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 C H E M I S T R Y
922
P R O P O S E D METHOD
Carefully sample t h e lot of citric acid on hand, b y grinding a sufficient q u a n t i t y t o get a n average sample through a coffee or other suitable mill. Mix thoroughly, a n d weigh 7 g. into a liter flask. Dissolve in water, a n d dilute t o mark. Pipette out 50 cc. or 0 . 3 j g. of t h e citric acid, a n d t i t r a t e with N / I O caustic soda a n d phenolphthalein. If t h e acid is pure a n d uneffloresced, just 50 cc. of N / I Oalkali will be required. Weigh 1 8 5 0 g. of pure uneffloresced acid or its equivalent in acid value of effloresced or impure acid into a large bottle or carboy, a n d cover with 7 liters of cold water. Calculate t h e exact number of g. of anhydrous citric acid present. R u n from a burette 2 5 cc. of concentrated ammonia into a 500 cc. flask containing cold distilled water. Dilute t o mark a n d mix. Carefully measure 2 5 cc. of this solution a n d t i t r a t e with N/2 acid a n d methyl orange. Calculate t h e volume of concentrated ammonia necessary t o neutralize t h e citric acid in t h e ratio of I of a m monia t o 3.763 of anhydrous citric acid. (If a stock of approximately I O per cent ammonia is on hand, i t is perhaps preferable t o use i t instead of concentrated ammonia using, of course, a correspondingly suitable volume of water for t h e citric acid.) Add t h e carefully measured ammonia solution t o thecitric acid i n t h e bottle or carboy, close immediately with a tightly fitting rubber stopper, a n d shake till t h e acid is dissolved; allow t o s t a n d tightly stoppered until cold, t h e n shake again before removing t h e stopper. Bring t o a gravity of 1.09 a t 20’ C. The volume of t h e solution should approximate I O liters. T h e accuracy of t h e solution may be confirmed if desired, b y analysis, using either t h e distillation method already described in this paper, or t h e method of P a t t e n a n d Marti,’ or t h a t of E a s t m a n a n d Hildebrand.2 It was suggested b y one of my associates t h a t we a t t e m p t t o prepare t h e pure salt, tri-ammonium citrate, a n d determine t h e ratio of ammonia t o citric acid in it. As anticipated it was found impossible t o prepare, by evaporation a n d crystallization, b u t by adding t o a solution of ammonium citrate made distinctly alkaline with ammonia, a large excess of strong alcohol, a salt was precipitated which on standing over night became beautifully crystalline. T h e supernatant liquid was filtered o f f , a n d t h e crystals washed thoroughly on t h e p u m p with a large excess of strong alcohol; t h e mass which was a felt of interlaced crystals, was dried quickly b y pressure between blotting pads, a n d a portion dissolved in water; its reaction with corallin was distinctly alkaline, a n d a n analysis of t h e solution showed t h e ratio of ammonia t o citric acid t o be I t o 3 . 7 6 8 . T h e remainder of t h e crystals left exposed over night t o the summer temperature of t h e laboratory had entirely changed t h e n a t u r e of its crystalline structure, a n d a portion of i t , when dissolved in water a n d tested with corallin, was decidedly acid t o t h a t reagent a n d upon analysis showed a ratio of I t o 3.94. It is evident, therefore, t h a t t h e normal salt is not entirely hypothetical, t h a t i t can be actually 1 2
THISJOURNAL,6 (1913). 567. I b i d . . 6 (1914). 577.
Vol. 6, NO.
