April, 1929
I X D U X T R I A L A N D ENGINEERING C H E M I S T R Y
A series of purifications was finally made by using the 2aminoanthraquinone that was obtained from the autoclaves, after first removing the nitrobenzene and excess of ammonia by distillation with steam. The precautions previously mentioned were closely observed. The results recorded in Table XI11 indicate that a satisfactory product can be obtained. Since the yields on the crude product always ap-
375
proached the theoretical, the reported figures closely approximate the actual net yields. Of particular interest is the fact that a satisfactory purification cannot be made with material containing unconverted 2-chloroanthraquinone. This of course was to be expected, since it was previously ascertained that almost a quantitative precipitation of the halogen derivative was obtained with a residual acidity of 88.0 per cent.
Observations on Recent European Fertilizer Developments' H. R. Smalley THENATIONAL FERTILIZER ASSOCIATION, WASHINGTON. D. C.
N EUROPE the war and post-war reconstruction and
I
readjustments have brought about profound changes in the use of fertilizers, both as to rates of application and ratios used. I n this brief paper an attempt will be made to show the changes that have taken place in Germany, France, Holland, and Great Britain. These four countries and the United States consume three-fourths of all the fertilizer used in the world. The discussion will be confined to changes in the use of fertilizers and will not include technical changes in manufacturing processes, and the comparison will be between its use just prior to the World War and in the latest years for which figures are available.
European Fertilizer Consumption
GERLfAh-Y-Germany is by far the largest consumer of fertilizer in Europe, having used, in the fertilizer year 1926-27, 30 per cent of the total plant food consumed in the world and on a comparatively small acreage. Table I shows an increase in consumption of nitrogen and potash but a drop in the phosphoric acid figures. The table does not tell the whole story, however, for during the war (1914-1918) and for several years thereafter the consumption of phosphoric acid was much less and the consumption of nitrogen and potash continued to be relatively great. In 1913 the plant-food ratio in Germany was 3.06:8.54:8.40 and the total consumption there was equal to 7,025,000 tons of mixed fertilizer conWorld Consumption of Fertilizers taining 20 per cent of total plant food. I n 1926-27 the ratio In discussing the change in plant-food ratios attention is had shifted t o 5.02:5.96:9.00, and the consumption had risen called to the world consumption of superphosphate and basic to 8,755,000 tons, an increase in total plant food of 24.6 per slag, the two principal sources of phosphoric acid. I n 1913 cent. the total production of superphosphate was 11,810,000 tons; FRANCE-France is now using exactly twice as much niin 1925 it was 13,546,000 tons. In 1913 the world production trogen, five times as much potash, and somewhat more phosof basic slag was 5,910,000 tons; in 1925 it had declined to phoric acid than before the war. (Table I) I n 1913 the 4,235,000 tons. Comparison of the combined content of plant-food ratio was 2.64: 16.04: 1.32, and the total consumpPZOS in 1913 and in 1925 (Table I) shows a slight decrease. tion, expressed in terms of a mixed fertilizer of the above ratio, There were decided increases in Italy, Spain, France, and was 2,711,000 tons. I n 1927 the ratio was 3.42:12.26:4.32, Australia, and considerable decreases in Germany and Eng- and the total tonnage in terms of mixed fertilizer was 4,185,land. On the other hand, the world production and con- 000 tons, representing an increase in plant-food consumption sumption of nitrogen has doubled during the same period. of 54.4 per cent. With rich phosphate deposits in her North The total consumption of potash increased 44 per cent in the African Colonies and her enormous potash deposits in Alsace, same time. Germany uses almost exactly half' the total France is admirably provided with supplies of fertilizer raw potash consumed in the world. materials and will undoubtedly increase her consumption If all the fertilizing material produced in the world were still further. mixed together and standardized as containing 20 per cent of HOLLAND-Since 1913 Holland has multiplied her conplant food, the ratio for 1913 would have been 2.82:12.50: sumption of nitrogen by two and a half and her potash con4.68, and for 1925-27 it would have been 4.52:10.04:5.44. sumption by two, and she has added about 25 per cent to her The total production in 1913 would have been 23,615,000 tons use of phosphoric acid. (Table I) In 1913 the plant-food and that in 1925-27 would have been 29,195,000 tons, an ratio in Holland was 2.28:11.88:5.84 and the total consumpincrease for the period of 23.6 per cent. tion was equivalent to 821,000 tons of mixed fertilizer of that analysis. I n 1926-27 the plant-food ratio was 3.45: Situation in the United States 9.05:7.50 and the total consumption was equal to 1,325,000 Before turning t o the European fertilizer situation, let us tons of our hypothetical mixed fertilizer, representing an consider for a moment the situation here in the United increase of 61 per cent in total plant food consumed. ENGLAND-England is the only important fertilizer-using States. Table I tells the story in a nutshell, the figures showing a substantial increase in nitrogen but very small country that made no increase in its total plant-food conincreases for phosphoric acid and potash. The ratio shifted sumption from 1913 to 1927. (Table I) There has been a decided change in ratio, however. The ratio in 1913 was from 3.54:12.12:4.34 in 1913-14 to4.66: 11.30:4.04 in 1925-27. The total increase in plant-food consumption has been only 3.22:14.68:2.10 as against a ratio in 1927 of 3.66: 12.24:4.08. The total consumption of plant food in England is practically 12.7 per cent. the same as before the war. The figures for 1927 are estiPresented before the Division of Fertilizer Chemistry at the 76th mates, but they are based on information obtained from Meeting of the American Chemical Society, Swampscott, Mass., September 10 t o 14, 1928. reliable sources.
