DECEMBER, 1935
INDUSTRIAL AND ENGINEERING CHEMISTRY
1491
T h i s w o r k is being c o n t i n u e d , using inorganic salts to react with cy The decomposing acIso the barium sulfate. Also :I25 other barium compounds tion of calcium chloride '&loo w i l l b e t r i e d . Similar solutions on ground I work is well under way mineral barytes has been 2 0 I O 20 30 do 50 80 70 a0 90 PERCENTAGE CONVEQSION on analogous strontium amply proved according to the procedures outFIGURE4. DECO\IPOSITIO\: OF BARIUM SULFATE WITH CALCIUM salts under the direction CHLORIDE FOR Va~rousPERIODS of the s e n i o r a u t h o r . lined in the Farr patent (4)* Patent application proThe barium chloride formed, and any excess calcium chlotecting these procedses is now on file with the United States Patent Office. ride used, are easily removed by the organic solvent. A semicommercial method for carrying out the described procedures Acknowledgment for the manufacture of barium chloride is now under way. It is a pleasure to acknowledge the continued helpful sugSolvents other than the methanol-ethylene glycol mixture gestions and advice from H. V. Farr, and the courtesy of the will be investigated, as well as recoveries of solvents used. furnishing of chemicals and apparatus on the part of the MalHowever, it is not anticipated that any great difficulty will linckrodt Chemical Works. be met in the recovery of the solvent. I n the commercial application of this reaction there is also no great difficulty in Literature Cited separating the barium chloride and calcium chloride by aqueous crystallization, especially when using only the small mo(1) Arth, M. G., Bull. soc. chim., [31 27, 293-302 (1902). (2) Booth, H. S., and Ward, R., J . Phys. Chem., 36, 961 (1932). lecular excess of calcium chloride needed when the mixture is (3) Bundikov, P. P., and Shilov, E. A., J. Soc. Chem. Ind., 47, 297-9 heated sufficiently long to evaporate off all the water. This (1923). heating can be continued, if necessary, t o incipient infusion. (4) Farr, H. V., U. 9. Patent 1,752,244 (1930).
,u' zw
Commercial Application
I r~ 175
'
( 6 ) Gaudin, Compt. rend., 54, 687 (1862).
Summary The decomposition of barium sulfate with calcium chloride in aqueous solution was investigated at loo", 125", 150", and 175" C. varying the time up to 12 hours, using the following weight concentration ratio.;: Mixture A
B C
Bas04
1 1 1
CaCh L
1.67 1.33
HzO 1.5 1.5 1.5
sufficient time (about 12 hours) was allowed to elapse, The
mostdilute mixture, C, gave conversions under 5 per cent. By fusing calcium chloride with barium sulfate, conversions u p to 95 per cent resulted.
(6) Hershman, P. R., U. S. Patent 1,240,571 (1917). (7) Ipatieff, V. N., and Freitag, C., IND.EXQ. CHEM., 27, 342 (1935). (8) Kharmandar'yan, M. O., and Brodovich, K. I., Ulzrain. Khem. Zhur., 8 , Wiss-tech. Teil, 110-15 (1933). (9) Marohal, G., Bull. eoc. chim., 39, 401-8 (1926). (10) Martin, E., M o n . Sci., [5] 5, 228-32 (1915). (11) Morey, G. W., U. S. Patent 1,688,084 (1928). (12) Morse, "Quantitative Analysis," p. 419 (1905). (13) Mosttowitsch, W., Metallurgie, 6, 450-67 (1909). (14) Newberry, S. B., and Barret. H. N., U. S. Patent 1,133,392
RBCBIVED M a y 6, 1935. Presented before the Division of Industrial a n d Engineering Chemistry a t the 89th Meeting of t h e American Chemical Society, Kew York, N.Y., April 22 t o 26, 1935. P a r t of a thesis submitted by N. Pritchard, Jr.. in Dartiai fulfillment OT the requirements f o r t h e degree of doctor of philosophy a t Purdue University.
w.
Composition of Nitrogenous Fertilizer Salts Sold in the American Market HENRY E. CUTTS, Stillwell and Gladding, Inc., N e w York, N. Y.