11
prepared a n d dissolved in water, a n d its solution then shows a n alkaline reaction t o corallin a n d has very nearly t h e ratio of I of ammonia t o 3 . 7 6 5 of citric acid. There seems little reason t o doubt t h a t t h e neutral ammonium citrate solution which t h e A . 0. A . C. h a s been prescribing since t h e d a t e of its organization many years ago, a n d which able a n d conscientious chemists have ever since been earnestly trying t o make exactly neutral, succeeding sometimes perhaps b y accident, but usually only approximating i t , was really intended t o be a solution of t h e normal salt. This opinion was expressed b y t h e writer in his report as Referee in t h e following words: “While t h e referee has a strong conviction t h a t t h e only proper method of making the solution is b y analysis a n d calculation of t h e exact quantity of ammonia a n d citric acid t o be added t o i t , still he hesitates t o urge i t officially, as no w o r k has yet been done by a n y other referee along this line, a n d because t h e referee is himself no longer a n official chemist.” I n this opinion he has since been supported by those who have given t h e most earnest thought a n d painstaking experiment t o t h e subject, as P a t t e n a n d Marti, E a s t m a n a n d ‘Hildebrand a n d others. The laboratory with which t h e writer is identified still makes its solution &s prescribed by t h e A. 0. A. C., approximating neutrality as closely a s possible by t h e use of corallin, since t h a t is still one of t h e legal a g d official methods, b u t the writer knows of other chemists who have already adopted t h e neutralization by analysis, a n d it is little wonder t h a t under these conditions analyses for available phosphoric acid on tankages a n d bone meals, a n d fertilizers containing those ingredients should v a r y quite widely. Let us hope t h a t t h e A. 0. A . C. a t their next meeting will conclude t h a t t h e subject has been investigated long enough, a n d t a k e some definite action a t t h a t meeting, or else appoint a small committee in whom they have confidence, with power t o act in prescribing a method which shall be legal and official after a definite d a t e . MCCANDLESS LABORATORY ATLANTA,G A .
THE INFLUENCE OF FINENESS UPON THE AVAILABITJTY OF BONE MEAL By S. S. PECK Received July 6, 1914
It has been thoroughly established t h a t the availability of raw phosphate rock or of basic slag depends primarily on its fineness of subdivision. These t w o purveyors of phosphoric acid a n d bones or bone meal comprise t h e three forms in which insoluble phosphoric acid is supplied in fertilizers. I n t h e case of basic slag, t h e phosphoric acid exists as a tetra-calcic or a four-lime phosphate. I n phosphate rock a n d bones t h e phosphoric acid is combined with three parts of lime, a n d is known as tri-calcic phosphate, t o which t h e general term of bone phosphate is applied. As superphosphate, phosphoric acid is supplied in a form soluble in water. It is termed available not because after being applied t o t h e soil i t remains permanently soluble b u t because i t is fixed in a finely divided
Nov., 1914
T H E J O G R N A L O F I i V D U S T R I A L ,4ND E N G I N E E R I N G C H E M I S T R Y
form a n d well distributed. From this i t can be logically concluded t h a t t h e finer t h e state of subdivision of rock phosphate, and t h e more thorough its distribution in t h e soil, t h e greater will be its availability t o t h e crop. As a matter of fact, t h e latter condition is directly dependent on t h e former, since a n y given quantity of material can be more evenly distributed as its state of fineness increases. T h e influence of fineness in increasing yields has been demonstrated by t h e New York Agricultural Experiment Station,’ and t h e University of Wisconsin Agricultural Experiment Station2 has shown t h a t thoroughness of mixing has a decidedly beneficial effect on plant growth. Truog has published tests showing t h a t t h e availability of raw phosphate rock is directly influenced by t h e simultaneous presence of fermenting organic material, this favoring t h e chemical a n d biological processes t h a t give rise t o carbon dioxide a n d other agencies which attack t h e fine rock a n d ultimately give t h e material a finer a n d more uniform distribution through t h e soil. For this reason t h e experimental d a t a from phosphate rock experiments cannot be used in arriving a t conclusions relative t o bone meal action, since here t h e solvent action is influenced directly by t h e decomposition of t h e nitrogenous p a r t of t h e bone particles, with the accompanying evolution of carbon dioxide a n d formation of nitric nitrogen. Experimental data, however, is not wanting on this point. T h e Berlin Agricultural Experiment Station has found t h a t t h e finer bone meal is ground t h e better its utilization, coarse meal having b u t 66 per cent of t h e action of fine meal, when each contained t h e same phosphoric acid per cent. T h e importance of this condition has always been recognized. A hundred or more years ago when bones first bega.n t o be used in England, they were applied either unbroken, or later in coarse fragments, at t h e rate of t e n or twelve hundred pounds t o t h e acre. Afterwards, when bone meal came t o be manufactured, 600 or 7 0 0 pounds of t h e meal per acre were deemed a sufficient dose, while later I O O or 2 0 0 pounds of superphosphate (in which a state of subdivision is reached t h a t would be impossible b y grinding) were. found t o produce t h e same effect on t h e same soils a n d crops.3 Storer4 says: “ T h e fineness of t h e meal t o which bones are ground is a very important consideration. Not so many years ago i t was t h e custom t o use crushed bones,. . . . . . b u t there is no longer a n y question t h a t fine meal is greatly t o be preferred t o t h a t which is coarse. The finer t h e meal, so much t h e more readily will i t putrefy a n d dissolve in t h e earth, so much t h e more quickly can t h e plants be fed by it, a n d so much t h e sooner a n d t h e more surely will t h e value of the crop be increased.” S‘oorhees5 also states in positive terms t h e necessity of fineness of division of bone meal. Many of t h e experiment stations in t h e United States a t t a c h different values t o t h e phosphoric acid and nitrogen Bulletin 368, Feb., 1913.
