T H E J O U 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
Feb., 1918
permanganate, a n d t h a t t h e reaction occurs according t o t h e equation 2KC103 3HCHO = 2KCl 3H2O 3C02. Experiments have shown t h a t t h e proportion of 2 5 g . of chlorate t o IOO cc. of formalin is approximately t h e one giving best results, t h a t is, with these proportions there is practically no liquid left in the residue after the reaction subsides, t h e formaldehyde being either driven off as gas or oxidized a n d t h e water ,evaporated a t t h e same time. A simple calculation shows t h a t , according t o t h e above reaction, 25 g. KC103 will theoretically oxidize 9.18 g. HCHO or nearly 23 per cent of t h e formaldehyde in t h e IOO cc. of formalin, leaving t h e remaining 7 7 per cent t o be volatilized. It is probable, however , t h a t other reactions occur, such as KC103 3HCHO = KC1 3HCOOH. I n fact, appreciable amounts of formic acid, as well as COa, are evolved by t h e reaction of formalin with either permanganate or chlorate. I n a n attempt t o determine in a simple manner t h e best proportions of formalin a n d chlorate, a series of roughly quantitative experiments were made, using varying proportions of t h e two materials. A weighed amount of powdered KC1O3 was treated in a beaker with a weighed amount of the 40 per cent formalin a n d t h e beaker immersed in hot water in order t o start t h e reaction. The residue left in the beaker after t h e reaction had ceased was dissolved in water a n d titrated with standard solution of silver nitrate t o determine t h e amount of chloride present. From t h e amount of KC1 found, t h e weight of formalin representing t h e formaldehyde destroyed in t h e reduction of KC108 t o KC1 was then calculated from t h e reaction 2KC103 3HCHO = 2KCl 3C02 3Hz0. The results of these tests are shown in t h e following table. I t is t o be noted t h a t if t h e reaction KC103 3HCHO = KC1 3HCOOH is assumed, t h e calculated amounts of formaldehyde consumed will be just twice those given in the table.
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chlorate was effected a n d t h e amount of formalin oxidized much less. A number of qualitative tests were made using formalin and sodium chlorate in proportions varying from 6 : I t o 2 : I, the maximum temperatures reached during t h e reaction being noted. With t h e ratios 2 : I , 2 . j : I, and 3 : I, this temperature was 108-109’ C., while with lower proportions of chlorate (4 : I and 6 : I) t h e temperature was slightly less, 104’ t o I O j o C. I n each case t h e reaction started a t 60-65’ C., was violent a t about 7 j ’ C., and lasted only about 30 seconds, t h e maximum temperature being indicated near t h e end of t h e reaction. The writer hopes t h a t comparisons of t h e actual disinfecting efficiencies of t h e permanganate a n d chlorate methods will be made by those who may be interested in t h e practical side of t h e question and t h a t t h e chlorate method may be found t o be of some use. O R ~ N A N CDFPARTMENT, E U. S. R. WASHINGTON,
D.
c.
