Apr. , I 9 I 6
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
B a ( O H ) z t o neutralize t h e active acidity, a n d diluting i t t o I jo cc. with COz-free water. The soil a n d acetate solution are vigorously shaken together i n a 300 cc. flask for t w o minutes a n d t h e n quickly filtered on a Buchner funnel a n d titrated with N/2j N a O H using phenolphthalein. Calculations are made as follows: Let a = avidity of acetic acid (conveniently taken as 1000) b = cc. i V / 2 j N a O H required b y titration c = cc. N K C 2 H 3 0 2used x = relative avidity of active soil acids (average of all) Then: x = ab/ 2 jc- b , and b y substitution of known values, x is solved for. Since soil acids are quite insoluble compared t o acetic acid, t h e relation between t h e figure obtained for avidity of soil acids a n d t h a t taken for acetic acid (1000) does not represent t h e strength of t h e active soil acids compared t o acetic acid. However, since t h e acids in different soils are practically all insoluble, t h e avidity figures for different soils are comparable. G E N E R A L DIscussIox-In Table 11 are given a few values of avidity secured b y this method together with t h e active acidity in tons per acre of CaC03 as measured b y t h e method described in this article, a n d also t h e degree of active crop-injurious acidity as measured b y t h e new test previously described. It is clearly evident t h a t t h e avidity of t h e active soil acids in different soils varies greatly, from which i t must be concluded t h a t t h e seriousness of a soil's acidity a n d t h e urgency of t h e need of lime are not indicated by t h e total active acidity alone. It is necessary t o also consider t h e avidity of t h e active acids. Soil 7 , for example, is much higher in t o t a l active acids t h a n No. 6, yet in cultural practice No. 6 responds decidedly t o liming a n d No. 7 does not. What is t h e explanation? I t is clearly a matter of avidity, since t h e avidity figure for No. 6 is nearly 8 times t h a t of No. 7 . From this i t is evident t h a t a n y practical method for t h e determination of t h e urTABLE 11-AMOUNT OF ACTIVES O I L ACID%AVIDITYOF ACTIVESOIL ACIDS, DEGREEOF CROP-IXJURIOUS ACIDITYIN SEVERALSOILS Degree of Active Acidity Avidity Crop-Injurious in tons CaCOs of Acidity by KIND OF SOIL N o Der acre Active Acids New Test Silt loam.. . . . . 1 72 4.9 Slight to Medium Silt loam.. . . . , 2 42 3.1 Very Slight Silt loam.. . . . . 3 96 9.3 Medium to Strong Clay. . . . . . . . . , 4 6.6 152 Very Strong Sand ... . , . . . . , 5 1.2 26 Very Slight Sand.. , . . . . . . , 3.4 113 Strong P e a t . , . , . .... , . Very Slight 5.6 15 AND
P
gency as t o t h e need of lime must t a k e into account both t h e q u a n t i t y a n d t h e quality (strength) of t h e soil acids. T h a t t h e new simple test for acidity actually does this is evident from Table 11. The degree of acidity indicated b y this test is t h e resultant of two factors, viz., quantity a n d strength of active soil acids which may conveniently be called t h e degree of crop-injurious acidity. Because of this feature, i t is superior t o a n absolute quantitative method in indicating t h e seriousness of t h e acidity and t h e advisability of using a light, medium or heavy application of lime. Because of t h e varying needs of different crops, t h e enormous yearly loss of lime through
345
leaching, a n d t h e great complexity of soil acidity a n d related phenomena, it is ridiculous t o advocate methods for practical purposes which are said t o indicate down t o hundreds of pounds per acre t h e amount of lime which a farmer should use. An approximation in tons or perhaps half tons is t h e best t h a t can be expected a n d all t h a t is necessary. However, a n a b solute quantitative method is of t h e greatest value as a n aid in many lines of research on soils., Since nearly equivalent amounts of different hydrates are required, as shown b y Table I, t h e intervention of a t r u e chemical reaction is indicated, a n d i t may safely be accepted t h a t soil acidity is due t o true acids a n d not selective ion adsorption b y colloids a n d other adsorbing substances, as often stated. The reason t h a t N a O H sometimes gives a slightly higher result a n d C a ( O H ) 2 a slightly lower result t h a n Ba(OH), is undoubtedly due t o side reactions, such as action on organic matter, latent acidity, etc., which clearly would be different for t h e different hydrates. For a further discussion regarding nature of soil acidity see previous publication.' T h e enormous supply of latent acid substances in many soils of t h e humid region as indicated b y these methods is of t h e greatest importance in preventing excessive losses of bases b y leaching. It also offers a further explanation why MacIntirelZ Hardy a n d Willis were able t o secure large decompositions of MgC03 when this material was left in contact with soil t h a t supposedly had been completely neutralized. A more detailed paper regarding t h e nature of soil acidity is in preparation. S C M 41A R Y
