cluding t h a t it is added in case of poor fermentation, such as is the case with sugar solution over old, dry pornace. In this event the chlorine will be close t o 20-30 mg. per IOO cc. \Then the chlorine figure approaches IOO mg. per IOO cc., with a corresponding increase in the content of soda, bne has practical proof t h a t corn sugar has been used in the preparation of the mine and, with t h e aid of other determinations: t h a t it is pomace wine. Polarization a t 8;’ C. after inversion is useful in substantiating the presence of corn sugar or corn-sugar residue. The practice of using corn sugar for sweetening or gallizing wines! once considerably in vogue. has greatly decreased and it may often be disregarded. soDa--The ranges and interpretation of this figure are similar t o those for chlorine. T O T A L T A R T A R I C ,\cIn---Pomace wines are low in tota! tartaric acid as compared with wines with which they are likely t o become confused. A figure of 2 0 cg. per IOO c c . or under is suspicious, and any unfortified wine falling beion- I O cg. of this constituent may usually be deemed spurious. The author has been informed of some supposedly pure unfortified European wines whose tartaric acid content is below I O cg. per IOO cc., but tlie history of the wines proved t o be incomplete. F I X E D A C I D A S TARTARIC--Any figure below j0 Cg. per T O O cc. is ground for suspecting pomace origin. Asa-For white dry wines an ash of 2 0 cgs. per IOO cc. or over indicates pomace. For red wines this Figure is of but general value. A L K A L I N I T Y O F AsH-The alkalinity of the watersoluble ash of pomace wines often falls as low as 8 cc. S ~ IHC1 O per IOO cc. wine or under, which is unusual for American wines. \Then the alkalinity of t h e water-insoluble ash exceeds the alkalinity of the vc-ater-soluble ash t h e fact is very characteristic of pomace nines. XOA-SCGAR ExTRacT--Xny figure be1ow I . j g. per 100 cc. for white wines and 2 . 0 g. per T O O cc. for red wines is suspicious. PExTosAxs-For white \Tines, any figure below j o mg. per IOO cc., and for red n.ines, belov- TOO mg. per 100 c c . , is suspicious. P E R C E X T P 2 0 j IN asa-Having this figure below 10 is almost a constant property of pomace wines. K E U T K A L I Z A T I O K TEsT-This test, which is communicated by Dr. B. G. Hartmann, of t h e Bureau of Chemistry, has been found very valuable as a.n aid in the detection of white pomace wines: “Straight wines or gallized wines, when neutralized with sodium hydroxide, darken slightly and acquire a brownish pink t i n t ; pomace wines acquire a brownish color and very often contain a sedimenr after standing.” A D J U S T n I E N r O F . i S H A K D X O N S U G A R EXTR.lCT---In cases where corn sugar is indicated in the manufacture of the suspected wine it is advisable t o adjust the figures for ash and nonsugar extract t o those of true grape material, i, e . , make allowance for the effect of the corn-sugar residue o n these constituenm. The corrections t o be made can be determined b y referring
t o t h e analyses of pomace wines given above. Secessarily these corrections will be more or less arbitrary, but t h e results obtained \Till be of value in differentiating between pomace wines and wines gallized with corn sugar. The following determinations are of secondary importance in judging pomace origin, h u t they are of value in sustaining interpretations of the cardinal determinations given above: F R E E T A R T A R I C ACID-Pomace wines contain little or no free tartaric acid. C R E A M O F TARTAR-Below 1,; Cg. per IO0 C C . is S U S picious. S U L F U R I C ACID(S08)-Belon. 5 mg. per IOO cc. is Suspicious. 