S 639 .G41 Copy 1 ■ METHODS OF Analysing Fertilizers 1884. PUBLISHED BY THE National fertilizer association, Baltimore. METHODS OF ANALYSING FERTILIZERS GERMANY AND THE UNITED STATES, -AND EFFORTS MADE IN BOTH COUNTRIES FOR ARRIVING AT UNIFORM METHODS AND RELIABLE RESULTS, PRECEDED BY SOME DATA ON THE FERTILIZER INDUSTRY IN GERMANY. COMPILED AND TRANSLATED BY A. de GHEQUIER, Secretary. PUBLISHED BY THE NATIONAL FERTILIZER ASSOCIATION Baltimore, March, 1884. Pkess of GUGGENHEIMER & WEIL, BALTIMORE. PREFACE, The subject of analysis and of commercial valuations of fertilizers claimed the earnest attention of the Board of Directors from the very time of the formation of this association. The great discre- pancies between analyses of the same goods in different States, and the practice of assigning commercial valuations to fertilizers on the basis of these analyses, seemed to call for energetic efforts to bring about, in some way, greater uniformity as regards the former and a different modus operandi as regards the latter. With this object in view, the association endeavoured to obtain information on that subject from official sources in European coun- tries and it is gratifying to be able to state that very kind and very full replies to the numerous inquiries made by the Secretary have been received. These inquiries were extended over the num- ber of manufacturing establishments engaged in Germany in the production of artificial manures, their total production and consump- tion, the control exercised by the government and by the agricultu- ral experiment stations, finally the status of the analysis question. Dr. Gr. Krause, the proprietor and editor of the "Chemiker Zeitung," responded by forwarding an exhaustive paper, from which copious extracts are made in the following pages. The Minister of Agri- culture for the Kingdom of Prussia, to whom the communication addressed to the Minister of Agriculture of the German Empire had been referred, forwarded in a printed pamphlet, compiled by Privy Councellor Dr. H. Thiel, the work of the latter. Then several prominent chemists, who had been written to for full descriptions of the methods used by them in the analysis of fertilizers, obligingly complied with the requests made of them. From the material obtained from these threefold sources and from other official documents the following compilation has been prepared. The Board of Directors concluded to append to it a synopsis of what so far has been done in this country towards accomplishing uniformity of method of analysis, and submits the following pages as the result of the work. Baltimore, March 1884- The important part which the comparatively young fertilizer industry plays in the German Realm, becomes apparent when it is borne in mind that about four hundred (400) establishments are engaged in the manufac- ture of artificial manures within its borders. According to the official import lists, there were imported 1 during the year 1882, 116,150 tons of guano, of which quan- tity about 52,544 tons consisted of Peruvian guano, while the balance of 63,606 tons were phosphate guanos. These figures represent approximatively an average for a term of 9 years. Besides the above quantities there were imported — Mineral Phosphates 20,739 tons. Bone Meal (exclusive of export) -3 2 >354 " And used Phosphorites and Coprolites from German Mines. ..38,718 " German Bone Meal, &c 4M7 8 " Of this aggregate quantity, viz : 249,439 tons were manu- factured in German factories — 38,713 tons Peruvian Guano, requiring 12,997 tons Sul. Ac. 63,600 " Guano Phosphate, 1 J= o 9,402 " Phos. ofvar. kinds, I |||2 159,278 " 20,740 " Imp. Mineral Phos. .' |||-< 73,832 " BoneMeal,boneblkj | 38,713 " Nat. Phos. Rocks, @ 75$ 29,035 245,000 " Raw Material, requiring 201,310 tons Sul. Ac. The quantity of Sulphuric Acid tallies with the fact that of the total productions of this article in 1882, after de- ducting export and adding on import, about 298,647 tons were consumed, of which fully Yi found employment in the manufacture of fertilizers. The quantity of raw material on the other hand, tallies with the estimated production of fertilizers as made by the Association of German Fertilizer Manufacturers. Under the supposition that the superphosphates contain on an average 15$ of soluble phosphoric acid valued at 9c. per pound or $24 per ton, The total production represents a value of. $9,246,300 To this must be added About 121,671 tons Chili-Saltpetre 6,806,800 44,244 " Sulph. Ammonia 3998,400 58.070 " Peruvian Guano "1 5,530 " Fish Guano. J 3' '7 24,889 " Imported Bone-meal } 55,305 " German do. J '^ ^'' Making a total of. $25,477,900 This does not include blood and horn and hoof prepara- tions, &c, nor Potash-salts of which were consumed, 29,865 tons Kainit by farmers $122,094 22,122 " Chlorkalium by farmers 725,900 2,765 " Kali-Magnesia 40,460 11,061 " Salts of other kinds 36,220 About 65,813 tons of the value of. $924,674 How much all other classes are interested in and affected by the fertilizer industry appears best from the considera- tion that the freights on raw and manufactured manures and materials amount to about 2 million dollars ; that 2 /i of the products of Pyrites-mines are consumed by it; that bag factories depend upon it to the extent of bags for 663,660 tons, representing nearly $600,000; that the iron and coal industry is constantly engaged in keeping factories supplied with machinery and coal, the farmers in raising food for nearly 20,000 laborers, the banking establishments in furnishing credit to the trade to the amount of 15 to 20 "million dollars, finally the tax-departments in levying at least 1,000,000 dollars on real-estate, &c, depending .upon or belonging to this industry. In the quantity consumed there were contained about 150,000,000 lbs. Phosphoric acid and 63,000,000 lbs. of Ammonia, which, calculating 20 pounds to the Morgen '(1 Morgen=li acre) would indicate that about 10 million acres have been supplied in 1882 with artificial manures. With the steady progress in the application of fertilizers, the German industry will before long be confronted by the task to supply fertilizers for about 58 million acres, which constitute the area of Germany under agricultural cultiva- tion, hence it will have to become twenty times larger than it is now. From this consideration results as it is stated the duty of the government to protect this industry and to pre- vent by a duty on imported, particularly English fertilizers, •a competition fatal to the prosperous expansion of the 'German industry. It is a matter of national interest in the estimate of Germany to see this industry grow vigorously •and to encourage capital to make investments in it. The foregoing extracts and condensations from the report •of Dr. Krause do not claim to give absolutely correct statis- tical information, yet they possess enough intrinsic value to serve as a measure of the magnitude and importance of this industry in Germany. The following data have been com- piled here from tabulated statements which, in their origi- nal form would hardly have given a correct insight into the 'commerce of Germany with other countries in articles de- fend ent upon the fertilizer industry. The imports during the year 1882 of natural guanos, -crude potash, nitrate of soda, sulphate of potash, muriate of potash, and other fertilizer materials amounted to 467,739 tons, while the exports of the same articles for the same .year consisted in 326,039 tons. For the first 6 months of the year 1883 the respective -figures are: Imports, 214,631 tons; Exports, 139,428 tons. A communication, dated Berlin, October 4, 1883, from the ministry of Agriculture, Domaines and Forrests con- tains the following significant passages : " The manufacture- of artificial manures