I-A
new form of apparatus for t h e determination of soil carbonates is described. I t has certain marked advantages. 11-Evidence is given indicating t h e existence of two kinds of soil acidity, which are conveniently called active a n d latent soil acidity. 111-Methods are proposed for t h e determination of active a n d latent soil acidity, a n d also t h e average avidity of t h e active soil acids. IV-Data are given indicating as follows: Soil acidity is due t o t r u e acids a n d not selective ion adsorption b y colloids; t h e avidity of t h e active acids in differe n t soils varies greatly, which is of prime importance; a n d t h e new test for soil acidity previously described gives a more reliable indication as t o t h e seriousness of t h e acidity t h a n a n absolute quantitative method. DEPARTMENT OF SOILS. WISCONSIN EXPERIMENT STATION UNIVERSITY O F \%'ISCONSIN, MADISON
T H E COMPARISON AND IDENTIFICATION OF VARIOUS TYPES OF SMOKING OPIUM3 By FRANK D. SIMONS Received November 29. 1915
DESCRIPTIVE
Smoking opium may be classified, according t o t h e method of preparation, as t h e product obtained b y : Science 42 (1915), 5 0 5 . Tenn. Agric. Expt. Sta., Bull. 107. a Published b y permission of the Secretary of the Treasury and the U. S. Appraisers of Merchandise, Baltimore. Md. 1
2
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I-Simple aqueous extraction of t h e crude gum opium, filtration or straining of t h e mass, and evaporation of t h e filtrate t o a thick sirup containing ~j t o 20 per cent water.‘ 11-Careful heating, kneading and partial roasting of t h e crude opium before extraction, filtration a n d evaporation2 as in I. 111-Addition t o either of t h e above products of a n appreciable amount of yen shee (pipe scrapings), I\’-Mixing materials foreign t o opium with a n y of t h e above, or substituting factitious substances for t h e whole body. T h e first method of manufacture is essentially t h e same as t h a t described in t h e old U. S. Pharmacopoeia for t h e preparation of t h e extract of opium, It is t o be noted t h a t in t h e eighth revision of t h a t w o r k t h e aqueous extract is directed t o be evaporated, instead of t o “proper consistence,” t o “constant weight,” when, after powdering, etc., it becomes t h e official extract. Further, too, t h e larger manufacturing drug houses in this country have now, and for several years past, discontinued t h e preparation a n d sale of t h e moist extract. TTThether this elimination was due wholly t o its omission in t h e present Pharmacopoeia or in part t o apprehension t h a t their product might be used for smoking purposes, thereby making t h e m liable t o controversy with t h e government as traffickers in smoking opium, is uncertain. I n this connection a definition of smoking opium by t h e judge, presiding in a somewhat recent criminal prosecution for t h e illegal manufacture of t h a t material, is of i n t e r e ~ t . ~Holding t h a t Wyeth’s Aqueous Extract of Opium was not a n illegal manufacture a n d was not suitable for smoking, he said in comparing i t with a n extract similarly prepared b u t intended for smoking: “ B u t in the process of boiling instead of stopping at the point where the substance becomes merely sticky they (Wyeth Co.) carry it further and they boil it down until it gets to a greater consistency than the ordinary smoking opium. This opium they sell for medicinal use * * * * * * * that is not opium manufactured for smoking purposes.”
It is well known, however, t h a t t h e ordinary pharmaceutical extract can be and has been used for smoking. T h e second method yields a product much iavored b y certain smokers-notably t h e Chinese-who desire t h e elimination of those disagreeable volatile substances said t o be present in the raw opium and t o be destroyed in t h e process of roasting. This particular t y p e of smoking opium is variously designated tschandu. tschandoo, tjandoo, chandu, etc., a n d its method of preparation is briefly as follows: Two or three balls of opium, after removing the leaf covering, are cut u p and macerated with water. After standing one day t h e opium and t h e extract are transferred t o a shallow copper pan and carefully evaporated over a free fire, with constant rotating and skimming of impurities, until t h e mass contains j or 6 per cent of water. This is then kneaded for a few minutes with a copper spatula and afterwards spread over 1 Adams and Dorman, THIS J O U R N A L , 4 (1912), 429; also Thorpe’s Dict. Appl. Chem.. Vol. 111, p. 72. Browne. .A@oth. Z e i l . , 1910, p. 489. 8 Herman Seidler 2’. U. S. A,, Court of Appeals, 2nd Circuit N. Y. Original Indict., Jan. 28, 1914.