11AGKESIA-FO~ white wines. any striking variation from I O mg. per 100 cc. is Suspicious. I n searching for pomace origin in wines the determination of any single constituent never closes t h e problem. and it is equally true t h a t few, if any, pomace wines will shorn all the peculiarities of this product. The organoleptic examination is of grea.t aid in malting the final decision and the color of the wine is often helpful. I n conclusion, the author wishes t o express his sincere appreciation t o J f r . D. IT. Campbell, of Sandusky, Ohio, for t h e untiring interest shown in the collection of the vines represented in the a b o w analyses. Thanltful acknomledgment is also extended t o several coileagues in t h e Internal Revenue Laboratory for timely aid in t h e analysis of t h e mines: t o Mr. W. V. Linder for determining nitrogen, volatile acids and pentosans in Samples 61882-96; Mr. J. M. Doran, total acid and tannin, Samples 61882-96, and lime and magnesia, Samples 61869-80; hfr. P. I‘alaer, specific gravity and tannin, Samples 6303 1-42. U. S. IKTERSAL REVENUE L A B O R A T O R Y , WASHIKGTOS
CHEMICAL COMPOSlTION OF ALFALFA AS AFFECTED BY STAGE O F MATURITY, MECHANICAL LOSSES, AND CONDITION OF DRYING By c. 0.S W A K S O X .4ND \v. L. LhTSHAW Received April 17, 1916
This paper i s a partial report on the chemical work done on alfalfa cut a t the time of budding, one-tenth bloom, full bloom, and a t seed formation, in an experiment carried on jointly b y the departments of chemistry, agronomy, and animal husbandry a t t h e Kansas Experiment Station.’ This paper discusses one phase of the work. ciz., the chemical composition as affected by 7-ariations in maturing and curing. The aifalfa was cut f r o m duplicate and triplicate As soon as cut, a sample was taken 0 . 1 acre plots. from the green material and spread in an attic room t o dry. \Then the cut hay in the field was dry enough t o stack, it also vias sampled: this sample \vas weighed and taken t o the same attic room t o d r y thoroughly. d f t e r the green sample was partially wilted a srnal! sub-sample was taken and the relative amount of 1 W e desire here t o expres9 our appreciation of t h e hearty cooperation received from Professors L. E . Call, Ralph Kenney, a n d \V. A. Cochel T h e expense of this experiment mas met by t h e Adami F u n d , K a n s u z Agricultural Experiment Stxtio.:
Aug., 1916
T H E JOCR,VAL O F I N D C S T R I A L A N D EiVGI,VEERING C H E M I S T R Y
leaves and steam was determined on a n air-dry basis. Samples of alfalfa cut a t t h e same stages of maturity were also obtained a t the time of feeding. These five different kinds of samples will be designated a s . s a m p l e d w h e n c u t , s a m p l e d w h e n s t a c k e d , leaves f r o m t h e m a t e r i a l s a m p l e d green, s t e m s f r o m t h e m a t e h a 1 s a m p l e d g r e e n , and s a m p l e d wheqz f e d This experiment has been carried on for two years. The summer of 1914 was moderately dry, while 191j was unusually wet. By analyzing t h e samples from each cutting, d a t a were obtained in regard t o t h e change in composition during each of these seasons. I t was found, however, t h a t t h e stage of maturity so strongly influenced t h e composition t h a t i t more t h a n offset a n y effect due t o the time of season. Therefore, only the averages calculated on a I O per cent moisture basis, for each stage of maturity, are given in the following tables. There were from 4 t o 6 cuttings on the first three stages, and 3 cuttings on t h e last stage. TABLE I-COMPOSITION
