible and containing, let us say, twenty-five per cent, of ])hos- phoric acid, for §10. If his land be tolerably acid he will get a rapid return, but if it be not, the phosphate will not decompose, and he will have to wait perhaps several years before obtaining any ap- preciable results for his outlay. On the other hand, he buys a ton of superphosphates, containing only fourteen per cent, of phos- phoric acid, for -^20, and applying it to a j)hosphate-barren soil, produces the desired results on his veiy next crop. Hence it is apparent that the phosphoric acid of the latter is more readily as- similable than that of the former case ; and this assimilability can only be due to its absolute state of division, which enables the phosphate to come into contact with the acid sap of a greater num- ber of root hairs and thus to be dissolved and absoi'bed by the plant. We therefore repeat, that to define with scientific accurac)'^ the exact merit or intrinsic value of any specific phosphate is a matter of very serious difficulty ; since besides that of its own phys- ical condition, so much depends upon the nature and com2)osition of the soil in which it is to be employed. Dr. Chai'les Graham, of University College, London, was one of the first to realize the facts we have noted, and writing upon the sub- ject some ten years ago, said that " the vitriolating process, whereby soluble phosphate is formed, was of value where nothing but bones was employed, since it gave agriculture a convenient means of distributing over the land an easily soluble substance in the jjlace of the pieces of bone ])reviously used. With coprolites the same thing was supposed to hold, and as years rolled on acid was more and more used in the preparation of phosphatic materials, until at last these have become rather vitriol-carriers to the ])rofit of the manure manufacturer than to the benefit of agriculture. Analyti- cal chemists attached so high a value to the soluble phosphates that the factor 30 became with many the multiplier in calculating the commercial value from the centesimal c(>m])Osition of the superphosphates. Some, indeed, went beyond this ; and in time analytical chemists came to think of soluble phosphates as the only test of vitriolated })hosphate minerals — the insoluble being regarded as of little or no use." The same subject received much attention at the International Congress of the Directors of Agricultural Experimental Stations, held in Paris in June, 1B81, and the result was a general approval of the efficacy of the undissolved forms. 24 The Phosphates of America. It appears to be established by the record of this congress that French and German agricultural chemists are now in accord in re- gard to the comparative value of soluble and precipitated phos- phates {i.e., those which had once been soluble but have returned to the insoluble state in fine division), French chemists having held for some time that they should be on an equal footing. They also assented to the value of raw ground i)hosphate of lime, and declared that " The congress is of opinion that in reports of analyses the directors of stations should state the solubility of phosphates by the expressions 'phosphoric acid soluble in cold citrate of ammonia' or < soluble in water,' and not that of ' assimilable phosjihoric acid ; ' the Congress believing that to apply the term assimilable to the phosphate soluble in the citrate would be to class implicitly and necessarily in the category of substances not assimilable, the phos- phates which are evidently soluble in the soil, such as those in bone ash, guano, bone powder, farm-yard manure and fossil phos- I^hates." There is probably not a single one of our agricultural experi- ment stations in which the assimilability of raw mineral phos- phates finely ground has not been the object of intelligent study, but so far as we have been able to ascertain by diligent inquiry up to date, the results have varied, as we have already premised, in accordance" with the kind of phosphate used and the nature of the soil into which they were introduced. Nothing of any serious mo- ment has in fact occurred to modify the conclusions formulated in 1857 by the well-known Frenchman, De Molon, Avho, reporting on a very extensive series of trials of ground raw coprolite in many different departments of France, said that 1. It might be used with advantage in clayey, schistous, grani- tic and sandy soils rich in organic matter. 2. If these soils were deficient in organic matter or had long been under cultivation, it might still be used in combination with animal manure. 3. It may not be used with advantage in chalky or limestone soils. Here, as it strikes us, is a fairly representative case where an intelligent discrimination is demanded of the farmer, and Avhere he must realize that the term soluble as a2)plied tojjhosphate fertilizers is an entirely relative one. In one portion of his lands he may use raw phosphates, and they will prove to be soluble and produce Tlie FhospJiates of America. 25 excellent results ; in another portion, owing to different constitution of the soil, they Avill remain insoluble and the result "vvill be nil. In England and in some parts of Germany it is still the cus- tom, as Ave shall show later on, to base the commercial value of a manufactured phosphatic material almost entirely upon its per- centage of phosphoric acid soluble in cold water, and to allow little or nothing for that which may exist in the "reverted" or water-insoluble form. As shown by our experiments and demon- strated by our practice in this country, however, the latter is entirely assimilable by plants, and should therefore have a com- mercial value approximately equal to that of the water-soluble phosphate. Neither English nor German chemists worthy of that name attempt to deny this fact, but they appear to be in advance of the philosophy of their lay contemporaries and have not yet acquired sufficient power to stamp out })rejudice and imposition. All newly discovered truths, when first communicated to an unprepared society, are first denounced and then put aside and for- gotten by the vast majority ; but by and by, Avhen a generation or two have passed away, we see those very truths, so long considered as without the pale of human possibilities, insensibly come to be looked upon as commonplaces which even the dullest intellects wonder how Ave could ever have denied. Men may come and men may go, but science remains behind. It sustains the shock of empires, outlives the struggles of rival theories and creeds, and, built uj)on a rock, must stand forever. How, then, can we expect the farmers to perpetually remain in ignoi-ance or darkness on this question, when we know that they are becoming less and less able to restore to their soils, in any other form than that of ])hosphate of lime the phosphoric acid taken from them year by year with their crops? Nothing can stem the demand for artificial manures ; it will go on increasing with such steadiness and rapidity that the visible sources of su])ply Avill soon become inadequate. Especially is this true of phosphates of lime, and the recognition of this fact by those engaged in the fertilizer industry explains the eagerness with which fresh deposits of the material are being sought for all the world over. The vast Avorkable deposits of the American continent are just at this moment the centres of attraction, and it will therefore be interesting to a large section of the public to know something 26 Tlie Phosphates of America, about the mode of their occurrence, how they are mined, handled, prepared for the market, and what they cost. All this informa- tion we shall endeavor to convey in as brief a manner as may be consistent with lucidity, and we shall add to it a jDractical descrip- tion of the manufacture of sulphuric acid, superphosj^hates and "high grade supers," and shall give a general outline of those methods of analyses shown by our long and varied experience to be best suited to each class of product. At the present time there is a great and regrettable divergency in the results of jthosphate analyses made by different chemists. To the uninitiated this is an unaccountable fact, to be explained only by a very excusable and popular conclusion, that analytical chemistry is not a reliable or exact science, and that it cannot jiro- duce in practice what it expresses by equation. Why, it is asked, should the chemist in the South — who is perfectly conscientious and Avho has no interest to deceive — differ materially in his find- ings from a chemist equally but no more honest and trustworthy working at the East or North? This is a consistent question, and it demands a jjrompt solution. Nothing could cast a greater aspersion on the highest of profes- sions than this state of affairs, and yet nothing on earth could be more easily and perfectly remedied. All that is necessary is for chem- ists to come together and agree upon certain methods, and to invite purchasers and sellers of phosphates and manures to regulate their settlements on a prescribed basis. In this manner all divergency of results should disappear, and, all other conditions being equal^ any further discrepancies would be attributable only to incompe- tency or bad faith. The hand, of course, is not always steady, nor is the eye always accurate, and Avhile we are liable to physical defects and weaknesses, we shall never be free from mistakes ; but it is nevertheless a fact which has forced itself upon all thinking men, that uniformity in manipulation is the prime factor in the attainment of uniform results, and nowhere is such uniformity a sine qua non as in the laboratory. The Phosphates of America. CHAPTER III. THE PHOSPHATES OF NORTH AMERICA. The greatest of our geologists have agreed ui)oii dividing the earth's crust into four classes or periods, which they have named respectively the ,4?y7halerite, molybdenite, etc. The two districts in Canada in which apatite has been thus far found to exist in workable quantities are Ottawa County, in the province of Quebec, and Leeds, Lanark, Frontenac, Addington and Renfrew Counties, in the Province of Ontario. The latter district, therefore, covers a much larger area than the former, but on the other hand the country is much lower, the rocks more hornblendic and the ajjatite much more "pockety" and scattered. In both dis- tricts the Laurentian rocks form immense belts, which traverse the country for many miles with a N. E. and S. AV. trend, and which, according to Dana, Hunt and other investigators, extend downward to a depth of at least twenty-five or thirty thousand feet. There is, as may be readily inferred, a great variability in their composi- tion. Sometimes they are entirely granitic gneiss, hornblendic gneiss, rust-colored gneiss and brownish , " 5 1 t c c The Phosphates of America. 31 currence and the continuity in depth of Canadian apatites. In- dustrially they have secured to the company some verv consider- able reserves of phosphate, which are now in sight and ready for extraction. The entire property consists of 200 acres, and it is traversed throughout its length by the pyroxene belt or band, which con- tains, besides the apatite, a large number of the characteristic minerals and has an average width of some 250 feet. The pyrox- ene is occasionally intermixed at the surface with bowlders of granite or gneiss. The trend of the belt or vein is in the usual northeasterly and southwesterly direction, and at intervals of from 50 to 75 feet it is intersected from east to west by faults, or chutes, Avhich dip to the south at an angle of from 45° to 60°, and as these all contain an abundance of apatite they have been chosen as the fitting points for sinking shafts and pits. Taking the southern boundary as a jjoint of departure, the belt of phosjihate-bearing matter has been prospected and j^i'oved by openings practised at intervals of from 25 to 50 feet. Proceeding along the vein towards the north for about 500 feet, we reach the first important opening sunk upon it and known as The Office Pit, a species of quarry 150 feet in length by 40 in width and about 35 feet deep. Here we find the usual masses of characteristic conglomerates, mica, feldspar and apatite alternating in predominance or heterogeneously mixed up together. In the west-end corner of the quarry a small pit, some 6 feet square, has been sunk ui)on a vein of apatite and has shown the same features to continue in dej^th. From a careful measurement and comparison of the entire matter in place, the proportion of pure apatite in this portion of the lode is estimated at eight per cent, of the total ma- terial to be removed. In other words, for every 100 tons of rock removed 8 tons of apatite can be secured. The next in line, at a distance of 100 feet, is the Alice Pit N^o. 1, an opening 25 x 15 and 10 feet deep. Here, in exactly the same formation as the preceding, there is a very fine vein of pure apatite, about 12 feet wide, running down from the surface with the usual dip to the south. Following the belt for another 60 feet we come to Alice Pit Nfj. 2, which has been opened up for a depth of 10 feet on a fault in the vein 30 feet long by 15 feet wide. Several small veins, or strinr/er.t, of apatite imbedded in the usual con- glomerate have merged into one, which has gradually widened out until at the bottom it has attained about 5 feet. This is an 32 The Phosphates of America. excellent prospect, with all the appearance of developing into a bonanza when brought into further working order. Passing over several other openings and faults of similar char- acter for about 250 feet, we come to Pit JVo. 3, which is now being developed and got into shape for exploitation. It has been sunk in solid vein matter and upon the dip of the chute to a depth of about 100 feet and still retains the appearance of an open quarry. Down its southwest side there run three well-defined veins of apatite, each of them occasionally interspersed Avith or hidden from sight by bowlders of feldspar, mica, calcite and pyroxene. The next opening upon the belt is at a distance of only 50 feet and is known as Shaft JVb. 1. It is sunk on the dip of the vein at an average angle of about 55° and is now about 600 feet deep. Its progress has been watched with the greatest interest by all who are in any way connected with or concerned in the apatite-mining industry, and it has served to prove beyond contestation that the sought-for material is not confined to a mere sujserficial stratum, but that it continues to accompany the other minerals with which it is so in- timately associated, in exactly the same manner, in depth as at the surface. The same mixture of rocks, the same conglomerates, the same alternating preponderances — these are the history of the shaft. Small veins or strings of apatite led into enormous pockets or bonanzas, yielding many thousand tons of pure phosphate ; these, in course of time, gradually pinched out and were replaced by pyroxene, feldspar or mica, through which the veins of apatite were followed until they again merged into a preponderating mass. At the time of our visit to the mine the shaft contained a great deal of water, which had drained in from the melting of the last winter's snow, but the managers were good enough to have the water pumped out in order to facilitate our inspection, and we were thus able to descend in it to within 50 feet of the bottom. After careful inspection, we became satisfied that there are very large reserves of apatite in the shaft, especially as the bottom is neared, and that it can readily be mined and brought to the surface. Under the peculiar circumstances of the geological formation it was imjjossible to sink this shaft with any great degree of regu- The Phosphates of America. 3:3 larity. Tlie run of the apatite is a capricious one, and was found to shift aljout from side to side and take the phice of other rocks in a maimer that baffled all calculations. We may, perhaps, better convey our meaning if we liken its occurrence to a long string of sausages, of very irregular shape and divided by very irregular lengths of skin, say, for instance, thus : These pockets were of course worked out as they occurred, with the result that the interior of the shaft now presents the a]»- pearance of a series of immense caverns alternating with narrow passages or tunnels. So far as it was possible to judge from the present appearance of the shaft and of the dumps by which it is surrounded, we estimated the amount of rock material already re- moved from it at al)out 160,000 tons and the apatite at about twelve per cent, of that total. At a distance of 100 feet further along the belt we reach The Shaft N^o. 2, a reproduction in the main of the No, 1 shaft already described. It has been carried down on the dip of the vein at an angle of 50° to 55° S. with a tramway which hugs the foot-wall. The width and height of the shaft range from 50 to 120 feet wide ami from 10 to 75 feet higli, all in solid vein matter between well-detined walls of granitic gneiss, with phos- phate overhead and underfoot. The apatite in the vein has fre- quently developed into large bonanza chambers or pockets, and there is every promise of a continuation of this phenomenon as 34 The Phosphates of America. the pit goes down, since the bottom and sides of it now consist almost entirely of massive green phosphate. From careful meas- urements in the excavation, the quantity of total material re- moved from this shaft Avas computed at about 40,000 tons and the proportion of apatite at about twelve per cent, of the mass. The average daily number of men employed in sinking this shaft and dealing with the ore has been as follows : Twenty-five miners and strikers Avith 1 steam drill underground ; 5 men at the surface unloading the cars ; 25 men and boys in the cobbing-house, engine-house and blacksmith's shop ; total, 55 men and boys. The average wages paid to these — grouped together — has been $1 per capita and per day. The average cost of powder and steam and the wear and tear of drills, engines, hoists, tools and other plant we estimate from prac- tical experience at 25 cents per ton of rock removed. From these data it is easy for us to compute the cost of the phosphate j^er ton. 55 men and boys at $1 per day for 300 days $16,500 40,000 tons of rock removed at 35 cents per tea for plant and wear and tear 10,000 Total cost of, say, 5,000 tons clean phosphate.. .|26, 500 or, say, $5.60 per ton at the mine. The width of the pyroxene belt in the neighborhood of this shaft is about 300 feet, and saving that in some places there is a considerable intermixture of huge granitic bowlders, there is no change in its predominating characteristics over the remainder of the property. The equipment necessary to the proper Avorking of an apatite mine must include : One or two good boilers of about 50 H. P. each. One or two double drill compressors. One or two hoisting engines of about 30 H. P. each. Three or four machine drills fully equipped. All necessary fittings and pipe for compressors. A first-class plunger pump. A first-class double forcing pump. A line of transport wagons of about 2 tons each capacity. A line of transport sleighs, for winter, of about 2 tons each capacitj'. A commodious blacksmith and carpenter shop, well provided with all kinds of tools. A cobbing-house fully equipped. z — S it" — p Tlie Phosphates of America. 35 A cooking and boarding house to accommodate, say, 250 men. A sleeping-liouse to accommodate, say, 350 men. A large warehouse for stores of all kinds. Offices and dwelling for a local superintendent. It has already been explained that tlie form in which the phos- phate occurs in the Canadian mines is that of a hexagonal crystal- line mass of fluor-apatite. Sometimes it is extremely compact ; at others it is coarse and granular. It has a hardness of 5 and a mean specific gravity of 3.20, and is generally so friable as to fall to pieces if struck Avith the pick. It varies in color from green to blue, red, brown or yellow, according to the greater or lesser pro- portions of impurities with which it is contaminated. A series of our analyses made from average samples taken from many of the largest working mines may be regarded as very fairly rejiresentatiAe of the average chemical composition of the ma- terial. COMPOSITIOX OF COMMERCIAL SAMPLES OF CANADIAN APATITE. \st Qtial. 2d Qual. 3d Qual. Phosphate of lime 88.20 78.65 66.22 Carbonate of lime 4.13 8.05 9.20 Fluoride of lime 3.10 3.04 2.97 Alumina and iron oxides 0.70 1.03 1.37 Magnesia 0.20 0.31 0.47 Insoluble siliceous matter 3.67 8.92 19.77 100.00 100.00 100.00 What is the origin of these remarkable }>hos])hates is a question that has been, and still continues to be, the cause of much contro- versy. Sir William Dawson, in a paper read before the Natural Histor- ical Society, Montreal, 18V8, "On the Phosphates of tlie Laurentian and Cambrian of Canada," discusses the probability of animjil origin, and holds that there are certain considerations which point in this direction. .Vniong these are the presence of the iron ores, the graphite, and of Eozoon Canadense, Avhich he, with others, hohls to represent the earliest known forms of life. lie further says that the possibility of the animal origin of this jdiosphate is strengthened by the presence of i)hosphatic matter in tlie crusts and skeletons of fossils of primordial age, "giving a j>resuiiiption tliat in the still earlier Laurentian a similar preference for pliosphatic matter may liave existed and perlia})S may have extended to still lower forms of life." 36 The Phosphates of America. Others, again, have contended that it must liave been ejected from tlie earth's interior by volcanic action, and i^rominent among these is the present Director of the Geological Survey of Canada, A. R. C. Selwyn, who says : "My own examinations of the Canadian ai)atite deposits (veins, etc.) have led me to a conclusion respecting their origin correspond- ing with that of the Norwegian geologists. I hold that there is absolutely no evidence whatever of the organic origin of the apatite, or that the deposits have resulted from ordinary mechanical sedi- mentation processes. They are clearly connected, for the most part, with the basic eruptions of Archaean date." This view is also taken by Mr. Eugene Coste, Avho, in his report on the "Mining and Mineral Statistics of Canada for 1887," con- cludes an article on "The Iron Ores and Phosphate Deposits (?) in the Archaean Rocks" by saying : " It is only natural that we should conclude, as many other geologists have done before, that the iron ore and phosphate to be found in our Archaean rocks are the result of emanations which have accompanied or immediately followed the intrusions through these rocks of many varied kinds of igneous rocks which are no doubt the equivalent of the volcanic rocks of to-day. These de- posits, then, are of a deep-seated origin, and consequently the fears entertained, principally by our phosjjhate miners, that their depogits are mere surface pockets, are not well founded. These fears are no doubt partly the result of the belief which has been somewhat prevalent that the apatite in them was the metamorphic equivalent of the phosphate nodules of younger formations, and it may be also that they have resulted from the fact that the apatite is irregularly distributed in these deposits and is often suddenly replaced by rock. But notwithstanding this, when the deposits are properly under- stood to be, as we hold they are, igneous dykes and veins accom- panying the igneous rocks, it will be easily seen why in the deposit itself the economic minerals can be suddenly replaced by rocks which may be said to be nothing else l)ut the gangue. If this origin is understood it will facilitate and encourage the working of these deposits in depth, because the accompanying igneous rock, forming a mass or a dyke alongside of the de])osit, will be easy to follow, and because if it is apatite or iron-bearing at the surface, it will always be a guarantee that it will also be in depth, as each sepa- rate mass of igneous rock is generally quite constant in composi- tion." The Phosphates of America. 37 Despite the great attention and care with which we have our- selves examined numerous specimens of the Canadian apatites taken from various })oints over the entire formation, we liave failed to discover by means of the microscope the least trace of anything that would lead us personally to connect them with organic life. We prefer to ascribe them to a decomposition of the pyroxenite by a process of segregation similar to that which in other places has resulted in the production of quartz and orthoclase, and we can see no reason for making any distinction between the character of the dejtosits. According to Dr. T. Sterry Hunt, the stratiform cliar- acter of these endogenous deposits, as seen alike in the individual portions and in the arrangement of these as constituent parts of a vein, is well shown at the Union mine, in the Lievres district. Here the great mass or lode is seen to be bounded on the west by a dark-colored amphibolic gneiss, nearly vertical in attitude, and with northwest strike. Within the vein, and near its western border, is enclosed a fragment of the gneiss, about twenty feet in width, which is traced some yards along the strike of the vein to a cliff, where it is lost froju sight, its breadth being previously much diminished. It is a sharjjly broken mass of gray banded gneiss, with a re-entering angle, and its close contact with the surround- ing and adherent coarsely granular pyroxenic veinstone is very distinct. Smaller masses of the same gneiss are also seen in the vein, which was observed for a breadth of about 150 feet across its strike (nearly coincident with that of the adjacent gneiss), and be- yond was limited to the northeast by a considerable breadth of the same country -rock. In one opening on this lode there are seen, in a section of forty feet of the banded veinstone, repeated layers of apatite, pyroxenite and a granitoid quartzo-feldspathic rock, including portions of dark brown foliated j)yroxene, all three of these being unlike anything in the enclosing gneiss, but so distinctly banded as to be readily taken for country-rock by those not a[)prised of the venous char- acter of the mass. A fracture, with a lateral displacement of two or three feet, is occupied by a granitic vein twelve inches wide, made up of quartz with two feldspars and black amphibole, which themselves present a distinctly banded arrangement. This same granitic vein is traced f(»r fifty feet, cutting obliquely across both the ])yroxenite and the older granitoid rock, and at length spreads out, and is confounded with a granitic mass interbedded in the greater vein. It is thus j)()steri(»i- alike to the older (juartzo-feld- 38 The Phosjyhates of America. spathic rock, the pyroxenite and the apatite, as are also many- smaller quartzo-feldspathic veins, which, both here and in other localities in this region, intersect at various angles the apatite, the pyroxenite and the granitoid rock into which the latter graduates. We have thus included in these great apatite-bearing lodes quartzo-feldspathic rocks of at least two ages, both younger than the enclosing gneiss. A smaller vertical vein of fine-grained black diabase-like rock intersects the whole. No one looking for the first time at this section of forty feet, as exjiosed in the quarry, Avith its distinctly banded and alternating layers of pyroxenite and granitoid quartzo-feldspathic rock, including two' larger and several smaller layers of crystalline apatite, would question the stratiform character of the mass, whose venous and endogenous nature is nevertheless distinctly apparent on further study. In other portions of the same great vein, quarried at many points, this regularity of arrangement is less evident. Occasion- ally masses are met with presenting a concretionary structure, and consisting of rounded or oval aggregates of orthoclase and quartz, with small ciystals of pyroxene around and between them ; the arrangement of the elements presenting a radiated and zone- like structure, and recalling the orbicular diorite of Corsica. The diameter of these granitic concretions varies from half an inch to one and two inches, and they have been seen in several localities in the veins of this region over areas of many square feet. In the Emerald mine the stratiform arrangement in the vein is remarkably displayed. Here, in the midst of a great breadth of apatite, were seen two parallel bands (since removed in mining) of pyroxenic rock, several yards in length, running with the strike of the vein, and in their broadest parts three and eight feet wide re- spectively, but becoming attenuated at either end and disappear- ing, one after the other, in length, as they did also in depth. These included vertical layers, evidently of contemiK)raneous origin with the enclosing apatite, were themselves banded with green and white from alternations of pyroxene of a feldspar with quartz. Accompanying the apatite in this mine are also bands of irregular masses of flesh-red calcite, sometimes two or three feet in breadth, including crystals of apatite, and others of dark-green amphibole. Elsewhere, as at the High Rock mine, tremolite is met with. In portions of the vein at the Emerald mine pyrite is found in con- siderable quantity, and occasionally forms layers many inches in The PhosjjJiafes of America. 39 thickness. Several large parallel bands of apatite occur here with intervening layers of pyroxene and feldsj)athic rock, across a breadth of at least 250 feet of veinstone, besides numerous small irregular, lenticular masses of apatite. The pyroxenite in this lode, as elsewhere, includes in places large crystals of phlogopite, and also presents in drusy cavities crystals of a scapolite and occasionally small, brilliant crystals of colorless chabazite, which are implanted on quartz. At the Little Rapids mine, not far from the last, where well- defined bands or layers of apatite, often eight or ten feet wide, have been followed for considerable distances along the strike, and in one place to about 200 feet in depth, these are, nevertheless, seen to be subordinate to one great vein, similar in composition to those just described, and irjluding bands of granular quartz. In some portions of this lode the alternations of granular pyroxenite, quartzite and a quartzo-feldspathic rock with little lenticular masses of apatite are repeated two or three times in a breadth of twelve inches. The whole of the observations thus set foi'th sei've to show the existence, in the midst of a more ancient gneissic series, of great deposits, stratiform in character, complex and varied in com])Osi- tion, and though distinct therefrom, lithologically somewhat simi- lar to the enclosing gneiss. Their relations to the latter, however, as shown by the outlines at the surfaces of contact by the included masses of the wall-rock, the alternations and alternate deposition of mineral species and the occasional unfilled cavities lined with crystals, forbid us to entertain the notion that they have been filled by igneous injection, as conceived by Plutonists, and lead to the conclusion that they have been gradually deposited from aqueous solutions. As one of the most interesting results of the extensive and costly mining operations carried out during the i)ast few years, it has, we repeat, been demonstrated tliat the apatite really does traverse the entire stratum in Avliich it is found, and that, if it is extremely })ockety and deceptive in its occurrence, it nevertheless is perfectly persistent. It has also been proved that, to put it broadly, the same geological characteristics prevail throughout the belts. It hence follows that all the deposits maybe mined by the same method, and that, since we are called upon to deal with invariably mixed-up lodes, the quantity of apatite ])roduced will be in direct proportion to the amount of rock removed. MITINNU MINING AND SMELTING CO. LIMITED 40 The Phosphates of America. After duly and seriously considering the problem from every standpoint, we venture to say that, if the best working mines could be all grouped together, the total ratio of pure apatite to other ma- terial could be brought up to about seven per cent. It is true that there would be certain times when "bonanza" pockets would permit of very large production, but it is equally true that when the ordinary veins commence to "pinch," as they often do, the average j^roduction would be very small, or sometimes even nil until other bonanzas appeared. The figure of seven per cent, is therefore a very reasonable one as basis for calculations, when applied to Canadian mining as a whole. A properly equipped mine, itnder the direction of a careful and experienced miner, judicious in his use of explosives, should be al- lowed the following force of men, employed as set forth : 30 men at prospecting or preparatory work over various parts of the property at fl.lO per daj' each for 300 days $6,600 ~)Q miners and strikers in shafts or quarries with one steam drill at $1.20 per day each for 300 days 18,000 10 men at surface labor, unloading, dumping, etc., at $1 per day each for 300 days 3,000 10 men in engine or machine shop, blacksmith shop and carpenter's shop at $1.20 per day each for 300 days. . 3,600 .5 men in cobbing house at $1 per day each for 300 days. . 1,500 20 boys ia cobbing house at 7.5 cents per day each for 300 days , 4.500 115 men and boys employed daily — cost for the year $37,200 From practical experience in this class of work it is estimated that the miners and prospectors will produce 5 tons of rock matter from the lode or belt per day and per man, and it has been found that the other labor and the plant must be regarded as accessory to this production. Seventy men at 5 tons per day for 300 days will therefore pro- duce 105,000 toyis of material, which, at 25 cents per ton, will cost $2G,250 for steam, explosives, wear and tear of }>lant, tools and general stores. The cost of the apatite per ton at the mines, ready for ship- ment, will therefore be aj)proximately as under : Total yearly cost of labor $37,200 Total cost of stores, etc 26,250 Total expenditure at mine $63,450 Tlie PhospJiafefi of A7n erica. 41 Total 2)ro(luc'ti<)n of rock, 1 05,000 tons. Seven per cent, of this quantity = 7,;{50 tons phosphate of all grades, from seventy to eighty-five per ceiit. 163,450 -^ 7,350 tons = ^8.60 per ton. These figures are suggested, -sve repeat, as those of the average mining cost, and it is hardly necessary to add that while some of the mines now working may be doing better, others are certainly not doing so well as this. In any event Ave must add to the figures the salaries of various officers and the interest on the capital invested in the purchase of the mine. If these items be grouped together under one head, we shall probably be Avithin the mark if we charge them at the very moderate sum of |!l.40 per ton on the amount of ore produced. This would therefore place the average net cost per ton, at the mines, at SlO for the qualities named. Again, it must be remembered that Ave are estimating the averages over the entire year. It would be obviously unfair to object to them that, Avhen the mines are in "bonanza,'* the phosphate does not cost more than one-half the estimated amount, just as it Avould be unreasonable to claim, during a long period of "dead" Avork, that it costs tAvice or three times as much. AVhen studying this question of cost, Ave must bear in mind that, owing to the mixed-up nature of the \'ein matter, nearly all the output has hitherto been put through the expensive process of hand- cobbing, as shoAV in our illustration, in order to arrive at an aA'erage standard quality of from seA'enty-five to eighty-five jjer cent, of phosphate of lime. The impossibility of obtaining fairly remu- nerative prices in Europe, which is the market for the entire Cana- dian outjmt, for lower grades, has necessitated this cobbing and induced a state of affairs probably unprecedented in the history of any raining operations. We refer to the fact that the whole of the apatite mining companies have been shipj)ing no more than about one-third of their total 2)roduction ; the balance has been lost in the cobbing, and has been consigned to the dumps with the re- fuse, where it now remains as useless material ! That few, if any, of the enterprises have ))aid any dividends on their capital is not a matter for surprise iinder such circumstances as these, nor is any argument necessary to show how immeasurably their position Avculd be ameliorated if a market were created for lower grade ores. The cost of transportation now renders these unfit for the market of Europe, but they are just the very class of 42 The PhospJiales of America. material required for llie mamifacture of fertilizers for home con- sum])tion, and it Avould be wiser jjolicy to dispense Avith all the exi^ensive jirocesses of hand selection and cobbing at the majoi'ity of the mines, and to rest content with such an assortment at the quarry side as would insure an average grade of sixty per cent. The proportion of this quality to the total vein matter removed would be about double that of the pure ajjatite ; in other words, instead of seven, the output could be placed at fifteen per cent., and the cost of cobbing Avould be saved. The costliness of handling at the mine, however, is not the only imjjediment to the greater development of the apatite indus- try in Canada; another, and very serious obstacle, is the comparative inaccessibility of the deposits. One or two of the most important companies have gone to the expense of constructing shutes, or in- clined railroads, for the carriage of their product to the river's banks, but by far the greater portion of the outj^ut is at present rolled in Avagons or sleighs over very indifferent roads generally leading to a rough storehouse, provided with a weighing shed and a Howe's scale. At this point different compartments or bins receive the phosphate according to its grade or quality, and a sex'ies of tramways connect the stored heaps Avith inclined shutes, Avhence the material is loaded directly into scows or barges on the river. The actual cost of transport from the chief mining centres in the Quebec district to the Avharf-side at Montreal has been the object of sjiecial inquiry, and the following figures haA'e been ob- tained from official sources : COST OF TRANSPORTING APATITE FROM THE CHIEF MINING CENTRES IN OTTAWA COUNTY TO THE WHARF AT MONTREAL. Loading at mines, carting to and unloading at Riverside Store $1 50 Loading into scows 05 Towing to Buckingham Village 18 Unloading scows and loading on cars of C. P. R. R 12 Railwajf freight to Montreal 1 25 Wharfage, insurance and incidentals at Montreal. 50 Total cost of transport from the mines per ton $3 60 It would hence appear that the average cost of Canadian apa- tite delivered free on board vessels at Montreal outward bound for European ports must be placed at about ^14 j)er ton, and The Phosphates of America. 43 ngainst this it will be of interest to study the selling prices which prevailed for the material during 1890. TABLE SHOWING THE SELLING PRICES OF CANADIAN APATITE F. O. B. MON- TREAL DURING 1890. For phosphate guaranteed to contain 85 percent., $25 00 per ton. 80 '• 22 50 75 " 18 00 70 •• 14 50 65 •• 11 25 If we could assume that the two highest of the above qualities formed the bulk of the material exported, it is evident that Cana- dian phosphate-mining would have to be placed in the front rank of })rofitable enterprises. Whether the bulk is thus composed, however, is a very perplexing question iia the face of the following official figures showing the total quantities and values of ore yearly exported since the opening of the mines in 1877 : TABLE SHOWING THE YEARLY EXPORTS AND VALUES OF CANADIAN PHOS- PHATES. 'QUANTITY, TONS. VALCE, DOLLARS 1877. . . 1878. . . 1879. . . 1880. . . 1881... 1882... 1883... 2,823 10,743 8,446 13,060 11,968 17,153 19,716 47,084 208,109 122,035 190,086 218,456 338,357 427,668 I YEAR. QUANTITY, TONS. VALUE, DOLLARS 1884 1885 1886 1887 1888 1889 1890 21,709 28,969 20,440 23,152 18.776 29,987 22,000 424.240 496,293 343,007 433,217 298,609 394,768 330,000 From the values thus rec(n-ded we gather that in the year 1S85 about 29,000 tons were sold at the average of §17 per ton in Mon- treal, whereas in 1890 theoutput fell to 22,000 tons and the j)rice to an average of $15 per ton at tlie same place. This would indicate that the average quality of the entire yield was seventy to seventy- five per cent, of tricalcic or bone phosphate, and in such a case the net profit on the entire exploitation coidd not have been very large. Nothing could possibly be more confirmatory of our views of this mining field, therefore, than the official returns relating to it, and we cannot refrain from again insisting, and with additional em- phasis, upon the necessity for an immediate and radical change of policy. 44 The Phosphates of America. The custom of throwing the entire coBt of production upon the high grades is unfair and should be discontinued. In its stead a rule should be established of setting aside for foreign shipment only such portions of the pure apatite as may be obtained directly from the lode without hand-cobbing at the surface. There would be no difficulty in disposing of these choice lots in Europe at very high prices, and there is no doubt that with proper care and skill in the management they could be brought up to one-fourth of the total output. The balance of the material mined would certainly average more than sixty per cent., would probably go up to sixty- iive, and w'ould of course, as we have already explained, bear a far larger proportionate relation to the total rock removed than it does now. Since there is no lack of grinding facilities at Bucking- ham Village, quite close at hand, and since there are several abun- dant deposits of pyrites — the material required for sulphuric acid manufacture — in the immediate vicinity, it is self-evident that this low-grade material could be readily and cheaply transformed into an excellent snperphosj^hate, containing at least fourteen per cent, of soluble or available phosphoric acid. There would be no difficulty whatever in establishing a sale for such an article at a very fair rate of profit, and the demand simul- taneously created for sulphuric acid by the adoption of this method would stimulate the development of the chemical industry in vari- ous branches, and new channels would thus be opened np for the safe and profitable investment of capital and the constant and re- munerative employment of labor. The P]ios2)hates of America. 