PRE-WAR(1913-14)
COUNTRY
The World German United gtates France Holland Great Britain Total for five countries
Nitrogen
Phosphoric acid
Tons* 667,0004 215,000e 209,OOOk 71,7006 18,700b 40,000s
2,952,000h 600,000s 715,OOOb 434,0008 97 600b 182,’OOOc
554,400
2,028,600
Tons
POST-WAR(1925-27) Potash
Nitrogen
Tons 1,104,0000 590,000E 256,0001 36,000c 48,0000 26,000~
1,320,000b 440,000d 310,OOOk 143,OOOb 46,OOOb 45,0001
956,000
984,000
Tons
Phosphoric acid
Potash
Tons
Tons 2,929,000h 522,OOOd 751,000k 513,000b 120,500b 150,0001
1,590,000I 789,000d
269,000~
181,0001 100,0001 50,0001
2,056,500
1,389,000
major crops-wheat, rye, oats, barley, and potatoes-have been selected. These five crops include 70 per cent of the total crop acreage of Germany and 52 per cent of the crop acreage of France. The figures are given in Table 11. T a b l e 11-Comparison
CROP I LDS.
I
of Pre-War a n d Post-War Crop Yields in G e r m a n y a n d France
AVERAGG YIELDFOR GERMANY
I
AVERAGE YIELDFOR FRANCE
1909-13
1923-27 Decrease
1909-13
1923-27
Increase
Bushels
Bushels Per cent
Bushels
Bushels
P n cent
Rye Potatoes Oats Wheat Barley
Figurell-Present
Plant-Food C o n s u m p t i o n e r Acre of C r o p a n d Improved P a s t u r e and H a y {and
more or less unsatisfactory, because agriculture is very different in different countries, but they help to give a good general picture, provided one is careful not to draw too many conclusions from them. For example, practically all the land in Holland is utilized either for intensive pasture or for crops, and there is much farming under glass with very high fertilization. The total acreage of crop and pasture land in Holland is only a little more than 5 million acres. At the other extreme is the United States, which has more than 500 million acres of crop and plowable pasture land, over 200 million acres of which is so situated as to rainfall that it cannot be fertilized with profit. Comparison of Crop Yields
The high yields obtained under the intensive system of fertilization that is practiced in northern Europe are too well known to need special comment, but it may be of interest to note what changes in crop yields, if any, have been produced by pre-war and post-war fertilizer ratios. For this com-
This, or even a larger, increase in French yields was to be expected with a 54 per cent increase in total plant-food consumption. The 14 per cent decrease in German yields is undoubtedly due to one or both of two causes-namely, the weather, or a shortage of phosphoric acid. It is perhaps true that the weather has been rather unfavorable to German crops during recent years, but i t is significant that the yields of all five of the major crops have declined, and the writer is inclined to believe that lack of phosphoric acid has been partially responsible for this decrease. Change in Form of Nitrogen
Another important development in the European fertilizer situation is the change from the nitrate to the ammonia forms of nitrogen. This change involves considerations of soil reaction which are of interest to all agronomists and soil chemists. According to data presented by J. Bueb a t the International Nitrogen Conference in May, 1928, the world consumption of the various forms of inorganic nitrogen in 1913 and in 1926-27 was approximately as follows: 1913 Per cenf 54 36 3 4 3
1926-27 Per cent 23 24 2 14 37
INDUSTRIAL A N D ENGINEERING CHEMISTRY
April, 1929
377
sold in France, although, without any good basis for estimating the percentage of the total fertilizer tonnage that is factory-mixed, the writer feels sure that i t does not amount to more than 10 or 15 per cent. I n Germany, of course, various Nitrophoskas are being offered for sale by the Stickstoff-Syndikat, but there is no mixed fertilizer industry in Germany as we know i t here in the United States. Summary
CHILEAN NITRATESULFATE OF AMMONIA CYANAMIDE
I
Tons*
Tons
I
Tons
Tons
I
Tons
Tons
Holland Great Total a b
*
I
1,405,500 371,400 I 807,400 1,793,000 I 62,200 533,000
Using Lambert's estimated production of 1,500,000 metric tons. Lambert's estimate. All figures are in short tons.