* Reseavch
‘ 6
Bullelin 2 0 , January, 1912. E. H. Hite, Bulletin 80, West Virginia Experiment Station, April, 1902. “Agriculture,” Vol. I. “Fertilizers,” 1900, p. 7 3 .
923
in fine, medium, a n d coarse bone meal respectively, b u t do not in all instances agree in their definitions of these terms. I n general, by fine bone meal is signified such as will pass through a sieve with circular holes one-fiftieth of a n inch in diameter, a n d coarse such as will not. The New Jersey Agricultural Experiment Station uses values on this basis as follows: Fine bone meal-nitrogen 19 cents, phosphoric acid 4 cents per pound; coarse-nitrogen I j cents, phosphoric acid 3 . j cents per pound.‘ The Kentucky .Sgricultural Experiment Station2 defines fine bone meal as t h a t which passes through a 2 j mesh sieve, and medium as t h a t which passes through a 6 mesh sieve, valuing t h e phosphoric acid from t h e former a t 4 cents and from t h e latter a t 3 cents per pound. Other stations, particularly t h a t of California. no longer indicate valuations depending on t h e degree of fineness, since such a gradation is purely arbitrary; nevertheless, they insist on t h e necessity of such a condition. There is a limit t o which bone meal should be ground on three accounts: ( I ) When ground too fine t o a n impalpable powder, known as “floated bone,” it is a p t t o be carried away by t h e wind when being applied; ( 2 ) in this condition i t is extremely liable t o putrefy, especially in moist air; a n d (3) there is a question whether its availability is raised for ordinary cultural purposes in a measure commensurate with its extreme fineness. I n experiments with various crops, and using bone meal ranging f r o m t h a t passing a 60-inch sieve t o t h a t passing through bolting cloth, t h e New York Agricultural Experiment Station3 found t h a t within the limits tested, fineness seemed t o have little or n o influence on availability. Attempts have been made t o measure t h e availability of raw phosphates by their solubility in various dilute solutions of acids, organic or inorganic, b u t i t has not been found possible t o duplicate or even approximately represent conditions in t h e field with laboratory tests. The solvent action of the soil is being exerted on t h e insoluble phosphates over a long duration of time, during which a p a r t of t h e dissolved material is being gradually b u t constantly removed b y t h e growing crop, a n d also probably suffering other alterations in character not possible t o determine. I t m a y be said t h a t a t t h e present time, there is no chemical method of determining this point in which absolute confidence can be placed. It has already been stated t h a t bacterial action with its consequent evolution of carbon dioxide and development of acids increases the solubility of rock phosphate, and t h a t this condition exists in t h e decomposition of bone meal in t h e soils. I n an endeavor t o measure t h e availability of various grades of bone meal, this station has completed a series of tests in which attempts were made t o answer t h e question of availability, and in which the decomposition of t h e organic matter of t h e bone was presumed to have a direct relation t o t h e relative availability of the phosphate content. 1
8
Bulletin 269, September, 1913 Bullelin 168, December, 1912 Bullelrn 358, F e b r u a r y , 1913
T.4BLE IV-hfGS.
E X P E R I 11E N T A L W 0 R K
NO.