45 CHAPTER IV. THE PHOSPHATE DEPOSITS OF SOUTH CAROLINA. The amorphous and nodular deposits of phosphate of lime thus far discovered in the United States have been found in that portion of the rocks of the fourth geological period or " Cenozoic'''' time known as the Tertiary Formatioji, or " age of mammals," which immediately preceded the Quaternary Tonnation, or "age of man." It is j)r()bal)le that the earth's surf ace really began to assume its present geogra])hicai aspect in this tertiary age, and a great j»art of \X.'& fatnai audjfora either closely resembled or was identical with a large number of our existing familiar species. Chief among its characteristics was a marked and continuous subsidence of the seas and an accompanying increased elevation of the land. The seas underwent evaporation ; lagoons were formed ; marshes were dried up; lakes were drained, and mountain chains arose and towered above deep valleys. The climatic conditions were next revolution- ized, for the even temperature communicated by the earth's interior heat to an unbroken surface could no longer prevail. A redis- tribution oi fauna a.n<\. flora hence necessarily ensued, and number- less species were naturally exterminated before perfect acclimation could be accomplished. The fossilized remains of these extinct species, including incredibly gigantic reptiles and sea monsters, con. tiniie to afford a most interesting field for the study of paleontology, and have enabled us to recognize the pachydermatous anoplothe- rium as the oldest typical mammal, and to trace the succeeding true ruminant and carnivora and the endless swarms of shell-fish and bivalves right down to the present time. The sul)divisions of the tertiary age embrace three eras, which are respectively known to geologists as follows : The Eocene Era, or age of nearly extinct species. The Miocene Era, or age of which the species are more than half extinct. 2'he Pliocene Era, or age of which more than half the species are still living. The rocks of the tertiary have been classified according to 46 The Pliospliates of America. certa n characteristic differences in their essential features arising from the fact that one portion of tlieni was deposited by fresh and another hy salt water. The oldest of them comprise gradually ascending beds of sands, clays, compact sandstones, loose shell-beds and calcareous sandstones, and they gradually develop into marls, clays, chalk, solid limestones and greensands. No other age wa& subjected at various intervals to more severe eruptive action, and its close was marked by immense disturbances, of which most of our active volcanoes remain as monuments for our wondering con- templation. The portion of the tertiary strata in which our workable phos- phate deposits are found may be broadly said to hug the coast of the Atlantic Ocean and the Gulf of Mexico from New Jersey to Texas, and to embrace within its area the most extensive marl-beds in the world. Deposits of more or less commercial value and importance have been located and Avorked in Virginia, North and South Carolina, Alabama, Georgia and Florida, and there is no reason why they should not be found in large quantities in States where they are not at present known, or where they have only hitherto appeared to be of very low grade. If no further discoveries should take place in our time, however, the vast beds of South Carolina and Florida are capable of yielding more than sufficient to sujjply the entire needs of the world far into the future, and as they are the only present sources likely to be extensively exploited in this country, we may dismiss all others without further comment. In his work on "The Phosphate Rocks of South Carolina," Professor Francis S. Holmes tells us, in reference to their discovery, that in November, 1837, in an old rice field about a mile from the west bank of the Ashley River, in St. Andrew's Parish, he found a number of rolled or water-worn nodules of a rocky material filled with the impressions of marine shells. These nodules or rocks were scattered over the surface of the land, and in some places had been gathered into heaps so that they could not materially interfere Avith the cultivation of the field. As these rocks contained little carbonate of linie (the material of all others then most eagerly sought after), they were thrown aside and considered useless as a fertilizing substance. In December, 1843, in another old field he attempted to bore with an augur below the surface to ascertain the nature of the earth beneath, with the hope of finding marl. On TJie Pliosphates of America. 47 removing the soil above the rocks they were seen in a regular stratum about one foot thick imbedded in clay, and seemed to be identically the same as those found scattered on the surface of ad- joining land, all of them bearing impressions of shells and having similar cavities and holes filled with clay. It was on the 23d or '24th of February, 1844, while engaged in the removal of the upper beds covering the marl, that the laborers discovered several stone arrow- heads and one stone hatchet. Not long after finding these relics of human workmanship, and while engaged in his usual visits to the Ashley marl-bed, Prof. Holmes found a bone i>rojecting from the bluflf immediately in contact with the surface of the stony stratum (the phosphate rocks); he pulled it out and beheld a human bone ! Without hesitation he condemned it as an "accidental occupant" of quarters to which it had no right, geologically, and so threw it into the river. A year after, a lower jaw-bone with teeth was taken from the same bed. Subsequent events and discoveries show conclusively that the first-described bone was in "place," and that the beds of the post-Pliocene, not only on the Ashley River, but in France, Switzerland and other European countries, contain bone* associated with the remains of extinct animals and relics of human workmanship. The necessary lime or calcareous earth for manufacturing salt- petre on the west l)ank of the Ashley River during the Confederate war was obtained by sinking jtits int<^ the Eocene marl-bed. Ui)on the removal of a few feet of the upper layers the workmen, discovered in one pit a number of oddly-shaped nodules, resem- bling somewhat the marl-stones (phosphate rock) found in the stratum above the mail, but more cylindrical in form ami not perforated, and having their exterior polished, as though each in- dividual specimen liad received a coat of varnish ; they appeared to have been deposited in a large corner or pocket in the marl-bed. Upon submitting these samples to analyses their true value was revealed and South Carolina thereafter became a centre of attrac- tion. It was not until about 18G7, however, that a mining company could be organized to test the j)racticability of working the phos- phate on a commercial scale, but this company was no sooner started than it became a success, and the industry has since then progressed with such leaps and bounds that it has raised the status of South Carolina to that of the most productive jjhosphate field yet known to industry. 48 The Fhos2)hates of America. The geological formation of what is commonly called its phos- phate " belt " is made up of quaternary sands and clays. These overlie the beds of Eocene marls, upon whose surface and inter- mixed with which is found the phosphate deposit. The presumed total area covered by this characteristic formation, as shown by the map, is 70 miles in length and 30 miles in width, extending The Phosphates of America. 49 from the mouth of Broad River, near Port Royal, in the soiitli- east, to the head waters of the Wando River in the northeast. Its major axis is ])arallel to the coast, and its greatest width is in the neighborhood of Cliarleston. Whether the deposit is continuous or not over the whole of this zone, it certainly varies considerably in depth and thickness. In many ])laces we have seen it 3 feet thick and cropping out at the surface, whereas in others it has dwindled down to a few inches, or was found at depths varying from 3 to 20 feet. These two con- ditions, thickness of deposits and depth of strata, taken together with the richness of material in phosphoric acid, are of course the chief points for consideration in the economic working of the Charleston phosphate beds on an industrial scale. The most approved and generally adopted method of ascertain- ing the importance and value of the deposits is that of boring and pit-sinking. A careful topographical survey is first made of the country, and when this has been done there commences a sj^stematic series of bore-holes from any point that may be arranged, by means of a long steel borer or rod, specially designed for the purpose. The boring rod is worked down through the up})er strata until it is ar- rested by the solid bed of phosphate. Directly the slightest resist- ance is offered to its passage it is drawn up, and the distance it has traversed is measured with a foot-rule. The measurement havincT been noted, the rod is again let down, is forced through the resist- ing strata, and is then again withdrawn and measured. The differ- ence between the first and second measurements is taken as repre- senting the thickness of the })hosj)hate bed. These bore-holes are practised at distances of 100 feet apart over the total surface to be examined. The results obtained with the rod are verified and con- firmed by a series of exploratory j)its — 10 feet long by 5 feet Avide — which are dug over tlie course of the bore-holes at intervals of 500 feet. The bore-holes are driven to a maximum depth of 15 feet, and no pits are at present sunk on those portions of the land where at that distance no ])hosphale has been encountered. Im- mediately after removing the overlying strata the phosphate is carefully taken out, its depth and thickness measured, and an aver- age sample of the rock and nodules secured and laid aside for analysis. The practically invariable nature of the superincumbent ma- terial throughout the entire belt, as shown by the digging of a 50 TJie Fliospliates of America. large number of pits under our direction, is represented in the fol- lowing table, the figures being averages compiled from our field note-book : Soil very black and acid Mixture of sand and blue claj' Silicious clay Potters' clay mixed with shells Sandy, hard conglomerate Phosphate rock or nodules mixed with blue clay Depth of overlying beds Feet. 2 2 traces JACKSON- BORO. Feet. IK 9^ Feet. 1 4 3^ 3^ 12% Feet. 2 IK 4 2K Ilk' This is still further illustrated and will be probably more clearly- conveyed by the accompanying sketches of typical sections, pre- pared by R. A. F. Penrose, Esq., and borrowed from Bulletin No. 46 of the United States Geological Survey. Section ENE. and WSW. through Plnckney's phosphate field. South CaroHna. A, sand ; B, ferruginous sand ; C, phosphate rock ; D, Ashley marl. Scale : 1 inch = 60 feet. So far as we have been able to discover, no systematic inves- tigation has been made of those lands which contain the phosphate Average section in Pinckney's phosphate mine, Berkeley County, South Carolina. A, cla,y sand ; B, ferruginous sand ; C, phosphate rock ; D, Ashley marl. Scale : 1 inch = 6 feet. deposit at a greater maximum depth than 15 feet, it having been hitherto considered impracticable, under the conditions of abun- llie Phosphates of America. 51 dant surface supply and consequent low mining cost, to conduct a profitable exploitation at any greater depth. A far wider area of lands than those actually classed as mining properties may there- fore contain the very same deposit of phosphate, lying under acon- ^^iV'-<< ^- "-■ Section in one of Fishburne's pits, South Carolina. A, sand ; B, ferruginous sand ; C, phosphate nodules in clay matrix. Scale : 1 inch — 7 feet. sidcrably greater accumulation of the quaternary strata, and this is the view we are personally disposed to adopt as representing the facts. Whether or not, however, in face of the recent Florida phos- phate discovery, any economical means Mill ever be devised in our time to exploit them at a profit, should they really exist, is a ques- tion as to which we are in very serious doubt. The phosphate deposits in South Carolina are of two kinds, the "River" and the "Land," but the material found in the river bot- toms of the "belt" is of practically the same chemical description as that of the land, having, in fact, been merely washed into them from its original beds. It has been worked extensively and has jtroved to be of great commercial value, since it is obtained by the simple and inexpensive process of dredging, and is thus raised and washed free from all adhering imj^urities by one and the same operation. The dredging scoops are made extremely massive in order that they may break through the nodular stratum, and the boats are held in position at the four coiners by "spuds" or sti'ong square poles with iron points, which are dropped into the water before dredging is begun, and afford a strong support for the boat by going through the nodule stratum and down into the river-bed below. The nodules are thrown from the scoop into the washer, which is on a lighter alongside the dredging boat. The washer, in some cases, is the same as those used by the land-mining companies, to be presently described, but often it consists of a truncated cone, M-itli perforated sides, revolving on ,i horiztuital axis. It is sup- 52 The Phosphates of America. plied on the inside with steel spirals, arranged around the side like the grooves in a rifle, and heavy streams of water flow into its two ends. The nodules are dumped by the dredge into the small end of the cone and come out at the large end. They are then removed by a derrick to another lighter and towed to shore. The dredging machine is not the only means employed for rais- ing the river phosphate, some companies having adopted a contriv- ance consisting of six large claws, which 02:)en when they descend, and close, forming a kind of bucket, when they rise. It is said that some of these machines can dredge in 50 to 60 feet of water, while the ordinary dredging boat cannot raise the phosjjhate in over 20 feet. Both the rock and nodules from these river and land deposits occur in very irregular masses or blocks of extremely hard con- glomerate of variegated colors, weighing from less than half an ounce to more than a ton. The mean specific gravity of the mate- rial is 2.40, and it is bored in all directions by very small holes. These holes are the work of innumerable crustaceae, and are now filled with sands and clays of the overlying strata. Sometimes the rock is quite smooth or even glazed, as if worn by water ; at others it is rough and jagged. Intersj^ersed between the nodules and lumps of conglomerate are the fossilized remains of various species of fish and some animals, chiefly belonging to the Eocene, Pliocene or 2:)Ost-Pliocene ages. Very careful analyses of a large number of the samples of land rocks taken from the pits and made in our laboratory gave, after being well dried at 212° F., the following average : Moisture, water of combination and organic matter lost on ignition 8.00 Phosphate of lime 59.63 Carbonate of lime 8.68 Iron and alumina (calculated as oxides) 6.60 Carbonate of magnesia 0.73 * Sulphuric acid and fluorid(> of lime 4.80 Sand, siliceous matters and undetermined 11.56 Total 100.00 While it is shown by these figures that the grae of this phos- phate is not extremely high, it has been proved by experience all over the world to be admirably adapted for the purpose of manu- facturing commercial fertilizers, and it will doubtless long con- * The sulphuric aciil represents the sulphur eoinbined with iron as pyrites. The Pliosphates of America. 53 tinue for this reason to maintain a leading position as a raw niaterial. Before the land rock can be made available for industrial pur- poses, it is made to pass through three distinct and successive operations. 1. Mining or excavating. 2. Washing it free from sand and other impurities. 3. Kilning, to free it from moisture. Taking these in their order, it is customary to establish a main trunk railroad, starting at the river front or on the bank of some convenient stream, and passing right through the centre of the property to be exploited. Alternate laterals can be run off at right angles from any por- tion of this main line, at distances of, say, 500 feet, in conformity with the nature of the ground. Between and parallel to these laterals a ditch or drain is dug to a depth extending 4 to 5 feet below the phosphate strata. From this main drain the excava- tors start their lines at right angles to the laterals, commencing at one end of the field and digging trenches 15 feet wide and 500 feet long, the work being so arranged that the men are stationed at intervals of 6 feet. Every man is supposed to dig out, daily, a "pit" 6 feet long, 15 feet wide, and down to the phosphate rock. The overlying material is thrown out to the left-hand side of the trench. The phosphate itself is thrown out to the right and taken in Avheelbarrows to the railroad cars which pass at either end of the trench. The water drains from the trenches into the underl5'ing ditch, and is thence pumped out by means of a steam- pump worked by a locomotive engine. The 2)ump and the engine are secured to connected railway platforms, and run along the rail- road track from one ditch to another as occasion requires. The cars, loaded with the crude i)hosphatic material dug out of the pits, are run down to the washing apparatus, constructed at an elevation of some 30 feet fi-om the ground, and generally consist- ing of a series of semi-circular troughs 20 to 30 feet long, set in an iron framework at an incline of some 20 inches rise in their length. Through every trough passes an octagonal iron-cased shaft provided with blades so arranged and distributed as to form a screw with a twist of one foot in six, which forces the washed material upwards and projects the fragments against each other. The phosphate-laden cars are hauled up an incline and their con- tents dumped into the bottom trough, where the phosphate en- ■ 54 , Tlie Pliosjjhaies of America. counters one or more heavy streams of water, pumjjed up by a steam- ])ump. This water does not run off at the bottom, but overflows at the higher end near Avhere it enters. When sufficiently washed, the material is pushed out upon a half-inch-mesh screen ; the small debris being received on oscillating wire tables below. The phosphate is now ready for kilning or drying, and of all the methods hitherto ado])ted for this important process, that of simple roasting in an ordinary kihi, such as is generally used in the manu- facture of bricks, is said to have been found at once the most rapid, effective and economical. The rock is built on layers of pine wood, and owing to its con- taining a considerable quantity of organic matter, it readily lends itself to combustion and requires but a short time to become quite red-hot. The kilns are made sufficiently large and are so arranged as to allow free passage to a train of cars, which, running on the main line of railroad, can be loaded in the kiln, run down to the landing place and discharged directly into the barges or boats on the river. Since the beginning of ojjerations in 18G8, the yearly quantities of l)hosphate taken from the South Carolina rivers and mines have been: Year. Land Rock. Biver Rock. Total Tons. 1868-70 18,000 1,989 19,989 1871 33,000 17,655 50,655 1872 38,000 23,503 60,503 1878 45,000 45,777 90,777 1874 43,000 57,716 100,716 1875 48,000 67,969 115,969 1876 54,000 81,912 135,912 1877 39,000 126,569 165,569 1878 113,000 97,700 210,700 1879 102,000 98,586 200,586 1880 125,000 65,162 190,162 1881 141,000 124.541 265,541 1882 190,000 140,772 330,772 1883 226,000 129,318 355,318 1884 258,000 151,243 409,243 1885 224,000 171.671 395,671 1886 294,000 191 ,194 485,194 , 1887 230,000 202,757 432.757 1888 260,000 190,274 450,274 1889 250,000 212,101 462,101 1890 300,000 237,149 537,149 Totals, 3,031.000 2,434,557 5,465,557 1891, estimated total from all sources 650.000 The Phosphates of America. 55 And the number and the importance of the companies actually encrafed in mininrj are .shown in the following table : LAND PHOSPHATE COMPANIES. Xame. Address. Capital. Williman Island Co P.O.. Beaufort; works, Bull River. $200,000 Bolton Mines (K. S. Tupper). P. O., Charleston ; works, Stono River 50,000 Charleston Mining & Manu- facturing Co P. O., Charleston ; works, Ashley River 1,000,000 Campbell & Hertz P. O., Rantowles ; works, Ran- t jwles Creek 50,000 Bulow Mines (^Vm. M. Bradley) P. O., Charleston; works, Ran- towles Creek 350,000 Mt. HoUey Mining & Manu- facturing Co P. O., Charleston; works, Mt. Holley, N. E. R. R 50,000 C. H. Drayton P O., Charleston ; works, Ashley River 50,000 William Gregg P. O., Sumnierville ; works, Ash- ley River ."iO.OOO F. C. Fishburne P. O., Jaeksonboro ; works, Pon Pon River 50,000 Meadville Mines (E. Meade).. . P. O,, Charleston : works. Cooper River 300,000 Magnolia Mines (C. C. Pinck- ney) P. O., Charleston ; works, Ashley River 100.000 Rose Mines (A. B. Rose) P. O., Charleston ; works. Ashley River 100,000 Wayne & Von Kolnitz P. O., Charleston ; Avorks. Ashley River 50,000 St. Andrews Mining Co P. O., Charleston ; works, Stono River 200,000 Hannahan Mines P. O., Charleston ; works. Cooper River 50,000 Horse Shoe Mining Co. (Wm. Gregg) P.O., Charleston; works, Ashepoo River 50,000 Wando Phosphate Co P. O., Charleston ; works, Ashley River 200,000 T. D. Dotterrer P. O., Charleston ; works, Ashley River 25,000 Archdale Mines (Hertz & War- ren) P. O., Charleston ; works, Ashley River 20,000 Pacific Guano Co P. O., Charleston; works, Bull River 100,000 Eureka Mming Co P. O.. Charleston ; works, Jaek- sonboro, C. «& S. R. R 40.000 56 The Phosphates of America. RIVER PHOSPHATE COMPANIES. T^ame. Address. Capital. Beaufort Phosphate Co.. P. O., Beaufort ; works, Beaufort River. $100,000 Coosaw Mining Co P. O., Coosaw ; works, Coosawand Bull rivers 600,000 Carolina Mining Co P. O., Beaufort ; works, Beaufort River. 250,000 Farmers' Mining Co P. C, Beaufort ; works, Coosaw River. . 125,000 Oak Point Mines Co. . . P, O., Beaufort ; works, Winibe Creek... 150,000 Sea Island Chemical Co. P. O., Beaufort ; works, Beaufort River. 2o0,00(> Of the river companies, the Coosaw, which for many years has been one of the chief operators, has lately been compelled ta susjiend its production on account of a serious controversy with the State, and in this connection it will be interesting to refer to a message which was sent to the Legislature by the Governor of South Carolina on the 1st of March, 1891, in which he makes the following statement: "In 1870 the Legislature granted privileges to a corporation known as the River and Marine Company to mine rock in the navigable Avaters of the State for twenty-one years. The State re- ceived nothing for this valuable franchise. The Coosaw Mining Company obtained from the original grantors exclusive right ta mine in Coosaw River, and with a i)aid-u2J capital of ^275,000 com- menced oi)erations. \n 1876 the General Assembly passed an act confirming the exclusive right of the Coosaw Company to mine in that river for the term of twenty-one years at a fixed royalty of ^\ per ton, and this lease has now expired. The act of 1876 was drawn by the attorney of the Coosaw Company, and so adroitly Avorded as to give color to the claim that the grant of that river was per- petual *so long as that company shall make true returns,' etc., and under this the company claims that its tenure is not a lease expiring- in 1891, but a contract running for all time. This claim is pre- posterous, and this General Assembly must not hesitate to move for- Avard and act promptly and decisively. "The CoosaAV River, to Avhich this company lays claim,' is, ])er- haps, the best phosphate field in the world, and the lease under Avhich it has been mined for twenty-one years has made every stock- holder Avealthy. Their })]ant, Avhich has been obtained from the surplus profits, is valued at $!750,000or over; and in the mean lime, by fabulous dividemls, the original ca))ital of ^275,000 has been re- turned to the stockholders, as I am informed, over and over again. When you are told that the output of this company this year has been 107,000 tons, Avorth $7 ])er ton f. o. b., and that the cost of Tlie PJiosphates of America. 57 mining this rock, including royalty, cannot exceed !?«4.25 per ton, and is believed by many to be much less, you will see that the margin of profit exceeds one hundred per cent, on the original in- vestment. The total royalty secured by the State from its ])hos- phate has been over ^2,000,000, and of this amount over half has been paid by the Coosa w Company. "The expiration of the Coosaw lease in March next makes it pos- sible to double the income of the State from the ])hosphate royally without injuring the industrj'or interfering unduly with any vested right. We therefore demand a survey of the phosphate territory and the sale of its lease at auction to the highest bidder, after a minimum royalty has been fixed by the board of control upon each district surveyed. Anything less than a thorough and reliable survey would ^be a waste of time and money, and this will take a good deal of both. But it will repay its cost, and until we have the data which alone can be thus obtained, we cannot legislate in- telligently or derive the benefits from this valuable property that we ought. This year the royalty has been !??2.'3 7,000, and all of it except ^3,000 was j)aid by six large mining corporations, whose field of operations is confined to a territory within twenty miles of Beaufort. You Avill be told by some that this indicates an exhaustion of the deposits ; but I am sure it only means that good rock is more 2)lentiful or more cheaply mined there than elsewhei'e. A survey alone can demonstrate the truth or falsity of this belief, which is based upon the assurance of experts who themselves have mined in other waters of the State, and as the reliance of capitalists upon an estimate of the value of any given deposit of phosphates will depend largely upon the character of the man making the sur- vey, I have thought it best to obtain the help of the United States Government, if })ossible, and ask the detail of an officer of the Navy or Coast Survey to do the work. I think an a])propriation of ^10,000 will be sufficient to start with, and by the time the General Assembly meets a year hence, it will have something definite to go upon and can continue the work or not as it may deem best. In the mean time, by means of this survey and the oppor- tunity for further investigation, to which all my spare time shall be devoted, a clearer understanding as to the best system of manage- ment of this im])ortant industry can be obtained and the General Assembly can then act intelligently. "When the Coosaw lease expires, March 1 next, let us open that river to all miners Avho choose to enter it ; allow the board of 58 The Phosphates of America. control to parcel out the territory among them so as to prevent conHict ; raise the royalty to $2 per ton and place one or more inspectors on the ground to supervise the work and weigh the rock when shipped. All the river rock mined in South Carolina is exported to Europe, and last year the demand was so great as to necessitate the exportation of 40,000 tons of land rock, while the price has steadily increased since 1887," This is a strong message, and how far Governor Tillman is justified in assuming the river deposits to be either "practically inexhaustible" or to have been very little affected by the enormous drain to which they have been subjected during the past twenty years, is a question of extreme delicacy. To what extent it is politic or Avise on the part of the State to increase the first cost of a raw material which is just now threatened with fierce competition from a most formidable and naturally favored rival is also a matter for very serious consideration. In any event, the fact remains that the Coosaw Company has seen fit to disagree with the views of the Governor and has joined issue M^ith the State on the question of right. When the State Phosphate Commission, therefore, took possession of the Coosaw River territory, on the 2d of ]March, 1891, and made preparations to lease it to all who applied for a license, the company filed a protest, and on March 6th was granted a tem- porary injunction by Judge Simonton, of the United States Court, whereby the State Phosphate Commission was enjoined from enter- ing upon, or otherwise interfering with, that part of the Coosaw River which the company had previously occupied. As a first result of the litigation the Chief Justice of the Supreme Court has decided as follows : "The acts of 18/0 and 1876 must be construed \n pari maturla. Under the first act the State gave the grantees for twenty-one years the right to mine in its navigable streams. This grant was upon the condition that the grantees should pay annually -fil a ton on each ton dug and mined, and that they make a return of their operations annually, or oftener if required. This was not an exclusive right (Bradley vs. The Phosphate Company, 1 Hughes). It was upon condition ; that is to say, it existed so long as the con- ditions were fulfilled and no longer. The act of 1876 proposed modification of this contract in four particulars. " 1. The time for making the returns was definitely fixed at the end of each month. This was an advantage to both parties. The Phosphates of America. 59 " 2. The royalty was made payable on each ton dug, mined and shipped, not on the rock mined. This was in favor of the grantees. " 3. The royalty was made payable quarterly, not annually, this provision to-go into effect immediately and royalty for the two quar- ters of the current year to be paid at once. This was in favor of the State. "4. The right to mine, therefore, if not exclusive, was made exclusive on account of the acceptance of the State's j^jroposals. " The original contract was unchanged in every other respect. The royalty remained the same, fil per ton. The grant was wholly on condition, that is to say, existed so long as and no longer than the conditions were fulfilled. The duration of the grant dur- ing which these conditions were of force was unchanged — twenty- one years from 1870. "This is a reasonable construction of a doubtful act by which the doubt is resolved in favor of the sovereign grantor ; it is a familiar rule of construction that when a statute operates as a grant of public property to an individual, or the relinquishment of a public interest, and there is a doubt as to the meaning of its terms or its general purpose, that construction will be adopted which will sup- port the claim of the government rather than that of the individual. Nothing can be enforced against the State." This, then, is the present position of affairs, and pending an apj)eal from this decision the Coosaw Company has refrained from dredging the rivers and will certainly strain every nerve to jjrevent others from doing so, thereby reducing the output and quantity of river rock hitherto exported to Europe by about one-half. It will have been noticed that in the course of his message the cost of producing one ton of river rock in marketable condition was placed by the Governor at S4.25 per ton, including the Si royalty paid to the State, and that this is a fairly correct statement is borne out by the facts elicited in 1886 by a commission espe- cially appointed by the Legislature to investigate the subject. The same figures apply with equal fairness to the cost of the land phos- phate, as demonstrated by the testimony sworn to by various ex- })erts before the examining body and by our own practical investi- gation in the field. With a properly constructed plant, regular drainage and efficient and economical management, we find that the total cost of pi'oduction of land phosphate in clean, dry, mar- ketable condition may be thus stated : 60 TJie Pliosphate.s of America. Mining at a maximum depth of 15 feet $1.00 Draining the mine , 25 Loading on cars and carrying to washer 60 Washing 30 Drying and handling in kiln 50 Shipping from kiln into vessels on river 25 Interest on capital invested in plant and repairs to same. ... 15 Superintendence and management of mines 20 Towage to Charleston, say 25 Total per ton of 2,240 pounds $3.50 The present vselling price of dry phosphate containing a mean average of fifty-seven per cent, tribasic or "bone phosphate " of lime is $7 per ton of 2,240 pounds on wharf at Charleston, and if we may judge of the total net profits accruing to the miners during the past twelve months by the dividends actually distributed by some of the companies whose published accounts have been placed at our disposal, they cannot be estimated at less than $1,000,000. These figures are doubtless, in a great measure, responsible for the rapid intellectual and industrial growth of South Cai'olina, and they are significantly emphasized by the fact that of the total phosphate mined in the State, more than one-third is actually used in fertilizer factories situated in and around Charleston and owned_ by the following companies : Port Royal Fertilizer Co Port Royal, S. C. Baldwin Fertilizer Co Port Royal, S. C. Atlantic Phosphate Co Charleston, S. C. Ashley Phosphate Co , Charleston, S. C. Edisto Phosphate Co Charleston, S. C. Wando Phosphate Co Charleston, S. C. Berkeley Phosphate Co Charleston, S. C. Etiwan Phosphate Co Charleston, S. C. Ashepoo Phosphate Co Charleston, S. C. Stono Phosphate Co Charleston, S. C. Imperial Fertilizer Co Charleston, S. C. Mead Phosphate Co Charleston, S. C. Royal Fertilizer Co Charleston, S. C. Chicora Fertilizer Co Charleston, S. C. Wilcox & Gibbes Fertilizer Co Charleston, S. C. Globe Phosphate Co Columbia, S. C. Columbia Plijosphate Co Columbia, S. C. Greenville Fertilizer Co Greenville, S. C. The combined total output of superphosphates by these com- panies for the present year is estimated at about 400,000 tons.. Tlie Phosphates of America. 61 Assuming this quantity to require in round numbers 200,000 tons of raw })hosphate, and further assuming that the output of the latter will this year attain our estimated figure of 650,000 tons, as we believe it will, there remains an available surplus over local re- <][uireraents of 450,000 tons of phosphate of lime. Of this quantity about one-half may go to Great Britain and Germany and the balance will go coastwise to Richmond, Baltimore, Philadelphia and New York. There can be no doubt that, as we ha^e already remarked, South Carolina rock must be regarded as a raw material of the first class in the manufacture of soluble and available phosphates, and that, as such, it is and Avill continue to be everywhere held in the highest esteem. In Europe it is generally used in combination "with Belgian cretaceous phosphates and very high-grade Canadian apatites, and in this way yields results that cannot be surpassed by any other material as an all-round staple, uniform and reliable article. If we were asked to express an opinion in an off-hand way as to the probable extent and capacity of the yet untouched or unex- ploited deposits, we should hesitate to give any decided answer be- <'ause of the lack of sufficient data or reliable figures. From in- formation which we have been able to gather, however, from sour- ■ces in which we have every reason to place the fullest confidence, the explored but still unexploited area covered by land and river de- posits embraces an area of no less than thirty miles. Regarding this as a mere approximation to the possible truth, we might venture, in the same spirit of speculation, to place the yield of this area at the present average of 750 tons to the acre. The conclusion drawn from these hypotheses would be that the ^tate may be relied upon to still produce about 14,000,000 tons, and allowing for a continued average production and sale of, say, 50,000 tons per month, either for local consumption or export trade, it would appear as if the mines would all be exhausted in about twenty-eight years from the present time. Whether the mining companies now in the fiehl have or have not entertained this view of the matter, it is impossible to say, nor is it very material to the issue. The fact remains that the known avail- able and readily accessible deposits are all appropriated, and that 710 falling off in the demaud for the product has yet been traceable to the influence of any other source of supply. As time rolls on, local manufacturing requirements cannot fail to increase in large 62 The Phosphates of America. proportions, and we regard it as even highly probable that at no distant date this source of consumption will absorb all that can be produced, and thus while the present profitable nature of the min- ing operations will be maintained, there will be no balance avail- able for other markets. The Phosphates of America. 63 CHAPTER V. THE PHOSPHATE DEPOSITS OF FLORIDA. The existence of nodular amorphous phosphate deposits in Florida is not a matter of recent discovery, for they had been found in various directions many years ago, but were never believed to be of sufficient importance either in quantity or qualitv to merit the serious attention of capitalists. Like many other of our natural resources, therefore, they remained long dormant and unthought of. The first tentative mining operations were commenced in the year 1888 by The Arcadia Phosphate Company, on a very small scale, in Peace River, and they met with such marked encourage- ment that many who had hitherto remained sceptically watching their efforts came into the same field, and the year 1889 saw the Peace River Phosphate Company and the De Soto Phosphate Com- pany dredging the river with an expensive modern plant. The unostentatious and cautious manner in which these corpo- rations conducted their business for some time prevented their movements and successes from being noised abroad, but when the attention of those in the immediate locality could no longer be diverted from the facts, universal interest was aroused and j^ros- pectors went to work in all parts of the State. Discovery now fol- lowed discovery in rapid succession, and each new field was claimed to be of more value and inijiortance than its predecessor. The land-owners became excited ; wealth " beyond the dreams of ava- rice " danced before their eyes and reposed under their feet. The local newspapers started a "boom" and all Florida was in the throcf of a wildly exaggerated and feverish!)^ sj)eculative phosphate fever. Land*?' which heretofore were valued at from $1.50 to $3 per acre readily changed hands at $150 to $200 ])er acre, and many a "cracker homesteader" who went to bed a poor man woke up in the morning to find himself a capitalist. While, however, it is undoubtedly a very good thing to have big phosphate mines, very little use can be made of them without the necessary means for their exploitation, and money is still a rare commodity in the South. It hence became necessary to offer to €4 The Phosphates of America. Northern capitalists a shave in the benefits of the discovery, and tliis has led to the employment of many expert chemists and min- ing engineers. As one of the first of these to be called into the field, we have had occasion during the last two years to travei'se every county on the Gulf of Mexico, from Tallahassee to Punta Gorda, and the first difiiculty that confronted us in our hunt for the phosphate treasure was the total absence of a correct topo- graphical or geological chart of the State. It had always been customary, so far as we can remember, to speak and think of Florida as a combination of impossible sand- banks and uninhabitable tropical swamps, and apart from the few adventurous "Yankees" who had "gone in" for orange culture, no one seemed to manifest any interest in its destiny and nothing seemed more unnecessary than a prolonged visit from the officers of the Geological Survey. Nothing had therefore been attempted by that body, and the only imjjortant scientific data to M'hich we could turn were the old notes of Le Conte and Agassiz and the more recent jjaper which Professor Eugene A. Smith published in the American Journal of Science in 1881. At the present mo- ment the immense amount of capital promised to be involved in the development of Florida phosphates has awakened the govern- ment to the necessity for action, and several of its well-organized survey parties are in the field doing solid work that will eventually clear up many points now plunged in obscurity. The official public rejiorts of these arduous investigations must, however, naturally take a considerable time, and we are thus led to hope that a brief resume of the results of our own examinations will be acceptable, and assist in clearing away from the paths of others some of the embarrassing obstacles Avhich Ave have had to encounter. The topographical aspect of Florida is that of a very low-lying and gently undulating peninsula ; its highest point being no more than 250 feet and the average height about 80 feet above the level of the sea. The elevated points or ridges are composed entirely of sand and are covered with a very luxuriant growth of tall pines. The depressions or valleys, especially when situated along the coast, are composed of a mixture of calcareous marls and sand, from which outcrop, at irregular and frequent intervals, large and small bowl- ders of limestones, sandstones and })hos])hate rock. These valleys are principally known in the country as "hommock land," and are ^^|^^S==^ TOUT «'*^ <^ crLjr oj^ 7\^K:^r a o FLORIDA ROCK-PHOSFHATE MINING. Removing overburden of sand by the " Gopher" machine, DuQnellon Mines, Murion Co. The Flios2)hates of America. 