is perfectly free and in no way ham- pered by restrictions. About the mode of voluntary (not obligatory) control which the agricultural experiment sta- tions exercise over the fertilizer-trade, you will find full information in Dr. Thiel's work " Privy Councellor Dr. H. Thiel begins his pamphlet " on the consumption and control of artificial manures in Prus- sia" with an expression of regret that correct statistical information regarding consumption cannot be given. This alone, he says, would furnish a reliable gauge for measuring the intensity of the cultivation of the soil (high-farming), thus identifying agricultural progress with the development of the fertilizer industry. It would, moreover, he contends*, be the means of indicating to what extent care is bestowed upon the preservation of the fertility of the soil and enable us to draw valuable conclusions in regard to the elements- of plantfood required by the various crops and modes of cultivation. Last, but not least, he thinks that data of consumption would be the best argument against a saying which, strange to say, has not yet entirely lost currency > viz : that artificial manures on certain soils are inefficient and valueless. But, he adds, that only in districts which are very much behind the times in agricultural progress i& this absurd statement heard, since it is quite certain that the- farmer cannot attain the maximum yield from the soil- without providing by artificial means the indispensable plant nutriment. Apart from this consideration it is, he says, of great importance to know the manner in which the trade- in fertilizers is being done and the character and quality of these artificial manures. In this last respect Germany points with great and just pride to the development of this- industry. The numerous agricultural experiment stations- which originally were established for the investigation of purely scientific questions, rendered incalculable services to* agriculture by devoting themselves to the rather monotonous task of exercising a certain control over artificial manures. The old mode of selling fertilizers, called by a generic name^ 9 (brands), has been replaced by one where the analysis fur- nished with the goods determines their character, and even this mode is now already being superseded by a still more rational way. Farmers no longer buy so and so many bags. of guano or bonemeal, &c, but order from the manufac- turers so and so much of each desired plant-nutriment, viz :: phosphoric acid, ammonia and potash and the price of these ingredients is quoted to them. This stage of transition to- the most rational mode of dealing between farmer and manufacturer is now obtaining throughout Germany. Rep- resentatives of the fertilizer-industry endeavored at various times to have the government establish a compulsory con- trol of fertilizers and uniform regulations applicable to the whole trade, but this has been opposed by the Agricultural Experimental Stations and Agricultural Associations, as in- opportune and by no means required by the existing state of affairs. The following agricultural experiment stations, Inster- burg, Konigsberg, Danzig, Eldena, Regenwalde, Dahme, Posen, Breslau, Kiel, Halle a. S., Hildesheim, Gottingen, Munster, Bonn, Marburg and Wiesbaden exercise in the Kingdom of Prussia, a control, mutually agreed upon between each station and factory, over about 220 manu- facturing establishments. As regards the mode of control exercised by these agricultural experiment stations over the fertilizer-trade, Germany, as appears from the reports received, passed through the same stages through which Belgium passed and as the result was in both countries the same, it is well worth while to go more fully into the subject. In the first place the stations interfere in no way with the selling-prices, nor with the stipulations of the sale-contracts made by the manufacturers. In the second place the stations assume control over the products of such factories only, as voluntarily report them- selves, that is, desire to sell their goods subject to the control of the various agricultural experiment stations. In all such cases, namely, in cases where factories sell subject to the control of stations, these are notified of the sale-conditions- 10 ^and as appears from numerous forms of contracts appended to Dr. Thiel's report, the stipulations are pretty uniform. The purchaser must draw a sample according to the mode prescribed in the contract in presence of one or two wit- nesses, divide this into 3 equal portions and forward it to the station. Tins must be done, however, inside of a fort- night after the receipt of the goods. The chemist of the station, or the chemist agreed upon in the sale-contract, then analyses the sample and a discrepancy of 5-10$ in phos. acid, 3-10$ in am., and 5-10 in potash is not consid- ered an evidence of shortage of valuable ingredients, be- cause the chemists concede that such differences, in spite of close observation of the same method of analysis, are una- voidable. Any greater shortage is allowed for at a certain price agreed upon between buyer and seller, an excess of one ingredient being considered an offset to a shortage in another. It is the manufacturer who in all cases deter- mines the value of phosphoric acid, ammonia and potash and not the station. As Dr. Thiel well remarks, the differences established now and then, are so small that the control in no way im- pedes the healthy development of the fertilizer industry -and the same deserves iu his opinion to be called as so honest and clear a trade that one would wish the same could be said of the trade in seeds and feeding articles. All this applies to the present state of affairs since December 18th, 1881. Prior to that date there existed the same lack of uniform- ity in the results of analyses, which is the source of so just •complaints in this country. From letters received from Prof. Dr. Fresenius at Wies- baden ; Dr. Ulex, Hamburg ; Dr. Hugo Schulz, Magde- burg ; Dr. Saxhlot, Munich, and Prof. Kroker, Breslau, and from pamphlets published on the subject of analysis of fertilizers, it appears that several conventions of agricultural chemists, directors of experiment stations, and manufac- turers, were held before uniformity in the method of analy- sis was established. The first of these conventions was held 11 at Madgeburg in 1872, then followed those at Danzig and Munich, and, finally, on December 18th, the last one at Halle a. d. S., which resulted in the adoption of the follow- ing: METHOD OF ANALYSING EERTILIZEKS According to the agreement made by the Directors of Agricultural Experiment Stations, Chemists and Manufacturers in Con- vention assembled at Halle on December l§th, 1881. A— PREPARATION OF SAMPLES IN THE LABORATORY. 1. Dry samples may be put through a sieve for the better breaking up of lumps, if this on account of a lumpy condi- tion appears desirable. But whatever remains on the sieve should be as thoroughly broken up as to pass finally through the sieve, and this portion should be thoroughly mixed with the portions that passed first through the sieve. 2. "With moist samples the use of the sieve is impractica- ble ; the preparation of the sample is then confined to a thorough mixing in the mortar. 3. The weight of samples should be determined on their arrival and the whole sample should be prepared and pre- served in glass jars with tightfitting stoppers, if possible in a cool place. 4. When balances of samples are to be forwarded, either the whole balance should be sent to the controlling chemist •or a thorough mixing of the whole balance should take place before dividing it. In case of crude phosphates and of bone-black, the moist- ure should be determined for the purpose of identification at a temperature of 100°C with the former and 130°C with the latter. In case of fertilizers which during the process of drjing loose carbonate of ammonia, this should be determined. 