F o r t h e p u r p o s e of t h e s e t e s t s , a c o m m e r c i a l b o n e meal w a s s i f t c d a n d d i v i d e d i n t o f o u r sizes. T h e sizes a n d a n a l y s e s of e a c h lot w e r e as follows: Nitrogen Alumber S t a t e of division Per c e n t 1 Less t h a n 40 mesh sieve.. . . . . . . . . . . . . . . 3 . 9 8 2 F r o m 20 t o 40 mesh sieve.. . . . . . . . . . . . . 4 . 3 4 3 F r o m 12 t o 20 mesh s i e v e . . . . . . . . . . . . . . 4 . 2 0 4 Greater t h a n 12 mesh sieve.. . . . . . . . . . . . 4 . 0 9
Phosphoric acid Per c e n t 17.84 22.28 23.00 23.34
TEST S O . I
This test was intended to measure the relative rates of ammonification of the nitrogen of the different sizes of bone meal. To Station soil representing zoo g. of dry matter placed in beakers enough of each grade was added to supply zoo mg. of nitrogen; t o one lot no bone was added. The bone was thoroughly mixed, a n d then enough water added to bring the soil to two-thirds saturation. The beakers and contents were weighed, and every two days during the test were again weighed and water added to replace t h a t lost by evaporation. At stated times one series of each was analyzed for ammonia nitrogen by distilling the whole sample, thoroughly mixed and diluted with water, with recently calcined magnesia into N/IO acid. As the results of the fourth distillation showed a considerable drop in ammonia nitrogen, on the fifth and last test the residue from distillation was transferred t o a graduated \,esse$ cooled, made up to .the mark and filtered. I n an aliquot of the filtrate, nitrate nitrogen was determined. The results are given in Table I. TABLE I Bonemeal
No. Blank 1
2 3 4
Mgs. Ammonia Nitrogen
Mgs. after 18 d a y s a s -
7
2 davs 0.28 5.46 -1.96 1.40 1.26
5 davs 0.14 12.88 4.48 3.92 2.24
9 davs 0.14 6.72 2.10 3.92 2.10
TEST NO.
Total 2.24 31.12 16.48 11.92 14.66
2
This test was a repetition of the previous one with the exception t h a t the soil was kept a t a moisture content equivalent t o half saturation, and that nitric nitrogen as well as the ammonia was determined in each instance; except t h a t in the first determination. only the ammonia was determined, nitrification not having in two days sufficient opportunity tq make much difference, and a t the last determination only the nitrates w-ere determined. The results appear in Tables 11, 111, and IV. TABLE 11-AMMONIFICATION OF BONE MEAL-MGS. AMMONIA NITROGEN No. Blank 1 2 3 4
2 1.40 8.47 7.42 6.09 .5,18
4 2.31 9.80
9.94 10.08 8.12
TABLEIII--NITRIFICATION so. Blank 1
4 4.20 3.92 3.22 3.08 3.08
7 4.20 4.54 4.76 2. IO 2.24
7 0.70 12.32 8.68 12.74 10.22
10 0.84 7.42 5.18 4.76 2.24
OF BONE MEAL-MGS.
10 4.62 9.24 10.64 7.70 9.94
Blank 1
2 3
4
4 6.51 13.72 13.16 13.16 11.20
TOTAL NITROGENAMMOSIA A N D NITRATE 10 5.46 16.66 15.82 12.46 12.18
i
4.90 16.86 13.44 14.84 12.48
17 d a y s 5.46 20.30 16.94 16.54 14.56
14 5.32 21.56 15.40 10.78 10.64
In this test, the total water-soluble nitrogen a t the end of the 17-day period showed a direct relation to the size of the bone meal; this may be said to hold true for most of the tests, the few irregularities occurring being only what may be usually expected in investigations of this character. It was thought, however, that these irregularities might be explained by the fact that the nitrate nitrogen as formed was accumulating to a much larger degree t h a n usually obtained in nature (amounting to as high as 123 parts per million of dry soil), and perhaps the results would be more regular if the nitrate nitrogen formed were removed a t intervals. With this in view, a new series of tests was carried out as follows: TEST NO. 3-LYSIMETER
TESTS
For this purpose, galvanized iron containers, with facilities for collecting the drainage, were filled with station soil. The lysimeters were z feet in height b y eight inches in diameter, the bottoms being perforated and covered with coarse sacking, above which was one inch of animal charcoal, previously digested with acid and washed. Each lysimeter was given 40 pounds of soil. The analysis of this soil by the official acid digestion was: Per cent
Per cent Pota 0.29 Soda 1.56 Sulfuric offide., . , , . , , , 0 . 1 6 Phosphoric o x i d e . . . . . . . . 0 . 6 8 Chlorine.. . . . . . . . . . . . . . 0 . 0 1 Nitrogen.. . . . . . . . . . . . . . 0 . 2 1
.
