T H E J O C R S A L O F I l l - D C S T R I A L ALVD E Y G I S E E R I S G C H E M I S T R Y
4-28
very accurate results when properly carried out. While not so speedy as t h e simple titration, its freedom f r o m t h e usual sources of error entitle it t o the preference for all exact work. I n Table I are presented results obtained by several methods on a series of six soils. identical m-ith those supplied b y t h e Referee on Soils of the Association of Official Agricultural Chemists for cooperative work in 191j . The figures in parenthesis following sample No. I serve as an approximate measure of t h e extent t o which organic matter has been attacked hy t h e reagents in each case, and these percentages have been deducted in the cases of t h e next three samples in order t o afford a better comparison between methods. A similar blank for Nos. j and 6 was obtained b y extracting a sample of S o . 5 v i t h cold dilute hydrochloric acid ( I volume concentrated acid diluted t o I O , t h e same as used for those methods requiring boiling a t atmospheric pressure), then washing thoroughly with COi-free r a t e r . o.ooyy per cent carbon was obtained from t h e extracted soil b y boiling and estimation by double titration, while none whatever was obtained b y t h e LIarr method in either of two TABLE I-PERCENTAGES CARBOXB Y T'ARIOUS METHODS SAMPLES ANALYZED Loam, deficient in Organic M a t t e r a n d supposedly free from Carbonates 2-Xo. 1 a small amount of 100 mesh Limestone 3-No. 1 100 mesh Dolomite &No. 1 100 mesh Dolomite 5-Black Clay Loam, containing Carbonates and much Grit (meventing fine grinding) 6-Ko. 5 100 mesh Dolomite RESULTSBY MARRMETHOD(MODIFIED) Boiled a t Atmospheric (BrownPressure with 1 : 10 HCI (Cain's) Residual Escomhe) Double GasoBaCOs Ba(0H)z Double No. Titration metric Titrated Titrated Titration (0,0018) (0.0007) (0,0015) 1 (0.0096) (0,0093) 0.0276 0,0291 0.0274 2 0.0276 0,0276 0.0289 0 0279 0.0270 3 0,0276 0.0280 0 . 2 2 0 4 0.2194 0.2237 4 0,2133 0.2220 0.1454 0,1498 0,1462 j 0,1485 0.1508 0.2759 0.2868 0 . 2 i 5 0 6 0.2835 0.2880 1-Silt
+++ +
trials. I n this connection it is b u t fair t o state t h a t only one other analyst reported no carbon b y t h e Marr method from No. j after extraction, but, on t h e other h a n d , only one reported more from No. j after extraction t h a n from S o . I , although S o . j contains by far t h e larger amount of organic matter. The explanation may be either t h a t KO. I actually contains a trace of carbon dioxide. or t h a t extraction with cold dilute acid removes or causes the decomposition of the most readily attacked part of t h e organic matter. I t was noted t h a t the acid extract from No. j ITas 1-ery dark in color: I n conclusion, t h e writer wishes t o express his ohligations t o hlr. J . W , Ames, chief of the Department of Chemistry a t this Station, for helpful suggestions and permission t o publish this article. EXPERIMEXT STATIOX WOOSTER, OHIO
OHIO AGRICULTURlL
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~
SOME NOTES ON SANDALWOOD, ITS ASSAY, YlELD OF OIL, AND CHANGES IN THE OIL DURING DISTILLATION1 By
c.
11.
BRiGG5
Received September 13, 1915
The d a t a set forth in this paper have been collected a t various times during t h e last few years, and as 1 Presented at t h e 51st Meeting of t h e American Chemical Society, Seattle, Aog. 31-Sept. 3, 1915.