B T
HE following compilation of analyses of nitrogenous fertilizer salts is offered as a contribution to assembled and recorded information concerning the more exact and detailed composition or' fertilizer ingredients as currently distributed in the A4nierican trade. Such information, of course, is fundamental to an underetanding of questions arising in fertilizer chemistry and technology as well as in the agronomics of fertilizer use. Sitrogenous compounds, unlike potash salts, show a wide variation in the forms in which the nitrogen is present. The form is generally understood, but little information is readily available concerning the associated component3. The value of such information can be appraised only in terms of the use to be made of it. The analyes here reported are "complete" in the sense
that the constituents whose presence is suspected have been determined. The fact that the sum of these constituents approximates 100 per cent indicates that none of importance has been overlooked. The results are reported in the elemental form, not only to conform with the official method of reporting nitrogen but also to avoid the injection of uncertainties of interpretation. Since conventional combinations as acidic and basic radicals and their salts are generally understood, they are omitted as superfluous. The samples were secured through the esteemed collaboration of state agricultural chemists from those already collected during 1934, incidental to the routine sampling of fertilizers being offered for sale, under the appropriate state fertilizer control laws. Samples were sought of the six states-Maryland, Virginia,
IUDLTSTRI4L AUD ENGINEERIYG CHEMISTRY
1492
TABLE I.
PERCENTAGE COhfPOSITION O F i%Y.?IONIUY SULFATE"
No 15 N o 2C S o . 3d No.4e ~. Sitrogen 21.01 20.78 %O.i5 21.01 Sulfur 24.03 23.77 23.73 24.03 0.0'29 Trace Trace Iron 0.011 Moisture (105' C . ) 0.40 0.60 0.24 0.04 Insoluble 0.10 0.64 1.34 0.34 a From t h e analyses given, the average ( N H ~ ) ~ S O content I of these four samples is computed to be 98.53 per cent. 6 Pittsburgh Crucible Steel, f r o m South Carolina. C American Agricultural Chemical Company, f r o m South Carolina. d Domestic, from Virginia. C Foreign, from Virginia ~~
TABLE VI.
11.
PERCESTAGE COMPOSITIOlV O F
NITRATER
Nitrogen Sodium Calcium ,Magnesium Chlorine Sulfur Moisture (105" C.) Insoluble a T h e average of these three NaMOI". b 0
ri
DOMESTICSODIUM
So. I b so. 2c No. 8d 16.32 16.25 16.32 2 6 . 77 26.87 26,89 0.07 0.07 0.07 0 04 0.04 0.04 0.18 0.15 0.16 0.07 0 Oi 0.06 None 0 02 0.02 0 01 0.01 0 11 analyses shows the presence of 98.91 per cent
Arcadian Brand, representing 10 tons from S o r t h Carolina. The Barrett Company, from South darolina. Domestic, from Virginia.
TABLE111.
PERCEXTAGE COMPOSITION O F NITRATE" 1-0 l b. S o . 2 C
Nitrogen Sodium Potassium Calcium hlagnesiuni Chlorine Iodine Sulfur Boron Moisture (105'C.) Insoluble
16.27 26.79 0.16 0 07 0.04 0 35 0.009 0.08 0 005 0 14 0.10
16.22 26 60 0.16 0.07 0.06 0.27 0.09 0.05 0,012 0 12 0 23
16.18 26.61 0.13 0 21 0.04 0.36 0.024 0.10 0.005 0.08 0.26
15 92 26.43 0.45 0 21 0.04 1.17 0.017 0.08 0.017 0.36 0.20
N o . 51
15.98 25.75 1.10 0.24 0.07 0.55 0.011 0.12 0.01 0.40 0.30
No. 60 16.03 26.19 0.36 0.21 0.04 !2:': 0.06 0 058 1.24 0 20
a Samples 1-3, inclusive, contain a n average of 16.22 per cent nitrogen which, b y computation, is equivalent to 98.59 per cent NaNOa; samples 4-6, inclusive, average 15.98 per cent nitrogen, equivalent t o 96.57 Nah-Oa and 0.48 per cent KKOs. b Chilean nitrate of soda, Champion brand, representing 100 tons. from S o r t h Carolina. C Chilean nitrate of soda, Champion brand, representing 35 tons, from North Carolina. d Chilean nitrate of soda, Champion brand, from South Carolina. e Chilean nitrate of soda, Standard brand, representing 20 tons; from North Carolina. Chilean nitrate of soda, Standard brand, from T'irginia. a Chilean nitrate of soda, Standard brand, representing 5 tons, f r o m South Carolina.
TABLE Iv.
PERCENTAGE COhlPOSITIoX O F CALCIUM CY.4N.iMIDa
Nitrogen 22.3 Carbon (combined) 9.68 Calcium 41 Carbon (graphitic) 11.47 Magnesium 0.05 Silica 0.46 FeiOa, .&hO3 O,i5 Oil 5.0 Sulfur 0.47 hl oisture 0.15 .lero brand, typical analyeis provided by hinerican Cyanamid ComAero pany, New York. This product contains 63.55 per cent C a C K ? : t h e calcium constituent is the equivalent of 76.2 C a ( O H ) ? ; the combined carbon is computed f r o m the CaCN2 and CaCOz. (1
TABLEv.