Iron oxide.. , . . , , , , , . . , , 24.96 Alumina. . . . . . . . . . . . . . . . 1 9 . 5 6 Manganese oxide.. . . . . . . 0.15 Lime . . . . . . . . . . . . . . . . . . 2.01 Magnesia 5.35
7
11 d a v s Ammonia N i t r a t e 0.14 0.14 2.1 4.20 1.8 29.32 2.38 3.08 13.40 0.98 1.12 10.8 0.28 1.26 13.4
U p to the fifth day, the rate of ammonia formation was greatest with the finest bone meal and least with the coarsest. On the ninth day a considerable drop in ammonia content is noticed in the lot with the finest material, which progressed until the 18th day. From the figures obtained for nitric nitrogen, thjs can be explained by the fact that nitrification had started in and was progressing rapidly. On the ninth day the three coarser materials showed practically the same state of ammonification. The final figures for nitrogen, ammonia and nitrate of the 18th day show that decomposition of the bone meal had taken place in the fine material to double the extent it had in the coarser; and that in the coarser materials there were but small and irregular differences.
2 3 4
Vol. 6 , NO.I I
T H E J O C ' R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
924
14 4.62 20.30 14.70 9.66 9.94
14 0 io 1.26 0.70 1.12 0.70
17 d a y s 1.26 2.38 1.96 0.98 1.26
NITRATE P~ITROGEN 17 21 d a y s 4.20 3.08 17.92 24.64 14.98 15.40 15.56 14.70 13.30 14.40
To each test where bone was added, sufficient was given to represent an application of IOO pounds of nitrogen per acre, amounting actually to 363.5 mg. per lysimeter. In addition t o the bone tests, three were carried out with blood and fine ground phosphate rock (60 mesh), alone and together, to see if the effect of the decomposing action of the blood would render more of the phosphate rock soluble, and also to observe whether the presence of the phosphate rock would make any difference in the rate of decomposition of the blood. The blood supplied contained nitrogen a t the rate of 100 pounds per acre, while the phosphate rock was equivalent in its phosphoric acid content t o the fine bone meal. The plan of the tests was as follows : LYSIMETER TESTS 0.3635 g. N per lysimeter (100 lb. N per acre) G r a m s per lysimeter P o u n d s per acre J
h'o.
MATERIALADDED Material (Blank) ....................... Fine bone m e a l . , . . . . . . . . . . . 9 . 1 3 3 h-0. 2 hone m e a l . . 8.375 N o . 3 bone meal. 8.655 Coarse bone meal. 8.888 Blood. 2.878 7.218 Blood and phosphate rock.. Phosphate r o c k . . 4.340
Phosphoric Phosphoric acid LMaterial acid
.......... ........... ..........
1 :629 1.866 1.991 2.068
...........
11629 1.629
..................... ..
....
2513 2304 2381 2445 792 1985 1193
...
448 513 548 570
...
448 448
The materials were added b y removing from the top of each lysimeter the surface two inches of soil, incorporating thoroughly the respective materials with half of this, replacing in the lysimeters and covering with the remainder of the soil. The bone, etc., was thus one inch below the surface and thoroughly admixed in the second inch. To each lysimeter 500 cc. of water were added, and further additions of water made when the surface of the soil was showing signs of dryness. After three weeks, and every three weeks thereafter, the lysimeters were flushed with 3 liters of water and the percolates analyzed. In the interim between irrigations small applications of water were made when the surface soil showed need of it. I n the analyses, nitrate nitrogen and lime were determined in large aliquots of the percolates, the whole drainage being measured and the results figured t o milligrams removed. Por-
.
Nov., 1914
T H E JOLTRNAL OF I N D C S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
tions were concentrated and set aside for phosphoric acid determinations. I n all, six percolations were completed, representing a total time of 18 weeks. I n the following tables will be found the amounts of nitrate nitrogen and lime removed a t each irrigation. TABLE V-NITRATE NITROGENREMOVED(MILLIGRAMS) Irrigation
Lysimeter number r
I 49.0 23.3 18.1 13.0 17.9 13.6
2 56.2 41.2 27.8 20.5 29.0 25.5
Total 134.9
200.2
NO.
1
2 3 4 5 6
__ -
3 52.7 37.1 24.9 20.3 22.1 20.2
4 52.0 33.2 21.1 18.6 22.1 22.5
~
~
177.3
5 62.3 33.7 18.8 16.6 23.0 22.0
6 69.4 97.6 90.4 31.4 22.1 1,.1
__
~
169.5
176.4 328.0
7 67.2 81.9 95.7 45.8 27.3 17.3
8 91.2 40.5 19.7 9.8 19.4 14.9
335.2
195.5
~__
NO.