65 said to be very fertile. When nneultivated, however, they are covered with a dense wild growth of vegetation characteristic of the swamp. Without jiaiising to consider the climatic conditions, which are sufficiently Avell known and which, besides, are outside the scope of our work, and passing at once to the prominent geological as- pects, we may say that the entire State of Florida ai)pears to us to be underlaid, at greatly varying de])ths, with upj)er eocene lime- stone rock, and that its first emergence must, in our opinion, be consequently dated from that period. We have based this opinion on the careful examination of many artesian wells that have been practised in several directions, and It is well sustained by the one at Lake Worth, which Avas completed in June, 1890, and of which the following detailed particulars have been published by ^Nfr. X. H. Darton, of the United States Geological Survey : 0-400 feet. Sands with thin layers of semi-vitrified sand at .")() and 60 feet. 400-800 " Very fine-grained soft, greenish-gray quartz sand, con- taining occasional foraminifera and water-worn shell ■ fragments. 800-850 •' No sample. 850-860 '' White sands, witli abundant foraminifera of four or five species. 860-904 " No sample. 904-915 " Gray sands containing sharks' teetli, small water-worn shell and bone fragments, sea-urchin spines and lithi- fied sand fragments, 915-1000 " No sample. 1000-1213 " Samples at frequent intervals. Vicksburg limestone, containing orbitoides in abundance throughout, to- gether witli occasional undeterminable fragments of moUuscan casts, corals and echinoderras. It is a creamy-white, hard, homogeneous limestone through- out. Nor do Ave rely ujkju the artesian Avells alone, for the Vicks- burg limestone also apjtears as an outcrop at the surface in many localities, and has been specially noticed in Wakidla and Franklin counties, west of Tallahassee, in Marion and Citrus counties, in Tampa Bay, and on the banks of the Manatee and Caloosahatchee rivers. In the opinion of Mr. X. II. Darton, above mentioned, the phos- phates of Florida belong to three formations, distinctly separate stratigraphically, and each represents a long interval of geologic 66 The Phosphates of America. time. The rock phosphates appeal- to be the deeply eroded rem- nants of the phosphatized surface of the middle tertiary limestone ; the conglomerate deposits overlie these limestones unconformably, and in the Gainesville region, at least, appear to be miocene in age, and the river drift deposits are apparently entirelj^ subsequent to the great mantle of pleistocene white and gray sands which covers the entire peninsula to a greater or less depth. Excepting in its light color the rock phosphate is a physical counterpart of the brown limonite iron ores of the Ap2Jalachian limestone valleys, and the deposits have very similar structural relations. In a number of localities the massive phosphate grad- uates into the limestone, usually by short transitions, and many areas have been discovered in the phosphate belt and under the conglomerate in the Bartow region where the limestone is only par; tially jihosphatized. In the mines at Dunellon the massive phos- phate is apparently continuous with the limestones, but there are occasional casts and impressions of the middle tertiaiy mollusca undoubtedly lying as they were originally deposited. Mr. Darton further says that the origin of the j^hosphate of lime is not defi- nitely knoAvn, but that it seems exceedingly probable that guano was the original source, and that the genesis of the deposits is similar to that of the phosphates in some of the West Indies. Two pro- cesses of deposition have taken place, one the more or less complete replacement of the carbonate of lime by phosphate of lime, and the other a general stalactitic coating on the massive phosphates, its cavities, etc. The apparent restriction of the rock-phosphate deposits to the western "ridge" of Florida may have some sj^ecial bearing on their genesis, but at i^resent no definite relationship is pei'ceived. The aggregate amount of phosphate rock distributed in fragmentary condition in the various subsequent formations is very great, greater by far than the amount remaining in its original position, and it is possible that the area at one time included the greater part, if not all, of the higher portions of the State. As this region apparently constituted a long, narrow peninsula or archipelago during early miocene times, it is a reasonable tentative hypothesis that during this period guanos were deposited from which was derived the ma- terial for the phosphatization of the limestone, either at the same time or soon after. Mr. AValter B. Davidson, A.R.S.M., writing in the Engineering and Mining Journal on the probable origin of these phosphates,. FLORIDA ROCK-PHOSPHATE MINING. Open cut In Cove Bend Phosphate Comr>any'» mine, Inverness, Citrus Co. FORIDAL ROCK-PHOSPHATE MIXING. Working in " boulder " material after removal of top soil. Tlie Phosphates of America. C* suggests that at the close of tlie oenozoic i»eiio(l the waters of the ocean ■were probably more phosphatic than they are now. In these shallow warm seas there lived myriads of shell-fish, many secreting phosj)liate as well as carbonate of lime, as is shown by the analysis of a shell of lingula ovalis - ^ ^•'*^ X--33r> FLUKIDA liiK K.-1'll.isl'HATt: .\ilNK>. Remnrkable deposit of "diift" or "gravel" phosphate at Anthony. One cubic yard yields about 500 pounds washed material, averagingr seventy -six pi r cent, phosphate of lime and four per cent. oxides of iron and alumina. Tlie PJius2)hates of America. 69 1. A foundation of npper (.'OccMie limestone rocks very much cracked iip and fissured, the cracks having a general trend north- east and southwest. 2. Irregular beds, pockets or hanks of niiocene deposits, dried and hardened by exposure, and alternately calcareous, sandy or marly ; generally ])hosphatic, and sometimes entirely made up of decomposed organic debris, the phosphoric acid hei)ig combined Avith various bases (lime, magnesia, iron, alumina, etc.). After the disappearance of the niiocene sea there came some gigantic disturl)ances of the strata. There were upheavals and de- pressions. The underlying limestones .were ])rol)ably again split uj), and the niiocene deposit was broken and hurled from the sur- face into yawning gaps and from one fissure to another. Now came the pliocene periods, or end of the tertiary, and then the seas of quaternary age, with their deposits and drifts of shells, sands, clays, marls, bowlders and other transported materials, and the accompanying alternate or concurrent influences of cold, heat and |)ressure. If we take the whole of these phenomena broadly into consider- ation, we must be led to conclude that those portions of the phos- phatic niiocene crust which did not fall into permanent limestone fissures or caverns at the time of the disturbance of the strata, be- came at length very thoroughly broken up and disintegrated. They were rolled about and intermixed with sand, clay and marls, and were deposited with them in various mounds or depressions in con- formity with the violence of the waters, or with the uneven struct- ure of the surface to which they were transported. Occasionally this drifting mass found its way into very low- lying portions of the country, say into those regions where consider- able depression was brought about by the sinking and settling of the recently disturbed mass. At other times it was rolled to and deposited on slightly higher points. In the first of these cases we find a vast and complete agglomeration, comparable to an immense pocket, of broken-uj) phos])hate rock, finely divided phosphate debris, sands, clays and marls, all heterogeneously mixed in together. In the second case we find the phosphate in large bowlders, sometimes weighing several tons, and intermixed with but relatively small proportions of any foreign substances. Considering these phenomena, we reach the conclusion that the features in the Florida deposits of phosphate to be most particu- larly emphasized, are that the formation consists essentially of — 70 The Phosphates of America. 1. Original pockets or cavities in the limestone filled with hard and soft rock phosphates and debris. 2. Mounds or beaches, rolled up on the elevated points, and chiefly consisting of huge bowlders of phosphate rock. ;}. Drift or disintegrated rock, covering immense areas, chiefly in Polk and Hillsboro counties, and underlying Peace River and its tributaries. As we have already remarked, the work of exploration or pros- pecting has now extended all over the State in each of these vari- eties of the formation ; actual exploitation on the large scale by regular mining and hydraulic methods has also been commenced at various points ; and we have been able to make a very careful study of the Avorkings on several occasions, with the result that the theories we first formulated have been in every way confirmed. In several of the mines, notably in those of Marion and Ci- trus counties, there are immense deposits of phosphatic material, proved, by actual experimental work, to extend in many cases over uninterrupted areas of several acres. The deposits in each case have shown themselves to be combinations of the "original pocket" and the " mound " formation, and the superincumbent material, or over- burden, is principally sand, and may be fairly said to have an aver- age depth of about 10 feet. The phosphate immediately under- lying it is sometimes in the form of enormous bowlders of hard rock, cemented together with clay, and sometimes in the form of a white plastic or friable mass resembling kaolin, and probably pro- duced by the natural disintegration of the hard rock by rolling, attrition or concussion. The actual thickness of the deposits is too variable to be computed with any accuracy into an average, but in one case which specially interested us, the depth is 50 feet, and only a little over two acres of the land have already yielded more than 20,000 tons of good ore, without signs of exhaustion. Directly outside the limits of these combined "pockety" and " mound " formations the deposits of phosphate seem to abruptly terminate, and to give place to an unimportant drift, which some- times crops out at the surface, and which may l)e followed in all directions over the immediate vicinity without leading to another pocket of exploitable value. Since the same geological phenomena are 2>i'cvalent in nearly every section of the country, with the exceptions of Polk and Hillsboro counties, where they are somewhat modified, we consider ourselves, in view of these facts, warranted in declaring that the 21ie Phosphates of America. 71 Florida phosphates of high grade occur in beds of an essentially pockety, extremely capricious, uneven and deceptive nature. Sometimes the pockets will develop into enormous and deep quarries, and probably yield fabulous quantities of various mer- chantable qualities. At other times they will be entirely super- ficial, or will contain the phosphate in such a mixed condition as to render profitable exploitation impossible. An excellent, and indeed typical, example of this superficiality is afforded by one of our recent examinations, in Avhich the geo- logical conditions did not differ in any essential particular from those described. The area investigated may be thus represented : 5120 acres of land. A B C D E F G H Each division representing 640 acres. Very fine phosphate indications were scattered more or less all over this tract, sometimes in the form of big bowlders outcropping at the surface, sometimes in the form of small dehri.% brought up from below by the mole or the gopher. A local "expert" had es- timated that it contained millions of tons, and our own first im- pressions of it were of the highly sanguine order. A systematic exploration was, however, at once instituted and carried out ; first by boring all over the tract with a twenty-foot auger, and then by sinking confirmatory pits at short intervals to a depth of 15 to 20 feet, according to the plan described in the chapter on South Carolina. The result of our work was extremely disappointing, and may be briefly summarized thus : * A. — No phosphate in workable quantities. B. — A small basin or pocket of good phosphate, covering an area of about 15 acres. C. — No phosphate in workable quantities. D. — No phosphate in workable quantities. E. — Large quantities on surface, leading to a very large pocket, cover- ing about 35 acres. Very much niixed-up material, principally phosphate of low grade. F. — No phosphate in workable quantities. 72 The PJios2)hates of America. G. — No phosphate in workable quantities. H. — The highest point in the tract — very densely grown, big- bowlders of phosphate and sandy conglomerate on surface. Fifteen small pockets of phosphate, ending in limestone at a depth of thirteen feet. The total acreage covered by these widely scattered phosphate DEPOSITS was set down at eighty-three acres, and the character, quantity and composition of the phosphate itself, as shown by the pits dug and by the material extracted from them, were es- timated after exiieriment to be as follows : character and quantity of phosphate bed. Bowlder material, large and small, after screening 13 per cent, of the mass. Debris and whitish phosphate, soft and plastic 29 " " " Sand, clay, flints and Avaste 58 " " " 100 AVERAGE ANALYTICAL VALUE OF THE PHOSPHATES (AFTER SUN-DRYING). Bowlders. Debris, etc. Phosphoric anhydride {F.,0^) 37.00 30.00 Oxides of iron and alumina (clay) 4 . 25 7 . 50 After this analysis of the bowlder material had been made, the remaining lumps Avere all broken up Avith a hammer into pieces aA^eraging 1^ inches in size and Aeiy carefully Avashed, Avith con- stant shaking on a fourteen-mesh screen held under a stream of water. After being thoroughly dried in the sun, the AA^ashed ma- terial Avas put through a hand-crusher, then ground to the fineness of seA'enty-mesh, and submitted to analysis. The results, which have a most important bearing on the vexed question as to the form of combination in AA'hich the iron and alumina of these phosphates chiefly occur, were in this ease as foUoAvs : Phosphoric anhydride (P3O5) 38. 10 Oxides of iron and alumina 1 .73 The thickness of the phosphate bed varied in different places from 3^ to 27 feet, but AAas found to have an average of about 8 feet. Assuming that this thickness would yield, say, 5000 tons to the acre (a conservatiA'e computation), Ave reach a probable total of 415,000 tons for the entire tract, of Avhich, according to the experi- ments summarized above, about J^fty-Jive thousand tons might be higb-grade "boAvlder," containing, say, eighty per cent, of bone r 3 S .2 < 3 The riiosphates of America, 73 phosphate, and about o)ie Jniudred and twenty-Jive thousand ions debris and seconds, containing from sixty to sixty-five per cent, of bone phosphate. The capriciousness exhibited in this instance is not at ad ex- ceptional or singular, but has been confirmed in several others, and it is not quoted in any deprecatory sense, but as an example of tlie necessity for exercising unusual care and discretion when .naking expert examinations. In the case of the "pebble" or "drift"' dei)osits this caution needs not jjerhaps to be so extremely precise, for, as we have already stated, these are mai-ked by imusual regularity in the chief centres of their occurrence. The extensive area in which they have been found may be roughly said to take its point of departure in Polk County, a little to the south of Bartow, and thence, with a gradually narrowing tendency, to practically continue to within a very short range of Charlotte Harbor. As will be seen from tlie map, the country is very flat and swampy ; is intersected at frequent intervals by the Alafia, Mana- tee, Peace and other rivers, and by numerous small rivulets antl 'streams. Pit-sinking and boring is now going on over an area of many hundreds of miles, and so far as we have been able to ascei'tain, the l)rospectors have succeeded in demonstrating that this section of Florida is virtually underlaid vntJi a nodular phosj)hate stratum of a thickness varying from a feicinches to thirty feet, and covered by an overburden that may he fairly averaged at about eight feet. The actual chief working centre for "pebble" phosphates is Peace River, which rises in the high lake lands of l*olk County and flows rapidly southward into the Gulf of Mexico. Its course is extremely irregular, and its bottom is a constant succession of shallows and deep basins. Lakes Tsala-Opopka and Cliillicohatchee and Pains and Whid- den creeks are its chief tributaries and the main sources of its phos- j)hate deposits ; the pebljles being washed out from their banks and borne along their l)eds by the torrential summer rains. The exploitation of the pebbles is. performed, as illustrated, by means of a ten-inch centrifugal steam suction pump jilaced upon a barge. The pipe of the j)ump, having been adjusted by ropes and pulleys, is plunged ahead from tlie deck into the water. The mix- ture of sand and ])hosphate sucked uj) by it is brought into revolving screens of varying degrees of fineness, wlience the sand is waslied 74 The Phosphates of America. back into the river. The cleaned pebbles are discharged from the screens into scows, at the rate of about twelve tons per hour, and are floated down to the " works," where they are taken up by an elevator to a drying-room and dried by hot air, screened once more, and are then ready for market. The total cost of raising, washing, drying, screening and loading on the cars in execution of orders, is variously estimated at from 50 cents to $2 per ton ; but from special information recently afforded to us by one of the largest operators we are enabled to place it at $1.40, and this, to the best of our knowledge and belief, is the lowest yet recorded in the world's history of phosphate-mining The jDcbbles, when freed from impurities and dried, are of a dark blue color, and are hard and smooth, varying in size from a grain of rice to about one inch in diameter. Their origin is proved by the microscoi^e to be entirely organic, and they are intimately mixed iip with the bones and teeth of numerous extinct species of animals, birds and fish. There can be no doubt that these river deposits all proceed from the banks of " drift " situated on the higher lands in Polk County, and as a proof of it, if we take Lakeland and Bartow as the centre of these "drift" beds, we shall find that the "pebbles" are all of the same size, and only differ in that they are of a lighter color than those of the river, and that they are imbedded in a matrix of sand and clay, to which they frequently bear the propor- tion of about twenty per cent, by weight. Their separation from this matrix by most of the companies now working is effected in a very crude manner and on a great variety of plans. One of the largest concerns in Polk County em- j^loys a floating dipper dredge, the use of which, it claims, is natu- rally indicated by the fact that in this very low-lying section of the State, water springs a few feet below the soil, and thus enables the dredge to work in a canal which it deepens and extends as it removes the material. The entire mass, matrix and all, is brought up to the surface by the dredge and dropped into a species of dis- integrator or crusher. Thence it passes on into a revolving washer mounted on the same barge. From the washer, the matrix and water return to the canal, Avhile the clean nodules are carried by a spiral conveyer to a steam-heated dryer on another barge ; from the dryer they fall into a revolving screen, which removes any remaining j^articles of adhering sand, and the now marketable phosphate is caught up by elevators and delivered on board rail- The PhosjjJiates of America. 75 -way cars standing on a track parallel with the canal. AVe have been informed that the actual capacity of this plant is ;300 tons a hosphates taken from navigable waters within the application of the law a royalty of 50 cents per ton will be col- lected when the phosphatic material analyzes "fifty per cent, or less, and not to exceed fifty-five per cent., bone phosj)hate of lime ;" V5 cents per ton for " material analyzing over fifty-five per cent, and not exceeding sixty per cent.," and " $1 per ton for every ton of phosphate rock, etc., analyzing in excess of sixty per cent, bone phosphate of lime." Account is to be rendered to the board of commissioners and payment of royalty made to the State quarterly. The State grants the right to persons, either natural or corpo- rate, to mine the navigable waters of the State witliin certain well- defined limits, in no case to exceed ten miles by course of stream, for a period not to exceed five years, preference being given, how- ever, to riparian owners and to those who have commenced to mine in good faith before the passage of the act. The bill further enacts that no person or persons shall be per- mitted to mine the bed of any navigable water of the State until he or they shall have first filed with the board of phosphate com- missioners a bond, with good and sufficient sureties to be approved by the board and in such sum as the board shall deem propei-. Mining must begin within six months from date of contract and 76 The Pliosphates of America. continue to the full term of the contract, unless the phosphate or phosj^hatic deposit be previously exhausted. The })assage of this law has, of course, elicited a great deal of opposition, and will undoubtedly lead to litigation between the State and many of the companies which claim vested rights in the river deposits. A considerable number of these companies are, how- ever, unaffected by its provisions which do not apply in cases of navi- gable streams or parts thereof that are not meandered, and the own- ership of the lands embracing which, is vested in a legal purchaser. With the extremely low cost of production of the "pebble" ma- terial, however, it is hardly conceivable that so trifling a tax as that imposed by the new law can be regarded as a burden, or that it will have the least injui-ious effect upon the progress and profits of the industry. Nor will the present trouble between the Coosaw Mining Company and the State of South Carolina fail to facilitate and hasten the introduction of the new material, and when once this introduction has been thoroughly and favorably secured, it will soon win for itself the good opinion of European as well as of domestic superphosphate manufacturers. The chemical comi^osition of Florida phosphates, and more especially of those known as "hard rock" or "bowlder," is far from being constant or reliable, as would be naturally anticipated in such an irregular and varied formation as we have attempted to describe. Nor is it more uniform in its physical aspect, for w^hile in some regions it is perfectly white, in others it is blue, yel- low or brown. In many instances it is practically free from iron and alumina, but in not a few districts it is heavily loaded with these commercially objectionable constituents. A large proportion of the land rock is very soft when damp, but becomes so hard when dried that it has long been used by the natives, ignorant of its other values, as a foundation or building stone. For the purposes of general illustration we present the follow- ing averages, selected from the results of several hundreds of our complete analyses, made either in Florida or New York. The samples, in every case, Avere taken from exploratoi-y pits in differ- ent counties, and were marked before leaving the ground with full details of their origin. We have classed them as — 1. Bowlders of hard-rock phosphate, or cleaned high-grade ma- terial. 2. Bowlders and dehriK, or unselected material, merely freed from dirt. ^ -3 Tlie Phosphates of America. 77 3. Soft wliito phosi>liate, in which no bowlders arc found. 4. Pebble })hospliate from Peace River as sent to market. 5. Pebble phosphate from Polk C'cninty drift beds, washed and screened. Bowlders (carefully selected, 120 samples).. . Bowlders and debris (237 samples) Soft white phosphate (148 samples) Pebble from Peace River (84 samples) Pebble from drif l-beds, Polk Co. (92 samples) . OXIDES PHOS- op. iRQjj OFLIME. j,j„jj^ SILICA AND SIL- ICATES CAR- BONIC ACID. 80.49 2.25 4.20 2.10 74.90 4.19 9.25 1.90 65.15 9.20 5.47 4.27. 61.75 2.90 14.20 3.60 67.25 3.00 10.40 1.70 In working or quarrying the "hard-rock" or "high-grade bowlder" deposits, the details of most ini2)ortrince are the careful selection by conscientious and capable su])erintendents of the dif- ferent qualities, and the accurate samjiling and analyses of the different piles befoi-e shipment. There is at present a less remunei*- ative market in this country than in Europe for the richest grades, and it is therefore probalile that for some time to come the entire production of hard rock will be exported. As we have already said and shall more fully explain later on, the majority of foreign manufacturers will make no contracts for a raw material which contains a higher maximum than three per cent, of oxides of iron and alumina. To make shipments within this limit must conse- quently be the aim of the miners who would establish a good rep- utation, and nothing but experience in actual work, Itarm(»nousli/ conducted beticeen the mine and the laboratory, can be relied upon in the great majority of cases to accomplish it. To ourselves this matter has been a source of constant preoccupation, and in the mines with which we are professionally connected we have now succeeded in reducing objectionable constituents to a minimum by adopting the following general scheme of work : The pockets are located by boring and by confirmatory pits, and the results of these operations are daily transferred to a map. The pits are carefully sampled, foot by foot, as they go down, and the various qualities of "bowlder," "soft white," "gravel," etc., are sent to the laboratory with ample details of their origin. The re- sults of the analyses are daily placed upon the map, side by side with the other details of the survey. We thus finally acquire a geological and chemical map of our 78 The Phosphates of America. property, can form an approximately correct idea of the quantity and the quality of material at our command, and can decide with intelligence upon the best points at which to commence industrial operations on the desired scale. Our plant is so constructed as to enable ns to crush the whole of our rock material to a suitable size, say, 1^-inch ; to pass our en- tire output through washers and screens similar to those we have described in the chapter on South Carolina ; and to finally dry it by hot air, avoiding direct contact wi'th fire. The cost of produc- ing one ton of clean phosphate rock under these conditions, as shoAvn by our practical working experience, averages about 85, and from the fact that the method was based upon and has fully justified the results of a very lengthy series of laboratory experiments, we are enabled to claim for it — 1. That, the product being reduced to a uniform size, the difficulties hitherto experienced in obtaining fair and con- cordant samples on shipment and arrival are materially less- ened, if not entirely obviated. 2. That the objectionable iron and alumina, being nearly always present in the original sample in the form of clay which is held and secreted in the interstices or cracks of the rocl\ are nearly all removed by the water and the agitation during the Avashing process. On somewhat similar lines to these, a very ingenious and prac- tical as well as economical method of mining and preparing the land-rock phosphates is that devised by the Jeffrey Manufacturing Company, of Columbus, Ohio, and now being used by some of the larger companies. The rock is hoisted from the quarries by a der- rick, delivered to a crusher, and thence into a system of screens. The first is a dry screen, the second a washing screen and the third a finishing, or rinsing screen ; and the rock is delivered from one wet screen to the other by short elevators, and then taken from the last screen by slow-motion elevator, so as to drain off as much of the water as possible. It is then delivered at the top of a fur- nace having interlapping shelves, iznder which the flues conducting the products of combustion to the stack are carried. AVhile de- scending from one of these shelves to the other through the hopper- like aperture to the furnace, the rock is either heated to the neces- ary degree to dry it, or, by a retaining device at the bottom, may be kept until thoroughly calcined, after which it is delivered hot to the foot of an elevator. The flue connecting with this elevator FLORIDA ROCK-PHOSrHATE MI.MNU. View of the phosphate-drjing machine in u«e at the Ocala and Blue River Phosphate Cumpany- inln. Eltiston, Citrus Co. I. 1 j«^«.j^ - z 5 Tlie Phosphates of America. 79 and funiace is arranged Avitli three conduits, one for the smoke and heat, one for the buckets of the elfvator, and one for the dry- air draught. The jjartition between the smoke and combustion flues and that of the elevator is thin iron after reaching tlie height of the brick-work. Tlie buckets are constructed of screen wire, so that the escape of vapor from the heated rock is impeded as little as possible. The partition between th.e bucket-flue and the dry- air flue is perforated at intervals, so that the draught of dry air will produce the effect of drawing off the vapor from the buckets of heated rock as they pass upward through the elevatoi--flue. The movement of the elevator is so slow that about twenty minutes from the starting at the bottom, or boot end, are required to de- liver a bucket of phosphate-rock at the top ; after the deliveiy is once commenced, however, it is continuous. At the top, the chain of buckets })asses through a third, or drying-screen, Avhich revolves in a square, heated chamber, shown in the illustration at the top of the dryer-frame. In passing through this dry screen, all the sand or material that is not rinsed or washed out of the interstices and from the clay deposit of the rock, is knocked off in a separate par- tition of the hopper underneath the heated chamber. The phos- phate-rock is delivered, as shown in space broken away, to the hopper just underneath the open end of the screen at the rear of the dryer, and is delivered, it will be observed, in chutes from this altitude to the storage-bins in the warehouse, or on board cars at a railroad track, the buckets continuing their course down the in- clined flue to the boot, to receive the continuous flow of phosphate. There is a draught of hot, dry air thrown up this return flue, that meets the phos])hate being delivered from the dry screen, and carries off what remaining vapor there may be arising from the heated rock through an opening into the stack above. The operation of this system of machinery is automatic after leaving the crusher, and every motion of the rock is in the direc- tion required to reach storage or shipment. The water supply at different mines, re(juiring different arrangements of ])umping ma- chinery, the latter has not been included in our drawing. From the dry-screen, running back to the waste or culm pile, there is a conveyor which relieves the dry-screen of the sand and material that w^ould otherwise accumulate beneath it. Where the phosphate is found in a clay matrix, it is not j»racticable to use a dry screen successfully; the latter is therefore in such cases elimi- nated, and a pug introduced in place of it, similar to the machine 80 Tlie Pliosphates of America, used in M'asliing litMiiatite ores and pugging clay. To prevent the clay from balling up in the revolving screens, it is thoroughly soit- ened and disintegrated ; and -when this has been done it will easily wash out of the ])hosphate, the succeeding stages of the jjrocess being the same as in handling dry rock. AV^ith the mere addition of a dredging apparatus, this method of exploitation is ecpially applicable to the "j)ebble" and river-de- posits, the process of drying, elevating and storing being quite as economical and efficient as in the case of the hard rock. Our opening remarks on the speculative character of the " boom " are justified by the following partial list of the mining com])anies formed in Florida for various purposes within the past two years : Name. Address. Capital. Arcadia Phosphate Co De Soto County ; office, Sa- vannah, Ga Peace River Phosphate Co De Soto County, Arcadia, Fla. ; principal office, New York.. $300,000 De Soto Phospliate Co Zolfo, De Soto County ; of- fice, Atlanta, Ga 250,000 South Florida Pliosphate Co Liverpool, De Soto County. . 240,000 Charlotte Harbor Phosphate Co . . Fort Ogden, De Soto County Boca Grande Phosphate Co De Soto County ; deposit worked on Caloosahachie River 250,000 Lee County Phosphate Co Fort Myers, Lee Countj^ ; de- posit on Caloosahachie Riv- er 250,000 Fort Meade Phosphate, Fertilizer, Land and Improvement Co Fort Meade, Po k County 50,000 Homeland Pebble Phosphate Co . . Homeland, Polk County 100,000 Homeland Mining and Land Co . . Homeland, Polk County 120,000 Black River Phosphate Co Clay County 200,000 Pharr Phosphate Co Bartow, Polk Countj' Jackson and Peace River Phos- phate Co Apopka, De Soto County 1,000,000 Tampa Phosphate Co Tampa, Hillsboro County. . . 25,000 Prospect Phosphate Co Dunnellon, Marion County E. C. Evans Mining Co Dunnellon, Marion County Glenn Alice Pliosphate Co Bay Hill, Sumpter County Dunnellon Pliospliate Co Dunnellon, Marion County. . . 1,250,000 Sterling Phosphate Co Hernando County 3,000,000 Withlacoochee River Pliosjihate Co Panasofkee, Ma-rion County... 400,000 The Early Bird Phosphate Co Marion County 500,000 The New York Phosphate Co Marion County 4,000,000 •s-a 1 ■. 1 -s 1 'a 1 "" ? 4 fa 111 => o I < r-^''f=T 1 CO M CO d Z) 1 ■-■^■1 O ' ^ a: 1 C ^ < 1 $ 1 ^ X n aj ^.1 m pL - t=j- fc ^ Q The Phosphates of America. 81 Name. Address. Capital. The Eagle Phosphate Co Marion County 3,000,000 The Florida Phosphate Co., Lim- ited Phosphoria, Polk County 1,000,000 Whittaker Phosphate and Ferti- lizer Co Homeland, Polk County 500,000 Virg-inia-Florida Phosphate Co. . . . Fort Meade, Polk County 120,000 The Gulf Phosphate Mining and Manufacturing Co Liverpool, De Soto County. . 240,000 The Terraceia Phosphate Co Works in Manatee and Polk counties 1,000,000 The Lay Phosphate Co Bartow 575,000 The Moore & Tatum Phosphate Co.. Bartow, Polk County 100,000 The Cove Bend Land Phosphate Co Tompkinsville, Citrus County 200,000 Albion Phosphate Mining and Chemical Co Baltimore, Md 500,000 Belleview Phosphate Co Jacksonville 600,000 The Florida Rock Phosphate Co. . . Citrus County 125,000 Alachua Phosphate Co Gamesville 300,000 Alafia River Phosphate Associa- tion Bartow 100,000 Alafia River Phosphate Co Bartow 1,000,000 Alafia Phosphate Co Jacksonville 35,000 Albion Phosphate Co Gainesville 300,000 Albion Mining and Mfg. Co Gainesville 300,000 American Mining and Imp't Co . . . Bartow 1,200,000 Anglo-American Phosphate Co. . . . Ocala 400.000 Archer Phosphate Co Gainesville 100,000 Atlantic and Gulf Phosphate Co. . . Bartow, Fla., and Charleston, S. C 10,000 Berkley Phosphate Co Bartow 40,000 Farmers' Co-operative Mfg. Co. of Georgia 200,000 Florida Blue Rock Phosphate Co. . Bowling Green 150,000 Florida Phosphate and Fertilizer Co Tallahassee 100,000 Florida Phosphate Co Ocala 210,000 Gainesville Phosphate Co Gainesville 50,000 Globe Phosphate Mining and Mfg. Co Ocala 2,000,000 Great Southern Phosphate Co 30,000 Ichetucknee Phosphate Co Jacksonville 30,000 Jacksonville and Santa Fe Phos- phate Co 500,000 La Fayette Land and Phosphate Co Apalachicola 10,000 Lake City Land and Timber Co 50,000 82 Tlie Phos2)hates of America. Name. Address. Capital. Lake City Phospliate Co Lake City $100,000 Little Bros. Fertilizer Co. South Jacksonville 100,000 Madison Phosphate Co Madison 50,000 Magnolia Phosphate Co Gainesville 50,000 Marion Phosphate Co Savannah 5,000,000 Marion and Citrus Phosphate Co 200,000 North and South Alafia River Phosphate Co 360,000 Ocala and Blue River Phosphate Co Ocala 780,000 Orange County Phosphate Co Orlando 10,000 Panasofkee Phosphate Co Ocala 100,000 Paola Creek Phosphate Co Bartow 150,000 Peninsular Phosphate Co Ocala 200,000 Standard Phosphate Co Orlando 500,000 Standard Phosphate Co Ocala 2,000,0Q0 Stonewall Phosphate Co Jacksonville 500,000 Waukulla Lumber and Phosphate Co Tallahassee 10,000 Waukulla Phosphate Co Crawfordsville 10,000 Wekiva Phosphate Co Sanford 10,000 Zeigler Phosphate Co Ocala *. . . . 25,000 Columbian Phosphate Co Jacksonville Land Pebble Phosphate Co Bartow This list is, we repeat, only a partial one, and the number of companies is increasing daily. If, instead of the meaningless '•'■paper capitaV which most of them represent, fifty-odd millio'ns of dollars were really at stake, the fact would excite serious anxiety. We should be compelled to show that the amount of phosphate to be mined and disposed of at a profit in order to })ay afive-per-cent. dividend on the investment Avould surpass the total consumptive capacity of the entire world. Fortunately no such question is nec- essary; we know that the " capital " is merely nominal; that many of the companies are mere " mushrooms," and that, in brief, this phase of the question will regulate itself. From all that has preceded it will probably have been gathered that, in our opinion, Florida phosphate-mining Avill prove extremely profitable to those who purchase and work its fields with judgment, but that it will as certainly turn out in the highest degree disas- trous to those who purchase on insufiicient or incomplete examina- tion and allow themselves to be led away by their excited first im- pressions. The interior of the country is still practically unsettled, and travelling is attended by some difticulties and much inconven- z H Tlte PJiosphafes of America. S3 ience. The negro labor, which forms ninety-five per cent, of all that is used in the mines, is cheap, but is not very good and is far from plentiful. There are no wagon roads suitable for transporta- tion purposes, and the railroad facilities are altogether inadequate, the companies being at the present time very poorly provided with freight cars. Only relatively few mines are within access to the railway, and of these the larger number ship their '"high-grade rock*' by rail to Fernandina and thence to Europe by steamer, while a smaller number forward theirs to Tampa over the South Florida Railroad. The " pebble " phosjjhate is chiefly sent over the Florida Southern Railroad to Punta Gorda, but some of it goes over the same line to St. John's River via Sanford. The rock going to Fernandina pays a freight of about $2.20 per ton, that to Port Tampa about §1.10, and the "pebble" to Punta Gorda and St. John's River costs about 75 cents. The natural difficulties and impediments are at present rather discouraging, but the deposits themselves are of such immense extent, and the demand for them is likely to be so great and con- tinuous, that all obstacles to their exploitation must be of necessity eventually cleared away. With the disappearance of the obstacles the material of all grades will come forward in large quantities, and as its chemical composition is very satisfactory, it will soon compete favorably for superphosphate-making with any other phos- phates now poj)ular with fertilizer mauufacturers. 84 Tlie Phospliates of America. CHAPTER YI. SULPHURIC-ACID MANUFACTURE. Until Mr. Rodwell ijublished his book, " The Birth of Chemis- try," we had always been led to believe that the discovery of sul- phuric acid was due to Basil Valentine, but we have now reason to suppose that it was known long before his time. It was reserved for one Gerard Dornaeus to describe with tolerable exactitude what it really was, and this he did in a pam- phlet published in the year 1570. English makers originally jirepared it by burning copperas (pro- to-sulphate of iron) in brick ovens at a high temj)erature, and con- densing the vapors Avhich distilled off as an impure oil of vitriol, the commercial value of Avhich was ?!1000 per ton. This process gave Avay to the use of sulphur and nitre, burnt together in enor- mous glass globes and concentrated by boiling in glass retorts, the j^roduct being called " oil of vitriol made by the bell," Passing on by successive stages, at which Ave need not stop, Ave arrive at the year 1746, and find the first leaden chamber erected in that year in Birmingham by Messrs. Roebuck and Garbett, the proportions of raw material employed being seA'en or eight pounds of sulphur to one pound of saltpetre. This mixture AA'as placed upon lead plates standing in water Avithin the chamber, and Avas ignited by means of a red-hot iron bar thrust in through a sliding panel in the wall. Shortly after this time came the introduction of a separate aj)art- ment for burning the sulphur in a current of air, Avhich was regula- ted by a slide moving in the iron furnace-door, the vapors being taken off through the roof into the adjoining chamber. Progressively and finally, the industry in Europe has now reached a point which may be almost considered perfect, there be- ing little room for im])rovement in Avorks constructed to comply Avith all the requirements of modern progress and modification. In order to make ourselves completely understood by those Avho knoAV little or nothing of the subject, Ave have prejiared the an- nexed draAving of a modern sulphuric-acid Avorks, and may state that Avhen sulphur (S) is burnt in air it combines Avith the oxygen The Phosphates of America. 