Vol. 8, K O , 4
t h e whole dish in a layer I j-20 rnm. thick. The mass is now covered with a thin layer of wood ashes and t h e p a n turned so t h a t t h e contents face the fire. I n a few minutes t h e temperature of the opium rises t o 200-210°, and t h e surface layer 3-4 mm. thick, losing water and becoming blistered and brittle, is t a k e n off, heated on both sides, and transferred t o a larger copper pan. This operation is repeated until 12-14 layers are taken, when t h e united mass thus obtained is rubbed with water and allowed t o stand until t h e next d a y ; t h e n it is strained and filtered, first through bamboo a n d then through coarse filter paper. After completely exhausting t h e residue with hot water, t h e extract is carefully evaporated t o a thick sirup, and t h e n stirred for one hour (where there is a cons t a n t circulation of air) with a broad, wooden spatula. I t is now transferred t o a loosely covered earthenware vessel where i t is allowed t o ferment for several months, during which period bacteria-especially llIucor a n d Aspergillus ( A . tziger) develop, whereby it is claimed the taste of t h e opium is improved. Thus prepared for smoking, t h e yield of t h e material ready for use should be about 60 per cent. During t h e roasting there is lost through volatilization and carbonization from I j t o 20 per cent of t h e original opium. The insoluble residue, representing about 60 per cent of t h e roasted cake and remaining after the extraction of t h e tschandu, should be practically free (except some insoluble narcotine) of the characteristic opium alkaloids ; it is, however, further extracted, and this extract, known as ching ko, mixed with pipe scrapings, is sold as “refuse opium.” The better grades of smoking opium formerly imported, b u t now, b y reason of the prohibition, sporadically smuggled, into this country, are said t o have been prepared substantially as described above. Analyses, made in this laboratory of representative samples of a seizure at t h e port of Baltimore of a large number of cans of smoking opium, showed t h e material t o be practically identical with tschandu. The use of t h e product of t h e third method, aiz., the addition of yen shee (tinko, dross, pipe scrapings, etc.), or its evaporated aqueous extract, t o t h e extract of opium or t o tschandu, may be attributed t o one or more of t h e following reasons: I-Economy of the smoker. 2-Reduction of the cost to the manufacturer-yen shee being sold for about $12 a pound. 3-Taste to the smoker. The claim is made thatthisaddition, or adulteration, imparts an agreeable aromatic flavor to the drugmore especially to the unroasted opium, the acrid, harsh taste of which it is supposed to soften. This would seem to be borne out by the fact that a new (unsmoked) pipe is not fancied by the smoker, and becomes desirable only after extended use or when a substantial coating of incompletely burned opium has formed in the bowl and stem. It also may be stated that, by the addition of yen shee, the temperature in the pipe during smoking is considerably raised, thus promoting the decomposition or volatilization of the alkaloids, which may or may not be of advantage to the smoker.
The fourth class of smoking opium comprises simply sophisticated or factitious products which may even, in some cases, contain no trace of opium ex-
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
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t r a c t . Usually, however, there is present a considerable proportion of t h a t body, a n d often of t h e crude g u m itself. E X P E R I M E N T AI.
An examination of samples of each of t h e foregoing types of smoking opium was made in a n a t t e m p t t o classify t h e m correctly. To distinguish between Types I a n d I 1 seemed t o offer quite a problem. Organoleptic tests give, at t h e best, b u t t h e slightest clue-the odor of tschandu being perhaps more peculiarly sweet a n d suffocating t h a n t h a t of t h e extract of t h e unroasted gum. Comparison of t h e diluted aqueous extracts of t h e two samples showed t h e latter t o be of a brighter amber color t h a n t h e former, t h e appearance of which was a somewhat dirty brown. I n searching for a possible chemical change, resultant from t h e roasting process, wherein t h e opium attains momentarily a temperat u r e of ~ O G - ~ I O t~h,e melting points of t h e principal alkaloids were compared. These melting points are given as follows: ALKALOID Papaverine Codeine..
....... ........
c. 147 155
ALKALOID Codamine. . . . . Laudanine. . . .
Narcotine. . . . . . . . Hydrocotarnine. . . Meconidine. Laudanosine. Oxynarcotine, . . . .
176 50 58 Cryptopine.. 89 Gnoscopine 140-150 (carRhoeadine. bonizes) Pseudomorphine. , N o t fusible(a) ( a ) Above 120’ it decomposes without melting
.
,,
OC.
. ., ..
........
...