OF ALFALFACUT AT DIFFEREKTS T A G E S TURITY-SAMPLED WHEK CUT Crude PORTION STAGE O F ProCrude N-free YEAR AKALYZED MATURITY Ash tein Fiber Extract 1914 Whole P l a n t Bud 10.53 19.65 22.50 35.06 1/10Bloom 9 . 5 9 18.38 23.58 35.41 FullBloom 8 . 7 9 1 6 . 3 0 25.01 3 6 . 0 7 Seed 7.54 14.97 26.53 37.37 Leaves Bud 10.78 26.17 13.64 36.01 1/10 Bloom 10.52 26.16 14.06 37.40 FullBloom 9 . 1 1 22.10 13.66 39.32 Seed 8 . 7 0 21.25 14.55 39.66 Stems Bud 8 . 7 8 12.57 33.54 33.92 1/10Bloom 7.97 10.63 35.12 32.97 F u l l Bloom 7.62 9.72 36.33 35.83 Seed 7.12 10.22 36.41 34.86 1915 Whole P l a n t B u d 10.24 19.94 26.86 31.29 1/10Bloom 9 . 1 8 16.12 30.80 32.08 FullBloom 8 . 7 6 15.70 30.90 32.62 Seed 8 . 0 8 14.48 31.56 33.95 Leaves Bud 10.63 27.30 1 5 . 5 8 32.91 1/10Bloom 10.64 24.60 18.04 33.44 FullBloom 10.01 22.70 15.91 37.78 Seed 9 . 4 9 22.21 17.28 37.91 Stems Bud 8.77 13.04 36.62 30.58 l/IOBloom 6 . 7 4 10.80 4 0 . 6 0 3 8 . 8 5 FullBloom 6.38 9 . 8 3 43.37 29.15 Seed t.07 8 . 9 1 43.21 2 9 . 7 9
OF
MA-
Ether Extract 2.36 2.93 3.77 3.54 3.27 4.06 5.72 5.48 1.23 1.33 1.22 1.39 1.67 1.82 2.03 1.93 3.56 3.29 3.60 3.11 0.99 0.96 0.97 1.02
The percentage of feeding constituents in the whole plant, leaves, and stems for t h e two separate years is given in Table I . The ash and protein decrease regularly as t h e plant matures; crude fiber and nitrogenfree extract increase. Because of the large amount of chlorophyll in the ether extract, the figures do not give a n y significant d a t a . The ash content of the leaves is uniformly greater t h a n of t h e stems. The greatest difference between the leaves and stems, however, is in t h e content of protein and crude fiber. The leaves contain from z t o z ' / ~ times as much protein as t h e stems, while t h e stems contain over z ' / ~ times as ,much crude fiber as the leares. The samples of 191j , in comparison with those of 1914, have a slightly lower ash content, but a considerably higher content of crude fiber. These differences are most pronounced in t h e stems, and are probably due t o the larger growth in 191j . I n 1914 alfalfa was cut from a larger field a t t h e same stages of maturity. This was cured, baled, and stored in a barn, being sampled a t the time of feeding. A small amount was taken from each bale on opening, and placed in large bags. I n this way three t o five composites were obtained from each stage of cutting. These composites were analyzed separately, and the
727
average figures are given in Table 11. I n 191j,no samples were taken a t t h e time of feeding, b u t instead t h e average figures for the samples obtained a t t h e time of stacking are given in Table 11. A comparison of t h e figures in Table I 1 with those in Table I shows t h a t there is less ash and crude protein, and more crude TABLE11-COMPOSITIOK
YEAR 1914, when fed
1915, when stacked
OF ALFALFA CUT AT DIFFEREKT STAGES OF MATURITY-SAMPLEDAS H A Y Crude Ether STAGE O F ProCrude N-free ExMATERITY Ash tein Fiber E x t r a c t tract Bud 9 . 4 7 18.27 24.30 35.98 2 . 6 7 1/10Bloom 8 . 5 6 15.96 24.34 38.19 2.86 FullBloom 7 . 5 3 14.62 27.48 37.70 2.64 Seed 7.28 13.38 28.14 38.84 2.36 10.21 18.01 26.17 34.00 1.61 1 10 Bloom 8.76 15.46 31.53 32.72 1.53 ull Bloom 8.25 14.76 31.64 33.56 1.79 Seed 7.56 13.24 34.87 32.79 1.54 ~~~~
~~~~~
Y
fiber and nitrogen-free extract in the alfalfa sampled as hay. This difference is largely due t o mechanical loss of leaves. The relative amount of leaves and stems in the material sampled when cut was determined b y taking a handful selected from different parts of t h e large sample as soon as the alfalfa was wilted, and by separating this sample into leaves and stems. These were allowed t o dry under the same conditions as the rest of the sample, and t h e relative percentage b y weight was determined. The averages of all the cuttings are given in Table 111. I n 1 9 1 4 there was a larger percentage of leaves in the first three stages, b u t in 191; the percentage of -stems was larger in all of the stages. I n both years the proportion of leaves decreased and the proportion of stems increased as t h e plant matured. TABLE111-RELATIVE PER CENT OF LEAVES A N D STEMS I N ALFALFA SAMPLED WHEN CUT BUD--1/10 BLOOM FULLBLOOX -SEED--. YEAR Leaves S t e m s Leaves 1914 . . . . . . 5 7 . 5 7 4 2 . 4 3 5 6 . 4 0 1915 . . . . . . 4 7 . 8 9 5 2 . 1 1 4 1 . 5 4