Use of Complete Fertilizers
The third important development in European fertilizer practice has been the tendency toward the use of complete fertilizers. This tendency is most pronounced in Great Britain, where from 50 to 60 per cent of the entire tonnage is factory-mixed. Some complete fertilizer is manufactured and
1-Comparison of post-war (1925-27) with the pre-war (1913-14) years shows a marked increase in the consumption of fertilizers in Germany, Holland, and France, but no increase in Great Britain. 2-During the period 1913 to 1927 there have been big increases in the use of fertilizer nitrogen and potash, with phosphoric acid making little if any gain. As a result, plantfood ratios, especially in Germany, France, and Holland, have undergone radical changes. 3-A comparison of pre-war and post-war crop yields in Germany and France shows that German yields have declined 14 per cent, while French yields have increased 9 per cent. It is probable that unfavorable weather in Germany during some of the recent years will explain a part of this disparity in yields, but it is also probable that lack of phosphoric acid has played a part. 4-There has been a marked decline in consumption of Chilean nitrate in Europe, especially in Germany where its use has practically been discontinued, and a tremendous increase in the consumption of synthetic nitrogen, largely sulfate of ammonia and cyanamide. 5-There is a decided trend toward the use of complete, fertilizers in Europe. I n Great Britain from 50 to 60 per cent of the total fertilizer tonnage is factory-mixed, and the use of complete fertilizers is on the increase. I n France the sale of mixed fertilizer is very limited but increasing. I n Germany, Nitrophoska is making some headway.
The Hydration of Animal Skin by the Volume Change Method' Edwin R. Theis and Harvey A. Neville WILLIAM H. CHANDLER CHEMICAL LABORATORY, LEHICHUNIVERSITY, BETHLEHEM, PA
H E swelling of animal tissues has been studied extensively by many investigators. Wilson and Gallun2 have made exhaustive investigations on the plumping of calfskin as a function of the hydrogen-ion concentration. McLaughlin and Theis3 studied the swelling of fresh steer corium and cured steer hide. The methods used by these workers were those of measuring the increase in weight or the increase in thickness. So far as the writers are aware, no study has been made of the hydration of animal skin by the volume change method. Neville and Jones4 studied the swelling and hydration of gelatin by this method and obtained some very interesting and valuable data. They found that a t equilibrium the contraction in volume of the system gelatinacid or gelatin-mter was a function of the final hydrogen-ion concentration. When the contraction in volume was plotted against the final pH, the curve obtained agreed well with the
T
1 Presented before the Division of Leather and Gelatin Chemistry at the 76th Meeting of the American Chemical Society, Swampscott, Mass., September 10 to 14, 1928. Wilson and Gallun, IND.ENO.CHEM.,16, 71 (1923). a McLaughlin and Theis, J . A m . Leather Chem. Assocn., 18,339 (1923). Neville and Jones, Sixth Colloidal Symposium, Toronto, 1928.
*
'
well-known swelling curve of gelatin. These workers further found that a t the isoelectric point there was no volume change and that, in general, the amount of swelling or hydration was proportional to the decrease in volume of the system. Experimental Procedure
The apparatus used in these experiments is shown in Figure 1. It is essentially a simple dilatometer and measures accurately the slightest change in volume. Twenty grams of material (fresh corium or cured heavy hide), cut into small cubes of 2 mm. edge, were placed in the bottle, and the bottle in turn was filled with either acid or water. The rubber stopper containing the capillary tube was then inserted without entrapping any air bubbles and the screw clamps were adjusted until the liquid stood a t a definite height in the capillary. Readings were made on a millimeter scale placed behind the capillary tube. The apparatus and all materials were brought to a constant temperature (22" C.) in a thermostat. After loading, the apparatus was returned to the thermostat and readings were