5. Chemists should endeavor to receive only carefully . i ro moo « ChOO r*» N IT) J. LO o O O m < nco O ro» CO ONO « m m h a\ o m oo >o -<*■ N ( 3-~-3 coSH,5 3*3 jS"o rt 6 ■3 S o 2 o S U)PhHm?h<1 •a o (* O o X> jctf CD J3 •**; 45 CU •-Q 1 ■ M ■s 'xnopa^ <* ►; *° Jq *cu c a <» £ s a\ .s CO VO en o •i •xnopa^ ■*■ t^co a 3 .2 CO c-nvo t>. .2 rj g *■*• t^ rt ctf . H '»iii°d N rn > ■a P4 o H *3- 1— 1 r*. t^ 03 •J3UJS-E3 > 4-* u t^ CO J3 >^ H -X tj pjEdaqg m a. "-a o o\o* . cu. T3 "c3 •Siqa;^ CU •4-J o O 1 M C^ (^ 1 Oh •z'xnopaq ° "^ o CU )-l ■£ en 03 q J N o\ 6 •i 'xnopa^ H t^. H CO -O d o § woo HH • • W H ■< en -i- 1 CO ■J3JH03 6 0* 03 22 ** O en cu ^ en < X ■jranjsBQ f* S O 5 > •*w 1 l| G '3 << S < cu 46 Mr. Rasin also handed in letters received from a number of chemists expressing their views concerning the Oxalate' method : in some instances disapproving, in others express- ing their willingness to abide by the decision of the Con- vention. Professor Tonry discussed at length the disadvan- tage of the Citrate method, especially emphasizing the injustice which it did to those fertilizers containing large amounts of iron and alumina, and in which the reversion had been caused by these basis instead of lime. Recent experiments were cited which had been made in England, Scotland and Germany, to prove that in many instances,, at least, reverted phosphate of iron was as valuable agricul- turally and the equivalent of phosphate of lime. Dr. Simon called attention to the difficulty of obtaining neutral citrate of ammonia, or of maintaining it after it had been secured, and to the marked effect which was ex- erted by different degrees of alkalinity produced by the addition of ammonia for the sake of neutralization. In contrast to this, he called attention to the stability of oxo- late of ammonia. He was followed by Dr. Ledoux, who pledged himself, as bethought all chemists present would do, to adopt what- ever method the Convention endorsed. He called attention to the fact that the Washington and Boston meetings had each endorsed the method of Fresenius, Neubauer and Luck,. -provisionally for one year, that the year had already expir- ed, and consequently there is now no authorized or official method, so far as American agricultural chemists are con- cerned. He further called attention to the difficulty of filtering rapidly when the citrate solution is employed, and the consequent discrepancies in point of time which must exist where one solution, filtering rapidly, remained in contact with the solvent for a much shorter period than in the case of another. Mr. Stillwell said he had used the citrate method for years, and in his hands he finds this method quite satisfac- tory. He found no difficulty in filtering all solutions con- taining the citrate rapidly, if proper care was used. He 47 considered the oxalate and citrate methods, when carried on under the same conditions, entirely the equivalents of each other in guanos and ordinary superphosphates, except- ing when iron and alumina were present. In the latter case he had observed great discrepancies. The citrate pro- cess seemed to favor superphosphates free from iron and alumina, which, in his opinion, was rather unjust, as, in his experience, superphosphates containing iron and alumina, gave as good results on the field as any others. In his ex- perience, two chamists in the same laboratory could use the citrate method w T ith proper care, aud have their work agree within reasonable limits. The same was true of the oxalate^ In view of the fact that he has tried both methods, and that there was so much dissatisfaction with the citrate, and since he considered them, properly conducted, the equiva- lents of each other, excepting in the case of iron and alumina phosphates, he had concluded to adopt hereafter the oxalate method. Professor Lord said he considered that a great part of the discrepancies and variations was due, not so much to the solvent, but to the differences in carrying out the details. He hoped that whatever method was adopted, the details would be so clearly and plainly stated that it would be im* possible to have any more trouble on this account. He objected to the term "reverted" as not implying the whole truth about the phosphates dissolved by the citrate or oxalate solvent, and suggested tnat chemists adopt the term "Phosphoric acid soluble in at deg. 0." (whatever solvent and temperature might be adopted). He hoped that not only the methods of conducting the analysis would be very clearly and definitely agreed upon, but that even the apparatus to be used in each case should be specified. Dr. Lehmann stated that his home was in Weisbaden, that he had studied with Fresenius, and was thoroughly familiar with the method of Fresenius, Neubauer, and Luck, that he knows it was adopted mainly with a view to its application for the analysis of bone products and others where little or no iron was present. He too considers the 48 •difference in method and time of grinding, stirring, shaking and filtering, etc., etc., grave causes of discrepancy. In his experience oxalate of ammonia solutions filtered uniformly well. Dr. Tonry moved that instead of the so-called citrate of ammonia method, the Convention do adopt provisionally for one year oxalate of ammonia of as a solvent. Dr. Ledoux stated that there were three interests involved in whatever decision was arrived at by the Convention; the interests of manufacturers, the interests of farmers, and the professional interests of the chemists. Since it was appa- rently impossible, either in this country or in Europe, with our present lights, to arrive at thoroughly satisfactory methods, rendering it impossible to stand upon entirely scientific grounds in the discussion, chemists must consider the commercial points at issue between buyers and sellers, and observe a strictly neutral and just middle ground. Dr. White said that he had analyzed over 350 samples of fertilizers last year, and found iittle or no trouble with the Washington method. He not only checks his work by duplicate analyses, but again and again, when the same samples have been returned to him without his knowledge, "he has found his previous work corroborated. The new analysis agreed with the former. He acknowledged that his analyses did not alw r ays agree with those of other chemists. He stated that we were in posession of but few results making comparison of the Oxalate with the Citrate method, bmt he did know that "An especial British Commission, after considering the very subject which we are now •discussing for over two years, decided that the Oxalate process was the very worst of all, in regard to the discrep- ancies." Since, as has been stated, we are not all agreed as to what shall be included by the term "reverted," he w T as earnestly opposed to any change, for the present, from the Washington method, but preferred that the whole subject be again referred to a committee, with instructions to make •certain tests which could be suggested. He further stated that we could not base a scientific discussion on the analyses 49 •of the samples of Navassa Guano just reported, because we know nothing as to how they had been prepared, and their number was too i'ew to allow us to generalize trom their results. He therefore moved, as a substitute to Professor Tonry's resolution, that the subject be again referred to a committee to investigate and report ; and that, until said •report shall be made, the Washington method be adhered to. Dr. Dabney seconded this motion, and he declared that, following the Washington method as nearly as possible, •except in a few minor