85 of the latter, and sulphur dioxide is formed (SO.,). If this gas be brought into contact with nitric-acid vapor (HNO3) and steam (ILO), a combination takes place resulting in the formation of sul- phuric acid and nitric oxide, thus : 3 SOo + 3 HNO3 + 2 H2O = 3 HoSO^ + 2 NO. The nitric-acid vapor is jjroduced by heating a mixture of nitrate of soda and oil of vitriol in an iron pan contained within the brim- stone or pyrites burners, and it is carried into the lead chambers simultaneously with the suljjhur dioxide by means of a well, regu- lated air current. Reduced, as we have seen, to nitric oxide, it does not remain in this form, but immediately combines with the free oxygen introduced by the air-current and becomes nitric per- oxide (NO2). Assisted by the presence of steam, it thus constantly enacts the part of an oxygen-carrier to the sulphur dioxide, as may be gathered from the following figures: NO -<- O = NO2 Nitric oxide -(- Oxyjren = Nitric peroxide and — NOg -f- SO2 + H2O = HoSO^ + NO. Nitric peroxide + Sulphur dioxide + Steam. And SO oxidation and reduction go on, and the circle of opera- tions is complete and continuous. The air of the atmosphere contains about seventy-nine per cent, of nitrogen and about 20.90 per cent, of oxygen in every 100 vol- umes. This nitrogen plays no part at all in the changes we have de- scribed, and it hence follows that the required oxygen is accompa- nied by four times its volume of an inert gas wliich merely serves to fill up the chamber space and which calls for immediate and steadv removal in order that the working elements may have fair play. At one time a simple chimney arranged at the end of the works, oppo- site to that at which the gases enter the chambers, was deemed sufficient, but it was soon discovered — to the cost of the manufact- urer— that the nitrogen, in itself escaping, carried off with it a large share of the nitric oxide. As the preservation of this latter gas is so important a factor in the economy of the industry, means had to be devised whereby it could be saved without inconvenience, and these means were duly provided and are now universally em- ployed, as we shall presently see. From the commercial standpoint of economical ))roduction, the chief questions tiiat have to be seriously considered by fertilizer 86 The Phosphates of America. manufacturers who contemplate the erection of an acid plant may- be briefly summed up in the following manner: (a) Of pyrites and brimstone, which is the most economical and best source of sulphur? (b) If the preference be given to pyrites, what kind of furnace or burner is best adapted for effecting its complete combustion, including the " fines " V (c) What are the best dimensions to accord to the leaden cham- bers in Avhich are combined and condensed the gases induced by this combustion? {d) How may the maximum results be produced from the ore at a minimum expenditure of nitrate of soda ? (e) How to dispose of the residual cinders after desulphuriza- tion in order to lessen first cost. Of the first problem, the commercial aspect is the only part with which we need to deal, for it is at last understood and, if somewhat reluctantly, generally admitted, that from a pound of sulphur, whether it be taken in the form of pure brimstone or in combination with some mineral as a bisulphide, the same quantity of sulphurous-acid gas, generated by its combustion, will be ob- tained. From a purely scientific and theoretical point of view, and speak- ing with that impartiality which we are called upon to observe, there can be very little doubt that if all things were equal there would be no room for hesitation in awarding immediate preference to the cleaner, purer and in every way simpler brim- stone ; and we must even go so far as to admit that inasmuch as very few, if any, of the pyrites ores hitherto discovered and Avorked ai"e absolutely exempt from all traces of arsenic, there are certain branches of chemical manufacture in which it Avould be unadvisable, and others in Avhichit would be in the highest degree* dangerous, to use them. These, however, call for the employment of but a very insignificant quota of the gigantic total annually re- quired for the great chemical fertilizer industry, in which a trace of arsenic in the sulphuric acid employed is a matter of indifference. We may therefore leave the interests of small works where only fine or medicinal chemicals are produced, or where only com- jiaratively small quantities of acid ai'e required, out of the ques- tion. In comparing the relative cost of sulphuric acid derived from brimstone or pyrites, it must be borne in mind that in the latter we Tlte Phosphates of America. 87 have to deal with two very distinct species of sulphides — those con- taining little or no copper and those bearing it in proportions varying from one and a half to five per cent. Ores of the second category will, as it is hardly necessary to say, always be preferred as a source of sulphur when other things are equal, and will, from that very fact, serve the general purpose of keeping the price of brimstone within reasonable limits. They are now almost exclusively used by the larger European chemical makers, who, being compelled from lack of domestic material to import their pyrites, have adopted the copper-bearing ores of Spain and Portugal, and by a very slight addition to their working plant, recover from the cinders the copper, silver and gold, and apply the }>roceeds of the ready and profitable sale of these metals to the reduction of first cost. There are, fortunately, a few cases where our own intelligent manufacturers have kept pace with the times and obtained notably brilliant results by using pyrites and adopting modern processes, but these only serve to bring into more pi'ominent notice the lack of enterprise and energetic initiative so clearly ai)2)arent generally throughout the country. As regards the purely iron ores, dependent for their value en- tirely upon their sulphur contents, the greatest, if not the only, bar to their more extensive application by our manufacturers, is probably the distance by which the centres of consumption are separated from the mines. The actual cost of raising and render- ing them suitable for the market would appear never to exceed an average of i? 1.50 per ton, whereas the average cost of transport to all industrial centres is more than double that amount. If, after making all deductions for every possible source of loss, their actual sul])hur contents be estimated at forty per cent., and if their cinders be treated as a valueless factor, it follows from this that while in the vicinity of the mine the maximum cost of pyrites-suljjhur would be only $5.75 per ton, the price of railway and other transportation is so great that under normal market conditions it no longer offers great advantage over im- ported brimstone ui)on reaching the consumers' kilns. The question of freight being, therefore, such a momentous one, it is worth while to consider whether the railroad charge upon a finished fertilizer would be less onerous than that applied to the raw product, and if so, Avhelher the erection of acid works on or near the pyrites mines would not be the surest means of turning an important source of sulphur to profitable account. 88 Tlie Pliospliates of America. It would, of course, be folly to expect all those who are now in the fertilizer trade to become owners of good pyrites mines, but this fact need in nowise prevent them from erecting woi'ks near such mines in order to profit by whatever advantages are to be derived from using the brimstone substitutes. Let us therefore examine what those advantages actually are. To commence with the furnace. The various forms introduced during the past few years for burning pyrites in England, France and Germany by Spence, Perret-Oliver, Juhel-Maletra, Gersten- hoefer and others have all been accurately described by popular writers, and it M'ill suffice for present purposes to point out that the principal conditions to be realized with either lump or fines are : First. — To generate and convey to the lead chambers a maxi- mum of sulphurous acid and a minimum excess of atmospheric air. Second. — A combustion so perfect that less than one per cent, of sulphur shall remain in the cinder. Third. — To avoid any distillation of the sulphur or the forma- tion of ferrous sulphide (FeS). The necessary oxidation of the iron and the consequent jiro- portionate increase of the superfluous nitrogen carried by the air in the mixture of gases, cause the volume of the latter, produced by burning pyrites, to be much greater than that proceeding from the combustion of pure brimstone, and it will be hence understood that the proper regulation of the air-sujjply — important under any conditions — is especially so when pyrites are employed. The gases derived from pyrites are known to move only at the rate of about one foot per minute, and it therefore follows that they remain sufficiently long in the chambers to become so intimately and thoT-oughly mixed that any attempt to give a specific direc- tion, either to the manner of their entry or their exit, becomes unnecessary. According to theory, only three molecules of oxygen need to be admitted into the furnaces, two for the formation of sulphurous acid and the third to transform the latter into HjSO^. For one kilogramme of ordinary brimstone this would require 1500 grammes or 1055 litres of oxygen, or 52V5 litres of atmospheric air ; the amount of air necessitated by burning the same quantity of sulphur in iron pyrites being, according to the same calculation, 6595 litres. In practical industry, however, Mr. Schwarzonberg has shown that these figures do not suffice, and that it is necessary to intro- The Phosjjliates of A»ierica. 89 duce 6199 litres of dry air in the case of brimstone and 8114.0 litres in the case of pyrites, each being calculated on the basis of 0° C. and a barometric pressure of TOO millimetres. These figures serve to demonstrate that the quantity of sulphur to be profitably burned per cubic foot of chamber space will fluctuate with the higher or lower situation of the works. The ingenious differential anemometer invented by Pedes and modified by Fletcher, and the beautiful and simple apparatus for analvzing the chamber gases designed by Orsat, have so facilitated the general px'ocess that an exactly proportioned current of air may now be measured out to meet the varying leciuirements of both situation and material employed. An exani]ile of this is afforded by Buchner''s careful analyses, which show that the quantity of sulphurous-acid gas passed from the burners to the chambers varies from six to eight per cent., according to the nature of the pyrites, the construction of the furnace and the manage- ment of the air-supply. His greatest average by careful working was as follows: Sulphurous acid, 6.07; oxygen, 7.18; nitrogen, 86.74. The sul2)hurous acid requiring only 3.03 volumes of oxygen for its transformation into HoSO^, it will be seen that after sub- tracting this quantity from the above total there still remained 4.15 volumes to j^ass away with the nitrogen into the atmosphere, and the greatest watchfulness should be invariably observed by chamber managers to keep as nearly as possible within these proportions. In some of the works where pyrites ores are burned, it is still customary not to convey the hot gases from the burners directly to the chambers, but to previously cool and at the same time cleanse them from the dust by which they are generally ac- companied by causing them to jjass from the flues into an upright brick stack, carried from an independent foundation to about 10 feet above the level of the furnace arch. From this they enter a range of cast-iron pi])es 2 feet 6 inches in diameter and 27 feet long, in three lengths, cast in two halves, and each provided with a man-hole to facilitate cleaning. These pipes are fitted into a tunnel of lead 5 feet square and 40 feet long, connected at its opposite extremity with the acid chamber by a seven-pound sheet-lead pipe of about 1^ feet in diameter. Intelligent and thoughtful managers have now discarded this antiquated system in favor of a far siinpler and more rational 90 The Phosphates of America. arrangement of their plant, which we have endeavored to broadly outline in our illustration on opposite page, and at which a critical glance will he interesting. Acid Chambers. — The subject of chamber construction is well worn, if not exhausted ; their form and size have long been bones of contention over which certain wiseacres, with plenty of time for useless discussion, have growled ad nauseam. After a very varied experience and careful inspection of many working systems, we have concluded that the required object — i.e., the proper conden- sation of the gases — can take place equally well in one large cham- ber as in a series of two or three, and that a choice of either is essentially a matter of personal taste and personal opinion. A very excellent arrangement will be found to consist in a set of two, adopting as favorable dimensions 125 feet long by 24 feet wide and 18 feet high. The connections are made by a fifteen to eighteen inch diameter lead pipe hung from the roof, with a good fall at its end to prevent the accumulation of any condensed acid. As to the necessary thickness of lead, there is almost as much diversity of opinion as upon the dimensions of the chambers ; but remembering that a good chamber, properly started and soundly built, should last from ten to twelve years, a happy medium may be attained in this direction by adopting seven-pound lead for the first and six-pound for the second. The amount of chamber room should in no case be less than 20 cubic feet for every pound of sulphur consumed. The jjressure of steam should be as evenly distributed as possi- ble, and the faulty system sometimes adopted of introducing it from a single jet, which can only play upon one jjortion of the gases, must be carefully avoided. Since of every 100 tons of chamber acid produced one-half consists only of water originally injected in the form of steam, it has been urged by Dr. Sprengel that this warm steam unnecessarily expands the bulk of the gases, instead of lowering their temperature, and causing them to shrink in volume. To obviate this inconvenience he has therefore suggested the use of a spray of cold water, to be forced into the chamber by a pump of his own invention ; but the device, while ingenious, does not work Avell and has not been generally adopted. The preferred method is to inject steam into the entrance end of the chamber and into its side rather more than half the way alonir. 92 The Phosphates of America. The surest means of accurately knowing what is going on iir the chambers is afforded by the provision and maintenance in proper condition of "drips" and "caps." Tliis is a well-estab: lished fact among old and experienced acid-makers universally. The best apparatus for taking drips consists of a small lead dish placed within the chamber upon a 15-inch diameter earthen- ware pipe, about 3 feet high, and at about 1^ feet from the side. A small half-inch lead pipe, shaped like an S, is fixed into the bot- tom of the dish and pierces the chamber side, setting with its mouth over a leaden basin standing u])on a leaden ledge outside. The liquid acid passes as it is formed through the siphon, drips into the basin and, overflowing upon the ledge, is carried back again into the chamber by a small pipe. Two drips should be arranged in each chamber of the set, at equal distances from each other, and the contents of the basins will constantly represent the nature of the acid and indicate its strength, nitrosity, etc., at any moment. Certain openings should be left in each chamber ; a man-hole, and a small hole near the end for sampling. A couple of Avindows will also be useful, one fixed in the darkest side, about five feet from the ground, and the other in a direct line with it upon the top. The light shining through these windows reveals to an experi- enced eye the exact condition of the gases. The following indications are furnished by the caps of the chambers as to what is going on within, and are worthy of note : When one of those covering the first chamber is slightly lifted the gases should rush out with great force. This should become less noticeable or almost disappear in the second chamber. If the inside of the cap be quite dry and covered Avith small crystals, Avhich, upon being moistened, turn green, the evidence is certain of an insufficiency of steam. If, on the contrary, it be dripping wet, it is equally certain that the steam is in excess, and in either case the remedy is obvious and at liand. The regulation of the supply of nitre, after that of the draught, is an extremely important point, a mismanagement inevitably en- tailing one of two evils : First. — If the quantity supjdied be too large it ruins the lead and excludes all possibility of profitable working. Second. — If the quantity be too small there is an inevitable escape of sulphurous acid. The Pliosphates of America. 93 Volumes might still be devoted to a discussion of the reactions which go on between the gases in the chambers, and, from a truly- scientific point of view, few questions are of a more absorbingly interesting nature. Our present purpose, however, of pointing out how to avoid accidents or trouble in what is really, when properly understood, a very simple and natural process, will best be served T)y briefly summarizing a few leading facts. The nitric acid used in the process plays no other ])art, as we have previously explained, than that of carrying from the oxygen fD "^ O ^^^o^^^'Si' ~ p s 3 p p ■B ^ 3 5- p nt Lawrence stcr County', minius mine, ston County, ulding Count cktown, Tenn pleton, Canac ^ Tinto mines N P cr 3 . 1 <; 3 3' ' 3 5' = - = ^ p o 5' Vermo Count New Y Virgin North y, Geoi essee. . In /I 3- J w p 3 T> . • Oq O -• o ^ c ■D V. o ; >1 3; 5' - • 5' ■ ^ 0 \ \ p . o 2. to p )»>■ o: >«>- *>- *^ *^ 'X> *>• *> to.rfi.CO.t^*^l*>-COCO CO *^ CO K^:^ •~J *- lO -I 3S Ci X » o X O -I — 4^ C5 O OD lO wf C5 -^ *- OS cc 55 35 i-i c o o :.T to O O O O — O o o o S ^ SULPHUR. I-' *^ o O O C/T .. *i.>^C0*>.C0COff^C0CO z^ «w CO i*^rB l-i lO 05 X « »*>. i o »^ to O -■' O -} 05 4^ »f^ *^ o i.7 o 0 ^. -1 iO -1 'Jl -1 to c X to ct «o to o o o o? i-* o o W wl 0 li IRON. 00 o o LO => O c 3 00 CitOOOOOOOO o z> o 0 p; t-i o ! % to -1 CO CO o CO CT hP*. p h-i p CO _T o "o o 2 o 2 o CO __^ c;i p3 CO - «o 00 • 3 h^ ^T to l_l i-i *1- j-j l^j " COPPER. CO o • ^ O O CT O oooo^o^o o -^ "^ OT ?. _^ woo O - P < 1 o P P P O ., » o P <". 1-1. o to £> " 2 3 TO #-co2C ^^,,., •" ■3 3 0 5 ARSENIC. h^ H- O Jf »3 ' D 00 -J CO ^ (T. m 13 to ^ o c s> . 1-1 . o o 00 rfi. /-. O JO 4^ < D • to • CO to o 0 2 ZINC. o to O ' D • o • CT to o 0 p. ►^ "0 . o o <: Z> . O I-' 0 f^ • *» «5 - -7 • o . J1 3 2 LEAD. • o to J f- • CO to (T> ?i J 3 < p r" • c 5 .. • • • • c 3 »■ " p c GOLD. • • • • • (1 » c; ■ r < < '.'.'.'. : ^ 5 5 - J . S. . . g 1. : : - p ' - P p • . • -5 SILVER. .... 0 * ■ r ►tj . . >^ . < ^ to c ;^ o O O . 00 c CARBO- • • -3 • t 0 OT « 3 C5 CO «o • o 5 NATE LIME • • c;i • < 2 o s D 00 -JO' o e* n; . . o . O . ,-. SULPHATE ■ • cs • CT • 2 LIME. • • oi o • ■ r *fl 1-1. . • o CARBO- • • o • to . (I NATE • • Ol • • * Of ' • • ■ * ^ MAQNBSIA. ,. SS '-' , -* 1- ^ l-l h-i l-i to to to ^ to T) >*>• o to c 10 c jO CO t o to to CO «0 to 00 O -7 SS CI CO CO 05 -: -7 O ^ 1- -k c ij C5 C .T i,T tO*-*-000*^C50 Z.1 cc ;;, to 2 — 1 CO ~J « o « 3 C'l « » o OC5C0OOOOOO o CO o 01 pf 104 The PkospltcUes of America. From these figures it will appear that the avei"age may be safely taken at forty-six ])er cent, of sulphur, and of this amount, a varied ex])erience has demonstrated that at least six per cent, are generally unavailahle and should therefore he regai'ded as loss. The prices of raw material given in the following table are in- tended to cover all costs of delivery to works in readily accessible shipping ports, and are based, not upon the high values now pre- vailing for brimstone and communicated to it by speculation, but upon the average prices which have prevailed during the past five years. In the pyrites estimate, considerable additions have been made to the items of nitre and labor, and it has been considered wise in both cases to write off the whole value represented by the works in ten years, experience of this system in practice having proved highly satisfactory. Despite sundry di-awbacks the balance of advantage is \\x\- equivocally shown to be on the side of the pyrites, even when utilized at centres so far distant from the sources of production as to entail a very heavy freight. TABLE OF COMPARISON SHOWING THE ACTUAL COST OF PRODUCING ONE TON OF 53° BEAUME SULPHURIC ACID FROM BRIMSTONE AND PYRITES IN ACCESSIBLE SHIPPING PORTS. Brimstone (short tons). 1 ton of brimstone (98 per cent. S.) thirds, at $31 $31.00 50 lbs. of nitrate of soda, at 3| cents per lb 1 .25 500 lbs. coals, at, say, $4 per ton 1 . 00 Workmen's wages • 2 . 25 Superintendence and management , 2 . 00 General jobbing repairs 50 Interest on capital of $75,000 at 10 % per year, the works be- ing calculated to produce 20 tons daily and to last for ten years 4. 60 Total $33.60 Product equals 4}^ tons of 52° B. Cost per ton $7.65 Pyrites (short tons). 21 tons of iron pyrites at 46 per cent, sulphur, at 12 cents per vinit and per ton $13 . 80 60 lbs. nitrate of soda, at 2J cents per lb 1 .50 500 lbs. of coals, at, say, $4 per ton 1 .00 Workmen's wages 3 . 00 The Phosphates of America. 105 Superintendence and management 2.00 General jobbing repairs BO Interest on capital, same terms as above 4. 60 Total 126.50 Product equals Al tons of 50° B. Cost per ton $5 . 90 "We have already hinted at the feasibility of manufacturings the acid in the vicinity of the pyrites mines, but have not for- gotten to add that its practicability must be established by clearly demonstrating that the cost of carrying phosphates or 66° B. acid is less than the freights now paid upon the pyrites ore. The problem deserves to be inquired into by capitalists, since its favorable solution would still more reduce costs, as follows : COST OF ACm PRODUCTION AT THE MINES. 2^ tons of iron pyrites, containing 46 per cent, sulphur, at a maximum of 5 cents per unit delivered at the works . |5 . To Other charges, same as given in preceding table 12 . 70 Total cost of 4^ tons 50° B. acid $18.45 Cost per ton |4. 10 To put it plainlv, the manufacturer at the mines would be working upon sulphur which, on an exactly equivalent chemical basis of calculation, would cost him 815.25 less per ton than the price paid for brimstone by his competitors. 106 The Phosphates of America. CHAPTER VII. THE MANUFACTURE OF SUPERPHOSPHATE, PHOSPHORIC ACID, AND " HIGH-GRADE SUPERS." The process of superphosphate manufacture from mineral phosphates is not very generally understood, and while neither very complicated nor difficult, requires a certain amount of chemical knowledge and experience which the majority of those concerned in it do not possess. Hence it follows that no article in the market is more variable, both in its physical condition and chemical composition. Nor can this remain a source of surprise when we remember that each manufacturer adopts some peculiar system of his own, and that no two fertilizer factories bear any resemblance to each ■other. We have seen that raw phosjjhates, W'hether of animal or mineral origin, are made up of three molecules or parts of lime (CaO) combined with one molecule or part of phosphoric anhy- dride (PgOg). The words acid phosphate, superphosphate, water- soluble jihosphate, are all used to describe a product obtained by treating these raw phosphatic materials with a sufficient propor- tion of sulphuric acid to transform two out of their three mole- cules of lime into sulphate of lime or gypsum (CaSO^). To the lay i-eader, the chemistry of the mixture will be more readily understood if we briefly explain, that when a piece of pure phosphorus is bui*nt in contact with dry air it gives off vapors, every two atoms of which combine with five atoms of atmospheric oxygen to form a snow-white powder. This powder is the phos- phoric anhydride above alluded to, and it has a molecular weight of 142. Its chief characteristic is its attraction for water, and if left temporai'ily exposed to the air it rapidly deliquesces. In this moist state it is found to have combined with water in the molecular ratio of 1:3, and its composition has become Phosphoric anhydride (P2O5) 1 mol. = 142 by weight. Water (H3O) 3 mols. = 54 " Or, Phosphoric acid (H3POJ 2 mols. = 196 " In other words, every 100 parts of it contain The Phosphates of America. IC^ Phosphoric anhydride (PgOs) 72.45 Water (HgO) 27.55 100 And it may be regarded as typical of the tribasic combination in -which the anhydride is always encountered in nature. It has the faculty of exchanging one, two, or all three of its water-molecules, for molecules of various bases, and thus we are quite familiar with it as C^/V^w'/'/;'!^ CaO(IIoO)3P„Og, or acid phosphate of lime, in which it has taken one molecule of lime in place of one molecule of water ; v V (CaO)2HgO V.-,0^, or neutral jthosphate of lime, in which it has taken two molecules of lime in place of two molecules of water ; and (CaO)3P20g, or tribasic phosphate of lime, in which all the water-molecules have been displaced by lime. The first of these compounds is soluble in Avater. The second insoluble in water but soluble in neutral citrate of ammonia. The third is only soluble in strong acids. "When quite pure, every 100 parts of each of them is made up of — ^'l Ca Phosphoric anhydride (PoOj) Lime (CaO) Water (HoO) Acid Phos- phate of Lime. 60.68 23.93 15.39 100 Neutral Phos- phate of Lime. 52.20 41 .18 6.63 100 Tribasic Phos- phate of Lime. 45.81 54.19 100 The tricalcic or last of these compounds is the phosphate of lime which occurs in the deposits we have been engaged in con- sidering, and the problem of making it soluble in water or in neutral citrate of ammonia has been worked out by chemists on the following basis : Sulphuric acid is known to be more energetic in its action at ordinary temperatures than any other acid used in industry. It therefore has the power of displacing all other acids from their salts and of taking their bases to itself to form sulphates. The acids chiefly present in natural phosphates are phosphoric, carbonic, fluoric and silicic, and these, when brought into contact 108 Tlie Phosphates of America. with diluted sulphuric acid, are all dislodged. The bases become sulphates. The phosphoric anhydride combines with water and remains in the mass as free phosphoric acid, while the cai'bonic, fluoric, and part of the silicic acids, go off as vapor, the two latter generally combined in the very poisonous form of silicon tetra- fluoride. In the manufacture of fertilizers, however, as at present carried out, the object is not to produce free phosphoric acid, but " acid phosphate,'''' since, as we have already seen, this latter salt is quite soluble in water, and therefore can fulfil all the conditions that are deemed by some authorities to be essential in a plant food. It hence follows that the substitution of the bases must not be complete, but must be only carried to a sufficient point to displace all foreign acids, and to saturate two out of the three molecules of the lime combined with phosphoric anhydride. Lest this projjosition should appear too complicated, we may endeavor to make it more clear by an example, in which we shall assume that we are called upon to deal with a Florida phosphate, the composition of which has been determined by chemical analy- sis to be as follows : Moisture and organic matter 3.90 Tribasic phosphate of hme 79.40 (equal to 36.42 P2O3) Carbonate of lime 5.48 Phosphates of iron and alumina. . . 3.00 (equal to about 1.50 P2O5) Carbonate of magnesia 0.72 Sulphate and fluoride of lime 3.20 Sandy matters, silicates, etc 4.30 100 The sulphuric acid known as "chamber acicV when measured with Beaume's hydrometer at a temperature of 60° F., contains the following percentages of sulphuric anhydride (SO3) and pure mono- hydrate (H2SO1) : Degrees Beaume Percentage of Percentage of at 60° F. SO' (Anhydride) HiSO^ (Monohydrate). 48 48.70 59.63 49 49.80 61.00 50 51.00 62.47 51 52.20 63.94 52 53.50 65.53 53 54.90 67.30 54 56.00 68.60 55 57.10 ' 69.94 The Phosphates of America. 109 "With the analysis and this table before ns, we may proceed to find out in what jjroportions the powder and the liquid must be brought together to transform the insoluble phosphates into a water or citrate soluble form, and we acquire this knowledge by resorting to an equation, which we will endeavor, as au example, to produce in its simplest expression : Molecular Weights. 310 196 CajP.Og + 2H2S04 = 2CaS04 -f- 1 molecule of tri- + 2 molecules of = 2 molecules g"yp- + basic phosphate of monohydrate sum lime sulphuric acid CaH.PoOs 1 molecule of "super" or a c i d-c a 1 ci c phosphate. Mdecvlar Weights. 100 98 CaCOs + H3SO4 " CaSO^ + CO2 + HgO 1 molecule of + 1 molecule of = 1 molecule + 1 molecule + 1 molecule carbonate of monohy- of gypsum of carbon- o f water lime dratesulphu- ic-acidgas or steam. monohy- drate sulphu- ric ac'd Molecular Weights. 245 29-4 (A1P07)2 + 3H,S0, = AL(S0,)3 + (H^POJs 1 molecule of + 3 molecules of = 1 molecule of + 2 molecules phosphate of monohydrate sulphate of alu- phosphoric acid, alumina sulphuric acid mina Molecular Weights. 303 (FePOJ, 1 molecule of phosphate o f 294 3H,S04 3 molecules of = monohy d r a t e sulphui'ic acid Molecular Weights. Fe^CSO^), + (H3PO4), 1 molecule of + 2 molecules ferric sulphate phosphoric acid. 84 98 MgCO., + HgSO, = MgSO, + CO2 + 1 molecule + 1 molecule = 1 molecule 4- 1 molecule + carbonate of monohy- sulphate of carbonic- of mag- drate sul- magnesia acid gas nesia phuric acid 1 molecule water (or steam). 110 Tlie Phosphates of America. Molecular Weights. 78 98 CaF^ + H.SO^ 1 molecule of + 1 molecule of calcium fluor- m o n o h ydrate ide sulphuric acid CaS04 + 2irP 1 molecule of + 2 molecules of gypsum h 3 d r o fl u 0 ric acid. If three himdred and ten parts of trihasic phosphate of lime require one hundred and nhtety-six 2:>arts of the pure monohydrate of sxdphuric anhydride (H2SO4) for its transformation into mono- calcic or acid-phosphate, it follows that 1 part will require .632 parts of the acid. Assuming the chamber acid we are called upon to use to be of 50° B. strength, we refer to our table and find that it contains 62.47 per cent, of pure HaSO^. The quantity of it to be taken as an equivalent of .632 parts of the latter, therefore, is found by the equation: 62.47 : 100 :: 0.632 a; = 1.012 parts, and this is the method of calculation we must observe for all the bodies shown to exist in our sample of p)hosp)hate. TABLE SHOWING THE QUANTITY OF CHAMBER SULPHURIC ACID OF VARIOUS STRENGTHS —EXPRESSED IN POUNDS-REQUIRED IN THE MANUFACTURE OF SUPERPHOSPHATE FROM NATURAL PHOSPHATES IN ORDER TO PRODUCE ACID-PHOSPHATE. Every pound of the following substances re- quires— Acid at 48° B. Pounds. Acid at 49° B. Pounds. Acid at 50° B. Pounds. Acid at 51° B. Pounds Acid at 52° B. Pounds. Acid at 53° B. Pounds. Acid at 54° B. Pounds. Acid at 55° B. Pounds. Tribasic phos- phate of lime 1.060 1.036 1.012 .988 .965 .940 .921 .903 Carbonate of lime 1.640 1.605 1.565 1.535 1.495 1.456 1.428 1.411 Phosphate of alumina. . . . . 2.025 2.008 1.930 1.884 1.839 1.790 1.756 1.721 Phosphate of iron 1.630 1.595 1.558 1.521 1.485 1.446 1.420 1.390 Carbonate of magnesia.. . . 1.949 1.905 1.860 1.815 1.775 1.726 1.690 1.660 Fluoride of lime 2.006 2.059 2.010 1.962 1.916 1.866 1.830 1.794 "With a proper application of the data thus furnished there should be no difficulty in dealing with any phosphatic material of which the composition is accurately known, and it is only ueces- Bary, in proof of this, to give one more illustration. Returning to the phosphate we have already used, but assum- T^ie Phosphates oj America. Ill inej for the sake of variety that our chamber acid is of 52^ B, strength instead of 50° B., we shall find that 79. 40 lbs. phosphate lime X .965 = 76.62 lbs. 5.48 " carbonate " Xl.495= 8.19 " 3.00 " phosphates of iron and alumina combined X 1-839 = 5.52 '• 0.72 " carbonate of magnesia X 1-775= 1.28 " 3.20 " fluoride of calcium X 1.916= 6.13 " The total quantity of 52" B. acid required for every 100 lbs. of raw material, in order to bring the insol- uble phosphates into a soluble form, is therefore .. . 97.74 " It would thus appear to the unobserving, that a mixture of one ton each of the raw materials produces, after allowing for certain losses in the fabrication — such as evaporation — about two tons of fertilizer, and that we have gone to iinnecessary trouble to dem- onstrate a very simple fact. Such "rule-of -thumb" reasoning is no doubt responsible for the many bad " supers " we meet with in the trade, and the present is therefore the right time to ask what kind of a fertilizer has been thus prepared. As a matter of abso- lute fact, no question is so little understood by the majority of those who should be able to answer it, and yet no other is of so much importance. "We have been taught by chemistry that certain qualities are essential in a fertilizer in order that it may produce its results with rapidity and economy. Without a sufficient knoAvledge of the reactions involved, how can the possession of these qualities be in- variably assured and conscientiously guaranteed? Let us therefore examine a little more closely into the nature of this very complicated body. As revealed to us in our own practice and by the experience of other chemists, there can be no reasonable doubt that the tricalcic phosphates of mineral origin, when treated with sulphuric acid, become partially or wholly changed into three distinct forms : 1. Free phosphoric acid soluble in water. 2. Acid phosphate of lime soluble in water. 3. Neutral phosphate of lime insoluble in water, but readily soluble in neutral citrate of ammonia. There can also be no doubt that the nature and extent of this change, as well as the physical condition of the mass resulting from the mixture, will depend entirely upon two factors : A. The skill and intelligence of the practical operator. J5. The nature and composition of the phosphate to be handled. 112 The Phosphates of America. Assuming that A leaves nothing to be desired, the bulk of our average raw phosphates still offers two difficulties of considerable magnitude. If they are treated with the theoretical amount of acid, as in our example, they may yield a wet, pasty mass or mud which can only be dried with difficulty, and which therefore remains long unmarketable. If, on the other hand, something less than the theoretical quantity of acid be taken, a certain ])roportion of the substance remains unattacked and therefore becomes neither "water" nor "citrate" soluble. This is because there is in their composition, either a lack of some needed, or an excess of some objectionable constituent, and we are hence led to quite naturally inquire, what we are to regard as a defective phosphate. The result of prolonged investigations pursued under many and varying conditions has proved to us, that next to an insuffi- ciency of the phosphoric acid itself, a lack or insufficiency of car- honate of lime is the most serious defect. This defect is aug- mented in the presence of iron and alumina in any form. In Europe, and especially in England, high-grade phosphates have great commercial value, but they lose part of it when the oxides of iron and alumina, taken together, exceed three per cent. This is because the market price of the English manufactured fertilizer is made dependent upon its percentage of water-soluble phosphoric acid, and because, even when all other conditions are favorable, the presence of iron and alumina gradually causes *' water "-soluble to revert into " citrate "-soluble phosphates when kept for a short time ready made in the factory. When an acid of greater average strength than 50° B. is used for the attack on the phosphate — and stronger acids are frequently necessary — free ])hos- jihoric acid is at first almost exclusively produced as a result of the reaction. After a little time, when the temperature is at its maximum, this free phosphoric acid commences to react upon the undecomposed material, and first of all upon any iron and alumina that may be present. Bodies insoluble in water result from this reaction, and hence the English fertilizer makers studiously avoid all mineral i^hosjihates containing more than the stated maximum. In this country we are not handicapped by any such foolish prejudices. Our farmers are hard-headed and practical and have no marked j^reference for luater- soluble phosphoric acid. They have been taught by theory and have proved by their own field practice, that citrate-soluble phosphates are readily transformed into plant food by the elements in the soil. This being the case. TJie Pliosphates of America. 11 3 all they ask of us is the maximum of " available 2^^fosj)horic acid'''' in a fine, dry and merchantable condition, and this wg can give them without difficulty and without regard to a few units more or less of oxides of iron and alumina, by carefully regulat- ing the percentage of carbonate of lime in our raw product. When circumstances allow of this regulation, through the mixture of a phosphate containing much carbonate, with another containing little or none — as for instance, the blending of Canadian apatite with Belgian cretaceous phosphates — we personally prefer that course, but where such facilities are wanting, we invariably resort to the addition of finely powdered chalk, or any other cheap and available source of the carbonate. This method of facilitating spontaneous drying was suggested by us to a few manufacturers some years ago, and has been depre- cated and denounced as far too costly for general use. Those who denounced it, however, have not yet made known a cheaper or more practical plan, for the one which they proposed, of effecting the drying by the application of external heat in ovens or on hot floors, has invariably proved disastrous. How could it in fact do other- wise, when we know that raonocalcic or water-soluble phosphate of lime cannot exist in any other than the hydrated state? In making our projjosal, we had borne in mind that this hydrated state can only be preserved by spontaneous drying, and we had experimented enough to know that this drying can only be easily effected as we have described. We consequently can see no more valid reason to-day than we could ten years ago, why, under proper restrictions, the carbonate should not be used. The difficulties of a manufacturer only commence when he is called upon to use a refractory raw material, and it is only under such circumstances that he finds scope to develop the fertility of his resources. If our mineral phosphates were not of ever-varying composition, a knowledge of chemistry would not be so essential to their treatment, but as the case stands we are helpless without the assistance of the analyst. In his absence the manufacturer gropes blindly in the dark, for he knows not what elements he is mixing together and can predict nothing concerning the nature of the compound that will result from their reactions on each other. Figures, like actions, are more eloquent than words, and as our assertions are made on the strength of our own work, we will close this part of our argument by giving some examples that should carrv conviction. 114 Tlie Phosphates of America. The following experiments were made with Florida phosphate containing as high as eight per cent, of iron and alumina. After having been tried in several factories and pronounced worthless for the purpose, they Avere finally made into superphosphates of excep- tionally good quality. The composition of the material was : Phosphate of lime HI . 10 (equal to 37.20 Vfi^) Carbonate of Imie 3.70 Oxides of iron and alumina (combined) 7.90 Moisture, msoluble, and undetermined 7 . 30 100 One hundred pounds of it were treated with 94 jDOunds of 55° B. chamber acid, and one hour after the " super" liad dropped into the " den " a sample was drawn from various points, mixed, analyzed and found to contain : Total phosphoric anhydride soluble in liydrochloric acid. ... 20.01 Of which there was found to be Water-soluble phosphoric anhydride 15.90 Citrate-soluble " " 16.30 At the end of ten days this "super "was still in the "den" and in a very wet and unmanageable condition. Sampling and analyses were repeated, and it was now found to contain : Total phosphoric anhydride soluble in hydrochloric acid. . . . 19.96 Of which there was found to be Water-soluble phosphoric anhydride 15.10 Citrate-soluble " " 17.01 Another batch was made Avith the same lot of phosphate after adding to it eight per cent, by Aveight of very finely poAvdered chalk. Upon analyses before treatment Avith acid it Avas noAv shoAvn to contain : Phosphate of lime 75.03 (equal to 34.40 P.Os) Carbonate of lime 10 . 72 • Oxides of iron and alumina (combined). 7.27 Moisture, insoluble, and undetermined 6 . 98 100 One hundred pounds Avere passed through a 70-mesh screen and then Avorked up with 92 pounds of 55° B. chamber acid as before, and dropped into the "den." At the end of an hour^ Avhen the sample The FJiospJinfes of America. 115 was drawn as in the last experiment, it had already commenced to ♦' set," and the result of the analysis was : Total phosphoric anhydride soluble in hydrochloric acid. ... 18.97 Of which there was found to be Water-soluble phosphoric adhj'dride 16.30 Citrate-soluble •• •• 18.10 At the end of thirty-six hours after mixing, it was dry enough to be dug out of the " den " and was in a very porous and friable state, the analysis at this time showing it to contain : Total phosphoric aahj'dride soluble ia hydrochloric acid. ... 