1-01,
6 , No. 5
similar results have not been noted elsewhere in t h e literature, it vias thought it might be of interest t o others. A few years ago twelve samples of various grades of sandalwood were obtained from the hlysore Province. India. These samples consisted of small pieces of the unground wood representing certain types or classes of sandalwood which could be bought from the h>Iysorc government. The samples varied in weight from a few ounces t o a pound, and as there was a Considerable range of prices. we \\-ere naturally much interested in t h e content of santal oil in t h e different grades. X search of t h e literature failed t o reveal any method of assay for the amount of santal oil in sandalwood t h a t could be applied t o these small samples. At first it was thought t h a t this problem was hopeless, but after considerable experimentation a method of assay was evolved which proved t o be quite satisfactory. I t is as follows: Place I O O g. of the finely powdered drug in a Soxhlet extractor and extract with sulfuric ether for one d a y or until completely extracted. Transfer t h e ether extract t o a 200-cc. side neck distillation flask and evaporate off the ether on a steam b a t h with t h e aid of a stream of air. Add 3 j cc. of glycerine and distill in a vacuum until about z j cc. of the glycerine have distilled over. Add z j cc. of water t o the distillate and extract with chloroform, using three portions of about 2 5 cc. each. Evaporate the combined chloroform extracts in a tared dish on a water b a t h with the aid of a stream of air until the chloroform has all been removed, dry in a vacuum desiccator over sulfuric acid and weigh. Sandalwood contains a large amount of fixed oils as well as t h e essential oil and both are extracted b y ether. The essential oil cannot be separated quantitatively from this extract b y distillation in a vacuum unless glycerine is also added t o help carry over t h e last traces of t h e essential oil. The essential oil can he separated from t h e glycerine in t h e distillate by extracting v i t h chloroform. X j-g. sample of santal oil was dissolved i n ether a n d assayed b y the a b o r e method as a check: practically all of t h e oil was recovered. T h e twelve samples of sandalwood obtained from t h e Mysore government and representing as many different grades assayed as follows: To. h-0. yc OIL S O . 5 OIL I
2 3 4
3.7 i.44 5.9 8.3
5 6
3.7 6.5
7
4 7
s
i:73
12
3.84 3.53 3.66 3.8
SAMPI,E FROM STOCK, 6.0% Oil
I t will be noted t h a t these samples varied from 3 7 t o 8.3 per cent. I t would be of much value t o distillers of santal oil if t h e cost of the wood could be based on t h e content of oil, b u t t h e commercial conditions governing t h e sale of sandalwood are such t h a t this cannot be carried out successfully. H o w ever. t h e assay is of r a l u e in checking t h e yield of santal oil from t h e wood when distilled on a large scale CHASG$S
IS T H E O I L DURITG D I S T I L L A T I O X
During t h e course of this work, it was noted t h a t oil obtained from sandalwood b y this method of assay had a n optical rotation of --18' or above, whereas
M a y , 1916
T H E J 0 I ; R ; V A L O F I , V D C S T R I A L A N D E,VGI>YEERISG C H E M I S T R Y
the same wood when distilled with steam in a n ordinary essential-oil still yielded a n oil having a n optical rotation of -14' or less. I t was also noted t h a t t h e oil obtained b y t h e assay method was readily soluble in 5 volumes of 70 per cent alcohol at 2 j ' C., whereas t h e oil obtained b y t h e ordinary steam distillation required more t h a n j volumes of 70 per cent alcohol t o dissolve it. Thus a sandalwood which was known t o contain a n oil which would meet t h e U. S. P. requirements. would yield b y ordinary steam distillation a n oil which would no longer meet these requirements. There must, therefore, be some decided change in the oil during distillation with steam. T o study this condition, 5 0 0 lbs. of sandalwood were distilled with steam and samples of each day's r u n collected and the physical properties determined. T h e results were as follows: Day 1st 2nd 3rd 4th 5th 6th 7th 8th 9th 10th 1I t h 12th 13th
Sp. Gr. 0.969 0.970 0.972 0,974 0,976 0.978 0.978 0.9795 0.981 0.9815 0,9820 0.983 0.982
Ref. Ind. 1.5017 1.5020 1.5027 1.5030 1.5035 1.5037 1.5045 1,5046 1 ,5046 1,5046 1.5045 1.5045 1. 5046
Opt Rot -120 34' -120 22' -12' 46: -120 54 -13' 10' -120 39' -11'8 -1004' -90 10' -8' 20' -7 0 45' -7' 8 -6' 34'
Solubility a t 25' C. in 5 parts 707, alcohol C
I t will be noted t h a t there was a gradual increase in specific gravity with each day's run from 0.969 t o 0.982. Also t h a t the refractive index steadily increased from I . 5017 t o 1.;046. The optical rotation was fairly constant for j days a t -12 O t o -13 ' and then steadily decreased t o -6' 34'. With t h e exception of the first day's run, t h e oil mas soluble in j parts of 70 per cent alcohol a t 25' C. for the first 7 days, b u t the eighth day's r u n was no longer soluble a t 2 j ' C. and the solubility grew gradually less up t o the end of the distillation. To determine if this change in the optical rotation of santal oil during distillation was due t o prolonged exposure of the oil t o boiling water, a sample of oil having an optical rotation of -20' 40' was boiled continuously for several weeks in a glass flask with a reflux condenser. The same experiment was also carried out b y boiling with a I O per cent solution of sodium chloride. OBSERVATION At beginning of experiment Aitef. boiling 1 week.. . . . . After boiling 2 weeks.. , . . After boiling 2l/4 weeks., . After boiling 3 weeks.. . , . After boiling 3I/z weeks.. . After boiling 6 weeks.. . . .