details, his results agreed closely, and he was entirely satisfied with the present system. He, too, had found by experience, 'that in artificially prepared Reverted Phosphate of Lime, the Washington method was •entirely satisfactory, but did not consider it always so in Phosphates containing Iron. Professor At water said he was pleased to see a spirit of •concession and harmony in the Convention, and earnestly desired that all interests involved should be carefully considered and harmonized. It being one o'clock, he moved •that the Convention adjourn until two. Carried. The Convention came together at two o'clock, and Professor Tonry insisted that his motion should be put. He reiterated his previous statement that, in many legal con- troversies in which he has been engaged as expert, the Court favored the Oxalate method as used in Baltimore. He simply desired to press his resolution that Oxalate of Ammonia be adopted, leaving the question of method to be settled in •some other manner. He stated that he found the Oxalate method best in point of expedition and accuracy. Dr. Dabney protested against any change, explained the system of obtaining samples in North Carolina, and of making analyses. By courtesy, Mr. Tonry withdrew his resolution tempora- rily, to allow a motion that, in the discussion which should follow, each speaker should be limited to five minutes. Adopted. Dr. J. Lawrence Smith considered it possible that a fair way out of the difficulty would be to discard the term 50 "reverted" altogether, and simply report the amount of Phosphate soluble in a given solution, whether of aeid or not, as might be agreed upon. Dr. Dabney again spoke, repeating his convictions that the Citrate method would give equally correct, if not better results, than the Oxalate method. Mr. Rasin, on behalf of the manufacturers, stated that all manufacturers had been intensely annoyed, and their business interests seriously interfered with by the great difference in the analyses of their goods, and consequently in the great difference in the commercial valuations as applied by the various State Departments. While he, as President of the Chemical Exchange, had presented a petition stating candidly that they favored the Oxalate method, he wished to say that all they wanted was justice and uniformity, and was willing that the Convention should adopt the Oxalate method, or the Citrate method, with certain changes ; either would satisfy the manufacturers. Drs. Simon, Lehmann, I.edoux and others followed, dis- cussing the Oxalate method. The last stated that since the European chemists have failed to agree on a definite method, examining the question from a chemical standpoint ; since they have been discussing the question longer than we in this country, he feared we, too, would find it impossible to agree on any result. He had found it exceedingly difficult to keep the temperature absolutely within the limits pre- scribed by Presenilis, Neubauer and Luck, but agreed with Mr. Rasin that we must strive for truth and uniformity. Dr. Atwater said that the manufacturers had put their case fairly and honestly, and had agreed to abide by the decision of the chemists. It was clear, he thought, that they demanded, and rightly, that our method, if not just, should be at least uniform. He believed that we should make any change which appeared to approach nearer to uniformity than we are at present, and he stated that it seemed to him that the Oxalate method was a shade nearer uniformity than the Citrate. 53 Professor Dunnington examined in detail the reports of analyses of JSfavassa Guano, which had been submitted to the Convention, and pointed out the fact that, although no instruction had been given as to what method should be employed in the Oxalate of Ammonia text, and definite instructions had been given for each of the Citrate tests, that the discrepancies with the Oxalate were considerably less than with either of the Citrate methods. Messrs. Stillwell, Ledoux and others stated their readiness to abide by the decision of the Convention, whatever it might be, as did Drs. Dabney, White and others. The question being called for, the Chairman decided it was on the substitute offered by Dr. White. Dr. White wa& requested to put his resolution in writing. It was as- follows: Resolved, That the method provisionally adopted by the Washington meeting be continued for one year, and that the matter of the relative merits of the Citrate and Oxalate methods be referred to a committee of five, appointed by the Chair, to report at a subsequent meeting. Dr. Ledoux called attention to the extreme improbability of our being able, by any amount of experiment, to arrive at a scientifically accurate method, and considered it necessary to simply agree upon the solvent and method to be employed for the coming year, and all stand by the agreement. The substitute of Dr. White being put was lost by the following vote : Aye — At water, Dabney, Lord, White. ISTo — Baker, Castner, Crowell, Davison, Lehman, Lowe, Mager, Simon, Stillwell, Tonry, Wheeler, Williams, Wilson. The following gentlemen were absent or refrained from voting : B. JN T . Baker, Bolton, Caldwell, Davison, Dunnington, Hale, Hopke, Kedzie, Ledoux, JMattison, Myricke, Smith, Schweitzer, Springer. A number of gentlemen explained theii votes : The motion was lost. 52 The question then recurred to the original motion of Dr. Tonry : that Oxalate of Ammonia be substituted for Citrate as a solvent. Professor Caldwell spoke upon this motion. He had listened to the statements of the various chemists with interest. He considered that the protection had been mainly for the benefit of the farmers and that it was time the rnanufactiirers were protected a little. He was, therefore, in favor of trying the Oxalate method for a while. It was all a matter of experiment, and if, at the end of the coming year, the Oxalate method is found to be unsatisfactory, it can be readily changed. The resolution of Professor Tonry being put, it was adopted by the following vote : Aye — Baker, Castner, Crowell, Davison, Dunnington, Ledoux, Lehman, Lowe, Mager, Stillwell, Simon, Tonry, Williams, Wilson. No — Atwater, Dabney, Lord, Wheeler, White. Absent or refrained from voting : B. N. Baker, Bolton, Caldwell, Davison, Hale, Hopke, Kedzie, Mattison,Myricke, Schweitzer, Smith, Springer. Dr. Ledoux offered the following resolution, which was unanimously adopted : Resolved, That a committee of seven be appointed to consider the best method, and its details, for the determina- tion of Insoluble or reverted phosphoric acid by the use of the Oxalate of Ammonia; that this committee be instructed to report as soon as possible; and that we pledge ourselves to adopt the method chosen by the committee ; that the committee be appointed as follows : one by the Chair, three by the President of the Chemical and Fertilizer Exchange, and three to be the State Chemists in charge of fertilizer •control present at the meeting, viz.: Drs. Dabney, Lord and White. The Chair appointed Prof. W. O. Atwater. The Presi- dent of the Chemical Exchange appointed Messrs. Lehmann, Simon and Stillwell. 