PERCENT.4GE COMPOSITION O F F O R E I G N POT.iSSII31
NITRATES No.
Sitrogen Sodium Potassium Calcium Magnesium Chlorine
15.34 18.69 11.17 0.14
so. 2c 13.44 0.64 36.74 0.42
0.35
1.12
15
0 . OB
0.23
N o . 1 6 No.
Iodine Sulfur Boron Moisture (1050 Insoluble
c.)
0.009 0.05 0.03 0.60
0.20
AMYOSIUM
PHOSPHATE^ Sitrogen Calcium llagnesium Iron
11.3 0.85 0.54 1.82
Aluminum Phosphorus Sulfur Moisture
2 C
0:;s
0:i: 0.21
0.69 21.63 1.4 1.8
a Ammo-Phos, 11-48-0. typical analysis provided by the .hnerican Cyanamid Company, Ne& York. This product contains 49.6 per cent PtOs equivalent, of a h i c h 48.5 per cent is available and 42.9 per (,en1 is n ater-soluble.
PERCENTAGE COMPOSITION O F CALCIUM NITRATEa
Nitrogen Calcium Magnesium Sodium FesOa, A 1 2 0 3
15.97 20.20 0.04 0.07 0.01
Chlorine Sulfur Insol. (acid) .Moisture
0.01 0.02 0.01 By difference
a Complete analysis provided by Synthetic Nitrogen Products Corporation New York. This product approximates 83 per cent Ca(N0s)Z a n d 5 per cent' "1x03; it is sold under a guarantee of 15 per cent nitrogen.
TABLEVIII.
PERCENTAGE CONPOSITIOS O F AMMOXIUM NITRATE ( C A L - N I T n o )
No. 10
FOREIGX SODIUhl
KO.3d S o . 4 *
PERCEXTAGE COMPOSITION O F
~
TABLE F'II. TABLE
VOL. 27, N O . 12
Nitrogen Calcium (water sol.) Jlagnesium (water sol.) Sulfur (water sol.) CaCO3 :and other insol.) llgC03 Moisture
16.09 1.43 0.08 0.16 48.02
...
2.48
No. 2 b 21.2
No. 3 c
..
20.8
20'3 15.5
38:22
... ...
2.30
a Synthetic Nitrogen Products Company, 16 per cent grade, from South
Carolina; 45.97 per cent N H ~ K O J . b Dolomitic Cal-Kitro, shipping analysis provided by Synthetic Nitrogen Products Company, New York: ammonia nitrogen, 10.4 per cent; nitrate (computed) 60.42 per cent; CaO, 11.4 nitrogen, 10.8.per cent: " I N & per cent. MgU, 7.4 Der cent. C Limkstone Cal-Nitro, shipping analysis provided b y Synthetic Nitrogen Products Company; ammonia nitrogen, 10.88 per c e n t ; nitrate nitrogen, 10.44 per cent; "4NO3, 59.28 per c e n t ; CaC03, 33.65 per c e n t ; C a s 0 4 a n d Si&. 4.57 per cent.
Sorth and South Carolina, Georgia, and Alabama-and were received from Virginia and S o r t h and South Carolina.' The choice of samples for analysis2 was based on consideration of the size of the lot sampled (where that was known), the brand, the distribution, and the origin (whether domestic or foreign)information provided by the collaborators mentioned. While but fex analyses are here reported, it is believed that there can be no question as to their being thoroughly representative. All analyses made are reported. Their uniformity is a further indication of their representative character. Ammonium sulfate and sodium nitrate, as is well k n o J v n , constitute the bulk of inorganic nitrogen carriers; in 1931 485,800 and 464,600 short tons, respectively, were used. Importations in that year amounted to 112,000 long tons of ammonium sulfate and 550,000 tons of sodium nitrate. Calcium cyanamide, potassium nitrate, and calcium nitrate are exclusively of foreign origin; importations in 1931 of 51,300, 14,500, and 29,000 long tons, respectively, indicate their position in American fertilizer trade. Synthetic ammonia, and urea produced therefrom, would by nature and origin contain no collateral ingredients of interest in this connection and are therefore omitted. 1 Through t h e esteemed courtesy of G. W. Koiner, Commissioner of dgriculture, a n d W.Catesby Jones, chief chemist of Virginia: W. G. Haywood, head of the .4nalytical Division. of North Carolina, a n d B. F. Robertson, chief chemist of South Carolina. 2 Except as otherwise stated, the analyses were made in t h e laboratory of Stillwell and Gladding, Inc.
RECEIVED F e b r u a r y 9, 1935.