1
2 3 4
5 6
Lysimeter number 7 -
1 47.; 54., 64.8 61.4 58.4 50.1
__
Total336.6
3 19.0 37.8 388 39.8 46.8 40.0
4 44.1 66.1 71.8 73.8 61.3 61.0
5 45.3 58.1 67.3 69.3 46.9 58.3
222.2
3i8.1
345.2
7
53.5 10.2
79.1 70.0 62.2 36.4 I _
371.4
__ __ __
6 48.6 85.5 111.6
77.1 66.8 41, 1 ~
430.7
7 53.4 86.3 116.6 94.2 22.2 94.8
8 63.6 80.6 95.8 70.4 121.4 82.1
-~
__
467.5
213.9
It will be noticed that in the first irrigation, the lysimeter to which phosphate rock only was added gave the highest returns for nitrate nitrogen, and of the bone meal tests, the coarsest ranked first in this respect. It is apparent that this discrepancy is due to a n unequal condition of the soil a t the time of being placed in the lysimeters, which was corrected after the first irrigation. I n the following tables, the total amounts of the elements removed in the last five irrigations are reported in terms of pounds per acre: TABLE VII-POCSDS ( C A L C b L A T Z I > OX
N i t r a t e nitrogen Lysim- ,-,-eter 1:xcess over No. Removed check 23.6 ... 39.6 16.0 10.7 34.3 32.3 8.7 3L.4 7.8 71. 1 47.5 73.7 50.1 28.7 5.1
OF
ELEMENTS REMOVED PER ACRE
St R F A C E AREA Lime
OF
from the bone. Where the phosphate rock alone was employed, a n increased nitrification of the soil nitrogen to the extent of 5 per cent is noted. With one exception, all the drainages from this test showed a higher nitrate content than the check. Of the nitrogen added as blood, 47.5 and 50.1 per cents were recovered in the period of 18 weeks as nitric nitrogen, while the best yield from the hone was 16 per cent. Nitrification of the blood nitrogen was accelerated by the addition of phosphate rock just as was the soil nitrogen, but to a lesser extent. More phosphoric acid was found in the test with blood alone than in the check, which points to a solvent effect exerted by the fermenting action of the blood on the soil phosphates. TEST NO. 4
'
il final test was made with an attempt to measure the amount
TABLEVI-CALCICAI OXIDE REMOVED(MILLIGRAMS) Irrigation
925
LYSIMETER) Phosphoric acid
-
Excess over Excess over Removed check Removed check 79.6 .... 4.39 ... 87'. 4 i.8 6.4 2.1 55.9 .... 3.2 0.9 91.9 5 .4 12.3 1.1 82.5 6.0 2.9 1.7 105.1 5.2 0.9 25.5 113.9 8.1 3.8 34.3 5.0 0.7 123 8 44.2
From this table it again appears that the fineness of division of bone meal is a measure of its rate of decomposition in the soil, based on the formation of nitric nitrogen from the organic matter in the bone. It was thought that the amount of lime found in the percolates might give some indication of the rate a t which the lime phosphate was dissolved within the soil, but the results are too irregular t o allow any interpretation. This is partly caused by the fact that, as in lysimeter 6, where no lime was added, the rapid nitrification of the blood and the consequent nitrate nitrogen produced, made for an increase in the lime withdrawn from the soil itself. At the same time, i t is interesting to note that the greatest amount of lime appeared in the test to which lime phosphate as phosphate rock was added, and in which the nitric nitrogen produced was less than in any other of the tests with the exception of the check. The phosphoric acid determination showed the greatest solubility in the case of the phosphate rock and blood test, and here the lime content is second in quantity t o that of the rock alone. I n the bone meal, the difference in results is within the limits of experimental error, but the fine bone shows a greater solubility than the coarser. The second size of bone shorn-ed a drop below the check in lime and was less in phosphoric acid than the two coarser bones; the lime drop is significant and points to some fault in the soil or its method of packing and nature of drainage, but the nitrogen transformation was apparently not affected. While not germane t o the question, i t is nevertheless of interest to compare the results of the blood and rock tests with those