19.19 Of which there was found to be Water-soluble phosphoric anhydride 16. 17 Citrate-soluble " •• 18.53 The increase in the last figure was due to decrease in moisture. In order to test the question of the advisability or otherwise of using calcined phosphates from Florida, made by the prevailing method of firing the material in heaps, a third experiment was j)erformed at the same works. Before treatment Avith acid the finely comminuted material (VO-mesh) was analyzed with the fol- lowing result : Phosphate of lime 77 . 18 (equal to 35 . 40 P0O5) Carbonate of lime 3 . 64 Quick-lkne 4 . 65 Oxides of alumina and iron (combined) 7 . 53 Moisture, insoluble, and undetermined 7 . 00 100 After being worKCCl up with 92 pounds of 55° B. sulphuric acid it was dropped into the " den" as usual, and sampled and analyzed at the end of an hour, as in the other cases. It icas still quite wet and yielded : Total phosphoric anhydride soluble in hydrochloric acid. ... 18.72 Of which there was found to be Water-soluble phosphoric anhydride 15.54 Citrate-soluble " '• 16.79 It was removed from the " den " on the eighth day after its manu- facture, in a very damp and iinsatisf actor tj condition, quite unfit to pass through the pulverizer or to be put into bags. It yielded on anal V sis : 116 The Plios2)hates of America. Total phosphoric anhydride soluble in hydrochloric acid. . . 18.93 Of which there was found to be Water-soluble phosphoric anhydride 15.03 Citrate-.soluble " " 17.01 Unless our conclusions are ill-founded in everj^ 2^^'"t'<-"^il''^i"; these figures and details confirm the position we have assumed. In the first place, they prove that raw mineral phosphates con- taining a fair proportion of carbonate of lime may carry a high percentage of iron and alumina and yet yield a perfectly dry and pulverulent product, in which nearly all the phosphoric acid is in a readily soluble or available form. As a necessary consequence, while this amount of carbonate certainly calls for an inci'eased outlay of sulphuric acid and thereby adds somewhat to the cost of manufacture, it is, nevertheless, in the end a source of the truest kind of economy and profit. Ill tlie second place, they prove what we have never ceased to claim, that the prevalent custom of calcining Florida phosphates is unscientific and harmful, and that Avhereas the production of a dry and porous "super" always follows the use of carbonate, the pres- ence of free lime always retards the drying action. In the third place, they jjrove the necessity for complete chemical analysis of the raw material, and demonstrate the utter worthless- ness of analytical reports which merely give the percentage of total phosphoric acid, calculated to its equivalent of tricalcic or "bone" phosphate. What kind of iron and steel Avould be produced, if those concerned in that industry were content to know the mere percentage of metallic iron contained in a sample of iron ore ? Turning now from the purely chemical, to that side of the industry which calls for mechanical details, Ave come first to the operation of grinding the raAV phosphate, and we may be allowed to say that this is a matter for the most serious attention. A growing recognition of the necessity for extremely fine grinding is one of the most satisfactory results of scientific teach- ings, and we are glad to see that progressive manufacturers now ad- mit it to be the only means of attaining high dissolving etticiency. In projjortion to the natural hardness of the phosphate rock this necessity for fine separation of the particles increases, and it has been the experience, Avith Canadian apatites for example, that imless the material is so disintegrated as to pass freely through a 70 or eA'en an 80 mesh screen, it is only very slowly and incom- pletely acted upon by 50° B. sulphuric acid. Tlie J'hosphates of America. ir: Several popular nielhods of grinding now give great satisfaction on the industrial scale, and of these we may mention the plant.'* which comprise — First. — A Blake stone-crusher for reducing the lumps to the size of small marbles, attached to a set of French burr mill-stones fitted with revolving screens up to 90 or 100 mesh. Second. — The Sturtevant mill and crusher, which is composed of two cylindrical heads, or cups, arranged upon the opposite sides of a case, into which they slightly j^roject, facing each other, and are made to revolve in opposite directions. The rock, being conveyed to the interior of the case through the oj^ening at the top, is re- THE STURTEVANT MILL IN CROSS-SECTION. tained and prevented from dropping below the revolving heads or cups by a cast-iron screen, and entering, as it must, the heads or cups in revolution, is immediately thrown out again f roni eacli cup, in opposite directions, with such tremendous force that the rock from one cup in the collision Avith the rock thrown oppositely from the other cup is crushed and pulverized, and the grinding, whicli otherwise would be upon the mill, is transferred to the material, which is at once reduced to powder. The mill is composed of four elementary ])arts — a case, two hollow heads or cups, and a screen. The principle of its construction is shown in the above cross- section of its elementary parts. 118 The Pliosplmtes of America. B B represent the two opposite heads or cujis of the mill hold- ing the two bushings E E, which slightly project into the case. At Z Z, the stone hollow cones are shown (which form themselves in each head by the packing of the rocks being ground after the machine has been run a few moments). The hopper is filled with rocks, which drop into the case of the machine between the two heads. In a few moments after the mill has started the two stone hollow cones Z Z form themselves and become as hard as the rock. When these hollow cones have formed, the centrifugal force given by their revolution Avill hurl out of the hollow cones in the general directions indicated by the arrows all the rocks that are forced into them. The iron confining-screen C is of very small diameter, and an important object is accomplished by this arrange- ment. The ground rock is let out of the screen at once. We have found it advisable to attach a set of rock-emery stones to this mill for grinding the fine tailings, Avhich amount to about thirty per cent. In this way the average milled product of TO-mesh may be fairly taken as about two tons per hour. Tliird. — The Griflin mill, which is of the class knoAvn as a roller and die mill, in which the material is reduced by being crushed by a roll running within and against the inner surface of a ring or die. It is a substantial mill and receives its power by a pulley run- ning horizontally. From this j^uUey is suspended the roller-shaft, by means of a universal joint, and to the lower extremity of this shaft is rigidly secured the crushing-roll, which is thus free to swing in any direction within the case. The illustration on the next page shows that the case consists of the base or })an (24) containing the ring or die (70), against Avhich works the roll (31) and upon the inner vertical surface of which the crushing is done. This pan or base has a number of openings through it down- Avard outside of the ring or die which lead into a pit or recejjtacle below. Upon this base is secured the screen-frame (44), which is surrounded with a sheet-iron cover (45) and to the top of which is fastened a conical shield (25) open at the apex, through which the roll-shaft works. To this cone is attached the feeder-arm (34) by means of which the automatic feeder is operated. The crushing-roll is attached to the end of the lower or roll-shaft (l), and just above the roll is the fan (7). On the under side of the roll are shown shoes or ploughs I'lie Phosphates of America. 119 (5), varying in shape according to the nature of the work to be done. The pulley (17) revolves upon the tapered and adjustable bearing- stud (20), which is in turn supported by the frame composed of the standards (23). Two of these standards (23a) are extended above SECTIONAL VTEW OF THE GRIFFIN MILL. the pulley to carry the arms (22) in which is secured the hollow journal ])in (12). Within the pulley is the universal joint from which the roll-shaft (l) is suspended. This joint is composed of the ball or sphere (n) with trunnions attached thereto. These trunnions work in half-boxes (11) which slide u}) and down in re- 120 The Fhosjjhates of America. cesses in the pulley-heafl casting (16). The joint in the pulley is inclosed by means of the cover (13), thus keeping the working parts away from all dust and grit, and lubricating oil is supplied for all partsneeding it through the hollow pin (12). When the mill is started, the jjulley and the roller-shaft revolve together, the roller hanging free in the centre of the ring, Avhen, the shaft being j^ushed outward, the roll on its lower end comes in con- tact with the ring or die and immediately begins to travel ai'ound on the latter's inner surface, jjressing against it with a force suffi- cient to effectually pulverize anything that comes in its way. The material to be reduced is fed into the mill in sufficient quantity to fill the pan as high as the shoes or ploughs on the lower side of the roll. The ploughs then stir it up and throw it against the ring, so that it is acted upon by the roll, and when fairly in operation, the whole body of loose material whirls around rapidly Avithin the j^an and up against the screens, through which all that is sufficiently fine passes at once, the coarser portion falling doM'n to be acted upon again. The universal joint, by which the roll-shaft is connected with the pulley, allows perfect freedom of movement to the roll so that it can easily pass over obstructions of any kind. Pieces of iron or steel, such as are usually found in all rock to be gi'ound, do no dam- age to the mill. In dry grinding the fine material that passes through the screens falls downward through the openings outside of the ring into the receptacle underneath, from which it is carried by a conveyer pro- vided for that purj^ose. The fan attached to the shaft above the roll draws a small quantity of air in at the top of the cone, forcing it through the sci'eens and out into the discharge, thus effectually keeping all dust within the mill. It is stated of this mill that four tons of South Carolina phos- phate rock (seventy-five per cent, of which would pass through a VO-mesh screen) may be ground and passed through the screens in an hour. Fourth. — The Frisbee-Lucop phosphate mill, which is built of steel and weighs about three tons. It is driven by belt, develops a speed of 300 revolutions under full feed, requires 18 horse power, and is said to be capable of grinding 15 tons of phosphate rock to a fineness of No. 1 50 mesh, per day of ten hours. The pulverization of the material is effected by heavy cylin- drical rollers which are caused to revolve upon the inner surface The FJiosjjhates of America. 121 of a steel ring, against which they exert a pressure of some 2000 pounds per square inch. The effect of this force is augmented by a differential grinding motion imparted by the drivers. As fast as it is produced, the pulverized is separated from the coarse material, by gravity, being drawn from the mill through pipes connected with the toj) of the casing by an exhaust-fan, and carried to settling bins or chambers. Five different varieties of steel, each having special character- istics suited to the requirement, are used for the interior or work- ing parts of the machine. The wearing parts, being few in number and simple in shape, are readily replaced when worn. The construction of the mill will be easily imderstood from the following transverse vertical section through its centre. The shaft S is of hammered steel, 39 inches between bearings. THE FRISBEE-LUCOP PHOSPHATE MILL. which are 3^ inches by 10 inches long. Pulleys are double-arm, fast and loose, 28 inches in diameter by 8-inch face. To the shaft is keyed the driving-arm A A previously forced on. This is a solid casting 6^^ inches thick through tlie ends and 9^ inches through the flanges or hub. The rear ends of the arm are made concave to receive the rolls Avhen the mill is at rest. Upon both sides of the arm are fastened the discs D D, annular plates fitting around the flanges of the arm and firmly secured to it by two disc-bolts 1| inches in diameter. Between the discs are placed the drivers B B, two in number, rigidly bolted to the discs by the two driver-bolts, H inches square. The drivers are cylindrical, e^V inches long by 6 inches diameter, made of cast-steel or forged iron, and weigh 45 pounds each. When worn by contact with the rolls they may be turned a quarter cir- cumference on the bolt. This may be repeated until the four sides are worn. 123 Tlie Pliospliates of America. There are two rolls, R R, of chrome steel, S inches in diameter by 6-inch face, weighing about 80 pounds each. They are held free in position by the discs between their drivers and the rear ends of the arm. The fan-blades F F, four in number, are of steel or wrought-iron and are firmly fastened on each disc exteriorly by the disc-bolt and dowel-pin, and distribute the material to be pul- verized into the path of the rolls. Four liners, L L, or thin steel plates are placed between the VIEW OF TRANSVERSE VERTICAL SECTION OP FRISBEE-LUCOP PHOSPHATE MILL. ends of the rolls and the discs (cut to receive them) and take the wear off the ends of the rolls. The revolving parts of the mill centred within the ring have all a uniform motion with the shaft, but the rolls have an inde- pendent motion around their axes. The ring G G is of rolled steel, 6 inches face and 3 inches in thickness, held in position by wedge-keys K K to the casing of the mill C C. Exterior to the "centre" are two small circulating fans (wrought blades in a cast hub), the purpose of which is to keep the pulverized material in circulation so that it may be readily withdrawn by the exhaust- fan which carries the product of the mill to the settling-bins. The casing of the mill is of cast-iron, divided horizontally. Tlie Pliosphates of America. 123 The upper and lower lialves are lield together by hinged bolts in slots cut in the flange of each section. The upper half is hinged to the lower at one side and is easily raised so as to give free access to the interior of the mill for examination and the replacing of worn parts. The casing and the three pedestal bearings for the shaft are seated upon a heavy bed-plate as indicated in the illus- trations. Being a balanced machine it does not require elaborate or expensive foundations. The difliculty of estimating the exact cost of grinding phos- phates to a fineness of 70 or SO mesh, either by the methods we have thus described or any others now in use and perhaps equally good, is naturally very considerable, since so much must, perforce, depend upon the nature of the material itself. We have seen it va- riously estimated at from 50 cents to $2 per ton, and have even met those who claim to be able to do the needful work for less than the first figure. As a matter of sober fact, however, we have found that in practice, when breakages, repairs and general wear and tear are taken into account, Si. 50 per ton is more like the projier figure, and w^e therefore usually adopt it as a fair basis for calculations. The operation of grinding having been satisfactorily performed, the phosphate is submitted to complete analysis and, its chemical composition being thus known, is finally conveyed to the mixer. The mixing together of the raw materials in the proportions determined by proper computation is performed in a commodious shed, of which the annexed drawing will convey the necessary under- standing. It must be near to the sulphuric-acid chambers, and directly connected with a high shaft or chimney and a condensing apparatus or scrubber ; the latter for absoibing the noxious fumes set free by the decom])Osing mass. A strong brickwork shell with a good foundation is built in the centre of the shed. This shell is divided off into from six to twelve chambers or "dens" some 15 feet square and 20 feet high, each of which must communicate, by means of a good-sized flue, with the scrubber and factory chimney. The air-tight iron doors of the "dens" must slide easily back- w-ard or forward when the superphosphate has become dry enough to be dug out. The tops of the "dens" are fitted with mixers of cylindrical shape about 10 feet long, 3 feet in diameter and 4 feet high. The mixer may be constructed of wood lined with sheet lead, or 124 The Phosphates of America. of brick, or of iron, or in fact any suitable material in accordance with the fancy. It stands over the dividing wall of two " dens ;" is generally provided with movable traps for discharging its contents at either of its ends and with a revolving axle or shaft fitted with arms or spirals. It should have a hopper and a gas-flue, and the driving gear must be of Avrought-iron. Running into it from the SroE VIEW OF A SUPERPHOSPHATE WORKS. A, Discharge from mixer to " den." 1, 2, 3, 4, Exit-flues conducting fumes to condenser. top directly under the hopper is a 2-inch lead pipe fitted with a stop-cock and connected with a tank of sulphuric acid placed di- rectly overhead. The acid tank is provided with a gauge which shows the exact amount of liquid run into each batch as required by calculation. The tank communicates in its turn Avith the acid reservoirs from which, when emptied, it is replenished by a pump. The phosphate is brought forward from the mill in buckets on an The Phosphates of America. 125 I'tidlcss chain. Each Imoket liohls a known weight of material and <'ach empties itself into the hopper of the mixer. AVliere there is no convenience for establishing an endless chain, the material can he carried to the hopper in sacks direct from the mill. When this hopper contains 1000 pounds of the powder, the acid tap underneath it is turned on, the agitators of the mixer are set in motion, and then the powder is allowed to ruji in a steady stream from the hopjjer. When all the acid and the phosphate are in the mixer, the agitators are made to revolve with swiftness and energy for about two minutes, after which the trap of the mixer is opened and its ^-v^i^^fp^ SUPERPHOSPHATE MIXER. contents, a thick mud or mortar-like mass, are shot from it into one of the "dens" at its either extremity. These operations are repeated until the "den" is full, care being taken to keep the gas-flues open and to see that the acid always runs into the mixer in advance of the powder. A neglect of the latter precaution invariably results in serious difficulties from clogging. Each charge should be equal to an average of about 1900 pounds, and each "den" should hold about 120 tons. Assuming, therefore, the length of time required for running a charge to be five minutes, it is an easy matter to fill up a "den" each day of ten working hours. The mixed mass enters the "dens" in a semi-liquid state and 126 The Phosphates of America. soon becomes extremely hot, generally attaining a temperature of from 230° to 240° F. AVhen properly composed it commences to " set " almost at once, and at the end of the second day is suffi- ciently hard to be dug out of the "deu" with picks and shovels. In this state it is loaded into automatic dumping-cars and piled up in heaps, all large lumps being broken down by a blow from the shovel. In a couple of days it is ready to pass through a dis- integrator and may then be put uj) in bags. The average superphosphate manufactured in this country con- tains about thirteen to fourteen per cent, of "available" P2^5> but the rapid development of the industry during the past few years has led to the introduction of what are known as "high- AUTOMATIC DUMPING CAR FOR SUPERPHOSPUATE WORKS. grade supers," containing about forty-five })er cent, of jAosphoric anhydride (PgOg) in a "water" and "citrate" soluble form. The plan upon which these goods are produced is perfectly scientific and rational, much more so, in fact, than the one we have just described, for it consists in using phosphoric acid as the solvent in lieu of the oil of vitriol. The theory of the action of phosphoric acid upon pure phos- phate of lime may be explained by either of the two following simple equations, or, to speak more correctly, by a combination of both of them : CaaPgOg -t- 4(H3P04) + 6HaO 1 insoluble tri- + 4 phosphoric + 6 water calcic phos- phate = 3 CaH,(P04)3(H30)2 = 3 crystallized " acid '* or " soluble " phos- phate. X iPo^)^ ^ ^^^ The Phosphates of America. 127 SCagPoO, + SCH^PO,) + I2H2O =3Ca2H2(PO,)3(HoO)4. 2 insoluble tri- + 2 phosphoric + 12 water =3 crystallized neutral calcic phos- acid phosphate, soluble in phate neutral citrate of am- monia. The advantages offered by the cheap production of such an article as this in commercial form are, of course, too manifest to need any elaborate explanation, but it may nevertheless not be out of place to mention a few of them. In the manufacture of superphosjihates we have seen that the desired sohibility, either in M'ater or in citrate of ammonia, is at- tained at the cost of doubling the bulk of the raw material by the addition of an acid which practically serves no other purpose and has no other value than as a dissolvent. If the original material, therefore, contain sixty per cent, of tricalcic phosphate, the " super " can only contain thirty i)er cent., and this, from the agricultural consumers' standpoint, is cei-tainly an anomaly, and, apart from any question of solubility, must remain so for two reasons : 1. A ton of sixty-per-cent. phosphate of lime, finely ground but insoluble in water or citrate of ammonia, can be purchased at some central point for, say, ^10. 2. A ton of superphosphate, containing only thirty per cent. I)hosphate of lime, cannot be purchased at the same spot for less than ^15. In the one case, freight is paid upon only forty per cent, of inert material, whereas in the other it is })aid upon seventy per cent. Apart from the perfectly legitimate profits attached to the manipulation and transformation of a sluggish into an active body, those who at present derive the greatest benefit from the trade in fertilizers are the railroad companies. If it Mere for no other object than the reduction of freight charges to a minimum limit, it is consequently wortli while to consider the advisability of substi- tuting for the old method of manufacture, the one which we shall now attempt to describe. The details of superphosphate mixing, and the reactions involved in the jjrocess, have been gone over in a sutficiently amj)le manner to prepare the way for the statement, that the cheapest and best- known method of producing phosphoric acid is by disj)lacing it from its combination with phosi)hate8 of lime by means of oil of vitriol. The proportion of jjhosphoric acid contained in the raw material being a matter of only relative importance, the ado])tion of such a 128 T]ie Phosjjhaleis of America. method would open up a channel for the use of many low-grade phosjihates, which now, for lack of a market, are practically of no value. The only essential conditions to be fulfilled are : A. That the material shall contain a minimum of carbonate of lime, in order that no unnecessary excess of sulphuric acid need be used. B. That it shall contain as small a percentage as possible of any combination of iron and alumina, both of which, besides being difii- cultly soluble, conti'ibute to the formation of a gelatinous mass that seriously interferes* with the j^roper carrying out of the operations. In order to ascertain the quantity of sulphuric acid necessary to insure the desired reaction, it is of course essential that the exact comjiosition of the raw material be first determined by a reliable analysis. Supjiosing ourselves to be in possession of this informa- tion, we may imagine that we are called upon to deal with a mineral jjhosphate containing : Moisture and organic matter 4.00 Phosphate of lime 55.00 Carbonate of lime 3.50 Phosphates of iron and alumina 6.50 Carbonate of magnesia 0.75 Fluoride of lime 2.25 Sandv and siliceous matters 28.00 100 The quantity of oil of vitriol of various strengths required for the complete liberation of all the jihosjphoric acid, and the satisfac- tion of all the bases in such a sample as this, is very readily calcu- lated from the figures in the following table : TABLE SHOA\aNG THE AMOUNT OF CHAMBER SULPHTTRIC ACID OF VARIOUS STRENGTHS REQUIRED IN THE MANUFACTURE OF PHOSPHORIC ACID FROM NATURAL PHOSPHATES. Every pound of the foUowinfr substances re- quires— Acid at 48° B. Pounds. Acid at 49° B. Pounds. Acid at 50° B. Pounds. Acid at 51° B. Pounds. Acid at .52° B. Pounds. Acid at 53° B. Pounds. Acid at 54° B. Pounds. Acid at 55° B. Pounda Tricalcic phos- phate of lime 1.590 1.554 1.517 1.483 1.446 1.408 1.383 1.352 Carbonate of Imie 1.640 1.605 1.565 1.535 1.495 1.456 1.428 1.411 Phosphate of iron 1.630 1.595 1.558 1.521 1.485 1.446 1.420 1.390 Phosphate of alumina 2.025 2.008 1.930 1.884 1.839 1.790 1.756 1.731 Carbonate of magnesia 1.940 1.905 1.860 1.815 1.775 1.726 1.690 1.660 Fluoride of lime 2.006 2.059 2.010 1.962 1.916 1.866 1.830 1.794 Hie Phosphates of America. 139 Selecting an acid strength of 50° B. for our illustration, we shall find that our sum Avill Avork out thus : 55 lbs. phosphate of lime X 1 .517 = 83.441bs. vitriol of 50° B. 3.50 " carbonate of hme X 1.565= 5.48 " " " 6.50 " phospliate of iron and alumina X 1.930 = 12.55 " " " 0.75 " carbonate of magnesia X 1.860= 1.40 " " " 2.25 " fluoride of lime X 2.010= 4.52 " " " Total sulphuric acid of 50° B. strength re- quired for every 100 pounds of the above phosphate 107.39 lbs. The decomposition of the raw material is effected in large wood- en tanks made of suitable wood and provided with wooden agitators. 2147 pounds 60° B. sulphuric acid are run into each tank and diluted with water until its strength is reduced to 14° B. The agitators are now set in active motion, and 2000 jjounds of the phos- phate, finelj' ground as directed for superphosphate manufacture, are slowly added and the stirring is continued for five hours. Open steam is occasionally blown in by an injector through the side of the tank, in order to keep up the temperature of the mixture. At the end of the specified time the creani from each tank is run off into filters — large wooden vessels lined with lead and pro- vided with false bottoms. The hydrated sulphate of lime here separates from the solution of phosphoric acid, the latter passing through the filter as a bright straw-colored fluid, of a gravity which, at first, is about 12° B., but which gradually gets reduced by careful washing to 1° B. By the e.vercise of ordinary care and precautions, all cracks on the surface of the gypsum contained in the filters may be avoided, for were they to be formed, too ready an outlet would be afforded for the wa.shing-water. The washing is stopped directly the grav- ity reaches 1° B., and the hydrated sulphate of lime is first jailed up in the centre of the filters to drain, and is then carried to the dump ; the last runnings from the filters, which are too weak for economical concentration — everything under 5° B. — being used to dilute the sulphuric acid in subsequent operations. If the wooden tanks be put up on the large scale in series of ten, a batch of the emulsion can be discharged from them, one after the other, every half-hour, when once they are all in proper working order, and in this manner twenty tons of phosphate can be treated per day. 130 The Phosphates of America. All the phosphoric-acid liquor above 5° B. which has passed through the filters is blown by an "egg" (similar to the one de- scribed in the chapter on sulphuric acid) into an elevated tank, and thence it runs by gravitation to the evaporators, a series of leaden pans of any convenient form of construction, and heated either by a direct fire from the top or from the bottom or by the waste steam from the boilers. If any choice is to be awarded to either of these modes of evaporation, it mxist, in our opinion, fall upon top-heating ; for as the hot gas comes into direct and immedi- ate contact with the acid and the vapors produced are at once re- moved by the draught, it is evidently the quickest, while the pans are much less acted upon and freer from the danger of being burnt through than those which are fired from below. The vessel must, however, be kept constantly full and at a uniform level, in order to protect the lead from any direct contact with th^ flame ; nor is this a matter of any difticulty, since the heavy concentrated acid continuously sinks downward, and may be drawn off from the bottom, in a stream directly proportionate to that in which fresh acid from the tank above is allowed to run in at the top. In works where it is thought best to heat the pans from the bottom, the latter are generally so arranged in sets, that the weak acid flows in at one end in a regulated stream, and is transferred from pan to jjan by overflow-pipes. The j)ans themselves in this case are placed on cast-iron plates, those at the fire end being very thick, to protect them from the extra heat, and generally lined with clay and fire-brick. The fireplace comes under the strongest of the pans, and the flame gradually travels towards the weakest, such an arrangement being required by the fact that the concentration be- comes more difiicult as the acid gains in strength. According to extensive and perfectly trustAvorthy experiments, a series of pans having a total area of 118 superficial feet, with a fireplace of 6^ superficial feet, can pi-oduce, when properly constructed, eight tons of j)hosphoric acid in twenty-four hours, concentrated to 45° B., with a consumption of no more than twelve to fourteen per cent, of its own weight of coal. During the progress of the evaporation, the acid solution de- posits a considerable quantity of sulphate of lime, and it is there- fore generally necessary to decant off the fluid before the final degree of concentration can be attained. The gypsum can be re- moved to one of the filters already described, and washed out with any liquid that may be running into them from the mixing-tuns. Tlie PJtosphates of America. 131 The finished liquid at 45° B. should contain nearly forty-tivi' j)er cent, of phosphoric anhydride, with only a mere trace of lime. It ^vill probably be contaminated to some extent by magnesia anil iron and alumina, but neither of these, provided it is not present in any great quantity, "wlU be a source of serious difficulty for the pur])ose in view. We are now in possession of an acid body, which can take the place of suljjhuric acid in the manufacture of soluble and assimilable phosphates, and we have only to come back to the old superphosphate mixers, and use the same modes of manipulation and the same system of calculation as in superj^hosphate manu- facture. All that is needed is to change the numbers, in order to accord with the different composition of the two acids. A raw phosphate of about the following composition may be taken as a typical material for economical treatment : Moisture and organic matter 3.00 Phosphate of lime 75.00 (equal to 34.40 F.O.J Carbonate of lime 7 . 50 Alumina and iron oxides (combined) 3.00 Fluorides, silicates and sand 11 .50 100 The quantity of phosphoric acid of 45° B. required to trans- form this insoluble phosphate into a "soluble" or readily "avail- able" form may be taken from the annexed table. In calculating it we have assumed in a practical way, and without j^retension to absolutely theoretical accuracy, that an acid solution of 45° B. "factory test"Avill contain, say, forty-two per cent, of phosphoric anhydride (P2O5) or about fifty-eight per cent, of phosphoric acid (H3PO,). TABLE FOR USE IN THE MANUFACTURE OF HIGH-GRADE SUPERPHOSPHATES FROM PHOSPHORIC ACID OF 45° B. Every Pound of the followiii;,' Substances Re- quires for its Transformation Into Wat^r- Solubleor "Acid Phosphate." Into Citrate-Solu- ble or Neutral Phosphate. Mineral phosphate of lime Pounds. 2.310 3.380 Pounds. 0.625 1.690 2.112 3.270 Carbonate of lime Iron oxide Alumina oxide We therefore proceed to ascertain that 132 The PJiosjihates of America. 75 lbs. phosphate of Ume. . . X -625 require 46.88 lbs. phosphoric acid. 1% lbs. carbonate of lime.. X 1.690 " 13.68 '6 lbs. iron and alumina as oxides, .say X 3.000 " 9.00 " " So that the total phosphoric- acid solution of 45° B. required to render 100 pounds of the above phosphate soluble in neu- tral citrate of ammonia is 68 . 56 pounds. This quantity being the known required minimum, it is easy after one or two trials of the drying capacity of the mixture, to increase it at will up to any desired limit, it being evident that the more it is increased the greater will be the amount of '■'■ water-sol- xible ''"'phosphate produced ! The mixture, when made, is dropped, charge by charge, into the " dens," where it very soon sets into a porous mass, not quite dry, but sufficiently so to be easily dug out. This mass is cut up into pieces of reasonable size and dried by hot air, in sheds constructed for the purpose, in any form, or on any plan, that Avill facilitate effective and rapid work. Directly it is sufficiently dryfor the market it is put through a disintegrator and filled into bags. In Europe the great superiority of this method of dealing with raw phosphates over the more generally established plan has been recognized for some years, and the high-grade product is much in vogue in Germany and France. The rough-and-ready plant which we have outlined has been supplemented in those countries by much labor-saving machinery in the form of mixers and filtering jjresses, the majority of which are protected by patent and chiefly manu- factured in Germany, at Halle an der Saale. For the purposes of experimental demonstration, however, we have deemed it preferable to dispense with a description of all costly foreign apparatus, feeling that we may trust to the well-known genius of our American me- chanical engineers for the construction of such plant as may be necessary in different localities, and under varying circumstances. When we bear in mind the proverbial conservatism of the farmer and his distaste for innovations, we shall see the necessity for going slow in this matter, for it will doubtless take some time to create an active demand from his direction for a concentrated superphos- phate. Meantime, however, those who are engaged in handling fertilizers as middlemen will be more readily convinced, especially when they appreciate the economy in transportation, if in nothing else, which such a product will afford. How great this economy The Phosphates of America, 133 really is can easily be sho\m by a few figures which, while not pre- sented as the actual cost at which large and well-situated manu- facturers could produce it, will suffice for purposes of illustration. Commencing with the cost of phosphoric acid and assuming the factory to be located at a point within easy access by rail or by water, or both, we may calculate that 1 ton of 2000 pounds mineral phosphate, containing M\.y to sixty per cent, phosphate of lime will cost |4.00 Grinding same to a fineness of 70 to 80 mesh. .. •• 1.50 2130 pounds chamber sulphuric acid of 50° B. at. say, $7.00 per ton will cost 7.50 Labor of mixing and filtering, wear and tear, etc., cal- culated at the rate of, say, $1 per gross ton of raw material handled will cost 2.00 Concentration, labor, wear and tear of plant, calculated at $1 per gross ton of raw material will cost 2.00 Total net cost of producing, say, 1000 pounds of 45° B, phosphoric acid $17.00 Cost of the 45° B. phosphoric acid per ton of 2000 pounds $34.00 Passing now to the manufacture of JiigJi-f/rafJe superphosphate by decomposing the mineral phosphates with this acid instead of with chamber sulphuric acid, we shall find that it works out thus: 1 ton mineral phosphate, containing seventy-five to eighty per cent, tribasic phosphate, and of about the general composition shown in the examples selected for former calculations will cost $14.50 Grinding same to 70 or 80 mesh " 1.50 1 ton phosphoric acid of 45° B " 84.00 Cost of mixing, manipulating, drying, pulverizing and bagging the finished material, calculated at $2 per ton of material used 5.00 $55.00 The net product of the mixture after allowing fifteen per cent, for loss, by evaporation and in manufact- ure, will be, say, thirty-four Jiundred pounds. It will contain //fee« hundred and thirty j)ounds of phosphoric anhydride (PgOj) and costs $55.00 Its cost per ton, ready for market, and containing forty- five per cent, of mixed tvater-soluhle and citrate- soluble jihoHphoric anliydride will tlierefore be $32.50 Or a little over 3.^ cents per pound of phosphoric anhydride. 134 The Phosphates of America. Since, as we have already explained, the great bulk of our super- phosphate is not made to contain more than from twelve to four- teen per cent, of phosphoric acid soluble in water and ammonium citrate, and since it, for this reason, only represents on an average the equivalent of thirty 2^er cent, of bone jyhosphate of lime made solu- ble, it necessarily follows that more than three tons of it would be required to equal one ton of the concentrated or high-grade ma- terial. The latter contains the equivalent of ninety-nine per cent. of bone phosphate of lime, made practically as soluble and equally available, and is therefore, as we have said, specially adapted to the requirements of the middleman. The distributer Mould onl}- pay freight on one ton where he now pays it on three, and could, if he so desired, dilute it down to the ordinary commercial strength by the addition of gypsum, or any other convenient and low-priced tiller. A fruitful subject for angry discussion and costly litigation has been that bearing on the noxious vapors evolved during the manu- facture of fertilizers from any of the phosphates we have described. It has been urged, and, to our minds, very consistently, that we should apply to them the same methods so successfully used in suppressing the devastating fumes from other chemical works, and there cannot be a doubt that if this were done, the present menace to the health and comfort of the workmen, and others employed in and about the neighborhood, would disappear. As we have already pointed out, the fumes of fertilizer fac- tories chiefly consist of carbonic acid, hydrofluoric acid, silicic tetrafluoride, sulphuric acid and steam ; and of all these, the most dangerous to life and health are the compounds generated by the liberation of fluorine from the fluoride of calcium, the average pro- portion of which in our phosphates may be safely taken at about three per cent. The quantity of deadly vapor thus becomes very large in some of our big works, but it need not necessarily be alarm- ing provided the gas-flues be properly Avorked. A ventilatiug-fan woiild easily conduct it all into the scrubber, where, meeting with a fine spray of very cold water, it would immediately be decomposed, hydrofluosilicic acid and gelatinous silica being formed. The acid could either be washed aM'ay into the main sewers or passed off into an open drain, and the finely divided silica could be allowed to de- posit itself on the bottom of the condenser. Mr. John jVIorrison, an English chemical engineer of great abil- ity, who has done a great deal of valuable work in this connection TJie Phosphates of America. 135 and devised the very practical scrubbing apparatus shown in the annexed sketch, says that the mixer fumes possess within them- selves every element needed for their speedy destruction and but a single element (heat) to in any Avay retard it ; and this is quite 5 3 true. He objects, therefore, to the introduction of steam, on the ground that with every ton of superphosphate produced at least five per cent, of water in the form of steam is evolved, and as such a quantity is quite sufficient to saturate the effluent gases it is use- less to employ any more. "While a steam-jet will aid the draught ; augment the agitation of the gases ; and hasten the purification of 136 Tlie Pliospliates of America. an atmosphere thickly laden Avith noxious vapors, it is nevertheless^ demonstrable that to the extent of the heat liberated in its own condensation, it retards the perfect filtration of the residual vapors, and any benefit accruing from its introduction is wholly disprojior- tionate either to its quantity or its expense. The most important point is to cool the gases by draughtage into chambers or flues of sufficient area or length, and where this can be managed economically little more is required, for the fume will quietly subside of itself. In the majority of cases, however, a maximum of condensing work must be accomplished in a minimum of space, and here the better way is to submit the gases to a sort of dry-scrubbing process so as to hasten the deposition of tlie fluorine compounds. How this is to be done must depend upon the sjjecial circumstances in each particular case, but there sliould al- ways be provided, within a suitable flue, a sufficient number of im- pinging or baffling diaphragms, to momentarily arrest the motion of the gases and divert them into another direction, it being found that the greatest deposition of silica takes place at these eddying points. The great bulk of the solid matter being thus early arrested, only the residual vapors now remain to be dealt with, and these are caused to traverse, in an upward direction, one or more Avater tow- ers or wet scrubbers, simply packed with Avood spars, to pass aAvay to the chimney. The necessary draught is created by an exhaust-fan of special construction actuated by the mixer engine. It is best fixed be- tween the towers and the chimney, and its power is controlled by a damper just sufficiently to secure a slight " j)ull in " at the mixer mouth. The den doors are, of course, made as tight as possible to avoid unnecessary dilution of the gases and interference Avith the efficiency of the fan. Gas dilution means reduced condensing efficiency. Yet there have been hosts of failures, due to a total misapprehension of the necessities of the case, and to the impracticable construction or Avholly insufficient capacity of the condensing plant. In the erec- tion of the latter two things have to be constantly borne in mind : First, that the evolution of the gas is spasmodic and (especially in the case of hot vitriol) extremely violent Avhen the spasm is on ; and, second, that every chokable part of the apj)aratus must admit of the readiest possible access. To provide for the first of these, the plant has to be of ample dimensions, and unless the second be The Phosphates of America. 