53 It was moved that a committee be appointed to continue the investigation of the whole subject of the determination of insoluble phosphoric acid, comparing the various methods now in use and reporting to this convention when prepared to do so. The Chair appointed Messrs. Ledoux, Goessman, Jenkins, Liebig and Stillwell. It was moved that the committee appointed last year to provide for the absorption of the present convention into the American Association for the Advancement of Science, as a sub-section of chemistry, be continued with full power to act. — Carried. It was moved that the committee appointed to fix upon the method for determining insoluble or reverted phos- phoric acid, by means of oxalate of ammonia, be instructed to report to the secretary of this convention, and that he shall forward copies of their report to agricultural and other chemists throughout the country. On motion the convention adjourned, to meet upon call of the Chair, provided a meeting was necessary before their organization as a sub-section of the American Association for the Advancement of Science. (After adjournment nearly all the chemists present, who were not already members of the American Association for the Advacement of Science, joined said Association.) A. K. LEDOUX, Secretary. KEPOKT. The following is the report of the committee of seven, appointed for the purpose of preparing the details of the oxalate method. The accompanying letter is also published, as it explains somewhat the action of the committee. 54 Grand Rapids, Mich., Aug. 25, 1881. Dr. A. R. Ledotjx, Sec. Conv. Ag. Chemists, 17 Cedar St., K Y. Du. Sir : — Herewith I send you the minutes of the com- mittee appointed to propose a method for determination of "reverted" phosphoric acid by ammonium oxalate. As Dr. Stillwell, the secretary of the committee, was obliged to hurry away from Cincinnati, and was not to return directly to New York, and, further, as it seemed to him, as well as myself, desirable to submit the draft of the report to the other members of the committee for approval? I undertook to attend to the latter task and forward the report to you. As I left Cincinnati somewhat hurriedly also, I have not found convenient opportunity to forward it until now. As you will see the committee felt that, under the cir- cumstances, they could do no more now than propose a provisional and' temporary plan, but have taken steps toward the proposing of something more nearly adequate to the demands of the case. It was, however, the feeling of nearly all, I think, that the requisite data will be gotten only after considerable research, and that without them it will be im- practicable to propose a method that will command, or even be entitled to the following of chemists generally. Will you please see that Mr. Stillwell has opportunity to correct the proof of the report. Yours truly, W. O. ATWATER, Chairman. REPORT. Cincinnati, Aug. 19, 1881. Report of proceedings of the committee appointed by the Convention of the Agricultural Chemists, Aug. 18, 1881, to prepare directions for the use of ammonium oxalate as a solvent in the estimation of reverted phosphoric acid. 55 Present — Prof. W. O. Atwater, Chairman, Drs. White, Lord, Dabney, Simon, Lehmann, and Stillwell. This committee, which has been charged with the duty of proposing a method for the estimation of so-called re- verted phosphoric acid by the use of ammonium oxalate as a solvent, finds itself at the outset seriously embarrassed ; — •on the one hand by the lack of exact information as to what compounds of phosphoric acid are dissolved by ammonium oxalate and under what conditions ; and on the other by the facts that so few of the chemists officially connected with the work of fertilizer analysis were present at the Con- vention, and that all such who were present felt themselves, under the circumstances, unable to favor the proposed •change. In the first place it seems best to the committee to pro- pose for temporary use a method which approaches as nearly as may be to those which have already been employed by •some chemists ; second, to attempt at least some investiga- tions in the hope of obtaining more light upon the action ■of ammonium oxalate ; third, so soon as they shall thus be placed in condition to warrant it, to suggest a plan for the •coming year as they have been directed to do. I. PREPARATION OF THE SAMPLE. At least 250 to 300 grammes are to be put through a sieve with meshes 3 m. m. square (about one-eighth of an inch). All lumps are to be prepared by grinding in a mor- tar or by cutting until they will pass through the sieve. The whole is well mixed and an average sample bottled for analysis. Special care must be taken during this operation ■of sifting that no drying of the sample take place. 2. Determination of tne soluble and undecomposed phos- phoric acid. (a) Two grammes of the material, transferred to a suit- able vessel, are rubbed up with a small quantity of cold water (carefully avoiding any pulverization), transferred to •a filter and there washed with cold water, which is added 56 at first in small successive portions until the washings no* longer react acid. Soluble phosphoric acid is determined in the filtrate. (b) The residue upon the filter containing the reverted and undecomposed phosphates is carefully washed into a lipped porcelain mortar with the aid of a wash-bottle hold- ing 100 c. c. of a perfectly neutral solution of pure, crystal- ized oxalate of ammonium. Each one hundred cubic centi- metres of this solution contains two grammes of the salt. The coarser portions are allowed to settle, and the fluid,, with the suspended particles, is put into a suitable vesseL The residue remaining in the mortar is rubbed to a very fine paste and brought, with the remainder of the ammo- nium oxalate solution, into the same vessel. A water bath containing 400 c. c. of water for each sam- ple treated is brought to a boil, the flame is removed, and the vessel containing the oxalate solution is immediately placed in the boiling water. It is then left in the water bath for sixty minutes, being shaken every ten minutes. At the end of sixty minutes ths vessel is removed from the water bath and the contents immediately filtered. The- residue is thoroughly washed with cold water and used for the determination of insoluble phosphoric acid. The Chairman and Secretary were directed by vote to prepare samples, and a schedule for experimental work, and to invite the co-operation of chemists for trial analyses of' the samples submitted. The Committee adjourned subject to call by the Chair- man. CHAS. M. STILLWELL, Secretary.. 57 SUPPLEMENT To Report of Proceedings of the Cincinnati Convention, of Agricultural Chemists. New York, September 23d. The following letter from Prof.' S. "W. Johnson, has only just reached the Secretary, after the foregoing report was printed and partially distributed. It failed to arrive in time for the Cinainnati Meeting, although mailed before the middle of August, owing to misdirection. Owing to the great value attached to anything from Dr. Johnson in the line of agricultural chemistry, and the regret of our Convention at the absence of his report, the Secretary pub- lishes the letter in this form, rather than not at all. A, E. LEDOUX, Secretary. New Haven, Ct., August 14th, 1881.. Dr. A. R. Ledoux, Secretary. Dear Sir : I must beg you to present to the Association of Agricul- tural Chemists my deep regrets at being unable to make any satisfactory report on Methods of Analyses of Super- phosphates. I accepted the chairmanship of the Committee, with appointment to which I was honored at the .Boston Meeting, after much hesitation and with many misgivings in view of the probability that I could command neither time nor strength to discharge the duty satisfactorily.. 