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 t h e 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 t h e neutralizing effect of t h e 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 t h e 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 t h e whole seed previously ground i n 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 t h u s 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 s h o r t diameter and is covered with soft green spines, a f a c t which explains t h e origin of t h e name "echinos" o r hedgehog. It becomes lighter in color as t h e seeds reach maturity, and breaks open a t times a t t h e free end, leaving t h e 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 i n 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 t h e foothills. It i s 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 t h e seeds of t h e plant called Echiizocystis oregana, but more commonly known as t h e 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 t h e 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 t h e seeds of t h e Echinocystis belongs t o t h e cottonseed oil group. The oil tastes like olive oil. Both t h e extracted and expressed oils become turbid when cooled t o a temperature of 5 " C., b u t a t - S o C. t h e 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 i n a few days in bright light t o a golden. 1
All analyses were made in August, 1917.
Feb., 1918
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
yellow. Seeds which were ground for two weeks before pressing gave an oil of greenish red color in reflected light and dark olive-green in transmitted light. When subjected t o hydrogenation a t 2 2 0 t o 240' C., with powdered nickel-prepared from nickel oxide just previous to its addition t o the expressed oil-there was produced a bland yellowish white f a t with a melting point of 29 t o 36' C., a solidifying temperat u r e of 2 5 ' C., and a n iodine number of 7 6 . 6 . Feeding experiments with mice attested t h e nonpoisonoils character of both the original oil and the hydrogenated f a t . IIEPARTMENT OF CHEMISTRY OREGON STATEAGRICULTURAL COLLEGE CORVALLIS
VARIATION IN THE ETHER EXTRACT OF SILAGE' By L. D. HAIGH Received M a y 26. 1917
Having occasion t o repeat t h e analysis of some samples of silage I O months after t h e first analysis was made, considerable variation in t h e samples was
Silage Date No, Analyzed 1....... 3/16 2/17 2 . . . . . . . 3/16 2/17 3 4/16 2/17 4 5/16 2/17
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127
cipally t o t h e presence of acetic acid, and lactic acid. T h e former is volatile in a vacuum! t h e latter is not. Table I11 illustrates t h e determination of t h e acidity of silage based on this fact. TABLE 111-ACIDITY OF AIR-DRY SILAGE TOTAL ACIDITY ACIDITY A s Lactic Acid VOLATILE TOTALACIDITY Original After in V a c u o Recalculated as
Silage Air-Dry Drying No. Silage in V a c u o 4.13 1 . . . . . . . . . . . . . 4.43 4.40 Z . . . . . . . . . . . . . 4.78 4.25 3 4.66 3.56 4 3.93
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Figured as Lactic Acetic 0.20 0.30 0.38 0.26 0.27 0.41 0.37 0.25
Acetic and Lactic A c i d s 4.33 4.66 4.52 3.81
Comparison was made of t h e acidity of t h e samples before a n d after t h e determination of moisture a n d before and after t h e determination of t h e ether ext r a c t , in order t o s t u d y t h e effect of t h e acidity upon these two determinations. T h e results are shown in Tables IV a n d V. The last column in Table V shows t h a t water will wash from silage not only t h e acid b u t also other substances soluble in ether. N o a t t e m p t is made in this report t o explain t h e causes for t h e above variation. Further studies are being made with a view of ascertaining what these causes are. We only wish t o indicate a t this time t h a t variations do occur in value for ether extract
TABLEI-ANALYSIS O F AIR-DRY SILAGE-NEW AND 10 MONTHSLATER ,--B-RESULTS I N PERCENTAGES ON DRY BASISNitrogenA-RESULTS IN PERCENTAGES ON AIR-DRY BASIS--Ether Crude Protein Nitrogen-Free Ether Crude Protein Free Moisture Extract Fiber Ash Nitrogen NX6.25 Extract Extract Fiber Ash Nitrogen N X 6.25 Extract 22.31 5.51 1.40 8.73 59.63 56.33 3.82 8.25 5.20 1.32 21.07 5.54 3.61 5.59 1.19 7.45 2.71 20.68 63.58 7.00 59.75 1.12 19.43 5.25 6.02 2.55 20.53 5.15 1.19 59.45 3.98 7.45 62.92 7.00 1.12 19.40 4.87 3.76 5.52 6.51 2.99 17.74 4.88 1.08 6.75 61.13 3.20 18.98 5.22 1.16 7.22 65.39 7.85 4.81 20.05 5.72 1.24 7.75 53.82 5.22 21.76 6.21 1.35 8.41 58.40 5.67 2.71 19.53 5.74 1.20 7.50 58.85 2.87 20.70 6.09 1.27 7.95 62.39 7.28 5.10 22.68 6.42 1.27 7.94 50.58 5.50 24.46 6.92 1.37 8.56 54.56 6.09 2.75 21.67 6.53 1.25 7.81 55.15 2.93 23.07 6.95 1.33 8.32 55.73
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noted. The ether extract in particular showed great variation, much less being found in t h e old t h a n in t h e fresh silage. Table I shows t h e comparative results of t h e analyses of silage when new a n d also I O months, later. T h e results show t h a t some factors entered into t h e determination when t h e silage was fresh which did not appear in t h e silage I O months later. Inasmuch as t h e sample must be dried before t h e ether extraction t h e effect of vacuum a n d oven drying on t h e percentages of moisture obtained was first studied. T h e results are shown in Table I I A . T h e effect of vacuum a n d oven drying on t h e results for ether extract are shown in Table I I B .