137 remembered, the most annoying failures will ensue at most incon- venient seasons. Where such failures involve stoppages they are fatal to every semblance of manufacturing economy, since every unnecessary reduction in the day's dissolving tonnage, adds to the cost and diminishes the profits. The wet scrubbers are packed with wood spars for two reasons: First, because spars exert no thrust on the tower sides and so save the necessity of tie-rods ; and, secondly, because they seem to afford a maximum of interstitial, or scrubbing surface, to a minimum of solidity. The fire-brick packing sometimes adopted is less eco- nomical, for it not only largely augments the dead-weight of the towers, but decreases the ratio of useful surface to solid material by its pigeon-hole overlap. The spars are made of wedged section, in order to delay the choking of the towers, both by affording extra space for the deposit of silica, and by facilitating its detachment and convey- ance to the tower base by the action of the water. Silica depos- ited on the sides of square-sectioned spars, clogs the tower by reducing the packing spaces, whereas on wedged-section spars, a considerable deposit can take place without at all affecting the packing- mesh. Where economy of water is an object one tall tower is prefer- able to two or three shorter ones, but the best arrangement is a tower of moderate height, divided into two packed upcasts, with a downcast flue between Tlie Pliosphates of America. CHAPTER YIII. SELECTED METHODS OF PHOSPHATE ANALYSIS AND GENER- ALLY USEFUL LABORATORY DETAILS. The world's consumption of mineral phosphates and superphos- phates from all sources, amounts to several million tons a year. The commercial value, alike of these natural and artificial products, depends upon their percentage of phosphoric acid, and upon their freedom from certain undesirable or injurious constituents as re- V e aled by chemical analysis. The miner, the manufacturer, and the farmer, are hence equally dependent upon the analytical chemist, whose jjrovince it is to determine how much the two first shall receive, and how much the last shall pay for the merchandise. The responsibility is a heavy one for the analyst, and he must either justify it or bring a great deal of discredit upon his profession. We know that chemistry is the most precise of the sciences. It is not only capable of producing exact results, but it can fore- tell Avith unerring certainty, even before an operation is commenced, what those results will be. Complete concordance in phosphate analysis should consequently be " a thing of course," and a dozen chemists in as many different parts of the globe have no right to differ in the second decimal in their findings on the same sample. An average error of no greater importance than say one unit of phosphate of lime, worth 20 cents, would entail, when spread over a total year's consumption of raw material, a cash difference of iibout 1300,000. This difference, of course, constitutes a loss, which is sometimes borne by the miners who sell, and sometimes by the manufacturers who buy. We have seen that in certain cases where superphosphates are sold on the basis of their water-soluble phosphoric acid, iron and alumina phosphates as a raw matei-ial, have no commercial value. Any widely differing results obtained bj'' chemists in their deter- minations of these bodies in shipments of mineral jjhosphates, therefore, may cause infinite trouble between miners and manu- facturers. At the jsresent time there prevails between the contracting The Phosphates of America. 139 parties, what appears upon its face to be an equitable arrangement in this connection. The market price of the phosphate rock is fixed at a certain sum per unit of phosphate of lime, and it is agreed that this rock may contain a certain amount of oxides of iron and alumina without affecting its price. This tolerated amoinit, how- ever, must not exceed three per cent, by weight of the mass, and every additional per cent, of oxides of iron and alumina is to be compen- sated for by a proportionate deduction from the total quantity of phosphate of lime. To justify such a deduction, it is necessary to remember that in the initial stage of superphosjjhate manufacture, a great deal of free phosphoric acid is produced, which, in the presence of oxides of iron and alumina, enters into combination with them to form phosphates in the following proportions : Oxide of iron to phosphoric anhydride 1 : 0,88 Oxide of alumina to phosphoric anhydride 1 : 1,37 Ratio of the equally combined oxides to the acid 1 : 1,13 It follows from this that every per cent, of these equally combined oxides causes 1.13 per cent, of jihosj^horic anhydride (P2O5) to become insoluble in water. Where "reverted" phos- phates are valueless, therefore, the European manufacturer is jus- tified in declining to })ay for what will bring him no return for his money . A working example of this arrangement may serve to make it more clear, and will specially emphasize the necessity for conformity of analysis between shipper and consignee. We give an instance which actually turned out as follows : A cargo of phospliate rock was shipped from one of our ports to Liverjjool, in fulfilment of a contract, embodying the above arrangement in regard to iron and alumina, and fixing the price of the material at 25 cents per unit of phosphate of lime. The analysis of the cargo (1000 tons) by the chemists at the ports of shipment, and arrival, resj^ectively, showed the following variations: Shipment. Arrival. Phosphate of lime 78.30 77.10 Oxides of iron and alumina (combined) 2.95 5.01 These results were contested by the shippers, and the sealed samples, taken and reserved at both ports, were handed to four 140 The Fhosphates of America. reputable chemists. Two of these were in New York and two in London, and the following were the results of their work: New York chemist No. 1 New York chemist No. 2 London chemist No. 1 London chemist No. 2 SHIPPING SAMPLE. ARRIVAL SAMPLE. Phosphate of Lime. Oxides of Iron and Alumina. Phosphate of Lime. Oxides of Iron and Alumina. 77.80 77.40 78.01 77.25 3.70 4.01 3.95 4.15 76.95 77.30 76.80 77.15 4.86 4.22 4.90 5.12 These figures were, of course, unsatisfactory in themselves, but they made it clear that the greatest error had been made, in the first instance, by the shippers' chemist, and it was consequently arranged that the cargo should be paid for on the averages of the three English chemists, which Avere : Phosphate of hme 77 per cent. Oxides of iron and alumina 5 " The original invoices had been made out by the shippers on the basis of their own analysis at the price of $19.25 per ton, but the final settlement stood thus : Oxides of iron and alumina found by analysis 5 per cent. " ** " allowed by contract 3 " " " " to be paid for by sellers . 2 " 1 : 1,13 : : 2 : 2.26 phosphoric anhydride. The factor for converting phosphoric anhydride (P2O5) into phosphate of lime is 2.18 — consequently 2.26 X 2.18 = 4.92 phos- phate of lime. SETTLEMENT OF INVOICE. Phosphate of lime found by analysis Deduct the equivalent of two per cent, iron and alumina as above Total phosphate to be paid for at 25 c. per unit. . . Value of the phosphate per ton, $18. 77 per cent. 4.92 " r2.08 The difference between the amount of the original invoice and that of the settlement Avas therefore $1250. How are we to account for these divergencies ? Must they be put down to carelessness, incapacity, inexperience, bad faith, or must TJie Phosphates of America. 141 we attribute them, as we have already suggested, to the faulty methods of sampling at either or both ends, and to the lack of a uniform method by which all chemists should agree to work? The first four factors perhaps require to be counted with, but there is no doubt in our minds that the two last are the real causes of the trouble, and we have long endeavored to bring about an agreement that would go far in causing them to diminish or dis- appear. If chemists were not human, or if they were entirely superior to petty prejudices, an entente cordiale might not be very difficult. Unfortunately, however, every individual is prone to regard his own work as irreproachable, and from that very fact to look upon any outside suggestions of modification as presumptuous and unnecessary. In a former chapter we pointed out the advi- sabilitv of chemists cominsr toccether and arrivinsr at a definite understanding, but if all hope of this is to be finally abandoned as impracticable, there is still one way open by which to establish and enforce a method that shall alone be used in the settlement of phosphate affairs. The mine-owners must act in unison and fix their own basis for sampling, analyzing and valuation. There is no reason why the interests of the manufacturer should differ from those of the producer. If phosphate of lime in the required form be worth a certain price per unit, why should a door be left open to chicanery when the time comes to pay for it ? Why should there be any material difference between the shippers' and the buyers' samples, if both are faithfully taken according to prescribed rules and with a proper regard for the true interests of each party to the contract ? Whatever method of analysis be chosen, it must be accom- panied by comj^lete details of laboratory manipulation. The observ- ance of these details should be insisted upon, and must be com- municated to all the various chemical and industrial societies in order that they may be expeditiously and officially brought before analytical chemists all over the world. All contracts between miners and manufacturers should contain a si)ecial clause specify- ing that "The phosjihate sold under this contract shall be paid for at the rate of per unit and per ton of phosphate of lime, and shall not contain more than a maximum of per cent, of iron and alumina, calculated as oxides, on the dry basis. Every unit of these oxides, singly or combined, in excess of the maximum, shall be deemed to neutralize two units of the phosphate of lime, and 142 IIlb Phospliates of America. such excess shall therefore be deducted from the total phosjihate of lime found in the results of chemical analysis. "This chemical analysis shall be made in duplicate, from the same sample, by two chemists, one rej^resenting the buyer and the other the seller, and it shall be performed in strict accordance with the method, in all its details, hereunder sot forth. If the two analyses only exhibit on their face a maximum difference equalling one per cent, of phosphate of lime, such difference shall be adjusted by taking the mean of the two results ; but in case the difference should exceed this maximum, a third analysis shall be made by another chemist, to be mutually agreed upon by the contracting parties, and the settlement shall then and there take place upon the basis of an average between the results of this third analysis and those of that one of the other two first chemists which was nearest to its figures." EXAMPLE. Phosphate of Oxides of Iron and Lime. Alumina. Chemist No. 1 finds 78.20 .2.85 " 2 " 76.30 2.70 " " 3 " 77.40 3.00 Average of Nos. 1 and 3 77.80 2.92 To strengthen these preliminary suggestions we will now set forth what we regard as the best and the most practical methods of sampling and analysis. These methods are being constantly employed in our own work, and Avhile we claim no originality for them, they have stood the test of our experience in many fields and on every variety of material with perfect satisfaction. SAMPLIXG. As this work is generally undertaken rather by practical working- men than by analytical chemists, it is deemed advisable to point out, in the plainest possible way, the easiest, most effective and accurate method of conducting it. Nor need we dwell upon the importance of this operation and the necessity for its being carefully super- vised by all capable managers, for we have already shown that enor- mous losses have continually been made and must ever surely result from ignoring or disregarding details. When the phosphates are sampled upon the mine for the con- trol of the daily Avork, it is necessary to take them from the piles. The latter are therefore very carefully gone over, and averages are The Phosphates of America. 14^ Kelected from their every part aiul placed aside until, in the opinion of the sampler, a sufficient quantity has been amassed to make it representative. The big lumps are then all broken uj) "with a hammer, and the entire material is spread out upon the surface of a level floor, well mixed iip, and passed through a crusher to reduce all the lumps to a small uniform size. It is then again spread upon the floor, shovelled up in a circular direction into a cone-like heap and then once more spread out flat. About a fourth part is next separated from the whole by taking out with a spade two strips crossed at right angles, and adding a small por- tion from each remaining quadrant. This fourth is made to go through the same process of spreading, heaping and dividing into fourths until the last operation leaves no more than about five pounds, Avhich, after thorough mixing on a table, is ground to an impalpably fine powder, emptied into wide-mouthed bottles, ,well corked, securely sealed and labelled. When the sampling takes place either at the port of shipment or discharge, it must not be lost sight of that the result is to form the basis of the price per ton Avhich the miner is to realize for his cargo. It has, therefore, to be performed in the presence of trusted and reliable representatives of both seller and buyer. If the loading and unloading is done by means of buckets, every twentieth bucket of the whole cargo is set aside. The entire sample is then passed through a stone-crusher in order to reduce all the lumps to a very small size, and is then spread out upon a level floor and tossed up into a heap and treated in the same general way as described for the smaller sample at the mines. "When it has been reduced, however, in the present case, to about five tons, it is taken to a mill, ground to a fineness of 80 mesh, and filled into bags of 200 pounds capacity, which are securely tied and placed in a row. Each one of these fifty sacks is then sampled at both ends by means of a sharp-pointed augur, 18 inches long and 1^ inches diameter, Avhich is first plunged into the top and then into the bottom for its entire length, being emptied of its con- tents into a large tin plate by giving it a tap on the side after each operation. When all the sacks have been sampled in this way, the powder is thoroughly mixed by passing it through a sieve twice or even three times, and is then divided into three equal parts, each of which is put in a wide-mouthed glass bottle and sealed with the seal of both parties to the contract. One of these sam- ples is handed over to some public officer, or other party mutually 144 T]ie Phosphates of America. agreed upon for safe-keeping in case of dispute ; the other two are taken, one by each of the contracting parties, for the purposes of analysis. ANALYSIS OF MINERAL PHOSPHATES APATITE, PHOSPHORITE, COPROLITE, ETC. The sample must bear the date upon which it was drawn, and must in every case be representative of the bulk. It must be clearly labelled with all particulars as to its origin and destination, includ- ing the name of the vessel or the number of the railroad car. When drawn as a working sample of the mine it must bear the mention ^'average scoitple froui Mine No drawn by from piles No representing tons." All these details are entered in the laboratory journal, and this having been done, the entire sample to be analyzed is first made to pass through a screen of 80 mesh by the analyst. The following determinations are then proceeded with : Moisture. Water of combination and organic matter. Carbonic anhydride (CO 3). Insoluble siliceous matters. Phosphoric anhydride (PgOg). Sulphuric anhydride (SO 3). Fluorine (Fl). Lime (CaO). Magnesia (]\IgO). . Iron and alumina as oxides (combined). Moisture. Two grammes of the substance are very carefully weighed in accurately tared and well-ground watch-glasses. The latter are then adjusted Avith the clip so as to leave a sufficient opening for the passage of steam, and are placed in the gas-oven at 110° C. At the end of three hours the glasses are taken out, closed tightly, placed in the desiccator until quite cold, and then brought upon the scale. The diiference between the present and the original weight -^ 2 = moisture in one gramme of the material. Water of Combination and Organic Matter. The residue from the moisture determination is carefully brushed into an accurately-tared platinum crucible. The crucible is placed The Phosphates of America. 145 over a small Biinsen flame for ten minutes, and is then brought to.i while heat by means of the blast. After being kejit at this high temperature for five minutes the flame is removed, the crucible is covered ; placed in the desiccator ; and allowed to become quite cold. It is then weighed, and the difference betw-een the present Aveight and that of the residue from the moisture deter- mination -^ 2 rej)resents the " loss on ignition " in one gramme of the material. The total of this loss on ignition includes water of combination, organic matter, and carbonic anhydride, and as the latter is to be determined separately, its Aveight Avhen found must be deducted from this total. Carbonic Anhydride (COj). This is one of the most essential of the determinations, and should be made in every sample destined for factory use. There are numerous excellent methods of j^ei'forming it, but the two most commonly used in our laboratory are those of Scheibler and Schrotter. The first-named is based upon the principle that the quantity of carbonic anhj'dride contained in pure chalk can be used as a measure of the quantity of that salt itself. Instead of estimat- ing the carbonic-acid gas by Aveight, therefore, this method allows of its estimation by volume, and Avhen skilfully handled it yields very rapid and very accurate results. The second is a far simpler, and in our experience equally expeditious, method, and our students consequently take more readily to it than to the other. It only re- quires ordinary care in its manipulation to give jjerfect satisfac- tion. A mere glance at the figure Avill suffice to shoAV that the appa- ratus is made of bloAvn glass, and that its principle depends upon the loss of weight Avhich occurs in a carbonate Avhen its carbonic- acid gas is expelled. Two grammes of the original substance are accurately weighed and introduced into A. The tube B is noAV filled with fifty per cent, hydrochloric acid and the tube C about a quarter filled with concentrated sulphuric acid. All the stoj^-cocks have meantime been kept closed, and the apparatus is now brought upon the scale and very accurately Aveighed. The Aveight being noted in the agenda it is withdraAvn from the scale, the stop-cock on tube B is gradually opened and the hydrochloric acid thus allowed to come into contact with the phosphate. When all the acid is in, the tap 146 T]i,e PlMspUates of America. is closed and the apparatus is allowed to stand in a warm place (say at 80° C.) for two hours with occasional agitation. The carbonic-acid gas passes off through C, the suljjhuric acid, however, preventing the escape of any moisture that might otherwise ac- company it. At the end of two hours B is opened, and the air SCHRotter's appaeatus for the estimation of carboxic-acid gas. is drawn through the apparatus Ly suction applied to a piece of thin India-rubber tubing connected with I) in order to sweep out all traces of the COg. B is then closed and the apparatus is allowed to become quite cold, when it is brought back to the scale and weighed. The difference between the jiresent and the first weight -^ 2 represents the COg in one gramme of the normal sample. The Phr).<:p]uitcs of America. 147 EXAMPLE. Weight of the carefully dried " Schrotter " charged with "1 Two grammes Phosphate in A I Diluted HCl in B j" ^^'^^^ Concentrated HoSO^ in C j Weight of the carefully dried apparatus at the end of two » ,'JOO hours, after the prescribed manipulation. [33..: Loss in weight by 2 grammes phosphate 0.087 Equal 0.0435 in 1 gramme, or 4.35 per cent. Insoluble Siliceous Matters. Five grammes of the original sample in its normal state are accu- rately weighed out and placed in a porcelain dish Avitli about 30 c.c. of aqua regia. The dish is placed upon a sand or air bath, cov- ered with an inverted funnel, gradually heated, and evaporated to dryness ; care being taken to avoid any spurting and consequent loss. As soon as it is dry, the residue is moistened Avith j)ure con- centrated hydrochloric acid, and again evaporated to complete dry- ness, after which the beat of the bath is increased to 125° C. and so maintained for about ten minutes. When it has become cool the silica will all be insoluble, and the residue is treated with 50 c.c. of concentrated hydrochloric acid and allowed to remain in this contact for fifteen minutes. The acid is then diluted, filtered through an ashless filter, and the porcelain dish and the filter care- fully washed with hot water until the filtrate measures 250 c.c. The residue on the filter, which should be quite white, is now dried in the oven, calcined and weighed. The weight -1- 5 = insoluble siliceous matter in 1 gramme of the material. Sulphuric Anhydride (SO 3). Twenty-five c.c. of the filtrate from the siliceous matter, repre- senting 0.50 gramme of the jjliosjibate, are placed in a beaker, boiled, and treated while boiling with 5 c.c. of a saturated solution of barium chloride. The hot liquid is brought upon a small ash- less filter ; the beaker and the filter are well washed Avith boiling water until the last washings shoM' wo trace of chlorides ; and the filter is then dried, calcined and weighed. The weight X .3429 X 2 = sulphuric aidiydride (SO3) in 1 gramme of the material. N.B. — The words "ashless filter" are used on this, and on all subsequent occasions, only in a comparative sense, and are meant to indicate the round cut filters, washed in hydrochloric and 148 The rito^jiliates of America. hydrofluoric acids manufactured by Messrs. Schleicher recipitate, consisting of phosphate, fluoride and some carbonate of lime, is washed several times by decantation with boiling water, collected on an ashless filter, dried and calcined. After being allowed to cool, the residue is treated with acetic acid and evaporated to dryness on the water-bath in order to trans- form the carbonate of lime into acetate of lime. The acetate is next well washed out with boiling water several times, and the final residue is brought on an ashless filter, dried, calcined and weighed. This time, the weight represents only the phosphate and fluoride of lime contained in the five grammes of the original sample. After taking due note of this weight, the residue is returned to the platinum dish, 5 c.c. of concentrated sulphuric acid are added to it, heat is applied, and the fluorine is all driven off. "When no more fumes are evolved, the source of heat is removed, the resi- due in the dish is treated with 100 c.c. alcohol, filtered and washed with alcohol up to 200 c.c. The alcoholic filtrate contains the phosphoric acid, and this is precipitated as ammonio-magnesium phosphate. The precipitate 150 The Pliosjyliates of America. is washed, dried, calcined and weighed as Mg^PgO;, every j^art of wliich X .1390 = phosphate of lime (CayP-jO^). We now refer to our note-book to find tlie weight of the com- bined 2>hosj)hate and fluoride of lime contained in the five grammes of the original sample asdetermined after the acetic-acid treatment,and by means of this weight we now make the following calculation ; EXAMPLE (TAKEN AT RANDOM FROM OCR AGENDA). Weight of the residue of combined phosphate and fluoride of lime in 5 grammes of the sample 3.900 Weight of the phospiiate of lime calculated fromi MggPgOy . 3.775 Fluoride of lime, by difference in 5 grammes 0.125 Therefore 5 : .125 : : 100 : x = 2.50 per cent, fluoride of lime, which X .4897 = 1.22 per cent, fluorine. Oxides of Iron and Alumina. This highly-important determination is the object of much con- troversy, and may be roughly said to be the jjivot upon which revolves very nearly every difference in the phosphate analyses of various chemists. A large number of schemes have been devised and experimented Avith, but only very few of them have proved worthy of general application. The chief jjoints reqi;ired of a method for practical work ai'e : that it should be accurate, that it should be easy and rapid, and finally, that it should be economical. All these we believe to be embodied in the following plan, which, when carried out with care and exactly as we shall describe it, produces constant and strictly concordant results. AVhen left to our own choice we have always preferred it to any other for our own work, and many of our pupils and former assistants who haive left us and are now emj^loyed either at phosphate mines or at fertilizer works throughout the country, continue to exactly accord in results Avitb our laboratory. We consider this to be a great point in its favor, and it is in fact the one Avhich mainly j^rompts us to so strongly recommend its general adoption. Fifty c.c. of the filti'ate from the siliceous matter, equalling one gramme of the j^hosphate, are placed in a beaker and made alkaline with ammonia. The resulting precipitate is redissolved by the addition of just sufficient hydrochloric acid, and the liquid is then again made alkaline with ammonia in very slight excess. Fifty c.c. of concen- trated and pure acetic acid are now added ; the mixture is stirred, Hie Pliosphatcs of America. 151 and allowed to stand in a cool place \mtil perfecthj cold. It is then tillered on an ashless tilter and the Leaker and residue are carefully washed twice with boiling water. The flask containing the filtrate is then removed from beneath the funnel and replaced by the beaker in which the first precipitation was made. The substance on the filter is now carefully dissolved in a little hot, fifty-per-cent. solution of hydrochloric acid, and the filter is washed twice with hot water. The filtrate in the beaker is next made alkaline with ammonia in slight excess ; then made strongly acid with pure con- centrated acetic acid ; well stirred up, and again alloAved to stand until absolutely cold. The flask containing the first filtrate is now replaced under the funnel, the liquid in the beaker is filtered into it, the filter is washed twice with cold Avater containing a little acetic acid, and then three times with boiling distilled Avater. The funnel containing the filter is now placed in the oven and com- completely dried, after which the filter and its contents are cal- cined, and weighed as phosphates of iron, and alumina in, one f/ramme of the material. For all the general purposes of the factory, or for the control of daily work at the mines, it is only necessary to divide the figure thus found by 2, and to state the result roughly as "oxides of iron and alumina (combined)." As we have given our reasons for this proceeding in an earlier jiart of this chapter, it is not necessary to repeat them, and we will con- tent ourselves with a mere example. The weight of the combined phosphates in one gramme was .058 ; then .058 -f- 2 = .020 = 2.^0 per cent, oxides of iron and alumina When reporting upon a sample for commercial pur])oses that is to say, when determining its value to the manufacturer of water-soluble superphosphates, it is sometimes necessary to carry this analysis a little further. In such cases, after carefully noting the accurate weight of the combined phosphates, they are dissolved in boiling hydrochloric acid. The solution is filtered into a 100-c.c. flask and Avashed uj) to the mark with boiling Avater. No residue should remain on the filter save perhaps a speck or two of carbon resulting from the recent incineration. In one half of the filtrate, the phosphoric anhydride is determined by the molyb- date method already described. The resulting MgaPgOj X .6396 X 2 equals the P-.O.^ in one gramme of the combijied i)hosphates. The remaining half of the filtrate is boiled Avith a small piece of zinc in a flask fitted with a Bunsen valve. When the iron is com- pletely reduced and gives no trace of pink coloration Avith pot as- 152 Tlie Phosphates of America. sium siilphocyanate, the liquid is cooled, about one gramme of mag- nesium sulphate is dissolved in it, and it is then titrated with -^^ N, permanganate solution, every c.c. of which = .00080 ferric oxide. The number of c.c. used X 2 will represent the amount of iron oxide contained in one gramme of the above phosphates. Two out of the three constituents being thus accurately known, the third, which is the alumina, can easily be determined by difference, as for example : Weight of the combined phosphates of iron and alumina. . .058 Phosphoric anhydride determined in the above 031 Iron oxide (Fe.,03) " " , 010 .041 Oxide of alumina (by difference) 017 In reporting upon the sample we should therefore state the presence of Oxide of iron , 1.00 per cent. Oxide of alumina 1.70 " Weight of these oxides combined 2.70 " instead of the 2.90 per cent, which were obtained by merely divid- ing the combined phosphates by 2. The only other method of determining the j^ercentage of iron and alumina which has been used in our laboratory with satis- factory results, was recently adopted at the request of clients, and is generally known as the Glaser method, from its having been first suggested and described by a German chemist of that name (in Ztschr. Angew. Chem., 89, 636). The way in which we carry it out, differs somewhat from the first description by its author, and is as follows : Two and a half grammes of the phosphate are dissolved in 10 c.c. hydrochloric acid ; evaporated to dryness ; taken up again with hydrochloric acid, raised to boiling, and washed out into a 250-c.c. flask with as little water as possible. Ten c.c. concentrated sulphui'ic acid are now added, and the solution is alloAved to stand for five min- utes, with frequent shaking. After adding some ninety-five per cent, alcohol, the mixture is cooled, made up to the mark with alcohol, well shaken, and when the contraction in volume has taken place, is again made up to 250 c.c. and mixed. After standing one hour it is filtered, and 200 c.c. (= 2 grammes phosphate) are taken and gently Tlie Pliosphates of America. 153 evaporated to a small bulk. "NVben organic matter is present, it is desirable to evaporate to pastiness, tbat tbe acid may j)artially de- compose it. Tb(^ solution is now wasbed into a beaker witb about 50 to 100 c.c. water ; boiled for a sbort time with bromine or other oxidizing agent, as suggested by II. II. B. Shepherd (in Chem. N'eics, 63, 251) ; and, after adding ammonia, it is again boiled for about half an hour. It is then cooled, and, after the addition of a little more ammonia, is filtered ; Avashed with a hot solution of ammonium chloride to prevent the })recipitate from passing.through the filter ; ignited, and weighed. The phosphoric acid is determined by dissolving the ignited precipitate, exactly as we have described in the former method, and the oxides of iron and alumina are obtained by difference. If magnesia is present, the phosphates of iron and alumina obtained as above must be freed from this im- purity by washing the precipitate off tbe filter, and boiling with water and a little nitrate of ammonium. As we have already stated, our own preferences are in favor of the first method, and this, not only because Ave believe it to be per- fectly exact and reliable, Avhen in the hands of a skilful operator, but because it is much more rapid and much less costly. AVe, however, have no positive objections to the Glaser scheme, and when carried out on the above lines should have every confidence in the accuracy of its results. Lime (CaO). The total filtrates from the iron and alumina determination first described are mixed by shaking the flask, and are then concen- trated by boiling down to about 100 c.c. At this point there ai-e added to the liquid about 20 c.c. of a saturated solution of am- monium oxalate, and the mixture, after stirring, is withdrawn from the fire, covered with a Avatch-glass and allowed to stand for six hours. At the end of this time the supernatant fluid is filtered through an ashless filter ; the residue is Avashed three times by decantation Avith boiling Avater, and then brought upon the filter, and the beaker and filter are thoroughly Avashed at least three times more. The filter is then dried, taken from the funnel with the greatest care, placed in a tared platinum crucible, and ignited at a Ioav red heat for ten minutes. At the end of this time it is brought to the highest possible temperature by the blast, kept there for five minutes, covered, and then rapidly re- moved to the desiccator. When quite cold it is Aveighed in the 154 'Tlte Phosphates of America. covered crucible. The net weight = CaO in one gramme of the material. It is customary in our laboratory to ignite and weigh this residue three times, or until the two last weights are identical. Magnesia (MgO). The filtrates and all the washings from the lime determination, as above detailed, are Avell shaken together, and concentrated by boiling to about 100 c.c. After allowing the liquid to become quite cold, it is poured into a beaker, the flask carefully rinsed out into the same with distilled water, and the liquid made very strongly alkaline with ammonia. After Avell stirring, the mixture is covered Avitli a watch-glass and allowed to stand over night. The precipitate of ammonio- magnesium-phosphate is then carefully filtered through an ashless filtei', the beaker thoroughly washed out with dilute ammonia by means of a rubber-tipped rod, and the washings brought on the filter. The latter is then finally washed twice with the ammonia water, ^^laced in the drying-oven, calcined in a tared porcelain cru ible, at first at a very low, then at the highest obtainable heat, and weighed as MggPgOy. The weight X .360 = MgO in one gramme of the material. If all the foregoing determinations have been performed wdth the required care, the quantities found should add up to a total very closely approximating 100. Assuming that this is the case, we suggest that a reliable opinion may at once be formed for the manufacturer, as to the industrial value of any mineral 2)hosphate, by combining the various isolated bodies as follows : The magnesia is multiplied by 2.10. Result — carbonate of magnesia. The carbonic anhydride left over by the magnesia is multiplied by.. 2.37 " = cai-bonate of lime. The fluorine is multiphed by 2.05 " = fluoride of lime. The sulphuric acid is multiplied by 0.75 " = iron pyrites. The lime remaining afler satisfying the carbonic anhydride and fluorine is multiplied by 1.84 "J = phosphate of lime. The phosphoric acid, if any, remain- ing after this satisfaction of lime is multiplied by 2.00 " = phosphate of iron and alumina. If all the phosphoric acid be used \\\) by the lime available under this scheme, the iron and alumina maybe regarded as having Tlie Phosphates of America. . 155 existed in the form of silicates or clay, ami, as we Lave pointed out in the chapter on Fk)rida phosphates, our own experiments have very conclusively proved that in a majority of cases, thej' really do so exist. They would therefore be to a great extent unacted upon by the dilute chamber acid, used in the manufacture either of superphosphates or phosphoric acid. ANALYSIS OF SUPERPHOSPHATES. The sample should be well intermixed and properly prepared and passed through a sieve having circular perforations one-twenty- fifth of an inch in diameter, so that separate portions shall accurately represent the substance under examination, without loss or gain of moisture. Jfoistiire. Two grammes are accurately weighed into the watch-glasses and heated for five hours at 100° in a steam-bath. Water-soluble Phosphoric Anhydride. Five grammes are weighed oiTt into a small beaker ; washed by decantation four or five times with not more than from 20 to 25 c.c. of water, and then rubbed uj) in the beaker Avith a rubber-tipped rod to a homogeneous paste, and washed four or five times by decantation with from 20 to 25 cc. of water each time. These washings are all run through a 9-c.c. — No. 589 Schleicher and Schiiell — filter into a 500-c.c. flask. The residue is finally trans- ferred to the filter, and washed with water until the flask is filled up to the mark. The flask is now shaken, and 50 c.c, of the clear liquor, equal to ^ gramme of superphosphate, are transferred to a beaker, and treated with 150 c.c. of molybdic solution. The mixture is digested at 80° C. for one hour, filtered and washed with water. After testing the filtrate for VX>^ by renewed digestion and addition of more molybdic solution, the precipitate is dissolved on the filter with ammonia and hot Avater (as described in the anal- ysis of raw phosphate) and washed into a beaker to a bulk of not more than 100 c.c. It is nearly neutralized with hydrochloric acid, cooled, and magnesia mixture is added slowly from a burette (one drop per second), with vigorous stirring. After fifteen minutes ■iO c.c. of ammonia solution of density -95 are added, and the whole is allowed to stand for two hours. It is then fillcrcd on an ash- 156 77^6 Phosphates of America. less filtcM", washed as in the case of raw phospliates, dried, calcined in a porcelain crucible and weighed as INIggPaOj. The weight of the residue X .6396 x 3 = the tiHiter-soluhle pJioKphorir anhydride in one gramme of the superphosphate. Citrate-insoluble Phosphoric Anhydride. The residue from the treatment with Avater is washed into a 200-c.c. flask, with 100 c.c. of strictly neutral ammonium citrate solution of density 1.09. The flask is securely corked and placed in a water-bath, the water of which stands at 65° C (The water- bath should be of such a size that the introduction of the cold flask may not cause a reduction of the temperature of the bath of more than 2° C.) The temperature of 65° C. is maintained for thirty minutes, with vigorous shaking of the flask every five minutes. The warm solu- tion in the flask is then filtered quickly and washed with water of ordinary temperature. The filter is transferred, Avith its contents, to a capsule, and ignited until the organic matter is destroyed. It is then treated with 10 to 15 c.c. of concentrated hydrochloric acid ; digested over a low flame until the phosphate is dissolved ; diluted to 200 c.c. mixed, and passed through a dry filter. One hundred c.c. of it are nearly neutralized with ammonia ; 10 grammes of ammonium nitrate are added ; the liquid is made quite warm and there are then added to it 150 c.c. molybdic solution. The process is completed exactly the same way as with raw phosphates. The weight of the MgoPgO^ X .6396 X 2 -^ 5 equals the citrate- insoluble phosphoric anhydride in one gramme of the substance. Total Phospho7'ic Anhydride. Two grammes of the superphosphate are weighed with great accuracy and treated in a porcelain capsule with 30 c;c. concen- trated hydrochloric acid. Heat is applied and there is added cau- tiously, and in small quantities at a time, about .5 gramme of finely-pulverized potassium chlorate. The mixture is gently boiled until all phosphates are dissolved and all organic matter destroyed, and is then diluted to 200 c.c, mixed and passed through a dry filter. Fifty c.c. of filtrate — equal to half a gramme of the superphosphate — are then taken and neutralized with ammonia, and about 15 grammes of dry am- monium nitrate are added. The solution is now made warm ; 150 c.c. molybdic solution are added, and thenceforward the process- is conducted exactly as in the case of raw phosphates. Tlie Pliosphates of America. 157 The weight of the Mg.PoO; x .0396 X 2 equals the total phos- phoric anh>/dride in one gramme of the substance. The three following determinations have now been made: 1. The P2O5 soluble in watev. 2. The P2O5 insoluble in ammonium citrate. 3. The total P2O5 contained in the substance. The figures obtained in the first two cases, added together and deducted from the last, will therefore show the amount of citrate- soluble phosj^horic acid in one gramme of the substance ; as for example : Total P0O5 in one gramme 0.160 gramme PgOj soluble in water 0. 140 PgOg insoluble in water and ammonium citrate . 0. 004— .144 " PgOj soluble in ammonium citrate 016 ' and the manner in Avhich Ave should state the result of such an analysis as this in our reports would be as follows : Moisture ? Water-soluble phosphoric anhj'dride (P0O5) 14.00 Citrate-soluble or assimilable phosphoric anhydride (PgOg). 