T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
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Vol. 6 , No. 8
TABLE111-RELATION EXISTING BETWEEN THE SULFUR, PHOSPHORUS AND MANGANESE I N THE GEOLOGICAL AREASOF KENTUCKY VIRGINSURFACE CULTIVATED SURFACE VIRGINSUBSOIL CULTIVATED SUBSOIL Sulfur Phosnhorus Maneanese Sulfur Phosnhorus Manzanese Sulfur Phosohorus Manzanese Sulfur Phosnhorus Manzanese D T T T T T T T T T St L - c C D C R A R A R A C R A R A St L - c S D T D C R A R A T C E C F E C F E C F Q R A R A P A R A S C S S St L - c S S Q W C F R A S S S W C F K- W E C F W C F E C F E C F Q W C F W C F S S W C F W C F E C F E C F E C F E C F Q Q D D W C F W C F St L - c St L - c W C F St L-c S t L-c Q Q St L - c K- W K-W W C F S W C F K-W K-W E C F E C F Q D K-a’ K-W St L-c K-W K-W St L - c D D D D Q S t L c K-W S t K-W K- W L-c Q
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Quaternary, Eastern a n d Western Coal Fields and finally t h e Keokuk-Waverly, which is generally regarded a s t h e poorest of all. I n a majority of t h e samples, t h e cultivated surface as well a s t h e subsoils show considerable losses of manganese when compared with t h e corresponding virgin. Furthermore, t h e surface soils of both generally contain more of this element t h a n their respective subsoils. T h e counties in which t h e soils were collected for this work were Wolfe, Graves, Warren, Henderson a n d Madison; also Nos. 8 1 3 t o 8 2 0 from Metcalfe a n d Jefferson, or a t o t a l of forty samples. The above holds t r u e in all with respect t o t h e manganese content of t h e surface compared with its subsoil, while in three instances t h e virgin surface contained less a n d in t w o t h e same amounts of manganese a s t h e cultivated samples. T h e remainder of t h e samples were generally selected from those sent in b y t h e residents of t h e s t a t e for chemical analysis a n d a s it is sometimes difficult t o obtain t h e accurate history of a field for several years past, since ,in certain sections much of t h e land is rented t o tenants, i t would have been better t o collect all for this work, b u t this would have caused considerable delay. I n t h e Keokuk-Waverly area, commercial fertilizers were used while in some of t h e others it is very probable t h a t commercial fertilizers or manure had been used in former years. This may partly account for t h e fact t h a t t h e manganese content has been maintained in t h e soils of this area a s well a s in some of t h e others. T h e large losses of manganese in some of t h e cultivated soils are hardly t o be explained as due t o t h e amounts removed b y t h e different crops grown on t h e m for t h e accumulated analyses show t h a t t h e ordinary crops do not contain sufficient amounts of this element t o justify this conclusion. It may be t h a t cultivation converts t h e manganese compounds into soluble forms which are readily leached out a n d t h u s lost in t h e drainage water. This is a m a t t e r t h a t needs further investigation, a n d t h e writer desires, as soon as a n opportunity affords, t o examine some of t h e surface a n d deeper drainage waters of t h e different areas in order t o determine t o what extent this elementispresent. SUMMARY
I-It
has been proven b y different observers t h a t manganese is universally present in soils, plants a n d many animals. 11-The majority of t h e experiments show t h a t t h e application of certain manganese compounds, particularly t h e sulfate, t o some crops, is decidedly beneficial. These experiments have further shown t h a t while small applications are in many cases beneficial t o plants, large applications are generally harmful.