of phosphoric acid rendered soluble by bacterial action. I n this test, quartz sand previously digested with acid and washed with water till free of acid was mixed with the variou5 materials. Fresh station soil was shaken thoroughly with water, allowed t o settle for twenty-four hours, and the sand tests moistened with the supernatant liquid. Two series were started, being allowed to stand three and five weeks, respectively. Five grams of the various sizes of bone meal were placed in zoo grams of sand. I n two furthcr tests, blood and phosphate rock or phosphate rock alone, were added, in amounts equivalent to the phosphoric acid and nitrogen content of the fine bone meal. At analysis, the contents of the beaker were transferred with water to a filter, and washed through paper until the runnings amounted to 300 cc. The entire filtrate w 2 s analyzed for phosphoric acid. I n the case of the phosphate rock tests, the filtrate was very turbid. The results, therefore, do not express what was in solution, but represent material in so finely divided a condition that i t passed through the pores of filter paper, and went into solution immediately on the addition of acid. The results were as follows: TABLE \'III-PHOSPHORIC
ACID D I S S O L V Z D IIi S A N U TESTS 896.5 h f G . O F PHOSPHORIC ACID APPLIED 3 weeks 5 weeks T o t a l Fine bone m e a l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.0 3.4 7.4 p\-0. 2 bone meal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 3.8 6.0 S o . 3 bone m e a l . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6 3 i h.? Coarse bone m e a l . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3 3.I 4.4 Phosphate r o c k . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1 7 8 12 0 Phosphate rock a n d Llood . . . . . . . . . . . . 7 , 5 11 1 I8 6
It would appear from these tests that the phosphoric acid in fine bone meal is more available than that passing a 20 mesh sieve by 23 per cent, and almost 7 0 per cent more availahle than that passing through a 6 mesh sieve. The two intermediate sizes are about equal, and both superior to the coarsest. The phosphate rock gave, as was expected from the appearance of the filtrate, a considerably greater phosphoric acid content of the filtrate, which was augmented t o an important extent b y the decomposing action of the blood. S U 11N A R Y
The r e s u i t s of these tests, b a s e d on t h o s e from t h e fine b o n e meal as 100.m a y be seen from t h e f o l l o n i n g c o m p a r a t i v e tables. TAnLE Days 1 Bone meal Size S o . 7 1 in0 7 32 3 77 4 19
__
IX--~XIMOXIFICATIOS
IN
5 9 Ammonia nitrogen '
100 34 30
1T
--ion--
;: 30
TWO-THIRDS SA'TCRATIOX 11
18 Soluble nitrogen
I00
100
5j
71 3
4(1 1 'i
--
4( I
4,7
TABLF; X-h~ITRIFIC.ATIOS I S HALFS h T 1 : R h T I O X Days 2 4 7 10 14 17 21 Bone meal Ammonia Ammonia and nitrate nitrogen Nitrate Size No. nitrogen ' nitroqen 1 100 100 i o n 100 100 100 1 on 2 85 92 71 92 62 27 57 3 66 92 83 62 34 15 54 4 53 65 64 60 33 62 52 I
Average l(10
Abtr.~gc
100
--
i,
67 56
T H E J O U R N A L O F I N D U S T R I A L AiVD ENGINEERIAVG C H E M I S T R Y
926
TABLEXI-NITRIFICATION IN LYSIMETERS Weeks 6 Bone meal Size No.
9
12
15
18
Average
TABLEXII-SAND TESTS-WATER-SOLUBLE PHOSPHORIC ACID 1.. 100 3 . . . . . . . . . . . . 85
..........
2 . . . . . . . . . . . . 81
4..
..........
60
c 0 N c L u S I 0 pis I-The fineness of bone meal determines t h e rate at which its nitrogenous part will decompose in t h e soil t o ammonia a n d thence t o nitric nitrogen. 11-The solubility of bone phosphate is directly influenced by bacterial action, and a n increased ammonia or nitrate decomposition may be held t o indicate a more efficient phosphoric acid solvent action. 111-Since there is a limit t o which bone meal can be ground to permit of its convenient handling, fine bone meal should possibly be defined as t h a t which passes through a jo mesh sieve. IV-Since, however, i t is not commercially practicable t o prepare so fine a product without also including a considerable proportion of the very fine dust, a standard of fine bone meal of 65 per cent t o pass a j o mesh sieve, and a t least 90 per cent of the remainder t o pass a z j mesh sieve is presented a s one t o which no reasonable objection can be offered by the dealers, a n d from which satisfactory results will accrue t o the crops. CHEMICAL LABORATORY, EXPERIMEXT STATION HAWAIIAN SUGARPLANTERS’ ASSOCIATION T. H . HONOLULU,
A RAPID METHOD FOR THE DETERMINATION OF CAMPHOR AND OF CERTAIN ESSENTIAL OILS WHEN IN SOLUTION IN ALCOHOL B y W. B. D. PENNIMAN A N D W. W. RANDALL Received June 1, 1914