1.60 Insoluble phosphoric anhj'dride (P2O5) 0.40 Equal to 34 per cent, of bone phosphate made soluble. THE VOLUMETRIC ESTIMATION OF PHOS- PHORIC ACID. While we have long discarded the use, in our commercial labor- atory, of all volumetric processes of determining phosphoric acid for commercial purposes, we nevertheless have always found the one that we shall now describe of considerable value in the factory. With a little practice it is possible to observe the end reaction with great accuracy, and 2)rovided not more than one per cent, of com- V)ined iron and alumina is present, the results are tolerably reli- able. The formulae for preparing the standard solutions required are given on another page, and the principle on which the method is based is the fact, that phosphoric anhydride and uranic oxide com- bine together to form a compound insoluble in acetic acid. P3O, + 2 Ur^O, = Ur.P/),. 142 + 576 = 718. 158 The riiosiiliates of America, It follows, therefore, that if a solution of phosphoric anhydride in acetic acid, be treated with a solution of iiranic acetate, the P2O5 is precipitated, and it has been found that the slightest excess of uranic acetate can be detected in the mixture, by bringing a drop of it into contact with a drop of freshly-prepared solution of potas- sium-ferrocyanide, and noting the reddish-brown color produced. The first step being to establish the accuracy of the solutions, 50 c.c. of the standard solution of sodic phosphate are run into a small beaker; made akaline with ammonia; and then distinctly acid with acetic acid. Five c.c. of the sodic-acetate solution are now run into the mixture with a pipette ; the beaker is brought over the flame of a Bunsen burner and the contents heated to about 70° C. When this point is attained the iiranic-acetate solution is run in very cautiously, drop by drop, from a burette, until a drop of the mixture in the beaker taken out and placed in contact with a drop of the ferrocyanide solution, on a white porcelain slab or plate, gives a slight, but yet distinct, reddish-brown color. When the necessary point has been attained — which generally requires two or three trials — the uranic solution is so arranged by dilution, or calculation, as to make 1 c.c. of it correspond to ex- actly 1 c.c. of the standard sodic-phosj^hate solution ; in other words, to .002 PgO.,. The accurate standardization being completed, the sample of mineral phosphate to be examined is now weighed out. One gramme is dissolved in nitric or hydrochloric acid in the usual way, and with the usual precautions is filtered and washed to about 200 c.c. Fifty c.c. (equal to .250 gramme phosphate) are now placed in a beaker, made alkaline with ammonia, then strongly acid with acetic acid and treated with 5 c.c. of sodium-acetate solution. The mixt- ure is then heated to 70° C, and at this temperature the uranium solution is run in, drop by drop, until the color reaction on the white plate is plainly visible. A second titration is made on an- other 50 c.c. of the solution of phosphate, and if the results are the same the ojjeration is ended. Every c.c. of the uranic-acetate solution used equals .002 gramme P2O5 in .250 gramme of the material. As will have been gathered from our opening remarks, the re- sults of this process, as we describe it, are seriously vitiated by tlie presence of more than one per cent, of iron and alumina. When, however, these two bodies arc present in any considerable amount there is a way out of the difficulty afforded by the fact The Phosphates of America. 159 that tliey will remain jJi'ecipitated in the acetic-acid solution as phosphates, especially in the presence of sodic acetate. When the liquid has become quite cold, therefore, the}' can be filtered off, washed, redissolved in hy-drochloric acid, treated again with ammonia and acetic acid, made cold, filtered, Avashed, dried, cal- cined and weighed as iron and alumina })hosphates. If the filtrates from these operations be mixed together and heated to 70° C, they may be titrated with uranic solution as usual, and the quantity of P2O5 found by titration, added to half the weight of the phosphates of iron and alumina, Avill give, very approximately, the total amount of phosphoric anhydride in the oricriual substance. ANALYSIS OF PYRITES FOR SULPHURIC -ACID MANUFACTURE. The sample is drawn from bulk in much the same manner as that described for tlie sampling of jjhosphates, and is ground to the fineness of 100 mesh, care being taken that every particle jiasses tlirough the screen. The requisite quantity, say eight ounces, is now put into a wide-mouthed bottle provided with a tight-fitting rubber stopper, and the analysis is proceeded with. The necessary determinations in the pyrites most ordinarily used in this country for acid manufacture are : Moisture. Siliceous matters. Sulphur. Iron. Copper. Moisture. One gramme of the sample is weighed between two tightly- ground watch-glasses of which the tare, including the clip, is accurately known. The necessary space to allow for evaporation having been adjusted, the glasses containing the powder are placed in the gas-oven and kept at 110° C. until no further loss of Aveight is observed. Three weighings shouM be made at intervals of about one hour. The difference between the original, and the final 160 TJie Pliosphates of America. weight of the pyrites, and watch-glasses, represents the moisture in the sample. Siliceous Matter and Silicates. One gramme of the original sample is treated with about 20 c.c. of a mixture of three vols, nitric acid (specific gravity 1.4) and one vol. strong hydrochloric acid, both ascei-tained to be absolutely free from sulphuric acid. All spurting is carefully avoided and heat is gently applied, and the mixture evaporated to dryness in a water-bath ; 5 c.c. of hydrochloric acid are now added, and once more evaporated (no nitrous fumes ought to escape now), and finally the dried residue is treated with a little concentrated hydrochloric acid and 100 c.c. of hot water and filtered through a small filter and washed with hot water. The insoluble residue on the filter is dried, ignited and weighed. It may contain besides silicic acid and silicates some sulphates of barium, lead and calcium, but these may be disregarded. Sulphur. The filtrate and washings from the last determination, are slightly saturated with ammonia, filtex'ed while hot, and washed on the filter with hot water, avoiding channels in the mass. Sufli- ciently dense, but yet rapidly-filtering paper, must be used, and choice made of funnels with an angle of exactly 60°, whose tube is not too wide, and is completely filled by the liquid running through. The washing is continued until the addition of a little BaCP to the last runnings shows no opalescence even after a few minutes. The filtrate and washings must not exceed 200 c.c, or if they do, they should be concentrated by evaporation. Pure HCl in very slight excess is now added ; the liquid is heated to boiling ; removed from the burner ; and treated with 40 c.c. of a ten-per-cent. solution of BaClg, previously heated to boiling. After precipitation the liquid is left to stand for half an hour, Avhen the precipitate should be completely settled. The clear portion is decanted through a filter, and the precipitate is washed with hot water by decantation three or four times, until the liquid loses all acid reaction. It should then be washed on to the filter, dried, ignited and weighed. Its weight X .1372 = sulphur in one gramme of the ore. Iron. The ferric hydrate, precipitated from the original solution in the sulphur determination, is dissolved in dilute sulphuric acid, Tlie Phosphates of Amei'ica. IGl warmed, and reduced Avith pure zinc until no coloration is produced when a drop of the liquid is brought into contact with a droj) of potassium-sulphocyanate solution. It is then cooled, and titrated with \ N j^erraanganate solution, until the faintest possible pink color remains constant for two minutes. Every c.c. of the permanganate employed = .0056 Fe in one gramme of the ore. Copper. Five grammes of the original sample are treated with concen- trated nitric acid, and evaporated to dryness. The residue is treated with concentrated sulphuric acid ; heated on a sand-bath till the free acid is all driven off ; and then cooled, treated Avith water, boiled, cooled again, finally treated with one-fourth its volume of alcohol, and allowed to stand for twelve hours and filtered. The residue on the filter is washed three times with a mixture of one part alcohol and two parts water, and the dilute filtrate is then saturated with hydrogen sulphide and allowed to stand for some hours. The precipitated sulphides are washed with a solution of IlgS ; dissolved in aqua regia ; neutralized with an excess of ammonia ; and made slightly acid again with hydrochloric acid. If not clear, the solution is then filtered, and the filter well washed until no longer acid. The solution is now boiled ard treated with 25 c.c. of a strong mixture, containing equal weights of potassium sulphocyanide and sodium bisulphite. The addition is made by degrees and with constant stirring, and, Avhen completed, the beaker is removed from the fire and allowed to stand until quite cold, when the white pre- cipitate of copper snh-sulphocyanide will have all gone down. The liquid is now filtered carefully through a double-tared filter, and the precipitate is Avell washed several times, first by decanta- tion with cold water in the beaker, and finally on the filter. The washing is complete Avhen all traces of chlorides have disappeared, and the precijjitate is then thoroughly dried in the gas-oven. When pierfectly dry it is weighed, the tare of the double filter is deducted from the weight, and the balance X '^-f-^ = Cu in one gramme of the ore. 162 The Pliospliates. of America. ANALYSIS OF BRIMSTONE. Moisture. In order to prevent the evaporation of moisture during grinding, an average sample of the unground or only roughly-crushed ma- terial weighing 100 grammes is dried at 100° C. for some hours in an oven or water-bath. Aslies. Ten grammes are burnt in a tared porcelain dish and the res- idue is weighed. Direct Estimation of Sulphur. Fifty grammes of the finely-ground brimstone are dissolved in 200 c.c. carbon bisuljihide, by digesting it in a stoppered bottle at the ordinary temperature, and the specific gravity of the liquid = s is estimated. This must be reduced to the specific gravity at 15° C. = S by means of the formula (valid up to 25° C.) S = s 4" 0.0014 (t — 15°). The following table gives for each value of S the percent- age in this solution, which number must be multiplied by 4 to in- dicate the percentage of sulphur in the sample of brimstone : Spec. % Spec. % Spec. % Spec. % Spec. % Spec. % Grav. S. Grav. S. Grav. S. Grav. S. Grav. S. Grav. S. 1.271 0 1.292 5.0 1.313 10.2 1.334 15.2 I.a55 20.4 1.376 28.1 1.2T2 0.2 1.293 5 3 1.314 10.4 1.335 15.4 1.3,56 20.6 1.377 28.5 1.273 0.4 1.294 5.6 1.315 10.6 1 .336 15.6 1.357 21.0 1.378 29.0 1.274 0.6 1.295 5.8 1.316 10.9 1.337 15.9 1 1..3.58 21.2 1.379 29.7 1.275 0.9 1.296 6.0 1.317 11.1 1.338 16.1 1.359 21.5 1.380 30.8 1.276 1.2 1.297 6.3 1.318 11.3 1.339 16.4 1.360 21.8 1.381 30.8 1.277 1.4 1.298 6.5 1.319 11.6 1.340 16.6 1.361 22.1 1.382 31.4 1 278 1.6 1.299 6.7 1.320 11.8 1.341 16.9 1.362 22.3 1.383 31.9 1.279 1.9 1.300 7.0 1.321 12.1 1.342 17.1 1.361 22.7 1.384 32.6 1.2bO 2.1 1.301 7.2 1.322 12.3 1.343 17.4 1.364 23.0 1.385 33.2 1.281 2.4 1.302 7.5 1.32-J 12.6 1.344 17.6 1.3&5 23.2 1.386 33.8 1.283 2.6 1.303 7.8 1.334 12.8 1.345 17.9 1.366 23.6 1.387 34.5 1.283 2.9 l.:i04 8.0 1.325 13.1 1.346 18.1 1.367 24.0 1.388 35.2 1.284 3.1 1.305 8.2 1.326 13.3 1.347 18.4 1.368 24.3 1.389 36.1 1.285 3.4 1.306 8.5 1.327 13.5 1.348 18 6 1.369 24.8 1.390 36.7 1.286 3.6 1.307 8 7 1.328 13.8 1.349 18.9 1.370 25.1 1.391 37.2 1.287 3.9 1.308 8.9 1.329 14.0 1.3.i0 19.0 1.371 25.6 (satur ated) 1.288 4.1 1.309 9.2 1.330 14.2 1.351 19.3 1.372 26.0 1.289 4.4 1.310 9.9 1.331 14.5 1.3.52 19 6 1.373 26.5 1.290 4.6 1.311 9.4 1.33i 14.7 1.353 19.9 1.374 26.9 1.291 4.8 1.312 9.7 1.333 15.0 l.a54 20.1 1.375 27.4 ESTIMATION OF SULPHURIC ACID. According to our experience, the amount of actual HjSO^ con- tained in a given bulk of chamber acid is best determined in the volumetric way as described by Lunge — i.e., by titrating a meas- ured volume of the acid with standard soda solution, using me- thyl orange as the indicator (.31 grammes pure sodium oxide in 1 litre distilled water, standardized with very accurate normal HCl.) The PJiosjyJiaies of America. 163 The results are always expressed in percentages of monoby- dratecl sulphuric acid (H2SO4) by weight. The specific gravity of the acid is taken with a hydrometer and called a*. Ten c.c. of the acid are then taken Avitli an accurate pipette and diluted to 100 c.c. Of this solution 10 c.c. are taken for titration, and, if the number of cubic centimetres of normal soda solution = 0.031 gramme XaoO per cubic centimetre consumed is called y, the percentage of the acid IS ^. RAPID ANALYSIS OF LIMESTONE OR CHALK. Insoluble. One gramme of the substance is dissolved in hydrochloric acid and the residue is filtered, washed, dried, and ignited. In the presence of appreciable quantities of organic substance the filter is Aveighed after drying at 100°, and afterwards ignited. The difference be- tween the first and second Aveights is taken as organic matter. l^ime. One gramme of the substance is dissolved in 25 c.c. normal hy- drochloric acid and titrated with normal alkali. The amount of alkali used is deducted from 25 and the remainder is multiplied by 2.8 to find the percentage of CaO, or by 5 to find that of CaCOj. If any magnesia be present it would be calculated as lime, and provided its amount be not very large, this is admissible in the manufacture of "supers" on the plan we have suggested. When, however, the magnesia exceeds, say two per cent., it can be separately estimated as follows, and the result deducted from the figure given above. Maff7iesia. Two grammes of the substance are dissolved in HCl ; the CaO is precipitated with NH3 and ammonium oxalate, and filtered with the usual precautions. The magnesia is precipitated in the filti-ate by sodium phosphate, filtered, washed with ammonia water, dried, ignited, and weighed as MggPzO^, which X .3603 = MgO. Iro)i. Two grammes of the substance are dissolved in IICl, reduced by zinc, and diluted. Some manganese solution free from iron is then added and the mixture is titrated with I N. ])ermanganate, of which each c.c. = .0080 FejOj. 164 The Phospliates of America. TABLE GIVING THE ATOMIC WEIGHT OF THE ELEMENTS ACCORDING TO THE LATEST DETERMINATIONS. Name. Aluminum. Antimony. . Arsenic Barium Beryllium. . Bismuth. . . Boron Bromine. . . Cadmium. . Caesium Calcium Carbon .... Chlorine. . . Cerium. Chromium. Cobalt Copper Didymium. Erbium. . . . Fluorine. . . Gold Hydrogen. . Indium Iodine , Iridium. . . . Iron Lanthanum Lead Lithium. . . Magnesium, Manganese. Mercury. . . Atomic Weij,'ht. 27. 122. 74. 136. 9. 210. 11. 79. 111. 133. 39. 11. 35. 141. 52. 58. 63. 147. 169, 19, 196, 1, 113, 126. 196, 55. 139. 206. 7, 23, 54. 199.; Name. Molybdenum Nickel Niobium. . . . Nitrogen. . . . Osmium Oxygen Palladium. . . Phosphorus. , Platinum. . . Potassium. . . Rhodium.. . . Rubidium Ruthenium . . Selenium. . . . Silicon Silver Sodium Strontium . . Sulphur Tantalum . . . Tellurium . . . Thallium. . . , Thorium. . . . Tin Titanium.. . . Tungsten. . . Uranium. . . . Vanadium. . , Yttrium Zinc Zirconium. . , Atomic Weight. 95.6 58.6 94.0 14.01 198.6 15.96 106.2 30.96 196.7 39.04 104.1 85.2 103.5 78.0 28.0 107.66 22.96 87.3 31.98 182.0 128.0 203.6 231.5 117.8 48.0 184.0 240.0 51.2 93.0 64.9 90.0 The Phosphates of America. 165 WEIGHTS AND MEASURES OF THE METRICAL SYSTEM. Weights. 1 milligramme = .001 gramme. 1 centigramme = .01 gramme. 1 decigramme = .1 gramme. 1 gramme = weight of a cubic centimetre of water at 4^ C. 1 decagramme = 10.000 grammes. 1 hectogramme = 100.000 grammes. 1 kilogramme = 1000.000 grammes. Measures of Capacity. 1 millilitre = 1 cubic centimetre, or the measure of 1 gramme of water. 1 centilitre = 10 cubic cent. 1 decilitre = 100 cubic cent. 1 litre — 1000 cubic cent. Measures of Length. 1 millimetre = .001 metre. i centimetre = .01 metre. 1 decimetre = .1 metre. 1 metre = the ten-millionth part of a quarter of the earth's meridian. STOCHIOMETRY, OR CHEMICAL CALCULATIONS. Conversion of Thermometer Degrees. °C. to 'R., multiply by 4 and divide by 5. "C. to °F., multiply by 9, divide by 5, then add 32. "R. to °C., multiply by 5 and divide by 4. °R. to "F., multiply by 9, divide by 4, then add 32. °F. to 'R., tirst subtract 32, then multiply by 4 and divide by 9. °F. to °C., first subtract 32, then multiply by 5 and divide by 9. To Find the Percentage Composition having the Formula Given. Find the molecular weight from the formula, then Molecular weight Weight of constituent in a molecule. 100 ~ Percentage of constituent. Or, proceed thus : Multiply the atomic weight of the element by 1, 2, 3, etc., according to the number of atoms of the element there are in the molecule ; multi- ply the number thus obtained by 100 and divide by the molecular weight. To Find the Weight of any Element Contained in any Given Weight of a Comi)ound Substance. Molecular weight Weight of constituent in a molecule. Given weight ~ Required weight. Or, multiply the atomic weight of the element by 1, 2. 3, etc., accord- ing to the number of atoms of the element there are in the molecule ; nmltiply the number thus obtained by the given weight and divide by the molecular weight. 1C6 The Fhosphaies of America. DETERMINATION OF THE SPECIFIC GRAVITY OF SOLIDS. Solids heavier than, and insoluble in, water. a. By weighing in air and water. „ (weight in air) ^ ' (loss of weight in water) h. By Nicholson's hydrometer. Let w-^ be the weight required to sink the instrument to the mark on the stem, tlie weight of the instrument being W ; to take the specific gra^^ty of any sohd substance, place a portion of it weigh- ing less than iv-^ in the upper pan, with such additional weight, say Wg, as will cause the instrument to sink to the zero-mark. The weight of the substance is then rvj —w^. Next transfer the sub- stance to the lower pan, and again adjust with weight ic^ to the zero-mark. Sp. gr. - —^ J?. Sp. , By the specific-gravity bottle (applicable to powders). Weigh the flask filled to the mark with water, then place the substance, of known weight in the flask, fill *o the mark with water and weigh again. (weight of substance in air) + (weight of flask and water) — (weight of flask and water and substance) (weight of substance in air) Solids lighter than, and insoluble in, water. The solid is weighted by a piece of lead of known specific gravity and weighed in water. c fy. _ (weight of substance in air) '*'*"" (weight of lead in water) - (weight of lead and substance in' water) + (weight of substance in air) Solids heavier than, and insoluble in, water. Proceed as in a, using instead of water some hquid without action on the solid. (weight of bulk of liquid equal to substance) = (weight of substance in air) — (weight of substance in liquid). (weight of bulk of liquid equal to substance) (weight of bulk of water ^ ^^^^ ^^_ ^^ ^^,^^^^^ equal to substance) = (sp. gr. of liquid) " ^ (weight of substance in air) Sp. gr. = (weight of bulk of water equal to substance) Tlie Phosphates of America. 167 NOTES OX STANDARD ACID, ALKALINE, AND OTHER SOLUTIONS, CALLED FOR IN THIS WORK. In the conduct of volumetric examinations, which are frequently extremely useful, expeditious and exact, it is essential that all "standard" solutions be prepared and employed as nearly as jios- sible at a constant temperature. This temperature should be that of the surrounding atmosphere, or as cool a place as may be avail- able in the laboratory, say 60° to 70° F. The liquids should be kept as clear as possible, and always shaken up just previous to being used. The indicator most commonly used in alkalimetry and kcidi- metry is tincture of litmus, Avhieh must be kept in open vessels, to avoid its being spoiled. When employing litmus, the liquid to be tested must be kept boiling for some time, in order to expel all COj ; and normal acid must be added as long as further boiling causes the color to change back from red to purple or blue. This takes a long time ; sometimes half an hour or even more. This time may be saved by replacing litmus by a very dilute solution of methyl-orange (sulphobenzene-azodimethyl-aniline) ; but in this case the liquids must never be hot, but of the ordinary temj^erature, and none but mineral acids may be employed. The cold solution of sodium carbonate is colored just perceptibly yellow by adding a drop or two of the solution of methyl-orange, preferably by means of a pipette ; if the color is too intense, it will on neutralization cause the transition into red to be less sharp. Methyl-orange is not acted upon in the least by CO,, and Avhen all NajCOj has been decomposed, the slightest excess of IICI causes the yellow to change suddenly and sharply into pink. The rule is, therefore, to run in the normal acid quickly and with constant agitation till the change of color has taken place. The opposite change of color from pink to faint yellow is just as sharp when titrating mineral acids Avith sodium hydrate or carbonate. The results are identical with those obtained by litmus, but, as we have said, they are obtained very much more quickly, and without heating the liquids. Other indicators in constant use are phenolphthalein and coral- line, of which it is always useful to have a small supply. NORMAL SODIUM CARBONATE. Dissolve 53 grammes of pure, dry monocarbonate, prepared by 168 The Phosphates of America. igniting the bicarbonate to redness, in water, and make up to one litre. NORMAL SULPHURIC ACID. Dilute about 30 c.c. of pure sulphuric acid (sp. gr. 1.840) to one litre ; then determine the strength of this solution by titration with normal sodium carbonate, and dilute so as to make one c.c. of the sulphuric acid neutralize one c.c. of the alkali ; after dilution check the strength by another titration. DECI-NORMAL OXALIC ACID. Dissolve 6.3 grammes of pure, recrystallized oxalic acid, dried between paper, in one litre of water. NORMAL HYDROCHLORIC ACID. Dilute 181 grammes of the pure acid, of sp. gr. 1.10, to one litre ; N check by titration with — silver solution or by sodium carbonate. •^ 10 NORMAL NITRIC ACID. Take some pure nitric acid and dilute to one litre. The strength of this solution must be ascertained, and the acid diluted accord- ingly. The most exact method of checking the nitric acid is by pure calcium carbonate, one gramme of which requires 20 c.c. of normal acid. NORMAL CAUSTIC ALKALI. Take about 42 grammes of ^j?/re sodium hydrate and dis- solve in 800 c.c. of water ; titrate with any normal acid, and dilute until it corresponds with the acid, volume for volume. Normal POTASSIUM HYDRATE may be made in a similar manner. normal AMMONIUM HYDRATE is made by diluting strong ammonia to the required strength, and checking by titration Avith normal acid. DECI-NORMAL SILVER NITRATE SOLUTION. Dissolve 10.8 grammes of pure silver in pure dilute nitric acid, heat gently, and when dissolved dilute to one litre. If a neutral solution is required, take 17 grammes of pure silver nitrate and dissolve in water to one litre. Of this solution The FhospJiaies of America. 169 1 c.c. = .01080 gramme Ag. " = .01700 " AgNos. " = .00355 " CI. " = .00585 " NaCl. DECI-XORMAL SODIUM CHLORIDK SOLUTION. Dissolve 5.85 grammes of pure sodium chloride, dried by gentle ignition, to one litre. 1 c.c. = .00585 gramme NaCl. " = .00355 " CI. " = .01080 " Ag. BARIUM CHLORIDE SOLUTION. Dissolve 122 grammes of barium chloride, dried between paper to one litre. 1 c.c. = .0490 gramme HaSO^. " = .0480 " SO^. " = .0400 " SOs. " = .1230 " BaClgiSHgO). " =: .1040 " BaCL,. «' = .0685 " Ba. STANDARD URANIUM SOLUTION. Take about 40 grammes of uranium acetate, dissolve in water ; add about 25 c.c. of glacial acetic acid, and make up to one litre. This solution is then titrated against the sodium phosphate and diluted until 50 c.c. are equivalent to 50 c.c. of the latter. 1 c.c. — .002 gramme P2O5. STANDARD SODIUM PHOSPHATE SOLUTION. Take 10.085 grammes of pure, crystallized, non-effloresced, di- sodiura hydrogen phosphate, dried between paper, and dissolve to one litre. Check this solution by evaporating 50 c.c. to dryness and igniting. The residue should weigh .1874 gramme. 50 c.c. = .1 gramme P^Og. SODIUM ACETATE SOLUTION. Dissolve. 100 grammes of the salt in water, add 100 cc. of pure acetic acid (sp. gr. 1.04), and dilute to one litre. E.xact quantities are not necessary. 170 Tlie Pliospliates oj America. MAGNESIA MIXTURE. Dissolve 110 grammes of dry crystallized magnesium chloride and 280 grammes of ammonium chloride in one litre of distilled water. Filter, add 700 c.c. liquor of ammonia of specific gravity .96 and shake. Allow to cool and then add sufficient distilled water to complete two litres, mix thoroughly and label. XEUTEAL AMMONIUM CITRATE SOLUTION. Mix 370 grammes of commercial citric acid with 1500 cubic centimetres of water ; nearly neutralize with crushed commercial carbonate of ammonia ; heat to expel the carbonic acid ; cool ; add ammonia until exactly neutral (testing by saturated alcoholic solution of coralline) and bring to a volume of two litres. Test the gravity, which should be 1.09 at 20° C, before using. AMMONIUM NITRATE SOLUTION. Dissolve 200 grammes of commercial ammonium nitrate in water and bring to a volume of two litres. MOLYBDIC SOLUTION. Dissolve 150 grammes of ammonium molybdate in one litre of distilled water. Pour the solution slowly and in small portions at a time into one litre of nitric acid of s^^ecific gravity 1.20. After each addition of the ammonium molybdate solution the mixture must be shaken and the agitation kejit uj) until the liquid is en- tirely clear. Keej) the mixture in a warm place for several days, or until a portion heated to 40° C. deposits no yellow precipitate of ammonium phospho-molybdate. Decant the solution from any sediment, and preserve in glass-stoppered vessels. Fifty c.c. of this solution suffice to precipitate 0.100 gramme P.O.. SATURATED SOLUTION OF AMMONIUM OXALATE. Place about eight ounces of pure ammonium oxalate in a litre bottle, fill up with pure distilled water, shake occasionally during a few hours, finally allow to settle and use the supernatant liquid, drawing it off with a i^ipette as required. STANDARD POTASSIUM PERMANGANATE SOLUTION. For the accurate determination of iron in small quantities we prefer the permanganate to any other reagent. The iron is re- Tlie Phosphates of Amei'ica. 171 0.;8HoO BaCOg SrO SrCOa MgO MgCO., HNO3 HCl h;so, H^CoO^ H.CaOg HeC,0« C.,0,H,+H.,0 62 40 106 84 94 56 138 100 17 96 56 74 100 171 315 197 103.5 147.5 40 84 63 36.5 98 136 60 150 210 Grammes. 3.1 4.0 5.3 8.4 4.7 5.6 6.9 10.0 1.7 4.8 2.8 3.7 5.0 8.55 15.75 9.85 5.175 7.375 2.00 4.20 6.3 3.65 4.9 6.3 6.0 7.5 7.0 .031 .040 .053 .084 .047 .056 .069 .100 .017 .048 .028 .037 .050 .0855 .1575 .0985 .0575 .07375 .020 .042 .063 .0365 .049 .063 .060 .075 .070 Ammonium carbonate. . Calcium oxide (lime) " hydrate " carbonate Barium hydrate '" (cry.).... " carbonate Strontium oxide " carbonate... Magnesium oxide " carbonate. . Nitric acid Hydrochloric acid Sulphuric acid Oxalic acid Acetic acid Tartaric acid Citric acid In order to find the amount of pure substance present in the material examined multiply the number of c.c. by the " normal factor." TABLE COMPARING THE DEGREES OF BAUME WITH SPECIFIC GRAVITY DEGREES AT 15» C. Desrs. of Baum6. Sp. Gr. De<,'s. of Baum6. Sp. Gr. Deprs. of Baum6. Sp. Gr. Degs. of Baum6. Sp. Gr. 0 1.000 19 1.147 37 1.337 55 1.596 1 1.007 20 157 38 1.349 56 1.615 2 1.014 21 166 39 1.361 57 1.634 3 1.020 22 176 40 1.375 58 1.653 4 1.028 23 185 41 1.388 59 1.671 5 1.031 24 195 42 1.401 60 1.690 6 1.041 25 205 43 1.414 61 1.709 7 1.049 26 215 44 1.428 62 1.729 8 1.0.57 27 225 45 1.442 63 1.750 9 1.064 28 234 46 1.4.56 64 1.771 10 1.072 29 215 47 1.470 65 1.793 11 1.080 30 256 48 1.485 66 1.815 12 1 . 088 31 267 49 1.500 67 1.839 13 1.096 32 278 50 1.515 68 1.864 14 1.104 33 289 51 1.5.31 69 1.885 15 1.113 34 300 52 1.546 70 1.909 16 1.121 35 312 53 1.563 71 1.935 17 1.1.30 36 324 54 1..578 72 1.960 1« 1.138 ' 174 The Plwsphates of America, ANXnOX'S TABLE BY WHICH TO PREPARE SULPHURIC ACID (OIL OF VITRIOL) OF ANY STRENGTH BY MIXING THE ACID OF 1.80 SPECIFIC GRAVITY WITH WATER. 100 parts of Water at 1S° to 20° bein dica- 5 " phenolphthalein ) ^ovs. Distilled water. Ferric chloride. Ferrous sulphate (crystals). Fine white pure sand. Hydrochloric acid (concent.). Hydro-disodic phosphate. Indigo solution. Iron wire and plate. Magnesic chloride crystal. Magnesic sulphate. Nitric acid (concent.). Nitro - hydrochloric acid (aqua regia). Oxalic acid (crystals). Platinic chloride. Potassic carbonate (dry) Potassic chlorate. Potassic dichromate. Potassic ferricyanide. Potassic ferrocyanide. Potassic hydrate. Potassic permanganate (crystals). Potassic and sodic carbonates (mixed). Potassic sulphocyanide. Sodic acetate. Sodic carbonate. Sodic chloride. Sodic nitrate (crystals). Sulphuric acid (concent.). Sulphuretted hydrogen. Uranic acetate. Zinc, granular. The End. INDEX Acid Chambers. Arrangement of drips, windows and caps in 92 Construction of 90 Dimensions of 91 Exit gases from 94 General hints in management of. .93, 94 Pressure of steam in 90 Reactions of gases in 93 Regulation of nitre supply in 93 Sprengel pump in 90 Thickness of lead for, and amount of space in 90 Acid Phosphate of Lime. Composition of 107 Production of, in the manufacture of superphosphate Ill Acid siphon or "egg," Description of 98, 99 Acid solution. Concentration of 130 Acids and alkalies. Table for syste- matic analysis of 173 Agricultural produc4;s, Value of, in U.S 14 Agriculture, Theory of scientific 9 Air Supply. Importance of regulating, in sul- phuric acid manufacture 89 Regulation of, in pyrite biirners 88 " " for burning brim- stone 88 Alkalies and acids. Table for system- atic analysis of 173 Alumixa axd Iron. Combination of, in Florida phos- phates 134, 155 Determination of oxides of 150-153 Elimination of, from Florida phos- phates 78 Estimation of, in raw phosphates 150, 151 Glaser's method of estimating. ..152, 153 In Florida phosphates 76, 78 Ammonia. Citrate solution of 170 Hydrate solution (normal) of ItJS Nitrate solution of 170 Oxalate solution of 170 Table showing strength of various solutions of 175 Analysis. Determinations necessary in 144 Divergence in, of phosphates. 26, 139, 140 Of alkalies and acids. Table for 173 " brimstone 162 "chalk or limestone 163 " fertilizers. Normal solutions use- ful m 167-171 Analysis. Of Florida phosphates 77 " phosphates. Volumetric 157-158 " pyrites ores 159-161 " raw phosphates 138, 141, 151 " soils 13 " sulphuric acid 16? " superphosphates . . 155-157 Preparation of sample for phos- phate 144 Selected methods of '. ... 138 Volumetric, of phosphates 157, 158 Apatites. Average cost deliverad at Montreal 42 " " of mining 40,41 Canadian, see Canadian Apatites. Chemical composition of 35 Combination of various bodies de- termined in phosphate If 4 Continuity of veins of 39 Coste, Eugene, on the origin of Canadian 36 Dawson, Sir William, on Canadian. 35 Geological aspect of Canadian 27 In rocks of Laurentian period 27 Methods of mining, in Canada.. 34, 40, 42 Mines, Principal working of, in Canada 28 Output of, from 1877 to 1890 43 Probable origin of Canadian 35, 37, 38, 39 Ratio of, to other rocks in Canadian mines 40 Selling price of, in 1890 43 Selwyn, A. R. C, on the origin of Canadian 36 Transportation of 42 Values, Yearly, of 13 Apparatus, List of chemical and other, chiefly required in " phos- phate mining" and " fertilizer fac- tory " laboratories 177 ARCH.a:AN rocks. Composition of 27 Artesian wells in Florida 65 Artificial heat. Evil effects of , when used to dry superphosphates 113 Assimilability of phosphates 18-22 Atomic weights. Table of 161 Barium Chloride. Standard solution of 169 Table showing strength ot various solutions of 175 Bartow as a phosphate-producing re- gion 74 Baume degrees compared with speci fie gravity 173 Boom in Florida phosphates 63 180 Index. BoussiNGAULT on the migration of phosphates in plants 17 Brimstone. Air supply in burning 88 Analysis of 162 Cost of manufacturing H2S04 from. 104 In sulphuric acid manufacture 86 Moisture, Determination of, in 162 Possible yield of H0SO4 from 102 Sulphur. Determination of, in 162 Calcining and drying Florida phos- phates 74 Calcining phosphates, Fallacy of, ex- posed 7o Canadian Apatites. Chemical composition of 35 Companies now engaged in mining. 28 Cost of production of 42 Dawson, Sir William, on 35 Geological aspects of 27 Methods of mining 29. 34, 40. 42 Natural impediments in the way of mining in Canada 42 Necessity of a change in the meth- ods of mining in Canada 44 Occurrence of 27, 35 Origin of 35-40 Output of, mines from 1877 to 1890. . 43 Principal working mines of 28 "Value of lands containing 29 Veins of 39 Wasteful methods of mining 42 Canadian Phosphates 29-42 Equipment necessary for mining of. 34 Mining, Extravagant method of 42 Carbonate of lime as an important ingredient in the manufacture of superphosphates 112 Estimation of, in phosphates 145 Carbonic Acid Gas. Estimation of, in phosphates 145 Schrotter's apparatus for estimation of 146 Cenozoic time 45 Chalk or Limestone. Analysis of 163 Determination of magnesia in 163 Chamber Acid. For decomposition of phosphates, Table of quantity of 110 In manufacture of phosphoric acid, Table of 128 SO3 and H2SO4 in, Table showing value of 108 Chemical knowledge required in the manufacture of fertilizers Ill Chemicals, General list of those, chiefly required in phosphate an- alyses 178 Cinders from pyrites burning. Value of 87 Citrate. Insoluble PjO;.. Determination of, in superphosphates 156 Soluble P.jOs, Determination of, in superphosphates 1.57 Soluble phosphates Ill, 112 Clayey soils 11 Combination of Iron and alumina in Florida phos-" phates 154, 155 Raw materials used in the manu- facture of superphosphate 125 Various bodies determined in phos- phate analysis 154 Combined water and organic matter in raw phosphates, Determination of 144 Companies, Bogus, in Florida and their evil influence 82 Companies now engaged in Canadian apatite mining 28 Florida phosphate mining 80, 81, 82 South Carolina phosphate mining, 55, 56 Composition op Phosphoric acid solution of 45° B. . . 131 Plants 13 Principal phosphates 20 Superphosphates as manufactured in United States 126 Concentration of acid solutions 130 Condensing plant for the fertilizer factory 134-137 Construction of fertilizer work=.l-.^3, 124 Contracts, Proposed modifications in present forms of making 141, 142 Conversion of thermometric degrees 165 CoosAW Mining Co., History and earnings of 56-58 Copper. Determination of, in pyrites 159 Estimation of, as subsulphocyanide in pyrites ores and residues 161 Coralline, as an indicator 167 CoRENWiNDER, On the migration of phosphates in plants 17 Cost of Production of Canadian apatites 42 Florida phosphates 74, 78 High-grade superphosphates 133 Phosphoric acid 133 South Carolina phosphates 59, 60 Sulphuric acid 104- 105 CosTE, Eugene, on the origin of Canadian apatites 36 Crops, Percentage of mineral matter in the U. 3 14-16 Crust of the earth. Geological divis- ions of the 27 Dawson, Sir W., on probable ori- gin of Canadian apatite 35 Index. 181 DECOMPOSITION of phosphates, Table of quantity of chamber acid re- quired for 110 Decomposition of rocks 10 Defects in the raw material used in superphosphate manufacture and how to remedy them 113 Degrees Baunie compared with spe- cific gravity 173 Dftosits. Of nodular and amorphous phos- phates 15 Of phosphate in America 25 Development of Florida phosphate deposits 63 Difficulties in the manufacture of superphosphate 112 Directions for manufacturing super- phosphate 123-126 Discovery of Charleston phosphates, PrOiessor Holmes on 45 Mineral deposits of phosphates 19 Phosphate in Florida 63 The fertilizing value of phosphates. 19 Disintegration of Phosphates. In the factory 117-123 Inthesoil 22 Liebig's theory of 22 Divergence in analysis of phos phates -^ Dredges, Mining by means of float- ing 74 Dredging system in South Caro- lina 51, 52 Drift deposits in South Carolina... 73, 75 Drips, Arrangement of. in manufac- ture of HiSOj 92 Drying. And calcining Florida phosphates. .. 74 Phosphates m South Carolina 53, 54 Washing and, of phosphates 72 Earth's crust. Geological divisions of the 27 Eocene era 45 Farmer, Relative value of phos- phate to the 23 Fertilizer analysis, Normal solu- tions useful in 167-171 Fertilizer Industry. Molecular weights of substances used in 171, 172 Per cent, composition of substances used in I'l, 172 Symbols of substances used in the, 171, 172 Fertilizer Works. Amount of fluorine in gases from . . 134 Fume condenSkir for, Sketch of ..135-137 General outline and plan of 123, 124 Mature of the fumes from 134 Fertilizer Works. Noxious fumes from 134 Fertilizers. Chemical knowledge required in the manufacture of Ill ManufacturcKS of, in South Caro- lina, List of 60 Production of, in South Carolina.. 60, 61 Fertilizing value of phosphates. Dis- covery of 19 Florida. Artesian wells in , 65 Mining livv in 75, 76 Topographical aspect of 64 Florida Phosphate. Analysis, Typical, of 77 Boom in 63 Calcining, Fallacy of 78 Chemical composition of a sample of 108 Companies now engaged in min- ing 80-82 Composition, Typical, of 72. 77 Cost of production of 74-78 Deceptive indications of deposits of. 71 Deposits, Development of 63 Discovery of deposits of 63 Drying and calcining. Methods of 74 Exploration, Systematic, of de- posits of 51 Formation of, Theories on the 66-69 Geological aspect of, deposits 66-69 Iron and alumina. Elimination of, from 78 Iron and alumina in 76-78 Lands and their inflated values 63-80 Maps of, deposits 78 Mining, by floating dredges 74 Pebble mining, Methods of 73, 74 Physical aspect of. Genera) 74, 76 Pockety nature of deposits of 71 Rock mining. Methods of 77, 78 Speculative dealings in, lands 63-80 Suggestions for working, deposits. ... 78 Washed and dried 72 Florida Phosphate Mines. Companies now working. Parti 1 list of 80-82 Extent and aspect of 70 In Lakeland and neighborhood 74 In Peace River and its tributaries. . 73 In pebble regions 73 JefTrey Manufacturing Co.'s plant for working 78 Negro labor in 83 Suggestions for working 78 Thickness of phosphate stratum in.70-73 Fluorine. Amount of, in gases from fertilizer works 134-137 Estimation of, in raw phosphates... 119 183 Index. 85 95 2? 18 153 10 Formation. Of the globe 10 "soils 11 Frisb E E-Lucop phosphate mill ... . 120-123 Fume condenser for fertilizer works, Sketch of 135-137 Fumes from fertiliz'^r works 134-137 Furnace. Varieties of, in pyrites burning Gay-Lu.'ssac towers. Construction and use of 94, Geological. Canadian apatite deposits, aspects of . Classification of tertiary rocks.. .45, 4fi Divisionofths earth's crust 27 Florida phosphate deposits, aspects of 63 69 Maps of Florida phosphate deposits 78 South Carolina phosphate deposits, aspects of , Glaser's method of estimating iron and alumina in raw phospha'es. 152, Globe. Formation of the Glover Towers, Construction and use of 95-101 Packmgof 97 Grain crop, Percentage of phos- phoricacidin 15 Griffin phosphate mill 118-120 Grinding phosphates. Various me- thods of 117-123 Hay Crop. Percsntage of mineral matter in the. 13 Phosphoric acid in the 16 Hish-Grade Superphosphates. Arguments in favor of 127 Chemical theory and desirability of manufacture of 123 Cost of manufacturing 133 JNIanufacture of 132 Plant used in manufacture of 132 Practical examples in the manufac- ture of 123 Tables for the manufacture of ...l-'8, 131 132 Holmes, Professor, on the discovery of Charleston phosphates 43 Hydrochloric acid table 176 Indications of Florida phosphate deposits. Deceptive 71 Iron. Estimation of, in limestone 163 " " " phosphates 151 " " " pyrites 161 Titration by permanganate of 171 Iron and Alumi.na. Combination of, in Florida phos- phates 154, 1.55 Iron and Alumina. Elimination of, from Florida phos- phates 78 Estimated by Glaser's method . . 152. 153 Estimation of.in raw phosphates, 150, 151 In Florida phosphates 76, 78 In phosphates 21,139 In superphosphates 1 12 Oxides of. Determination of 150-153 Jeffrey Manufacturing Company's plant for mining, washing and drying Florida phosphates (illus- trated) 78, 79 Lakeland, Florida, Phosphate mines in 74 Laurkntian period 27 LiEBiG's theory of disintegrating phosphates 22 Lime. Estimation of, in limestone 163 Estimation of, in raw phosphates. . . 153 Insoluble siliceous matter in. Deter- mination of 163 Iron in chalk or. Determination of. 163 Magnesia in, Determination of ... 163 Mineral phosphate of. Action of sul- phuric aeid on . ... 108 Limestone, Analysis of 163 Limy soils 12 Low-grade phosphates, Utilization of 128 Magnesia. In limestone or chalk, Determina- ti )nof 163 In raw phosphates. Determination of 1.54 Mixture, Preparation of 170 Manufacture of High-grade superphosphates 132-134 Phosphoric acid 1.'9-133 Sulphuric acid 84-102 Superphosphates I.i6-128 Map of Florida phosphate deposits 78 South Carolina phosphate deposits. 48 Measures aad weights of tne me- trical system 165 Methyl-orange as an indicator 167 Metrical system. Measures and weights of the. 165 Mill. Frisbee-Lucop 121 Griffin phosphate 118-120 Sturtevant, phosphate 117, 118 Mineral. Deposits of phosphates. Discovery of. 19 Matters in the crops of the United States 14-16 Phosphate? of lime, Action of sul- phuric acid on 108 Index. 183 Mining Law. In South Carolina 56-57 In Florida 75, 73 Miocene era 15 Mixers used iu production of super- phosphates 121 Moisture in raw phosphates, Deter- mination of 141 Molecular weiehts of substances used in the fertilizer industry... 171, 172 Negro labor in Florida 83 Neutral phosphate of lime, Chemi- cal composition of 107 Nitre in sulphuric acid manufac- ture 85, 92 Nitric Acid. In sulphuric acid manufacture 85 Table 176 Nodular deposits of phosphate of lime 45 North Star mine, Canada, Descrip- tion of the 30 Organic matter. Estimation of com- bined water and, in phosphate an- alysis 144 Origin of phosphates 17, 78 Output of Canadian apatite mine?, 1877 to 1890. 