S t e m s Leaves 43.61 5 1 . 5 4 58.46 37.65
S t e m s 1,eaves S t e m s 48.22 43.50 56.51 62.35 36.58 63.42
The exact amount of leaves lost in the process of haymaking is impracticable t o determine directly. However t h e approximate amount can be calculated if t h e chemical composition of alfalfa leaves and of alfalfa h a y containing all of the leaves is known. as well as the composition of the h a y when there is a loss of leaves due t o handling. The errors involved depend on the correctness of t h e assumptions made. Since t h e greatest difference in composition between the leaves and the whole plant is in protein, t h e figures for protein are used in t h e calculations. I t is assumed t h a t there is no loss of total protein in the process of curing, afid t h a t change in composition is solely due t o mechanical loss of leaves which contain a large aniount of protein. One source of error is in the determination of the relative amount of leaves and stems. The amount of material used in this determination is small in comparison with t h e total amouht of h a y under consideration. As this determination was made on a number of samples, however, the errors were largely eliminated in the average. The method of calculation was as follows: Let x =number of pounds of leaves lost. a = p e r cent of protein in alfalfa sampledwhen cut b = p e r cent of protein in alfalfa sampled as hay. c = p e r cent of protein in the leaves. Make the calculation on the basis of 100 lbs: air-dry
T H E .7 0 1 R S A L 0 F I S D C S T RI A L A N D E S G I X E E I I I N G C H E M I S T R Y
728
hay. Then 100 - .x = veight of hay after loss of leaves. The formula for calculation would then be: .b(~oo-x) .cx = a . Substituting the known values for a, h and r ; as obtained in the chemical analysis of any of the samples under consideration. as for bud stage samples of 1915,where a = 19.94,b = 18.01, c = 2 7 . 3 0 , the equation becomes 0.1801 (100- x! 0.2730 x = 19.94 (per cent loss of leaves b y weight). x = 20.77. Using this method of calculation, and t h e figures for the percentage amount of leaves given in Table 111, Table IT is produced presenting the percentage loss of 1ea.ies and crop.
+
+
TABLE IV-PERCENTAGE
LOSSES
OF
LEAVES A S D CROP
MATDRITY-BcD--l!lO BLOOM FULLBLOOM -SEED-YEAR Leaves C r o p Leaves C r o p Leaves Crop Leaves C r o p 1914 . . . . . . 2 5 . 0 4 1 4 . 3 5 1 9 . 6 7 1 1 . 0 0 2 3 . 8 5 1 2 . 7 2 2 5 . 7 7 11.67 7.22 3.00 11.84 4.46 13.82 5.06 1915 . . . . . . 20.7; 9.95
The figures in Table 1” show t h a t the loss of leaves is an important matter. The relative amount of leaves mas larger in 1 9 1 4 ,t ~ h e drier year, and t h e loss of leaves was also greater t h a n in 191j . T h e total amount of nutrients produced per acre was one factor t o be determined in the present experiment. The pounds of nutrients per acre in t h e total alfalfa crop as grown, as well as in t h e leaves and stems, may be obtained by using t h e d a t a of yield per plot at time of stacking, as obtained b y t h e agronomy department (see Table V), t h e figures for dry matter in t h e samples taken a t this time, t h e figures in Table ITr for loss in handling, and the figures for composition in Table I. I n 1914t h e largest amount of all nutrients was obtained in t h e bud stage. I n 191j the largest amounts were obtained a t full bloom.