As the result of series of experiments carried out in this laboratory a t intervals during several years, a method has been devised for the assay of spirits of camphor a n d of peppermint, a n d of the extracts of lemon, orange, peppermint, anise and nutmeg, which appears t o be more rapid and much more accurate t h a n any method with which we are familiar. The facts which form t h e basis of t h e method may be grouped under three heads, as follows: I-Camphor and t h e several oils enumerated above are completely expelled from solution in alcohol, when these solutions are mixed with from four t o ten volumes of a strong solution of calcium chloride. 2-The separated camphor or oil dissolves with t h e greatest ease in low-boiling gasoline, a n operation with which alcohol, a t least in t h e presence of such a calcium chloride solution, does not interfere. 3-Within certain fairly wide limits, t h e volume of the gasoline solution formed is exactly equal t o t h e s u m of t h e volumes of the gasoline itself and the solid camphor (or oil) which has been dissolved. The method here described is by no means entirely new. Schmatollal noted t h a t when camphor disApoth. Zeil., 16, 290; A6sfr. Chem. Cent?., 1901, 1 (20). 1117; J . SOC. Chem. 2nd.. 20 (1901), 756; Allen’s “Commercial Organic Analysis” (new ed.), Vol. IV, p. 200. 1
Vol. 6 , NO.I I
solves in light petroleum oil, the volume-relation stated in “ 3 ” obtains. He employed a burette graduated in tenths cc. as a measuring apparatus, and weighed out t h e camphor spirit, which was later precipitated by means of saturated sodium chloride solution. We have secured better results by t h e use of calcium chloride solution, and prefer graduated milk bottles and the use of t h e centrifuge as means of accurate measurement of small quantities. Arnost’ used a somewhat similar method t o determine camphor in celluloid, correcting for alcohol dissolved. Chittick,2 we have found since these experiments were made, used a method similar t o ours for peppermint, precipitating the oil with water and, by means of a blank, correcting for alcohol dissolved. We have not found water a satisfactory precipitant, and believe t h a t much time can be saved without decrease in accuracy by the use of pipettes and the avoidance of weighings. The apparatus called for consists simply of several accurate full pipettes, a Babcock centrifuge, and one or more accurately graduated Babcock milk bottles. If t h e divisions on the neck of t h e bottle be from o t o I O , then the graduated portion will contain just 2 cc. With a magnifying glass t h e volume of a column of supernatant solution in t h e neck of t h e bottle can be read with accuracy, probably t o 0.008, perhaps t o 0.004 cc. As t h e volume of gasoline used should not be much less t h a n , nor much more t h a n twice as great as t h a t of t h e camphor or oil t o be dissolved (if the volumerelation mentioned under “3” is to hold good), i t is well t o work with such quantities t h a t not much over 0.5 cc. of camphor or oil is t o be determined. Thus we have found t h a t j cc. of t h e alcohol solution serves well for strengths from j t o 15 per cent; I O cc. is probably better for 4 per cent solutions or anything weaker. The quantity of gasoline should in general be somewhat greater t h a n t h a t of t h e oil. METHOD OF ANALYSlS
FOR STRENGTHS B E T W E E N 7 AKD
I5
PER
CENT-
Pipette j cc. of t h e solution into t h e Babcock bottle; fill nearly t o the neck with clear calcium chloride solution of sp. gr. 1.37; shake, add exactly I cc. of gasoline (b. p. 40’ t o 60’ (2.); shake, fill with t h e salt solution t o near t h e t o p of the graduation; stopper tightly; shake violently, a n d whirl in the centrifuge a t high speed for about five minutes. If now the salt solution is still cloudy, shake thoroughly, and whirl again. Read t h e menisci as in a milk-fat determination; i. e . , t h e lowest point of t h e lower meniscus and t h e extreme edge of the upper. For example, suppose t h e readings are 9 . 3 2 a n d 1.77; t h e column corresponds t o 7 . 5 5 ( = 1.51 cc.). Of this j.00 ( = I CC.) is gasoline, a n d 2 . j j ( = 0.51 cc.) is oil. Then 4 X 2 . jj = 10.20 = percentage of oil in t h e extract. F O R S T R E N G T H S L E S S T H A N 7 P E R CEKT-use I O CC. of t h e solution a n d a quantity of gasoline not more t h a n twice t h a t of the oil or camphor t o be set free; 12.
Unter. Nahr. u. Genussm., 12 (1906). 532; Abstr. J . SOC.Chem. I n d . ,
26, 1169.
Proc. Assn Am. Dairy, Food & Drug Off., 1913, p. 160; Absfr. Chem. Absfr.. 8 (1914). 1847.