EXPERIMENT I
Water -20' 40; -18' 50
....,,
l 0 R NaC1 --?no 40' -19' 42'
......
-15' 40' -19' Flask broke -19'
., . . . .
45' 30'
....,.
-17'30'
,,, , , , ,
EXPERIMENT I1
Water -20' 40' , ,,,
-16'
loch NaCl -20' 40'
.,
10'
,, ,,,, , ,,,
-130
.,
16,
... . , ,
......
-19'
40'
......
Likb'40,
......
I t will be noted t h a t there was a very decided change in the optical rotation of the santal oil b y boiling with n-ater, the rotation decreasing from -20' 40' t o -13' 16' in 3l/2 weeks. The change b y boiling m-ith t h e I O per cent salt solution was much less, being reduced t o -16" 40' in t h e same length of time. K e must conclude then t h a t under certain tions prolonged contact with boiling water about decided changes in the composition of oil and greatly reduces the optical rotation. ~
condibrings santal These
429
same changes take place in t h e oil t o a greater or less extent during the distillation of t h e oil from the wood with steam and probably accounts for much of t h e santal oil on the market having a low optical rotation a n d poor solubility. T h e writer wishes t o express his thanks t o Mr. S. T. McCallum for his assistance during this work. CHCMIC.4L LABORATORY, PARKE, DAVIS& COMPANY DETROIT,MICHIGAN
NOTE O N AMERICAN CHARLOCK OIL By H. S. BAILEY AND L. B. BURNETT Received December 2 1 , 1915
During the course of a n investigation into t h e "Production, Botanical Composition and Volatile Oil Strength of American Wild Mustard Seed," Wint o n and Bornmann' separated from northwestern wheat screenings several samples of fairly pure charlock (Brassica arzensis) seed. These we combined and further purified in t h e laboratory until our material was 98-99 per cent charlock, t h e remainder being nearly all brown mustard (Brassica juncea). After taking out a sample for analysis, t h e seed was ground in a drug mill and pressed cold in a small hydraulic press, t h e material remaining under pressure over night. T h e press cake was t h e n reground and divided into two portions! one of which was extracted with petroleum ether (b. p. 35-60') and the other with ethyl ether in a Soxhlet apparatus. The original seed contained 4.1 per cent moisture, as determined in an atmosphere of C o n a t 100' C . , 30.0 per cent ether extract and 29.6 per cent petroleum ether extract. The chemical and physical factors of t h e expressed and extracted oils together with an analysis b y Grimme* of oil of charlock. probably t h e ether extract of Siizapis arveizsis, are given in t h e accompanying table. CHEMICAL FACTORS OF CHARLOCK OIL3 Petroleum Expressed Ether Ether Grimme's Oil Extract Extract Analysis Specific Gravity, 1 5 / 1 5 , . , , , 0.9121 0,9272 0.9212 0,9228 Refractive Index, 25'. , , , , , 1.4734 1.4739 1 ,4729 1.4720(a) Saponification KO... , . , , , , , 182.9 183. I 181.0 179.4 Iodine No., Hanus . . . . . . , , 1 2 1 , l 119.8 119.3 102,6(b) Insoluble Acids and Unsaponifiable, , . . , , , . , , , , , 9.5.3 95.4 95.2 94.21 Soluble Acids.. . . . . . , . , , . , 0.0 0.0 0.0 .... Mean Mol. Wt. of Ins. a c i d s 3 3 9 . 1 338.1 334,8 312.4 LIQIIID ACIDS: Per c e n t . . , , , , , , , , , . , . . . 8 9 . 3 90.0 90.0 .... Iodine No.. , , , , . . . . , , , , 126.0 122.3 125 0 , . . SOLIDACIDS: Per c e n t . . . . . , . , . . , , , , , , 3.1 1.6 2.0 .... Iodine No.. , , , . , . , , , , , , 62.0 ... 61.0 .... ( a ) Calculated t o 25' from Grimme's value 1 ,4738 a t 20'. ( b ) Probably not b y Hanus' Method. PHYSICAL AND
As has been pointed out by Winton and Bornmann, there are large quantities of so-called "Wild LIustard" which contain varying proportions of charlock and brown mustard separated from American grains. Some of this is already being utilized as an oil material. Whether or not this oil can be sufficiently refined t o make it suitable for food purposes remains t o be seen, b u t undoubtedly it can be used in soap making a n d possibly in cheap paints. BUREAUO F CHEMISTRY, \VASHINGTON
,
THISJOURNAL, 7 (1915), 684.
Lewkowitsch's "Chem. Tech. and Anal. of Oils, Fats and Waxes," 5 t h ~ d . vel. , 11, p . 271. 2