hearily on the carbohydrates, and t o a much less extent on t h e ether extract. Fleishmann found also t h a t there were very important changes in the form of phosphorus and nitrogenous compounds. These changes, t o an important extent, also occurred under favorable conditions of drying. Headden’ found t h a t great losses of nutrients, due t o chemical and bacterial action, occurred under unfavorable drying conditions. Honcamp2 also found t h a t losses of chemical constituents occur t o some extent even under fax-orable conditions of drying in the sun. He also found t h a t the digestibility of hay depends t o an important extent on the method of curing. This has been shown by other investigators.3 T h a t the amount of pure protein as determined b y Stutzer’s method is decreased by slow drying was found in t h e present investigation. The nitrogen b y Stutzer’s method4 was determined on all t h e samples taken a t t h e time of cutting and a t the time of stacking. The results are summarized in Table VI. The green alfalfa samples taken a t the time of cutting were usually brought t o t h e chemical laboratory in t h e evening. The temperature in t h e attic room where they were spread t o dry was always high in the summer. Xevertheless t h e drying here was much slower t h a n in t h e open field where there was a free mol-ement of air, and usually sunshine. TABLEVI-AVERAGE FIGURES SHOWING RELATIOKS BETWEEN TOTAL AND PURE(STUTZER’S)PROTEIN IN ALFALFASAMPLES WHEN C u r , IN THE LEAVES A N D STEMS
SAMPLED AS H A Y , AND MOISTURE-FREE FOR 1914
ALFALFA STAGE OF Percentages YEAR SAXPLED MATURITY T o t a l Pure 1914 When C u t B u d 22.27 15.96 1/10Rloom 20.62 15.33 Full Bloom 1 8 . 3 4 14,ii TABLEV-POUNDS OF NUTRIENTS PRODUCED PER ACRE IN THE TOTAL Seed 17.16 14.40 CROP, LEAVES A N D STEMS, 10 PER CENT MOISTCREBASIS As H a y Bud 20.01 17.24 1/10Bloom 18.82 15.76 S T A G E OF C r u d e C r u d e X-free E t h e r Full Bloom 1 6 . 2 2 13.9; MATURITY Ash Protein F i b e r E x t r a c t E x t r a c t VEAR ~. Seed 14.71 12.50 1914 Whole C r o p Bud 817.01 1483.66 1815.57 2674.92 186.75 1,eaves Bud 28.55 21.63 1 / 1 0 Bloom 664.35 1235.92 1734.61 2399.51 251.00 1,/10Bloom 2 6 . 9 4 2 1.04 Full Bloom 534.61 967.17 1589.52 2167.56 218.50 FullBloom 25.21 20.42 Seed 331.40 674.55 1310.24 1786.94 134.82 Seed 23.94 19.86 Leaves Bud 487.06 1145.44 582.41 1501.87 147.07 Stems Bud 14.12 9.56 1/10 Bloom 405.43 946.55 556.12 1422.32 167.22 1/10Bloom 12.09 8.68 Full Bloom 281.07 693.07 429.39 1258.41 159.93 F u l l R l o o m 1 1 . 2 5 8.34 Seed 182.21 423.12 286.00 804.76 93.93 Seed 1 1 . 3 2 8 .93 1173.05 39.68 Stems Bud 329.95 338.22 1223.16 TEKPER C E N T MOISTUREBASIS ( b y difference) 1/10 Bloom 258.92 289.37 1148.49 977.19 83.78 909.15 5 8 55 F u l l Bloom 253.54 274.10 1160.13 1915 W h e n C u t B u d 19.90 12.83 149.19 251.43 1024.24 982.18 40.89 Seed 11.28 1/10Bloom 16.73 10.89 F u l l Bloom 1 5 . 3 8 1915 Whole Crop Bud 878.31 1710.30 2303.80 2683.76 143.25 11.21 Seed 14.80 1/10 Bloom 1066.34 1767.20 3376.50 3516.62 199.52 F u l l Bloom 1165.08 2088.10 4109.71 4338.46 269.99 AsHay Bud 17.16 13.09 Seed 792.31 1419.88 3094.71 3329.07 189.25 ..._ 1/10 Bloom 1 5 . 2 5 11.33 FullBloom 14.85 11.26 Leaves Bud 436.63 1121.35 639.95 1391.65 107.21 Seed 13.79 10.42 1 1 0 Bloom 484.55 1120.28 821.54 1522.86 149.80 Full Bloom 501.25 1136.69 796.69 1891.82 180.29 Leaves Bud 26.59 19.23 Seed 340.40 i96.66 619.83 1359.82 111.55 1/10Bloom 24.50 18.18 Full Bloom 2 2 . 5 8 17.09 Stems Bud 441.68 588.95 1663.85 1292.11 36.04 Seed 22.45 17.34 ( b y difference) 1/10 Bloom 521.79 646.92 ?554.96 1993.76 49.72 F u l l Bloom 663.83 951.41 3313.02 2546.64 89.70 Stems Bud 12.81 7.29 77.70 2474.88 1969.25 623.22 Seed 451.91 1/10Bloom 10.91 6.33 Full Bloom 9.68 6.11 Seed 9.05 6.80 ~