EFFECT OF FERTILIZERS ON HYDROGEN-ION CONCENTRATION IN SOILS‘ By F. W. MORSE Received September 2 9 , 1917
Most of t h e fertilizer plots a t t h e Massachusetts Agricultural Experiment Station have been continuously treated for more t h a n 25 years, a n d there are marked differences in their crop-producing powers, which in some instances appear t o be due t o chemical or physical changes in t h e soil and not t o a deficit of t h e usual constituents of a fertilizer. Among methods of investigating these soils, t h e measurement of t h e hydrogen-ion concentration in water extracts of t h e soils has given some interesting results. T h e method of procedure has been as follows: 2 5 grams of air-dry soil were weighed into a n Erlenmeyer flask of 300 cc. capacity, a n d 250 cc. distilled water were added. T h e flask was repeatedly shaken during a period of a n hour, a n d then t h e mixture was filtered through a dry paper filter. The first portions of t h e filtrate were usually cloudy a n d were returned TESTS OF RESIDUEREMAININGAFTER REACTION BETWEEN FORMALIN t o t h e soil flask. When t h e paper became well coated AND POTASSIUM CHLORATB with soil, the filtrate would, as a rule, be clear, with HCHO oxi- Formalin (40%) Calc. KClOa dized (equiv. equiv. t o HCHO KClOa Formalin t h e exception of some limed samples which would Reduced t o KC1 found) oxidized TEST Used Used Grams Grams Grams persistently retain a slight turbidity from clay. T h e Grams No. Grams 1.439 3.59 1 7 12 3.917 soil and water were in contact for about 3 hours before 1,402 3.50 2 6 12 3.817 1.329 3.33 3 6 12 3.620 filtration was completed. 1.375 3.44 4 5 12 3.750 1.369 3.42 5 4 12 3.726 T h e colorimetric method was used for determining 6 3 12 2.990 1.098 2.75 t h e hydrogen-ion concentration. T h e range for t h e 0.738 1.85 7 2 12 2.010 soils was found t o be covered by t h e indicators methyl I n Tests 5 a n d 6 a very small amount of liquid red, paranitro phenol and rosolic acid. T h e standard remained in t h e residue after t h e reaction; in Test 7 a n salt mixtures used were Walpole’s2 acetic-acid-sodiumappreciable amount of liquid remained and a de- acetate mixture, Sorensen’s3 mono- a n d dibasic phostermination of formaldehyde showed 1.104g. HCHO, phates, and Clark a n d L u ~ s mixture ’~ of monopotassium equal t c ? 2.76 g. of 40 per cent formalin. I n Tests I phosphate and sodium hydroxide. T h e last named t o 5 , inclusive, where the weight of KClOs was a t least covers practically the same range as Sorensen’s a n d one-third of the weight of t h e formalin, t h e amount of is much more convenient t o prepare. HCHO oxidized was fairly constant, t h e KC1 found 1 Presented before the Fertilizer Division. a t t h e 5 5 t h Meeting of the indicating t h a t only part of t h e KC103 had been American Chemical Society, B o s t o n , September 10 t o 13. 1917. 1 Biochem. J . , 1914; J . Chem. Soc.. 1914. reduced. I n Tests 6 and 7 t h e excess of formalin a Ergebnksse Physiol., 1912. was such t h a t practically complete reduction of t h e 4 J . B i d . Chem.. 26 (1916). 504.
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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
126
Ten cubic centimeters of t h e soil solution were compared with a n equal volume of t h e standard mixture appropriate for t h e concentration of hydrogen ions in t h e former. Small porcelain dishes served t h e purpose for comparisons in nearly all cases, b u t tubes were used when necessary t o check doubtful results. The different fertilizers t h a t had been used on t h e plots under investigation were acid phosphate, nitrate of soda, muriate of potash, sulfate of potash, double sulfates of potash and magnesia, sulfate of ammonia, land plaster and agricultural lime. T h e range of H-ion concentrations was between PH -4.5 and PH - 7 . 0 . Neutral salts of strong bases and strong acids, sodium nitrate, potassium chloride, potassium sulfate, calcium sulfate, produced little, if any, effect on the soil reaction, in comparison with unfertilized soil. The acid phosphate, a strong base with a moderately weak acid, behaved like t h e neutral salts just mentioned. Sulfate of ammonia behaved like a weakly ionized acid and carbonate of lime like a weakly ionized base, and t h e extremes of t h e range were always due t o these two compounds. When agricultural lime was used in conjunction with t h e other chemicals, i t was noted t h a t plots dressed with nitrate of soda or calcium sulfate retained the neutralizing effect of the carbonate of lime longer t h a n t h e plots receiving potash salts, probably through a protective effect on t h e solution of t h e lime as bicarbonate. I have not yet demonstrated t h a t point, however. T h e effect of a n application of 2,000 lbs. of hydrated lime per acre is perceptible on the crop and on t h e soil reaction for several years, b u t ultimately disappears, probably due t o both leaching and transformation, b u t apparently due more t o t h e former. The comparative results obtained during this season's investigation of our plots are as follows: North South Field A Acid phosphate.. . . P, 5 . 2 P, 6 . 1 5 Nitrate of soda.. . . . . . P, 6 . 0 Nitrate of soda.. ... 5.22 6.5 Sulfate of ammonia.. 4.9 Muriate of potash.. 5.25 6.15 Calcium sulfate.. . . 5 .O 6 . 6 5 No nitrogen.. ........ 5.4 Calcium carbonate. 6.4 7 1 Unfertilized. 5.25 5 . 9 6 Lime . . . . . . . . . . . . . . . 6.0 MASSACHUSETTS AGRICULTURAL EXPERIMENT STATION AMHERST.MASSACHUSETTS
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TABLEI SAMPLE No. I Date of Collection. 19:s Ether Extract (Fat). ....... 30.10 23.71 Protein (N X 6 . 2 5 ) . 9.21 Starch 22.07 Crude Fiber.. 4.04 Moisture.. Ash 2.89
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1
A m J . Pharm., 48 (1876), 451.