43 Superphosphates in South Caro- lina 60. 61 Oxides of Iron and Alumina. Determination of, in South Carolina phosphates 150-153 Estimated by Glaz.r's method.. 152, 153 Oxygen in sulphuric acid manufact- ure 85 Packing. Of Gay-Lussac Tower 95 Of Glover tower 97 Peace River, Florida, Phosphate mines in 73 Phenolphthalein as an indicator. . . 167 Phosphates. Action of sulphuric acid on insoluble varieties of lf'7, 108 Alumina and iron, of 21, 139 Amorphous and nodular. Deposits of 45 Analysis of. Chemicals required in. 178 Analysis of. Determinations to be made in 144 Analysis of. Divergence in. ..23, 139, 110 Analysis of. Methods of I'S. 144, 154 Analysis, Volumetric, of 157, 158 Analytical list ot best Icno wn 20 Analyzing, Selected methods of 138, 144-154 Assimilability of 18-2i; Buying and selling. Contracts for. . . 141. 112 Canadian 29, 42 Phosphates. Chamber acid reauired to decom- pose. Table showing quantity of. . 110 Chemical composition of a sample ofFloriia 108 Citrate soluble Ill, 112 Combination of various holies de- termined in 154 Commercial value of 25, 133, 149 CDmposition of the principal 20 Consumption of. World's approxi- mate 138 Contracts for buying and selling 111, 112 Cost of production of Florida 71-78 Co'^t of production of South Caro- lina 59-60 Decomposition of. Table showing quantity of chambsr acid of any strength for 110 Deposits of. in America 25 Discovery of fertilizing value of 19 Discovery of mineral deposits of 19 Disintegration of, in the factory. .117- 123 Disintegration of, in the soil . 22 Disintegration of, Liebig's theory of 22 Drying of, Methods of, in South Carolina 53, 54 Farmer, Relative value of, to the ... 23 Florida, aee Florida Phosphate. Fluorine in raw. Determination of. . 119 Grinding, Methods of 117-l;i3 Iron and alumina. Determination of, in 150,151, 15,', 153 Iron and alumina in Florida 131, 155 " ii, ng Iron in. Estimation of 151 Liebig's theory on raw 22 Lime in raw. Estimation of 153 Location of deposits of 77 Low-grade, Utilization of 128 Magnesia in raw. Determination of, 151 Mill, Frisbee-Lucop's 121 Mill, Griffin's 118, 12 J Mill, Sturtevant's 117, 113 Moisture in raw. Determination of. 114 Nodular and amorphous. Deposits of. 45 Of lime, mineral, Actioa of sulphuric acid on 108 Of lime, neutral. Chemical compo- sition of 107 Organic matter. Determination of combined water and, in raw 14 J Origin of 17 Phosphoric anhydride in raw. De- termination of 148 Plants, Migra'ion of, in 17 Raw, used in various soils 23, 24 Sampling, at the mines 112, in before shipment 143. Ill Selling and buying, Contractsfor.l II. i;2 184 Index. Phosphates. Siliceous, insoluble, matter. Deter- mination of, in raw 117 SoU, Necessity for, on the 17 Soil, Reversion of, in the 23 Soluble and precipitated 24 South Carolina, see South Carolina. Sulphuric anhydride in raw. Deter- mination of 147 Tertiary strata, Workable strata of. 46 "Value of, to the farmer. Relative . . 23 Volumetric analysis of 157, 158 Water, combined, and organic mat- ter, Dstermination of, in raw 144 World's approximate consumption of 138 Phosphoric Acid. Calculations connected with the manufacture of 132 Chamber acid requii-ed in manufac- ture of. Table of 128 Chemical composition of 107 Commercial value of. Fixing 138, 139 Concentration of weak solutions of. 130 Cost of manufacturing 13^ Determination. Volumetric, of. 157-159 Gases produced in manufacture of. Volume of 88 Grain crop. Percentage of, in 15 Hay crop, Percentage of , in 16 High-grade superphosphates. Table of quantities of phosphoric acid re- quired in the manufacture of 131 Manufacture of, on the large scale from low-grade ores 129-133 Plant required in manufacture of, 129, 130 Solution of 45° B., Composition of.. 131 Solutions of. Concentration of weak 130 Solutions of. Strengths of 174 Straw, Percentage of, in 15 Superphosphate manufacture, set free in the Ill Superphosphate manufacture. Table of quantities of phosphoric acid re- quired in 131 Table for use in manufacture of high-grade superphosphates 131 Table showing strength of various solutions of 174 Tribasic, Composition of 107 Volumetric determination of 157-159 Phosphoric Anhydride 106 Chemical composition of 106 Determination of, in raw phos- phates 148 Determination of, in superphos- phates 155-157 Determination of, voluraetrically.. 157, 158 Phosphoric An'hydride. Determination of water-soluble, in superphosphates 155 Plant growth. Elements of 12 Plant Required in Manufacture of Phosphoric acid 129. 130 Sulphuric acid 90, 91 Superphosphate 123. 124 Plants. Composition of 13 Life of 13 Migration of phosphates in 17 Pliocene era 45 Pressure of steam in sulphuric acid chambers 90 Pyrite burners, Regulation of air supply in 88 Pyrites. Air supply in burning 83 Analysis of 153, 161 Average composition of 103 Burning, Furnace used in 86 Cinders from burning. Value of 87 Copper, Determination of 159,161 Insoluble siliceous matter, Deter- . minalion of 160 Iron in. Determination of 161 Methods of sampling 159 Residues, Utilization of 87 Samplings of, for analysis 159 Sulphur in. Determination of 160 Sulphuric acid manuf actiire. Use of, in 86 Pyroxe.ve, Occurrence and charac- teristics of 29 Qv. ebec, Canada, Apatite deposits of. 27 Reactions in sulphuric acid manu- facture 85 Rocks. Archaean 27 Decomposition of 10 Limestone, in Florida 65 Of the Laurentian period 27 Phosphates, of S. Carolina 16 Tertiary, Classification of . . . ' 45, 46 Varieties of 10 Sampling. Phosphate at the mines 143 Phosphate before shipment 144 Pyrites for analysis 159 Sandy soils 11 Scheurer-Kestner's experiments with the Glover tower 100, 101 SCHROTTER's COj apparatus 146 Selling prices of South Carolina phosphate 60 Selwyn, a. R. C, on the origin of Canadian apatites 36 Siliceous matter, insoluble. In limestone. Determination of 163 In py rites. Determination of 160 Index. 185 Siliceous mattek, insoluble. In raw phosphates. Determination of 147 Soil. Disintpgration of phosphates in the. 22 Formation of the 11 Limy 12 Raw phosphates. Use of, in various, 23, 21 Varieties of 11 South Carolixa. As a pioneer in the fertilizer in- dustry 60 Drift deposits in 73, 75 Drying of phosphates. Methods of .53, 51 Fertilizers, Production of, in 61 Manufacture of fertilizers in 60 Manufacturers of fertilizers in. List of 69 Mining law in 56, 57 South Carolina Phosphate. Companies now engaged in mining. 55, 56 Continuity of, deposits 48 Cost of production of 59, 60 Deposits 46-62 lines ploited, of 61 Dredging scoops used in mining. . .51, 52 Excavating and exporting. Methods of 53. 54 Exploring, Methods of, deposits ... 49 Extent of deposits near Charleston, 4S Geological formation of, deposits. . . 48 Holmes, Professor, on the discovery of, deposits 46 Map of, deposits 48 Mining of. Methods of 53-i5 Nature of material overlying 49, 50 O-Kides of iron and alumina in, De- termination of 150-153 Pit sinking in 49 Production of, Annual 54 River and land 51 Rocks 46 Specific gravity of 52 Table of annual production of 54 Thickness of strata in, deposits 49 Typical sections of, deposits 50, 51 Unexploited areas of 61 South Carolina .Superphosphates, Output of 60, 61 Specific Gravity. Comparison of degrees Baume with 173 How to determine 166 Of S^outh Carohna phosphates 52 Speculative dealing in Florida phos- phate land 63, 80 Sprengel pump in acid chambera 90 Standard solutions 167-170 Steam pressure in sulphuric acid chambers 90 Stoichiometry 165 Straw. Percentage of mineral matter in 14 Percentage of phosphoric acid in . . . 15 Sturtev ant's phosphate mill 117, 118 Subsulpiiocyanide, Estimation of copper as, in pyrites ores and resi- dues . . 161 Sulphur. Estima*/ion of, in brimstone 162 " " in pyrites 160 Sulphuric Acid. Action of, on mineral phosphate of lime 108 Air supply in manufacture of 88, 89 Analysis of 163 Chambers 90-93 Chemistry of manufacturing pro- cess of 84-90 Composition of pure 102 Cost of manufacture of. from py- rites and brimstone 104, 105 Gay Lussac and Glover towers m the manufacture of 91-101 Manufacture of 81-102 '■ " Early methods of.. ^4 Manufacture of. Plant required in.90, 91 Nitre in manufacture of. 85 Nitre supply in, Regulation of 92 Oxygen in manufacture of 85 Plant required in manufacture of 90, 91 Pumping siphon, or "egg" 98, 99 Pyrites in manufacture of 86 Reactions in manufacture of 85 Table for preparing various strengths of, by adding water 174 Table showing value of chamber acid in SO3 and H3SO4 according to Baume 108 Yields of, in actual practice from pyrites and brimstone 102 Sulphuric Anhydride. Determination of, in raw phos- phates 147 Table showing value of chamber acid in 108 Superphosphate Manufacture. Chemical equations involved in ... 109 Chemistry of 106 Superphosphates. Acid phosphate of lime. Production of, in the manufacture of HI Analysis of 155-158 Chemical theory of high-grade, man- ufacture 126 Citrate soluble. Water and 112 Composition of, as manufactured in United States 126 Composition of. Variability in 106 Consumption, World's, of 138 Cost of producing high-grade 132 Cost of transportation of 127 18G Index. Superphosphates . Desirability of high-grade, manufac- ture 126 Determination of citrate insoluble P2 05in 156 Determination of citrate soluble PaOjin 157 Determination of total P^Os in — 157 Deter mini tion of water soluble P2O5 in 155, 156 Difliculties in the manufacture of.. 112 Drying, Methods of 113 Equations involved in manufactur- ing 1C9 Examples of scientific and accurate methods of manufacturing... 114, 115 High-grade, Arguments in favor of. 127 " " Cost of Manufacturing. 133 Manufacture of.... 128, 132 " " Plant used in manufac- ture of 132 " " Practical examples in the manufacture of . 729 " " Tables for the manufac- ture of 128, 131, 132 Iron and alumina in 112 Manufacture of 106-128 " Calculations em- ployed in 110, lUv " " Difficulties in 112 " Directions for... 123 126 " " Equations involved in 109 " " Examples of scien- tific 114, 115 " high-grade 132-134 " " Plant required in, 123, 124 Merchantable, Methods of making, dry and 113 Mixers used in the production of... 124 Mixture of the raw materials in the manufacture of 123125 Moisture in, Determination of 155 Output of, in South Carolina 60, 61 Phosphates, mono-calcic, and di- calcic. Production of, in the manu- facture of Ill Phosphoric acid set free in the man- factureof Ill Phosphoric anhydride in. Determi- nation of 155-157 Plant required in manufacture of, 123, 124 Raw Material, Combination of, used in the manufacture of 125 Raw Material, Defects in the, used in the manulacture of, and how to remedy them 113 Raw Material, Mixture of, used in the manufacture of 123-125 Superphosphates. Raw Material, Qualities of, in man- ufacturing HI Sampling, Method of 155 Table showing the quxntity of chamber acid of any strength re- quired to decompose any phos- phate of known composition. 110 Water and citrate soluble 112 Symbols of substances used in the fertilizer industry 171, 172 Tables. For preparing sulphuric acid of various strengths by adding water 174 For systematic analysis of alkalies and acids 173 Of atomic weights 161 Showing amount of chamber acid of various strengths required in the manufacture of phosphoric acid from natural phosphates in rela- tion to the production of high- grade ''supers'' 128 Showing annual production of Ca- nadian apatite 43 Showing annual production of South Carolina phosphate 54 Showing quantities of phosphoric acid required in the manufacture of high-grade superphosphates from mineral phosphates 131 Showing quantity of chamber acid of various strengths required to decompose any phosphates of known composition 110 Showing strengths of various solu- tions of ammonia 175 Showing strengths of various solu- tions of barium chloride 175 Showing strengths of various solu- tions of hydrochloric acid 176 Showing strengths of various solu- tions of nitric acid 176 Showing strengths of various solu- tions of phosphoric acid 174 Showing the value of chamb2r acid in SOj and II^SOj, according to Baume 108 Teiitiary. Age, Characteristics of 45 " Subdivision of 45 Rocks, Geological ciassificaion of. 15, 46 Strata, Workable pho^hate de- posits of 46 Thermometric degrees. Conversion of 165 Tillman, Governor, on the Coosaw Mining Co 56 58 ToPOGKAPHiCAL aspect of Florida ... 64 Tribasic phosphoric acid. Chemical composition of 107 Index. 187 Uranium acetate Folution 169 Values of agricultural products 11 Volumetric estimatiun of phosphor- ic acid 157-159 Water, combined, and organic mat- ter in raw phosphates, Determina- tion of 141 Washing and drying Florida phos- phates 72 Weights. Measures and. Metrical system of.. 165 Table of atomic 161 Wells, Artesian, in Florida 6i Windows in sulphuric acid chambers 92 i ADYERTISERS' INDEX. Page. Abel's Mining Accidents and Their Prevention - - - . xiv American Ore Machine Co. - - - - - - vii Beckett Foundry & Machine Co. ...... xvii Bradley Fertilizer Co. ....... ix Chism's Mining: Code of ihe Republic of Mexico - - - - iv Eimer & Amend ........ xi Endlich's Manual of Qualitative Blow-Pipe Analysis - - - vi Engineering and Mining Journal ..... ii Frisbee-Lucop Mill Co. -..-.... xxi Harrington & King Perforating Co. ..... i Hell, Henry Chemical Co. ------- xi HovFe's Metallurgy of Steel ...... xiii Hunt's Chemical and Geological Essays ..... xxii Hunt's New Basis for Chemistry ..... xxiii Hunt's Physiology and Physiography ..... xxiv Hunt's Systematic Mineralogy ...... xxv Jeffrey Manufacturing Co. - ------ iii Krom, S. R. - - - - - - - - - xiii Kunz's Gems and Precious Stones of North America - - - xx Lawrence Machine Co. ....... xix Ledoux & Co. ....-----v Mason Regulator Co, ..------ xv Mecklenburg Iron Works ....... xiii Nor walk Iron Works Co. ....... xv Peters' Modern American Methods of Copper Smelting - - - xviii Poole, Robert & Son Co. ------ - xvi Richards & Co. - - - - - ■ - - - xiii Scientifiit Publishing Co. ....... xxvi Stetefeldt'sLixiviation of Silver Ores - ..... viii Sturtevant Mill Co. ------- - xv Trenholm, P. C. - - - - - . - - - xix Volk & Murdock Iron Works ...... iii Wedding's Basic Bessemer Process .----- x ADVERTISEMENTS. Metals of All Kinds Punched to Any Size and Thickness Required. PERPORATED TIN AND BRASS OP ALL SIZES. PERFORAIOBS OF ALL METALS FOR USE J.V ORE STAMPING AND DRESSING MACHINERY. For Coal and Ore Separators, Mining and Smelting Works, Fixed and Movable Screens, Reduction and Concentrating Works, Etc. Jigs, Trommels, Washers and Heavy Steel and Iron Plates and Sizers of all Kinds. Cylinders for Screening Ore, In Stamp Batteries. Coal, Stone, Phosphates, Etc. STAMP BATTERY SCREENS OF ALL KINDS AND SIZES PERFORATED FILTER PRESS PLATES, For ParafHne Wax, Cotton- Seed Oil. Sugar and other purposes. RUSSIA IRON, STEEL AND ALUMINUM OR MANGANESE BRONZE. Special Screen Plates To Withstand Action ot Acidulated Mine Water. With Hardness and life of best steel. COEEESPONDENCE SOLICITED, Prices and Samples on Application. THE HARRINGTON & KING PERF. CO., Main Office aii«l Works, 222 and 22VEKTISIIVO aiErnuMi. The Largest Circulation of any Tecfinicai Paper in America. SUBSCEIPTION, INCLUDIN& POSTAGE: "Weekly Edition (which includes the Export Edition), for the United States, Mexico, and Canada, 11.00 per annum ; $2.25 for six months ; all other countries in the postal union, $5.00. Monthly Export Edition, all countries, $2.50 gold value per annum. THE SCIENTIFIC PUBLISHING COMPANY, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. m CHARLESTON, S. C, MANUFACTURERS OF Machinery for Washing, Pulverizing and Manipulating Phosphate Rock. ENGINES, BOILERS AND MACHINERY, ETC., ETC. PHOSPHATE MACHINERY, OF EVERY DESCRIPTION, —FOR— ROCK AND PEBBLE PHOSPHATE. WE FURNISH ELEVATORS, CONVEYORS, CRUSHERS, WASHERS, SCREENS, DRYERS, ETC., ETC. We have equipped some of the largest Phosphate plants in the country. Will furnish plans and estimates on complete outfit, or any parts that may be desired THE JEFFREY MFG. CO., COLUNIBUS, O. IV ADVERTISEMENTS. THE MINING CODE REPUBLIC OF MEXICO. WITH THE Eegulations for the Organization of the Mining Deputations and the Schedule for the Levying of Pees and Dues, with all the Latest Official Circulars and Decisions of the Mining Section of the Ministry of Public Works and with the Laws of June 6th, 1887, upon the Taxation of Mines and their Products, the Concession of Mining Territory and the Purchase of a Process for the Treatment of Ores. TRANSLATED FROM THE OFFICIAL EDITION IN THE ORIGINAL SPANISH. RICHARD E. CHISM, MINING ENGINEER. MEMBER OF THE AMERICAN INSTITUTE OF MINING ENGINEERS. THE SCIENTIFIC PUBLISHING COMPANY, 37 PARK PLACE, NEW YORK. I i ADVERTISEMENTS. LEDOUX & CO., Analytical and Advising Ciiemists -AND- Ciemical Engineers. EXPERT EXAMINATIONS of Phosphate and other Mineral Properties. PROFESSIONAL ADVICE regarding the manufacture and manipulation of FERTILIZERS, treatment of rock, and valuation of fertilizing MATERIALS. PLANS and SPECIFICATIONS for the erection of plants for the manufac- ture of fertilizers, acid phosphates, and sulphuric acid. ANALYSES of phosphate rock, marls, earths, raw fertilizing materials, mixed fertilizers, sulphuric acid, pyrites, and pyrites cinder. Our long experience in this branch of work justifies us in guaranteeing prompt and accurate returns. CONTRACTS by the month or year for professional advice and analytical work. PRICES will be furnished on application, and will be made as low as com- patible with accurate work. LABORATORIES AND OFFICES: NO. 9 CLIFF STREET, NEW YORK. VI ADVERTISEMENTS. OF OUALITATIYE BLOWPIPE ANALYSIS AXD DETERMINATIVE MINERALOGY. F. M. ENDLICH, s. N.D., MINING ENGINEER AND METALLURGIST, LATE MINERALOGIST SMITHSONIAN INSTITUTION, AND UNITED STATES GEOLOGICAL AND GEOGRAPHICAL SURVEY OF THE TERRITORIES. Bound in Cloth. Illustrated. Price S^.OO. This work has been specially prepared for the use of all students in this great department of chemical science. The difficulties which beset begin- ners are borne in mind, and detailed information has been given concern- ing the various manipulations. All enumerations of species as far as pos- sible have been carried out in alphabetical order, and in the determinative tables more attention has been paid to the physical characteristics of substances under examination than has ever yet been done in a work of this kind. To a compilation of all the blowpipe reactions heretofore recognized as correct the author has added a number of new ones not previously pub- lished. The entirearrangement of the volume is an original one, and to the knowledge born of an extensive practical experience the author has added everything of value that could be gleaned from other sources. The book cannot fail to find a place inthelibrary or workshop of almost every student and scientist in America. T^BLE OF CON-TEISTTS. Chapter I.— Appliances and Reagents required for Qualitative Blowpipe Analyst?. Chapter II.— Methods of Qualitative Blowpipe Analysis. Chapter III.— Tables giving Reactions for the Oxides of Earth and Minerals. Chapter IV.— Prominent Plowpipe Reactions for the Elements and their Principal Mineral Compounds. Chapter V.— Systematic Qualitative Determination of Compounds. Chapter VI.— Determinative Tables and their Application. THE SCIENTIFIC PUBLISHING COMPANY, ]PXJBIL.IS H-EKS, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. VII INARODDRYPHLVERIZER THE NAROD DRY AND WET GRANULATOR. V. L. RICE, Patentee. M CI Q ' ^ -? f-' 5 ® ^ ^ ' - f" o ^ ** S|3 El r o 2 o oo §? ?- > G O '^ 5: cc •zi d o , n K t> m ;7 tr w H ^4 c^ cc H 2: Cf^ {- Z ^ H H > y. H "^ te-S o ?d o Pulverizer produces from 20 to 200 mesh fineness. Granulalor from size of wheat berry to 20 mesh. Botn mills fed in sizes one-inch cube and under. Deliver finished and uniform product throui?h screen into hopper below. Only wearing parts are rolls and ring, which are made of bes; chilled carbonized iron, dense and fiber- less, hence durable. PERFECT PRESERVATION OF GRANULATION. NO TAIL- INGS. NOREGRINDING. NO SLIME. ANY DEGREE OF FINENESS OBTAINABLE FINENESS REGULATED BY SIZE MESa OF SCREEN IN MILL. Capacity: Hard Quartz, 2!^ to 3 ; Phosphates, Cements, etc., 3H to 4 tons per hour. Only 15 to 20 Horse Power Required. Weig-ht of Each Mill, 5,600 Lbs. The heavier parts can be made suitable for mountain ti-ansportation. TESTIMONIAL LETTER (EXTRACT). Wilmington, N. C, Oct. 21, 1891. American Ore Machinery Co., No I Broadway, New Vork: t u- 1 Gentleme.v: After over nine mouths' experience with the Narod Mill, I thuik it by far the bes^ and most economical Phosphate Grinder on the market. I havu not known it to do less than 34 tons, and under favorable conditions 4 tons per hour. The Mill does not require 20 horsepower, run^ smooth without heating, and has never broken down. Yours truly, C. E. Bi'RDEN, Supl. Navassa Guano Co. AMERICAN ORE MACHINERYCO 1 Broadway, New York, N. Y , U S. A. VIII ADVERTISEMENTS. The Lixiviation of Silver Ores WITH 1-Iyposu.lphite Solutions. BY CARL A. STETEFELDT. In Cloth, Illustrated. Price, - - $5.00. Notices and Opinions. " We can unreservedl)' recommend this work." — Mexican Financier. Prof. Safford, of the Vanderbilt University, writes: "Mr. Stetefeldt has given us a most useful work and one well up with the times." Prof. Comstock, of the University of Illinois, says : "There is a crying need of more works like it upon cognate subjects." " It is in every respect a model of what such a book should be and is another illustration of German thoroughness." — Journal of Analytical Chemistry. Prof. Egleston, of the Columbia College School of Mines, writes : " The book is a very valuable contribution to onr knowledge of teaching, and I shall take great pleasure in recommending it to students, metallurgists and others." " It is particularly valuable for its descriptions of the chemistry of the process, in which the older works are woefully deficient. It gives all the facts, apparently which one engaged in milling ore by the process should know." — Mining Industry. Prof. Hofman, of the Dakota School of Mines, writes : " I have no hesita- tion in saying that the ' Lixiviation of Silver Ores ' is the best existing work upon the subject, and will, undoubtedly become the text-book for specialists in this in- interesting field." Prof. Sharpless, of the Houghton Mining School, writes : " One who has occasion to read up the recent advances of lixiviation processes will appreciate the work which has been done by the author in compiling and in original research, and the profession should extend its thanks to Mr. Stetefeldt for his successful effort ' to fill up a gap in metallurgical literature.' " Prof. Bruno Kerl, in a review of this book which he prepared for the Berg- unci Huetten7naennische Zeitung, of Berlin, says : " All the defects of the old process have been overcome by the Russell process as described by Mr. Stetefeldt in his book, which fills a real gap in metallurgical literature. ... Its translation into German would be a very desirable addition to our literature." John Heard, Jr., Mining Engineer, writes : "This treatise is the most valuable — indeed the only valuable — one on lixivia- tion. The amount of careful, intelligent, original and compiled research is enor- mous ; the tables and drawings must be invaluable and, indeed, indispensable to any manager of a lixiviation plant, and the figures there recorded are more convincing aro-unients as to the value and range of lixiviation as a method of extracting silver from certain ores than the author's dogmatic deductions. SCIENTIFIC PUBLISHING COMPANY, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. jx ■^ Middlesex County, I Suffolk. j ***• THE GRIFFIX MILL vs. THE FERTILIZER M'F'RS. I'ZZX: C; Xj .^^ X 3VE : J 1st. That the Griffin Mill is the latest and best mill manufactured for pulverizin{^ all hard or refractory suOstances. 2d. That it will do its work more satisfactorily, with less wear and at less expenditure of power than any other mill, requiring less than 20 horse power 3d. I hat it will grind to an even degree of fineness, with direct delivery and without taUinas. 4th. That it is being used by leading fertilizer manufacturers with positive success. 5th. That the mill is simple in construction, with no exposed jour- nals, and with very little wearing surface. ■rZZX: Z2 "^r Z 33 X3 IDa" O Z3 : >poo Mills, C October 2i, 1891 Wappoo Mills, Ch 'Rleston, S. C.,\ Bradley Fertilixer Co. : We have put in the finer of the two sets of screens sent u=!, and with svm-dried rock are getting out at the rate of 46V^ tons In ten hours. H. B. Jenxings. Superintendent. Alexandria, Va., \ October 24, 189J. / Dear Sirs : We have received a great deal of satisfactijn from our vlill ; it requires little or no attention, goes right along, does its work, and does it nicely. We are. Yours respectfully. (Signed) alexa.noria Fertilizer and Chemical Co. 88 Wall Street, New York. Dear Sirs : It gives me much pleasure to be able to say that, since we erected the two mills bought of you some eight months ago, they have done excellent work, and to our entire satisfaction. The power required to run them is very small, not over 20 horse each The repairs are very small and easily etfected. Each mill will easily turn out 3u tons in a run of 10 hou'S. producing a product all of which will readily pa's a 40 mesh screen, and 9i) per cent, of it will pass through a OO^mesh screen. We feel safe in saying you have in this mill very decidedly the best mill on the market, aad it will, without doubt, supersede all others. rtEAD Fertilizer Co., Cleme.nt Read, Tr^as. and Mangr. Cleveland, October 22, 1891. Gentlemen : We are at present pulverizing a trifle over two tons per hour through a 180-mesh wire. It requires only about 16 horse power, and so far the wear and tear has been very sliKh , not over two cents per ton. We consider this a very good showing, as our material is tough and bard. We can heartily recommend it to any- body requiring such a machine. We are. Respectfully yours, (Signed) Thb, Ohio Metallic Co., F. J. Drake, Secy, and Treas. That the Bradley Fertilizer Company has six of these Mills in constant use at their Weymouth factories, and are prepared to dem- onstrate to any one by practical tests that it pulverizes phosphate rock to the best condition for fertilizing purposes. E "^7-E3Il.I3 I CT: That by reason of the above, and much other testimony, the Court decides that the claimant's affirmations are true, and that the Court therefore recommends that every manufacturer of fertilizers send at once to the Bradley Fertilizer Company, 27 Kilhy Street, Boston, for their full descriptive, ill strated circulars of these Mills. ADVERTISEMENTS. BASIC BESSEMER PROCESS. By Dr. H. WEDDING. The Scient'fic Publishing Company has secured the rights of publication in the United States of a translation of this, the acknowledged authoritative work on the Basic Bessemer or Thomas Process, which is now for the first time placed before American metallurgists. Translated from the German by WILLIAM B. PHILLIPS, Ph. d., Professor of Chemistry and Metallurgy in the University of Alabama, and ERNST PROCHASKA, Met. e., Late Engineer at the Basic Steel Works, Teplitz, Bohemia, and at the Works of the Pottstown Iron Co., Pottstown, Pa. With supplementary chapter on Dephosphorization in the Basic Open Hearth Furnace, by Ernst Prochaska. The Standard Work, and the Only Book in English on this Subject. Bound in Cloth. Profusely illustrated. Price $3.50. THE SCIENTIFIO PUBLISHING COMPANY, IPTZT BILiISI3:EI?,S, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. xr ESTABLISHED 1866. INCORPORATED 1888. HENRY HEIL CHEMICAL CO., 208-212 South Fourth St., St. Louis, Mo., MANUFACTURERS AND IMPORTIRS OF CHEMICALS Am CHEMICA.L APPARATUS, j^SS^YERS' MA.TERI^LB, Crucibles, Scorifiers, Muffles, Furnaces and Supplies for Chemists, Mines, Smelters, Sampling Works and Stamp Mills. AGENTS FOK J. H. Munktell's Swedish Filtering- Paper, The Denver Fire Clay Co.'s Crucibles, Muffles and other Manufactures. BatterF^ea Crucibles, Muffles, Etc., Josef Kavalier's Unexcelled Bohemian Glassware, Etc. All and everything the Chemist and Assayer needs can be found ai our estab- lishment. We guarantee best quality and lowest prices. Write for our Catalogue, which is larger and more complete than any other, containing 3,000 illustrations. KIMER S- AMEND, NEWT YORK, Have Always Made a Specialty of Siipplles for Fertilizer Laloratories. KJELDAHL'S APPARATUS, COMBUSTION FURNACES, STANDARD GRADUATED APPARATUS, SCHLEICHER AND SCHUELL'S FILTER PAPER. BOHEMIAN COMBUSTION TUBING, PURE HAMMERED PLATINUM, ACCURATE BALANCES AND WEIGHTS. XU ADVERTISEMENTS. THE METALLURGY OF STEE HENRY M. HOWE, A.M., S.B. Royal Quarto, Handsomely Bound, Printed on Superfine Paper, and Profusely Illustrated. SECOND EDITION. rrice, _ - _ - - $10.00. This work is the most notable contribution to the literature of iron and steel metallurgy ever published. The series of papers on the subject which have appeared as supplements to the " Engineering and Mining Journal " during the past two years have attracted world-wide attention and have re- ceived the heartiest commendation from all quarters. The volume now published presents this material in much more convenient shape, with con- siderable additional matter, giving the results of the most recent research, experiment and practice. Mr. Howe also presents a complete review of all important conclusions reached by earlier investigators, and his masterly dis- cussion of them renders the work classic. Every statement and citation has been carefully weighed and verified and the references to the literature of the subject are given minutely, the book thus furnishing in itself a key to the whole range of steel metallurgy. It also furnishes the results of much new .and original investigation, specially undertaken for the present work. Every metallurgist, every manufacturer of steel in any form, and all who are interested in the iron or steel industries, and all engineers who use iron or steel should have this standard work and cannot afford to be without it. The unprecedented demand exhausted the first edition in a feiv weeks. The second edition has been revised and enlarged. SCIENTIFIC PUBLISHING COMPANY, PUBLISHERS, 27 PARK PLACE. NEW YORK. ADVERTISEMENTS. XIII KROM'S -PERFECTED STANDARD— Steel Rolls and Ore Breakers. Revolving Screens, Ore Feeders, Dry Kilns AND Concentrators. Plans for Lixiviation Concentrat- ing and Ore Crushing Works. S. R. KROM, 151 Cedar St., New York, U. S. A. MECKLENBURG IRON WORKS, CHARLOTTE. N. C, Washers for Phosphate Rock. CRUSHERS, ENGINES, BOILERS AND GENERAL MINING MACHINERY. RICHARDS & CO., LIMITED, importers and manufacturers of Chemicals, Assayers -.A.nsriD- Chemists Supplies. NEW YOBK : CHICAGO : NEWARK, N. J. : 41 Baxclay Street. 1 12 and 114 Liake Street. 863 and 865 Broad Street. XIV ADVERTISEMENTS. G ACCIDENTS AND THEIR PREVENTION. BY SIR FREDERICK AUGUSTUS ABEL. With Discussion by Leading Experts. Also, the United States, British and Prussian Laws relating to the Working of Coal Mines. Price, - - - $4.00 in Cloth, Contents : Mining Accidents. By Sir Frederick A. Abel. Wiih discussion by President Bruce, of the British Institute of Civil Engineers; and Prof. Arnold Lupton, C. Tylden Wright, Emerson Bainbridge, William Morgans, Sydney F. Walker, Col. Paget Mosley, Henry Hall, Col. J. D. Shakespear, Stephen Humble, Sir George Elliot, Sir Warington Smyth, A. R. Sawyer, A. Giles, R. Bedlington, Edward Combes, George Seymour, Henry Harries, William Cochrane, James Ashworth, J. B. Atkinson, W. N. Atkinson, Bennett H. Brough, T. Foster Brown, S. B. Coxon, C. Le Neve Foster, W. Galloway, Max Georgi, W. S. Gresley, J. A. Longdon, A. R. Sennett, M. H. N. Story Maskelyne, Arthur Sopwith, A. L. Steavenson, A. H. Stokes and others. List of safety appliances, with description of detachment of mineral from its bed, carriage of mineral to the surface, difficulties attendant on the presence of gases, etc. Safety lamps (oil and spirit), safety lamps (electric) and other appli- ances. The Mining Laws of Colorado, Illinois, Indiana, Iowa, Kansas, Ken- tucky, Maryland, Missouri, Ohio, Pennsylvania, Washington, West Vir- ginia and Wyoming; also those of Great Britain and Prussia add a feature of great value— for these laws have never before been collected or published in accessible form. Of the unanimously favorable criticisms of this book, we have only space to quote one : " It is a work that should be in the hands of every intelligent man connected with a colliery, no matter what his position. It is as valuable to the intelligent miner as it is to the mining engineer or the colliery ofhcial." — Co//iery Engineer. SCIENTIFIC PUBLISHING COMPANY, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. XV THE STURTEVANT MILL CO., 88 MASON BUILDING, BOSTON, MASS., SOLE MANUFACTURERS STURTKVANT MILL, For Crushing and Pulverizing "Phosphate Rock" and all Hard Material. Simple, Effective, Economical, Used and Endorsed BY MANY Prominent Fertilizer Manufacturers. ALSO ROCK EMERY MILLSTONES. Superior to the Best French Buhr-Stones. IF YOU WISH Any device for regulating steam, write to the MASON REGU- LATOR CO., of Boston, Mass. We also send, for 30 cents in stamps, our little booic, " Key to Steam Engineering," serviceable to anyone in charge of a steam plant. A!R COMPRESSORS. THE NORWALK IRON WORKS CO., Circidara. SOUTH NORWALK, CONN. XVI AD VERTISEMKNTS. ROBERT POOLE & SON CO., BALTIMORE, MD., U. S. A. ^^' 0^ ^' o^ ,v^ ,t»^ G^^ ^^^ ^4 ^^XT. ^a 'i? ^^^ ^^^. ^z Sji Qf> 4^5 ^i O^^ MACHINERY FOR FERTILIZER FACTORIES, Improved Mixing Machines, BAGGING OR SMITHERING MACHINES, F*hosf»haxe: Rock Crushkrs, CONVEYORS, ELEVATORS. x<^ (^^ XiV .\c ^ ^' ,G^^- ^4^^ '^^. %. '^1 SHAFTING, PULLEYS, HANGERS, ETC ADVERTISEMENTS. XYTT —THE— BECKETT FOlDEYillACHiE CO., ARLINGTON, NEW JERSEY, Works and OflSce Adjoining Depot, 30 Minutes from New York via Erie Ry. -BUILDERS OF- ENGINES, CRUSHERS, -AND- Mining Machinery. S£NB FOR CATALOGUE. XVIII ADVERTISEMENTS. n illERlClN METHODS EDWARD D. PETERS, Jr., m. e., m. d. No one who has a copy of the First Edition of this great work should fail to secure the Second Edition, Revised and Enlarged. Profusely Illustrated. Price $4.00. This is the Best Book on Copper Smelting in the language. It contains a record of practical experience, with directions how to build furnaces and how co overcome the various metallurgical difficulties met with in copper smelting. Chapter I.— Description of the Ores of Copper. Chapter II.— Distribution of the Ores of Copper. Chapter III. — Methods of i opper Assaying. Chapter IV.— The Roasting of Copper Ores in Lump Form. Chapter V.— Stall Roasting. Chapter VI.— The Roasting of Ores in Lump Form in Kilns. Chapter VII. — Calcination of Ore and Matte in Finely Divided Condition. Chapter VIII.— The Chemistry of the Calcining Process. Chapter IX.— The Smelting of Copper. Chapter X— Blast Furnaces Constructed of Brick. Chapter XI.— General Remarks on Blast P'urnace Smelting. Chapter XII.— Late Improvements in Blast Furnaces. Chapter XIII —The Smelting of Pyritous Ores Containing Copper and NickeL Chapter XI V.— Reverberatory Furnaces. Chapter XV.— Refining Copper Gas in Sweden. Chapter XVI.— Treatment of Gold and Silver Bearing Copper Ores. Chapter XVII.— The Bessemerizing of Copper Mattes. General Index, Etc. THE SOIENTinO PUBLISHING COMPANY, PTTEHjISII BUS, — -"gf PARK PLACE, NEW YORK. ADVERTISEMENTS. XIX THE LAWRENCE MACHINE COMPANY, Lawrence, Mass., MANUFACTURERS OF Centrifugal Pumps, Steam Engines AND GENERAL MACHINERY. SEND FOR CATALOaUE "C" AND DISCOUNTS. PAUL C. TRENHOLM, -BROKER IN- PHOSPHATE pOCK Brimstone, Chemicals, Fertilizers, etc, ALSO RICK. Charleston, S. C XX ADVERTrSEMENTS. THE UNANIMOUS OPINION OF THE BEST CRITICAL JUDGMENT OF THE WORLD IS THAT THIS WORK IS THE MASTEEPEECE OF LITERARY, ARTISTIC AND TYPOGRAPHICAL ART. GEMS AND PRECIOUS STONES OF NORTH AMERICA A POPULAR DESCRIPTION OF THEIR OCCURRENCE, VALUE, HISTORY, ARCHEOLOGY, AND OF THE COLLECTIONS IN WHICH THEY EXIST, ALSO A CHAPTER ON PEARLS AND ON REMARKABLE FOREIGN GEMS OWNED IN THE UNITED STATES .... ILLUSTRATED WITH EIGHT COLORED PLATES AND NUMEROUS MINOR ENGRAVINGS BY GEORGE FREDERIC KUNZ, CetH Expert vnih Messrs. Tiffany ir' Co , special agent o/ the United States Geological Surrey and of the Eleventh United States Census, member of the Mineralogical Society o/ Great Britain and Ireland, the Imperial Mineralogical Society of St. Petersburg, ike Societe Fran^aise de Alin^ralogie, etc; Price, - - $10.00 SCIENTIFIC PUBLISHING COMPANY, 27 PARK PLACE, NEW YORK. ADVERTTSEM EN TS. XX] PULVERIZING Forty of the most successful Fertilizer manufacturers of the United States use Frisbee-Lucop Mills. Their example should be followed. STANDARD SCREEN FRISBEE-LDCOP MILL. E. Frank Coe. \ Manufacturer of Standard Fertilizers, (_ 16 Burlins Slip. i New York, October 13, 1891. ' The Frisbee-Lucop Mill Co.: Gentlemen : We have been using your mills exclus- ively since 188."5, and are as well satisfied with them as ever. The cost per ton for grinding rock has been very light. I consider them one of the best mills in the market. Yours truly, E. Frank Coe, Julian D. Fairchild. FRISBEE-LUCOP MILL COMPANY, Manufacturers of Blast and Screen Mills for Pulverizing Phosphate Rock, Cements, Limestone, Graphite, Talc, Mica and all kinds of Ores and Metal- lurgical Products. Capacity up to .S tons per hour, finished product, no tailings. Records of seven years' continuous use. OFFICE: 145 BROADWAY, NEW YORK, U. S. A. XXII ADVERTISEMENTS. CHiMicii iND mmm KSSAYS BY THOMAS STERRY HUNT, m. a., li.. r>.. Author of "Mineral Physiology and Physiography,' "A New Basis for Chemistry," " Systematic Mineralogy," and " Chemistry of the World." FOURTH EDITION. REVISED AND ENLARGED. f:rxc:ei. 2. so. T^^JBLE OB^ CONTEISTTS. Preface ; XII. 1. Theory of Igneous Rocks and Vol canoes; XIII. II. Some Points in Chemical Geology ; III. The Chemistry of Metamorphic Rocks; XIV. IV. The Chemistry of the Primeval Earth ; XV. V. The Origin of Mountains; XVI. VI. The Probable Seat of Vocanic Action; XVII. VII. On Some Points in Dynamical Geology; fill. On Limestone, Dolomites and Gypsums; xviir. IX. The Chemistry of Natural Waters; XIX. X. Petroleum, Asphalt, Pyroschists and Coal ; XX. XI. Granites and Granitic Vein stones; The Origin of Metalliferous De- posits; The Geognosy of the Appala- chians and the Origin of Crys- talline Rocks; The Geology of the Alps; History of the Names Cambrian and Silurian in Geology; Theory of Chemical Changes and Equivalent Volumes; The Constitution and Equiva- lent Volume of Mineral Species; Thoughts on Solution and the Chemical Process; On the Objects and Method of Mineralogy; The Theory of Types in Chem- istry. Appendix and Index. THE SOIEKTIFIO PUBLISHINa COMPANY, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. XX III 1 NEI BASIS Ft CHBimy. A CHEMICAL PHILOSOPHY BY THOMAS STERRY HUNT, m. a., ll. d., Author of "Chemical and Geological Essays," " Mineral Physiology and Physiography," " Systematic Mineralogy," and " Chemistry of the World." THIRD EDITION, REVISED AND AUGMENTED, WITH NEW PREFACE. r»RICE, S2.00. T^BLTT; of COIN^TEISTTS. I. Introduction. II. Nature of the Chemical Process. III. Genesis of the Chemical Ele ments. IT Gases. Liquids and Solids. V. The Law of Numbers. VI. Equivalent WeiKlits. VII. Hardness and Chemi- cal Indifference. VIII. The Atomic Hypothesis. IX. The Law of Volumes. X. Metamorphosis in Chemistry. XI. The Law of Densities. XII. Historical Retrospect. XIII. Conclusions. XIV. Supplement. Appendix and Index. THE SCIENTIFIC PUBLISHING COMPANY, FTJBLISHEHS, 27 PARK PLACE. NEW YORK. XXIV ADVERTISEMENTS. MINERAL A SECOND SERIES OF CHEMICAL AND GEOLOGICAL ESSAYS, WITH A GENERAL INTRODUCTION. BY THOMAS STERRY HUNT, m. a., lt.. r).. Author of "Chemical and Geological Essays," "A New Basis for Chemistry," "Systematic Mineralogy," and " The Chemistry of a World." SECOND EDITION. REVISED AND ENLARGED. PRICE, $5.00. TABLE OF COITTEITTS. Preface. Chapter I —Nature in Thought and Language. Chapter 11.— The Order of the Natural Sciences. Chapter III.— Chemical and Geological Relations of the Atmosphere. Chapter IV.— Celestial Chemistry from the Time of Newton. Chapter V.— The Origin of Crystnlline Rocks. Chapter VI —The Genetic History of Crystalline Rocks. Chapter VII.— The Decay of Crystalline Rocks. Chapter VIII.— A Natural System in Mineralogy, with a Clas.sificatioa of Silicates. Chapter IX.— History of Pre-Cambrian Rocks. Chapter X.— The Geological History of Serpentine, with Studies of Pre- Cambrian Rocks. Chapter XI. —The Taconic Question in Geology. Appendix and Index. THE SCIENTIFIC PUBLISHING COMPANY, 27 PARK PLACE, NEW YORK. ADVERTISEMENTS. XXV SYSTEMATIC MINERALOGY BASED ON A NATURAL CLASSIFICATION. WITH A GENERAL INTRODUCTION. THOMAS STERRY HUNT, m.a., ll.d. Author of "Chemical and Geological Essays," "Mineral Physiology and Physiography," "A New Basis for Chemistry," and " The Chemistiy of a World. ' BOUND IN CLOTH. PRICE $5.00. The aim of the author in the present treatise has been to reconcile the rival and hitherto opposed Chemical and Natural History methods in Min- eralogy, and to constitute a new system of classification, which is " at the same time Chemical and Natural Historical," or, in the words of the preface, "to observe a strict conformity to chemical principles, and atihesame time to retain all that is valuable in the Natural History method ; the two opposing schools being reconciled by showing that when rightly under- stood, chemical and phy.'^ical characters are really dependent on each other, and present two aspects of the same problem which can never be solved but by the consideration of both." He has, moreover, devised and adopted a Latin nomenclature and arranged the mineral kingdom in classes, orders, genera and species, the designations of the latter being binomial. TA^IiLE OF COISTTEJCTS. Chapter I. The Relations of Mineraloery; Chapter X. The Constitution of Minora! II. III. IV. V. VI. 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