The change in composition due t o mechanical loss has been shown in t h e preceding paragraphs, b u t no a t t e m p t was made t o determine the total loss of any chemical constituent. T h a t there are losses of chemical constituents during t h e process of haymaking has been shown b y Fleishmann,2 these losses depending on the conditions of drying. He found t h a t the greatest losses occur under unfavorable m-eather conditions and t h a t the losses of chemical constituents fall most
T h e figures f o r protein used in t h e calculations, 1914, are found in T a b l e VI. 2 Die Lnndw. Vers. Slat., 76, 237-447. 1
T‘o~.8, SO.8
Protein P u r e Protein Diff. in % of Total 6.31 71.96 5.08 74.55 3.58 80.55 2 77 84.00 2.77 86.09 2.86 83.50 2.25 86.04 3.21 84.95 6.93 75.79 5.90 78.21 4.79 80.98 4.08 82.88 4.56 68.62 3.40 73.08 2.92 74.24 2.39 79 6 4 7.07 5.46 4.49 3.59 4.07 3.92 3.59 3.37 7.76 6.34 5.49 5.11
5,52 4.58 3.57 2.25
64.41 66.55 70.79 75.67 75.92 74.22 75.78 75.55 72.30 74.17 75.20 77.16 56.86 58.05 63.12 15.07
,4 study of the figures in Table V I brings out these facts: I-The per cent of pure protein in t h e total protein is less in the samples cured in the shade t h a n in those cured in t h e sun, or open field. The greatest difference occurs in t h e samples from the bud stage, and there is a gradual decrease t o t h e seed stage, where : 2
3 4
Colorado Experiment Station, Ruli. 110. Die Landw. Vers. Slat., 86, 215-275. I b i d . , 76 (1911). Bureau of Chemistry, Bull. 107.
Aug., 1916
T H E J O C R N A L OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
there is no significant difference; t h a t is. t h e protein in t h e younger plants was more profoundly affected b y this condition t h a n t h a t from the seed stage, which was very little changed. a-The differences between total and pure protein are greater in t h e alfalfa cured in the shade t h a n in t h a t cured in t h e sun or open field; t h a t is, t h e proportion of pure protein decreases during t h e process of drying. This is most noticeable in t h e earlier stages. The hay cured in t h e sun contains a larger per cent of pure protein t h a n t h a t cured in t h e shade. I n comparing t h e figures obtained on the samples for 1914 with those of 1915, important differences are noticed. The per cent of pure protein in the total protein is less in every instance in the samples of 191j 3 and differences between t h e alfalfa cured in t h e shade and t h a t cured in t h e sun are less. The more unfavorable drying conditions of 191j , with the necessity of curing under cock covers, allowed a prolongation of the vital activity of t h e protoplasm, resulting in protein cleavage. The per cent of pure protein in the total protein is from 6 t o 9 per cent less in the alfalfa dried in t h e shade in 1915 t h a n in t h e same lot in 1914, while t h e 191j samples dried in the open field show about 9 per cent less t h a n t h e 1914 samples. T h e larger, heavier plants of 1915 took longer t o dry. T h e stems, which dry the slowest, show t h e greatest differences in comparing t h e samples of the two years, a n d t h e leaves, which d r y t h e fastest, show t h e least difference. These facts point t o a very profitable line of investigation in regard t o t h e chemical changes which t a k e place under different conditions of haymaking. These changes no doubt include not only t h e proteins, b u t also t h e carbohydrates, fats, and phosphorus compounds. T h e feeding value of h a y is affected not only b y mechanical losses due t o handling, and the changes due t o bacterial action, b u t also b y chemical changes which are little known or noticed.