* I b i d . . 68
* I b i d . , 55
(1881), 384. (1883), 195.
No.
2
I1 1916 34.92 20.64 12.05 21.55 3.90 2.64
I11 1917 35.45 21.54 10.31 20.01 4.54 2.60
Samples of oil were prepared by extraction with petroleum ether, boiling point 44 t o 6 5 " C., and b y expression in t h e cold from the whole seed previously ground in a food chopper. The expressed oil was. thoroughly agitated with fuller's earth from which i t was separated by means of a centrifugal machine. The constants of t h e oils thus obtained were: TABLEI1
EXTRACTED OIL Color. Golden yellow Specific Gravity (at 2.5' C.). 0.9267 Refractive Index (at 25' C.) 1.4722 . . . . . . . . . . . . 5 t o -8 Solidifying Temperature.. Iodine Number, 116.5 Saponification Number.. . . . . . 193.4
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By MIGO REASONDAUGHTERS
Received October 26, 1917
IO,
side, which he called megarrhizin. The root of t h e Echinocystis is decidedly bitter and is therefore unfit for food. The Indians are said t o use it as a drastic purge i n dropsy. The fruit, which is borne on slender herbaceous stems varying in length from 3 t o 9 meters, is eggshaped. It varies from z j to jo mm. in t h e short diameter and is covered with soft green spines, a f a c t which explains the origin of the name "echinos" o r hedgehog. It becomes lighter in color as the seeds reach maturity, and breaks open a t times a t t h e free end, leaving the seeds more or less exposed. Each fruit contains from one t o several seeds, which a r e orbicular in shape, averaging 19 mm. in breadth and half as thick a s broad. Fourteen t o fifteen hundred of t h e seeds make a kilogram. The thin outer shell of t h e seed is readily broken and hence it is easily ground in a food chopper. The Echinocystis is distributed along t h e Pacific slope from British Columbia t o California, growing and thriving along railroad tracks, fence rows, in fields, along wooded ravines, and in the foothills. It is drouth-resistant, maturing its seeds under unfavorable conditions. So far as known no attempt has been made t o grow this plant in quantity. Bearing i n mind t h e character of t h e root it is readily seen why most farmers consider it a pest. Seeds collected for three successive years had t h e following percentage composition:'
THE SEEDS OF THE ECHINOCYSTIS OREGANA
This investigation was made t o determine t h e possible industrial value of the seeds of the plant called Echiizocystis oregana, but more commonly known as the Old-Man-in-the-Ground or Wild Cucumber. I t is a perennial plant, a remarkable feature of which is its gigantic root which penetrates t o a depth of I t o z meters and may weigh 30 or more kilograms. Heaney,' Manzj2 and Young3 examined the root of t h e Megarrhiza calijornica, a plant belonging t o t h e same order as t h e Echinocystis, and reported on its pharmaceutical value. Heaney found a bitter gluco-
Vol.
EXPRESSED OIL Olive-green 0.9166 1.4701 +5 to -8 117.0 189.1
Judged by these results, t h e oil from the seeds of t h e Echinocystis belongs t o the cottonseed oil group. The oil tastes like olive oil. Both the extracted and expressed oils become turbid when cooled t o a temperature of 5 " C., b u t a t - S o C. the former has t h e consistency of vaseline, whereas t h e latter is more solid. Nearly 40 per cent of t h e oil content was expressed with t h e apparatus employed for this purpose. T h e pressure applied was approximately 83 kg. per squarecentimeter or nearly 1200 lbs. t o t h e square inch. Freshly ground seeds gave a n oil of olive-green color, which faded in a few days in bright light t o a golden. 1
All analyses were made in August, 1917.