111-In a large majority of t h e soils examined, t h e writer found considerably less manganese in t h e cultivated surface t h a n in t h e corresponding virgin samples. T h e same holds t r u e for t h e subsoils. IV-In practically every case, t h e surface soils of t h e virgin a n d cultivated areas contain larger amounts of this element t h a n their respective subsoils. V-When some former work on these samples is considered, it is found t h a t a majority of t h e soils contain considerably more manganese t h a n phosphorus, b u t many samples have much less, while t h e losses of manganese in t h e cultivated areas are usually greater t h a n of phosphorus. VI-There are large differences in t h e manganese content of t h e soils of t h e different geological areas a n d sometimes in those from t h e same area. The amounts found in t h e surface soils vary from 0.005 t o 0.331 per cent, and in t h e subsoils from 0.002 t o 0.264 per cent. VII-As a rule, t h e better agricultural areas contain much larger amounts of manganese t h a n t h e inferior areas. KENTUCKY AGRICULTURAL EXPERIMENT STATION STATEUNIVERSITY, LEXINGTON
ONTHE COMPOSITION AND VALUE OF BAT GUANO By C. F. MILLER Received April 20, 1914
At various points in this country, especially in t h e warmer regions, caves exist which are frequented by bats in such numbers t h a t their excrement or “ b a t guano” has accumulated in amounts sufficient t o give i t some commercial importance a s a fertilizer. Generally, t h e amount of guano is rather limited in a n y one deposit a n d in t h e aggregate, t h e entire quant i t y now in sight, or probably t o be discovered in this country, is not sufficient t o appreciably affect t h e fertilizer industry. On t h e other hand, such a deposit may represent a considerable fortune t o t h e individual discoverer or owner, a n d t h e frequency with which these small deposits occur, justifies a short discussion of their composition a n d value. T h e following table containing t h e results of analyses of b a t guano samples sent t o this Bureau from time t o time, shows their composition as well as t h e locality from which t h e y were taken. BAT GUANOANALYSES Results in percentages, based on air-dry sample LOCATION N(a) Pi06 RaO VOLATILE ANALYST J. A. Cullen 4 . 2 4 2.31 1.28 Near Carlsbad, N. M . . . . Guadeloupe Mts., N. M . . 1.77 2.68 0 . 4 1 40:O C. F . Miller 10.82 1 . 0 8 1.01 . . W. H. Waggaman Torreon, N. M ......, . . . . . . . . . B. E. Brown Oregon Co., M o . . . . . . . . . . . . . 8 . 1 0 2 . 0 6 0 . 5 8 1 .OO 3 . 4 0 0 . 2 1 . . W. H . Waggaman San Juan, Porto Rico(6). . . . . . W. H. Waggaman San Juan, Porto Rico(6).. . . . . 0 . 5 0 2 . 4 0 0 . 2 9 El Fondo. Santo Domingo. 9 0 . 0 C. F. Miller Haiti. . . . . . . . . . . . . . . . . 11.84 4 . 8 0 1.61 (a) Determined by Mr. T C. Trescott. of the Bureau of Chemistry. ( b ) Both of these samples contained considerable calcium carbonate.
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AW.2 1914
TIIE JOURS.! L OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
Both potash (KzO) a n d phosphoric acid (P205) were determined b y t h e official method for fertilizers, t h e former b y t r e a t m e n t with concentrated sulfuric acid, ignition a n d extraction with dilute hydrochloric acid; t h e latter b y t r e a t m e n t with a solution of magnesium nitrate, evaporation, ignition a n d a similar extraction. A glance a t t h e table shows t h a t a wide variation exists, n o t only i n t h e percentages of t h e fertilizer constituents present, b u t also in t h e ratios of nitrogen t o phosphoric acid, nitrogen t o potash or phosphoric acid t o potash. This large variation is attributable t o either one, or both of t w o things: ( I ) T h e presence of considerable extraneous m a t t e r such a s rock dkbris, etc., or ( 2 ) t h e removal of some of t h e more available constituents b y leaching, or, i n t h e case of nitrogen, b y decomposition of t h e material a n d subsequent volatilization as ammonia. I t m a y be said in this connection, t h a t in t h e more recent deposits, nitrogen is t h e most valuable constituent, phosphoric acid a n d potash following in t h e order given; b u t on “aging,” t h e nitrogen content decreases very rapidly since most of i t is present in a n available form.’ T h e writer wishes t o place particular stress on t h e sample from Haiti as i t represents uncontaminated a n d practically undecomposed b a t guano which is very likely of recent origin, since thousands of bats2 spend their d a y s in t h e cave at t h e present time. As received in t h e laboratory, i t consists of a dry, dark brown powder, in which t h e wings a n d other p a r t s of insects can be seen b y t h e naked eye.3 Over 90 per cent of t h e phosphoric acid present is water-soluble as is also t h e greater p a r t of t h e potash; a n d if t h e high percentage of nitrogen, together with t h e large a m o u n t of organic m a t t e r (as shown b y t h e volatile determination), are reckoned with these facts, i t is evident t h a t t h e substance is very valuable. It has been calculated from d a t a concerning t h e Haitian cave (which h a d n o t been fully explored a t t h e time) t h a t i t contains approximately seven hundred tons of b a t guano. Based on t h e market prices of 2 0 cents per pound for nitrogen,‘ a n d j cents per pound for phosphoric acid a n d potash, t h e material is worth (not considering t h e organic m a t t e r , which is a big factor) very close t o $40 per t o n , or approximately $30,000 for t h e entire deposit. Whether or not this is a representative example is a m a t t e r for conjecture, b u t very likely it is above t h e average in quantity a n d i t certainly is in quality. N o specific d a t a on t h e extent of t h e American deposits already discovered, are available. I n several instances, however, t h e y were reported as being of considerable size. T h e facts given in this paper warrant t h e suggestion t h a t a further search for bat guano be made, since 1 Thompstone. E , “ B a t Guano in Burma,’’ A g r . J . Indra, 4 (1909). 379-81 1 I t has been reported that the “flight of the bats on leaving the cave, in rope-like formation, as large in diameter as an ordinary street car, requires over an hour, by actual timing.” 3 For further description see, Tod, W., “Ueber Fledermausguano,“ L a d w . ners Slalton, 1 (1859). 264-268. 4 “Quotation on Nitrogen of Bat Guano,” Bull. Texas E x $ . Stolion, 160, July, 1913, p 10
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there is a possibility, or even a probability, of t h e existence of other valuable, a n d as yet undiscovered deposits in this country. BUREAUOF SOILS
u. s. DEPARTMENT OF AGRICULTURE WASHINGTON
STUDIES IN SYNTHETIC DRUG ANALYSIS-I. ESTIMATION OF ACETANILIDE AND PHENACETIN IN ADMIXTURE By W. 0 . E M E R Y ~ Received April 30, 1914 INTRODUCTIOS
During t h e past few years, more particularly since :he inceptiTn of both federal a n d State drug enactments, a t t e n t ’ o n has been directed repeatedly t o t h e dearth of c,dequately tested methods for detecting a n d estimating medicinal agents. T h e need of these methods was most keenly felt in connection with certain iiiliibited substancc-s of synthetic character like acetanilide a n d i t s derivatives, antipyrin, cocaine, codeine, heroin a n d other similarly potent drugs, which find extended application in many of our proprietary medicines. .4side from these considerations, hon-ever, there existed in t h e case of acetanilide a n d phenacetin (acetphenetidin) additional cause, on t h e part of drug analysts a t least, for desiring quantitative methods. T h e relatively low cost of acetanilide, taken in connection with its pronounced physical resemblance t o phenacetin, has already suggested t o t h e unscrupulous t h e possibility of partial or even complete substitution of‘the former drug for t h e latter, a n d indeed several flagrant instances of such practice are on record. Accordingly, much time a n d effort have been expended in various quarters in t h e hope of devising a quantitative separation, though hitherto apparently without marked success. It is evident, however. t h a t any procedure, calculated t o determine even approximately t h e relative proportions of acetanilide a n d phenacetin in admixture, t h u s blocking t h e ways of t h e sophisticator, must prove welcome t o officials a n d chemists engaged in drug control. Ordinarily, t h e preliminary or gross separation of these t w o drugs from complex mixtures presents no unusual difficulties. being easily effected b y extraction with chloroform. I t is i n t h e subsequent quantitative partition of t h e mixture t h u s isolated where t h e real problem begins, since no purely physical method, involving, for example, water or a n y of t h e commonly available, organic solvents. lends itself t o a s h a r p separation. A partial separation may indeed be effected according t o Will2 with water about as follows: If I gram of a mixture of equal p a r t s of acetanilide a n d phenacetin be shaken with zoo cc. of water, all of t h e acetanilide goes into solution together with 0.13 g. of phenacetin, t h e remainder being unaffected. T h i s latter portion is t h e n filtered a n d weighed. Its weight, corrected b y t h e addition of 0.13, represents t h e phenacetin originally present in this particular 1 2
Chief, Synthetic Products Laboratory Pharm. J.. [ 3 ] 21, (1890), 377.