.
SURIMARY
I-The alfalfa cut in t h e bud stage had t h e largest a s h and crude protein and t h e smallest crude fiber and nitrogen-free extract. 11-In each successive stage t h e crude fiber a n d nitrogen-free extract increases, and t h e crude protein and ash decrease. I n pounds per t o n t h e alfalfa cut in t h e earlier stages has more of crude protein a n d less of crude fiber. 111-The total amount of a n y or all nutrients produced per acre depends t o a large extent on t h e yield, as shown b y t h e fact t h a t in 1914 t h e greatest amount of nutrients was obtained in t h e bud stage, while in 191 j t h e full bloom gave t h e greatest amount of total nutrients. IV-The leaves and stems differ in content of ash, e t h e r extract, and nitrogen-free extract, b u t the greatest difference is in t h e per cent of crude protein and crude fiber. The leaves contain over a 1 / 2 times as much protein as the stems, while t h e stems contain over 2 l / p times as much crude fiber as t h e leaves.
729
V-In harvesting and handling there is a large loss of leaves, which loss affects t h e composition of the hay in a n increase of crude fiber and a decrease of crude protein. VI-The alfalfa cured in the sun has a larger pure protein content as determined by Stutzer's method, t h a n t h a t cured in t h e shade. This difference is s o great as t o more t h a n offset t h e influence of the loss of leaves. The differences in respect t o pure protein content were most pronounced in the alfalfa cut in t h e earlier stages. CHEMICAL DEPARTMENT .kGRICULTURAL
EXPERIMENT STATION
MANHATTAN, KANSAS
THE VOLATILE OIL OF CALYCANTHUS OCCIDENTALIS By CHARLES C. SCALIONE
Received April 11, 1916
Calycanthus occidentalis, or Butneria occidentalis, also popularly known as spice-bush, belongs t o t h e family Calycanthaceae, 4 or 5 species of which are found in t h e United States. The species named is limited t o northern California and southern Oregon and is rarely found in large patches, b u t usually scattered along stream banks or river bottoms or on t h e lower slopes of hillsides. It is an unarmed shrub, which sometimes reaches a height of I O ft. It bears a n abundance of ovate t o oblong lanceolate leaves, somewhat scabrous and of a bright green color, and dark red flowers from I t o 1'/2 in. long. The leaves, bark and wood are all strongly aromatic; the flowers less so. Considerable interest has been attached t o some of the other species of this genus on account of their physiological action. An alkaloid was discovered in t h e seeds of C. glaucus C.Jerfilis, b y R . C. Eccles,' in 1888, and named by him Calycanthine. This was confirmed by H. W. Wiley2 in 1889. H. 1 4 . G ~ r d i n ,in ~ a number of papers, has shown t h e presence of two alkaloids, calycanthine and isocalycanthine. The volatile oil of Floridus has been studied b y Miller4 and his co-workers and found t o consist of pinene, cineol, borneol, bornyl acetate, salicylic acid, possibly linalool and some other esters besides the bornyl acetate. The cineol predominated. 1
EXPERINENTAL
Four hundred pounds of leaves and twigs from Oriental, California. t h a t had been kindly supplied by officials of t h e United States Forest Service, a t San Francisco, were submitted t o steam distillation under a pressure of 4 lbs. The yield of oil obtained from t h e united distillates amounted t o about 0 . 2 7 per cent of t h e weight of t h e original material. I n transit considerable decomposition of the leaves had taken place and the water distilling over with 1 2
Eccles, Proc. Am. Phaym. Assoc., 36, 84 a n d 382. U'iley, A m . Chem. J., 11, 5 5 7 . Gordin, Proc. A m . Phaum. Assoc.. 62, 345; 53, 224. Miller. J . A m . Chem Soc., 26, 2182.