58 Efforts to effect a meeting of the Committee failed, because of the wide distances that separate them. Various in- vestigations undertaken in the Laboratory of the Conn. Ag. Exp. Station, although yielding instructive and valuable results, could not be brought to a satisfactory conclusion, being interrupted by the regular and necessary work of the Station, and finally mj vacation leisure finds me without the strength to digest the material that has accumulated, and to report the progress attained in a manner at all com- mensurate with the importance of the subject. I will state a conclusion that is the result of much ex- perience, viz : that the citrate of ammonia method applied as directed by Fresenius, Neubauer and Luck may easily give reasonably satisfactory results on the low-grade super- phosphates usually found in our markets, but that it fails to extract the "reverted phosphates" when their quantity is considerable. Thus from " Curacoa Guano " so-called, containing 30$ of phos. acid, 50 C. C. of Ammonia Citrate, as exactly neutral as it could be made, in h half hour at 40° C, with constant and uniform agitation : Extracted, from 2 grms. Curacoa % P205 5.6 •' i " " A. 94 13-7 16.6 21.0 It is evident, then, that for such phosphates the quantity of solvent must be increased. In conclusion, I beg to be continued another year on the -Committee or preferably to be discharged. Yours very truly, S. W. JOHNSON", Chairman of Committee. 59 REPORT XDr Analysis Obtained from Samples and Schemes fok Experimental Work, Prepared by the Chairman and Secretary of the Committee Appointed at Cincin- nati, Ohio, Aug. 18, 1881, Consisting of W. O. Atwater, Chairman, Mess. White, Lord, Dabney, Simon, Lehmann, Stillwell. In accordance with the request of the committee a scheme was prepared, as follows : Schedule for tests of Solvent Action of Ammonium Oxalate and Citrate upon Phosphoric Acid in Fertilizers. In accordance with the request of the committee ap- pointed by the Convention at Cincinnati to propose a method for the determination of so called "reverted phosphoric acid," the following schedule for a series of investigations on the solvent action of ammonium oxalate has been pre- pared. The plan for the investigation discussed in the meeting of the committee involved determinations of phos- phoric acid, soluble, reverted, (by difference), insoluble and total, in samples of Navassa and South Carolina superphos- phates, the insoluble to be determined by ammonium oxalate under different conditions as described below. It was proposed rather hurriedly and with the feeling, evidently shared by all present, that it was at best only the beginning of a survey of a narrow portion of the field. In the present schedule, besides the determinations specifically included in that plan, a few others are suggested, to-wit : the action of ammonium citrate by the Washington method upon the same samples, the action of both oxalate and citrate upon samples of the raw phosphate from which the samples of 60 superphosphates are made and the repetition of at least- part of the analyses at a later date or dates to learn the effect of the reversion which may proceed with time. The work as thus laid out will serve to test, in the sam- ples operated upon, the uniformity or disagreement of results by the different analyses, the comparative action of oxalate- and citrate, the solubility of the crude phosphate in the reagents used, and, especially, the effect of the factors named below upon the solvent action of the oxalate. By "Washington Method" is to be understood the method: adopted by the Convention of Agricultural Chemists at Washington, July 28, 1880; See pages 23 and 24. By "Cincinnati Method" is to be understood the method- proposed provisionally and for temporary use by the com- mittee appointed for that purpose at the Convention of Agricultural Chemists at Cincinnati, August 18, 1881. See pages 55 and 56. The determinations of Total Soluble and Insoluble Phos- phoric acid are practically the same by both the above plans, and one of each in each sample will of course suffice.. The directions for extracting soluble Phosphoric acid be- fore proceeding to determination of insoluble by ammonium citrate or oxalate will of course be observed in each case. A. Study of Solvent action of Ammonium Oxalate un- der varying conditions. The factors whose influence it is proposed to investigate are :: I. Concentration of Ammonium Oxalate Solution. II. Patio of Yolume of Solution to Weight of Substance- III. Time of Digestion. IT. Temperature of Digestion. By the "Cincinnati Method" these are : I. 2 grms. Ammonium Oxalate Crystals in 100 c. c. of' Solution. II. 100 c. c. Solution to 2 grms. Substance. III. 60 Minutes, IT. Initial 100° centigrade, gradually cooled down. 61 It is proposed to test each of the above factors separately, •and by three determinations, to-wit : One in accordance with the Cincinnati Method, which may be for convenience be designated as "normal," b. One with higher concentration or higher ratio of solution to substance or higher temperature or longer time of di- gestion, a. One with lower concentration, etc., or shorter time, c. That is, there will be for each factor, one determination, 6, in which all conditions will be "normal," and two others in which the condition in question will be varied. The normal determination will ot course also suffice for the de- termination of "insoluble phosphoric acid" by the Cincin- nati Method, in the comparison between that and the "Wash- ington Method. The Details for each factor will be as follows : I. Concentration of Solution. Three solutions of Ammonium Oxalate will be required. a. 4 grms. crystals in 100 c. c. solution The three determinations of insoluble phosphoric acid in ■each sample will involve : Weight of Substance Weight of am. oxalate crystal. Volume of Solution Time of Digestion Temperature of Digestion. 2 grms. 2 grms. 2 grms. 4 grms. 2 grms. i grms. ioo c.c. ioo c.c. ioo c.c. 6o minut's 6o minut's 6o minut's Initial ioo° C. eld dwn Initial ioo° C. eld dwn Initial ioo° C, eld dwn II. Ratio of Solution to Substance. Solution as prescribed in Cincinnati Method: for a, 200 c.c; h, 100 c.c; c, 50 c.c. Details as follows : Weight of Substance. Volume of Solution. Time of Digestion. Temperature of Digestion. 2 grms. 2 grms. 2 grms. 200 c.c. ioo c.c. 50 c.c. 60 minutes. 60 minutes. 60 minutes. Initial 100° C. eld down. Initial ioo° C. eld down. Initial ioo C. eld down. 62 III. Time of Digestion. For a, 120 minutes ; b, 60 minutes; c, 30 minutes. Weight of Substance. Volume of Solution. Time of Digestion. Temperature of Digestion. 2 grms. 2 grms. ioo c.c. ioo c.c. ioo c.c. 120 minutes. 6o minutes. 30 minutes. Initial ioo C. eld down. Initial ioo° C. eld down. Initial ioo° C. eld down. IV. Temperature of Digestion. For a, 100° 0. continuous ; b, 100° C. initial and gradually cooled as by Cincinnati Method ; c, 40° C. continuous. Weight of Substance. Volume of Solution. Time of Digestion. Temperature of Digestion. 2 grms. 2 grms. 2 grms. 100 c.c. 100 c.c. 100 c.c. 60 minutes. 60 minutes. 60 minutes. 100° C. continuous. Initial 100° C. eld down. 40 C. continuous. B. Comparison of Solvent Action of Ammonium Oxalate by Cincinnati Method with that of Ammonium Citrate by Washington Method. This seems eminently desirable and can be accomplished by one more determination of insoluble phosphoric acid in each sample. The amount of this work which each of the co-operating analysts would be able to do, was discussed by the committee and it was felt to be of the greatest importance that the schedule be arranged and the work divided so as to secure the best results with the least labor and in the shortest time. If each analyst were to undertake the study of only one of the the above factors the united contributions would suffice for the immediate purpose nearly as well and at much less, cost than if each were to go through the whole. 