depending upon changes in t h e sample itself on standing a n d upon t h e drying operations employed. It is evident t h a t t h e analyses should be made as TABLEIV-EFFECT
OF ACIDITY OF AIR-DRY SILAGE UPON MOISTURE DETERMINATION %,Losson 7 MIXTURE ACIDITYOF SILAGE Acidity Original After Volatilized Drying a t 100' A& By Air-Dry Dryins Acetic Moisture Deducting V a c u o Silage Acetic b a t 100 and and Some Volatilized CorNo. Lactic Lactic Lactic Acidity Acidity Yecfed 1 80 2.53 8.78 I . . . . . 4.33{ 1:89 2.44 8.68 2.77 9.39 Z . . . . . 4.66{ 2.69 9.24 1 88 2.64 8.68 5.40 3 . . . . . 4.52 1:75 2.77 8.75 1.61 2.20 9.11 5.84 4 3.81 1.56 2.25 9.15
.....
1
!::;
::$if
;:;A]
TABLE V-EFFECT OF ACIDITYOF AIR-DRYSILAGE UPON THE DETERMINAAIR-DRY BASIS B Y DIFFERENTMETHODS TION OF ETHER EXTRACT O F DRYING ACIDITYA S LACTICACID Total ETHEREXTRACT A-PERCENTAGE OF MOISTURE Of Air-Dry Of Residue ExEtherLess After DRYINGMETHODUSED Silage 1 2 3 4 Silage after after tracted Soluble Ether- Washing 6.02 6.51 5.67 6.09 Vacuum Soluble with Silage Drying Extraction by Material Vacuum Oven (15 min.). . . . . . . . . . . . 6 . 3 0 6.90 6.18 6.64 Ether No. in V a c u o with Ether Found Acidity Water 9.31 8.71 9.13 O v e n ( 1 0 0 t o 105°Cc.). . . . . . . . . . . . . . . . 8 . 7 3 0.66 2.53 1.76 0.68 2.56 B-PERCENTAGESO F ETHEREXTRACT 0.71 2.90 DRYINGM5THOD USED Silage 1 2 3 4 1.82 0.77 3.08 Vacuum, before and after Extraction.. 2.55 2.99 2.7 1 2.75 0.63 2.88 2.25 Vacuum +Oven, before and after Extrac. 2.01 2.11 1 .90 2.12 0.63 2.55 1.92) 1.50 Vacuum before. vacuum oven after 0.52 2.70 1.30 Extraction 2.87 3.27 2.94 3.06 0.50 2.80 TABLE :II-RESULTS
ON
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+
i: :]
+ ........................
;:;:I ::;E]
.
I t w&s thought t h a t t h e acidity of silage might have some p a r t in t h e variation of t h e results for moisture a n d ether extract. T h e acidity of silage is due prin-
* Presented a t the 54th Meeting of the American Chemical Society, Kansas Ciiy, April 10 to 14, 1917.
soon as possible after t h e feed is used and t h a t a uniform method of drying be employed, if these variations are t o be avoided. AGRICULTURAL EXPERIMENT STATION COLUMBIA,MISSOURI