6a The following schedule will show the amount of work required of each analyst on this basis, taking as an example the series with the first factor, "I. Concentration of Solu- tion of Ammonium Oxalate." SCHEDULE OP DETERMINATIONS IN ONE SERIES. Raw Phosphates. Superphosphates Navassa S. C. Navassa S. C. Moisture, i i i i Phosphoric Acid. Total, i i i i Soluble, i i Insoluble in Am. oxalate, I. a. i i i i " " l.b. Cincin. Method i i i i I.e. i i i i Reverted, (calculated), " (i) (i) Available, " (i) (i) (i) (i) Insoluble in Am. citrate, Wash- ington Method. i i i i Reverted, (calculated) " 00 (i) Available, (i) (i) 1 (i) (i) In two raw Phosphates, In two Super-phosphates. In four Samples. Total, 224 Soluble, 2 2 Insoluble in am. oxalate, 6 6 12 Insoluble in am. citrate, 224 In all, 10 12 22 / The above schedule cover the ground specifically agreed upon for investigation by the committee. Individuals will naturally supplement these at discretion. It would be well to investigate other materials as apatite, bone, etc. Repeti- tion of the determinations of soluble and insoluble phos- phoric acid in the superphosphates at a latter date or dates, to be agreed upon, would be very valuable to test the effect of the reversion that proceeds or may proceed with time. It would also add greatly to the value of the work if analyses could be made of the several portions of the superphosphates- which are dissolved in water and in oxalate and citrate and 64 ■which are left undissolved. Researches of this latter sort will help materially toward the getting of the fundamental -data needed for the construction of just methods of analysis. Samples of Raw Navassa, Acidulated Navassa, Raw South Carolina, Acidulated South Carolina, were prepared and sent by the Secretary to the members of the committee, also to the following chemists ; G. A. Liebig, C. U. Shep- ard, Jr., S. W. Johnson, G. 1ST. Cook, F. P. Dunnington, C. A. Goessman, G. C. Caldwell, H. W. Wiley, T. R. Wolf, Peter. Collier, A. R. Ledoux, P. A. Genth, H. Y. Castner, W. M. Habirshaw, (in some of the packages sent was in- cluded a sample of Curacoa guano.) In order to lessen the work to these Chemists outside of the Committee, the experimental tests desired were appor- tioned as follows, with reference to the four factors of the ■ scheme. Raw & Acid. Navassa. Factor I. & Curacao 1 S. Car. I. Navassa " II. S. Car. " II. Navassa " III. S. Car. " III. Navassa " IV. S. Car. " IV. td n Rp Liebig. Johnson. Caldwell. Shepard. Goessman. Wiley. Wolf. Cook. "The following table gives the results received by the Secretary. The Phosphoric Acid results of Prof. Dunning- ton, are obtained by the uranium process, those of Dr. Ledoux are the average of two determinations, those of •Still well and Gladding by a double precipitation or the ammonia magnesic phosphate, checked by a duplicate de- termination made by the method adopted at the Convention of German Agricultural Chemists held at Halle, in Decem- ber, 1881, see pages 11 to 15, the results by the two meth- -ods differing- less than 0.10$ 65 NAME OF ANALYST. IS Stillwell Gladding. T3 u OJ a a; .c c/3 c a '5 c D Q y, Moisture at ioo° C. Raw Navassa, 3-55 9-85 1.30 6.50 8-55 * 5 .I2 *23.63 *i.90 *I2.70 3.60 14-55 i-37 7.41 7.92 Acid Raw South Carolina, 13-93 Acid " Curacao Guano, 7.17 7.80 Total Phosph. Acid. Raw Navassa, Acid Raw South Carolina, Acid " Curacao Guano, 28.57 16.20 26.58 18.25 26.50 29.81 15-53 26.38 17.91 28.14 28.59 15-69 26.66 18.34 27.42 14.27 25-47 19.69 30.72 16.70 27.64 20.05 29.66 15.84 Sol. Ph. Acid. Acid Navassa, Acid South Carolina, 4-15 10.45 4-15 10.99 4-38 10.81 4.18 11.82 4.29 11.66 4.46 Insol. by Cinc. Process. Raw Navassa, Acid " Raw South Carolina, Acid " " 26.64 5-47 25-32 4-35 I5-3I 27.81 5.22 24-75 3-73 26.26 27.71 4-33 25.09 4.89 25-74 4.42 22.61 4-65 28-57 4-35 25.29 4.82 27.30 27.72 4-05 Insol. by Wash. Process. 27.61 24.06 3-42 21.89 4.10 18.48 2.80 19.80 2.91 Acid " 10.12 Acid " " I7-05 24.82 *Determined in Air-Bath at 160 — 180 C. G6 Instead of giving the results obtained by each analyst from the different subdivisions of the four factors, we give below the total averages of the results obtained, selecting the two samples of acid, phosphates. Acid. Nav. Acid. S. Car. Insol. by Factor I. a. 3-25 3-34 " " " I. b- 4.64 ■ 4-49 << (i it I. c. 7.12 4-85 t i t( " II. a. 4.60 4-03 (i < i " . II. c. 5-5i 5.06 i i " " III. a. 4.80 4.11 " a " III. c. 5.I0 4.28 i t " . ( IV. a. 3.80 4-03 . ( i t " IV. c. 5.62 4.S4 It seems from the above table, taken in connection with the separate results given in the reports sent, that the con- centration of the solution and the temperature at which the digestion is made, are the two most important factors. But there is this to be considered — does either the normal cit- rate or the oxalate process extract all the so-called reverted phosphates, especially those of iron and alumina? If not, theD neither will answer and some modification must be made. The results of a long series of experiments on this point are given in a paper by Mr. Thos. S. Gladding, "on the Determination of Reverted Phosphates." Amer. Chem. Jour. Yol IY. p. 123. We also call attention to the marked difference between the results of phosphoric acid, especially in the total as given above. Certainly, if such differences are obtained in absolutely identical samples, the method for the determi- nation of phosphoric acid is not yet fully understood. In this connection see papers on the determination of phos- phoric acid by F. A. Gooch, Amer. Chem. Jour. Yol. I. p. 391, and T. S. Gladdings, Jour, of Amer. Chem. Sec. Yol. 4, p. 135. Respectfully submitted to the Committee. CHAS. M. STILLWELL, Sec. 67 During the spring of 1883 an experiment was made by the Committee on agricultural chemistry of the Chemical and Fertilizer Exchange. The following method was sent with the samples to the chemists mentioned below. METHOD. Pass the sample through a sieve twelve meshes to the inch. Put two grams of this into a beaker with about 20 c. c. cold water, stir wich a glass rod tipped with rubber, let set- tle, filter Supernatant Liquid into a 200 c. c. flask, repeat decantation five or six times, transfer residue to the filter and continue washing until the 200 c. c. are made up. Take 50 c. c. of the above and determine Soluble Phos- phoric Acid, (P205)as follows : — precipitate with Molybdic Solution, warm to about 50° C, set aside for three hours, filter, wash with a mixture of one-half Molybdate Solution and one-half water, dissolve in Ammonia Solution, add 10 c. c. Magnesia Mixture slowly with constant stirring or ro- tation of beaker, bring the volume of the liquid up to 100 c. c. with Ammonia Solution, warm to about 50° C, set aside in cool place for three hours, filter and wash. In calculating results add .001 grm. Pyrophosphate Magnesia for every 50 c. c. Ammonia Solution used in washing. Wash the residue from the two grams with the aid of a wash bottle containing 100 c. c. Citrate Ammonia Solution into a mortar, rub to a fine paste, decant and wash into a flask (about 200 c. c. capacity) with the remainder of the Citrate Solution. Heat a water bath containing 400 c. c. to 65° C, remove the flame, place the flask in the bath, let stand half hour, shaking every five minutes — the flask must be tightly cork- ed — filter, wash with 100 c. c. of a mixture of equal parts of water and Citrate Ammonia Solution. Incinerate the filter and undecomposed Phosphate, dissolve in Nitric Acid and proceed as in determining the Soluble Phosphoric Acid. 68 For total Phosphoric Acid, dissolve two grams directly in Nitric Acid, make up to 200 c. c. Take 50 c. c. and pro- ceed as in determining the Soluble, using 15 c. c. Magnesia Mixture. Determine Moisture in 5 or 10 grams at 100° C. MEMOKANDUM. The reagents mentioned in the above method are prepar- ed as follows : Magnesia Mixture, dissolve 55 grams Magnesium Chlo- ride, (fused,) 70 grams Ammonium Chloride in 650 c. c. water, and make up to one litre with strong Liquid Ammo- ma, (°/ .) Ammonia Solution is a mixture of one part strong Liquid Ammonia and two parts water. Ammonium Citrate Solution is a nentral solution of this salt sp. gr. 1.09. One hundred cubic centimeters of this solution contains about twenty grams of the Crystallized Salt. Molybdate Solution, one part Molybdic Acid dissolved in four parts Liquid Ammonia, (two parts strong Ammo- nia and one part water,) and 'poured into fifteen parts Nitric Acid, sp. gr. 1.20. The following will make about two litres. 4 oz. Molybdic Acid, 10 \ oz. Strong Liquid Ammonia, 5£ oz. Water, when cold pour slowly into 60 oz. Nitric Acid, sp. gr. 1.20, (about half C. P. Acid and half water,) with constant stirring. 69 Q i— ( < H W O w K CO h CO W K O 2 O •J o En w 'llOSIABQ - A\ - 3 icioH vo -^ o pi m m pi n O tOOsrON covO ■oipg "llOSIABQ - M 'O PI NmMCOiO VB N r^HCO O pi o\ p! pi covd M MM •o;iBg 'uuBiuqgq •£) -\\ PI ^t rONlOCI 10 0\N ON PI PI CT\ m m ^J-io M MM M CO CO M M CN O t~- -3; PI ro vo CO VO xj- m' co -j- M M •o;iEg 'uouiis - AV co m on o t^ t^ ■^- CO P) \o VO PI pi cfv pi m -^i-vo PI O VO VO m t^ PI CO O CO 10 CO ONVO IOH M»t M M ■oii^a 'Siqaiq 'V D 00* lOH IOVO CO lO^t o ■* ■* p< on pi pi -*vo O •* CO PI VO CO M NVO -st- ON co d vd -"d- h pi ■4' Stillwell Gladding, N. Y. Two Independent Analysis. H N tONO ^j PI lON'tcl ■^ on pi m "d-vd M M t^ Onvo nrin o >cf M M CO O vo VO ■* O co ^f -*C0 ^t- co rOffiCI h -3-vO O CO CO CO M O co co C^ co m LOCO co ^t M MM t/5 H w K U w H » H VO VO CO ^t ^cj- ON iO ON PI PI "sfvO ONVO Os 10 r-~ PI CO M ON M N ON ^NiOfOH -sj- M MM '■lOl^J. "H "AY VO PI *^-VO t-^ co t^ O C?N ON M M PI On "* co PI VO M MM CO !>. CO O M M ^O mo rjiH O o\vd ifjH ci 4 '3 'N •jf 'XauqBQ - A\ '3 •p9AI939J }OU S}[nS9J 5 l- to A\ J° ajnssgjd o; 2uia\o •Or J cd . "WIaI I^nsn CO u CO PI "d-vd M MM PI O OS ON CO PI IO IO M * "^t" M uocd to pi vd M MM •BO •a^IMM "3 "H 1ONH00 CO M VO CO MOO^O d t>. •<*• pi co >o M MM IO ^t* O <0 CO t^ O m PI ^D CO co ^d^d pi d pi M M Moisture, Soluble, Reverted, Available, Insoluble, Total, Moisture, Soluble, Reverted, Available, Insoluble, Total, '3 'S P3AIOSSIQ g^Bqdsoqj ppy (bssbabm 7g S p9A[OSSIQ) a^Bqdsoqa ppy 70 The compiler has been unable to ascertain whether at the last meeting of the A. A. A. S., held at Minneapolis, any action has been taken by the agricultural chemists attend- ing it, and if so, what the same has been. It is believed, however, that the meeting passed without discussing this subject at all. Messrs. Stillwell and Gladding, however, have gone over the whole ground very carefully and with painstaking minuteness and have from time to time published the re- sults of their investigations. (:Amer. Chem. Jour. vol. iv? No. 2; Chem. News, vol. xlvi, pp. 1831: Amer. Chem. Jour. vol. vi, No. 1:) Their work confirms what the trade has been aware of all along, namely, that the methods at present used in analysing fertilizers do not give accurate, uniform and just results. As Dr. Atwater stated (see page 50) the manufacturers may rightly demand that the method if not just, should be at least uniform. It appears also from the views of the chemists expressed in the foregoing pages that the reverted phosphoric acid whether derived from phosphates of lime or phosphates of iron and alumina is a very valuable ele- ment of plant food and that the main difficulty exists in determining the contents of that ingredient with uniform- ity. The discrepancies now existing on that point are so great that it seems hardly in conformity with principles of justice and equity to base upon results so greatly at vari- ance any commercial valuation. Whilst it is true that nearly in all States where the agricultural departments publish analyses and commercial valuations, they are pre- faced by some remarks to the effect that this is only a com- parative valuation and does not determine the agricultural value of the fertilizer in question, it is also true that the farmer may omit to read these brief remarks and even if he reads them, he may not fully comprehend the meaning con- veyed by them, so that it is fair to presume that he is large- ly guided in his purchases by the higher or lower commer- cial valuation as given at present. 71 Then, again, it is well known that the manufacture!' is not consulted in fixing upon the unit-prices used each year in each State for the commercial valuations. Phosphoric acid, ammonia and potash are said to be worth so and so much in one State and a different amount in another State and these estimates are understood by the farmer as the value of these ingredients to him at the place he pur- chases, which is, of course, entirely erroneous. In some States the insoluble phos. acid is taken in consideration in the computation of commercial valuations, in some it is dis- regarded. For instance in Georgia available phos. acid (soluble as well as reverted) is valued at 100 per pound, am- monia at 200, potash at 60, while in Alabama soluble phos- phoric acid is considered worth 120, reverted phos. acid 80, insoluble 40, ammonia 180 and potash 50, while the same figures in North Carolina are for avail, phos. acid 90, am- monia 200, potash 60 ; Ohio adopted 12^0 for avail phos. acid, 50 for insoluble phos. acid, 180 for ammonia and 60 for potash and in Connecticut a graduated scale applies making amonia worth from 260 down to 110, sol. phos. acid 110, reverted 80 and insoluble from 60 to 2|0, potash from 70 to 1J0. From these few instances it is evident that no uni- form standard exists and that these prices are more or less arbitrary. No doubt those who fix upon these prices do it in the belief that these represent fair and just equivalents, but after all, the sincerity and honesty of the intention affords a poor consolation to the manufacturer who finds his goods depreciated in the market. Besides, the prices of raw materials are subject to the same fluctuations as those of any other commodity and are regulated not only by the laws of demand and supply, but other circumstances, and only the buyer of raw material at the expiration of each year could compute the average price paid by him for each ingredient. Even these figures however, would not represent the value of the ingredients in the goods for sale, since time (equiva- lent to interest), labor and money are being spent by the manufacturer in the conversion of raw material into a com- mercial fertilizer. Thus the cost of manufacturing is tot included, while forming an unavoidable item and the farmer generally believes that at his place a pound of phos. acid, ammonia and potash represents the stated values for- getting that he is so and so many miles from the place at which these values perhaps are correct. The parental government theory so much detested in this country finds in this practice a unique and inconsistent application and it would seem as if the German policy of letting the manufacturer say what valuations he attaches to his goods, is better calculated to insure uniformity. The - law of competition necessarily rules out those who quote very high figures and the laws of trade by being accorded a free play would soon establish certain standard values for each season. With uniformity in the method of analysis and in the carrying out of the same, resonably uniform results would obtain everywhere and with standard valuations deter- mined upon by the trade, the existing unsatisfactory condi- tion of things would soon be replaced by one equally wel- come to chemists, departments and manufacturers. And these two issues once settled, more uniform and less contra- dictory legislative enactments on the subject of the trade should not remain beyond the precincts of possibility. Most of the grievances are so well recognized by State chemists, commissioners of agriculture and other State officials as serious obstructions to the development of the fertilizer- industry, that it is to be hoped steps looking towards bring- « ing about more harmony and accord will be taken and result in establishing that which the trade is justly very anxious to see established. LIBRARY OF CONGRESS