213-218 228-233
F r o m t h e above list of 2 0 alkaloids i t is seen t h a t 1 2 of t h e m melt a t or under zooo, 2 decompose below t h a t temperature, a n d 2 melt between Z O O - - ~ I O ~ ; t h u s leaving b u t 4 which do not melt under t h e temperat u r e reached in t h e production of tschandu. I t seemed, therefore, highly probable t h a t some appreciable volatilization or decomposition of p a r t of t h e m might have ensued when t h e opium was roasted. I n fact, it has been s t a t e d t h a t t h e exact melting point of narceine cannot be determined ‘as t h e alkaloid begins t o decompose before t h a t temperature has been reached, a n d also t h a t narcotine a t about 2 0 0 ’ is decomposed into meconin a n d cotarnine. Further, thebaine has been said b y some t o sublime a t 13 j O, b u t this is denied b y both D o t t a n d Hesse. The cont e n t of morphine, as would be expected from t h e melting point, was found t o be unchanged after t h e roasting process. With this fact established, a t t e m p t was made t o show a variation in t h e ratio of t h e morphine t o t h e total alkaloidal content in t h e tschandu from t h e average normal ratio existing i n t h e extract of t h e uncooked gum, a n d possibly also, t o prove a diminished a m o u n t , or even entire absence, of one or more of t h e more important by-alkaloids. T h e normal alkaloidal content of good raw opium, compiled from figures published b y a number of different analysts, shows a percentage composition approximately as follows: Morphine ........................ Narcotine., ...................... Codeine.. . . . . . . . . . . . . . . . . . . . . . . . . Thebaine. . . . . . . . . . . . . . . . . . . . . . . . . Narceine.. . . . . . . . . . . . . . . . . . . . . . . . Papaverine. . . . . . . . Other alkaloids.. . . .
Average 10.0 6.0 1.0 1.0 0.5 1.0 0.5
Range 8.0-12.0 4.0- 8 . 0 0.5- 1 . 5 0.8- 1 . 2 0.3- 0 . 7 0.8- 1.2 0.4- 0 . 6
347
T h u s a ratio of morphine t o t h e total alkaloids is indicated as about I : 2 . 0 . While working with this end in view, i. e . , t o show a decided variation from t h e normal alkaloidal composition, m y attention was called b y Dr. H. Engelh a r d t , of Baltimore, t o a n article written b y C. H a r t wich a n d N. SimonJ1 wherein t h e authors seemed t o have anticipated t o some extent this investigation. After a very comprehensive s t u d y of smoking opium and t h e active bodies present in its smoke, they were able t o s t a t e among other things t h a t “kneaded opium still shows the same composition as the crude material * * * * * however, when extract of opium is roasted decomposition of the alkaloids takes place. While the percentage of morphine is only slightly altered, some of the narcotine is decomposed. The presence of codeine, papaverine, narceine can hardly be proven after roasting, and thebaine is present only in traces. After treating the roasted cake with water the decomposition products and the free narcotine remain undissolved; of the alkaloids only the morphine and a part of the narcotine go into solution. The proportion of morphine to the total alkaloids is therefore relatively high in tschandu, since the other alkaloids are chiefly decomposed or remain undissolved.” In a series of four experiments t h e y obtained for raw opium a n d for Ischandu, prepared b y t h e m from duplicate samples, an average morphine percentage of 6 , 8 8 3 a n d I I . 650 and a total alkaloidal percentage of 1 5 . 287 a n d 13.770, respectively. This gives a morphine total-alkaloids ratio of I : 2.220 for raw opium, a n d I : I . 1 8 2 for tschandu; or, t o express i t differently, 45.03 per cent of t h e total alkaloids in raw opium is morphine, while in tschandu, t h e same relative percentage is 84.60. In t h e above samples t h e usual opium by-alkaloids, narcotine, codeine, papaverine, narceine a n d thebaine, were identified in t h e raw material, while only narcotine a n d thebaine were found in t h e resultant tschandu. Five samples of opium, prepared for smoking a n d purchased in China, etc., showed a n average morphine total-alkaloids ratio of I : I . 26, which closely approximated t h a t found for t h e tschandu prepared b y them. T h e experimental work conducted in this laboratory comprised a n examination of t h e following described samples: I-TWO samples of raw Smyrna opium imported through t h e port of Baltimore: partly air-dried when experimented with. 2-Aqueous extracts of duplicate samples of t h e above: made in conformance t o t h e directions given for t h e former U. S. P. Extract of Opium (moist). 3-Insoluble residues left after making t h e above extracts. 4-Tschandu (not fermented) prepared in this laboratory from duplicate samples of t h e raw opium (No. I) above a n d as nearly as possible in accordance with t h e method already described. j-Exhausted residues (from which ching ko is extracted) obtained in t h e preparation of t h e tschandu (No. 4) above. 6-Two samples of smuggled opium, representative of a seizure made b y U. S. Customs officers at Baltimore, of a number of cans of smbking opium. T h e cans, weighing about 5 taels (62/3 02s.) each, 1
A p o f h . Zeil., 68 and 69 (1903), 505-514.-Abstr
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bore labels inscribed with Chinese characters. a n d may or m a l not have been manufactured in China. y - O n e sample of yen shee: t h e residue a n d ext r a c t examined separately. 8-One sample of moist extract of opium prepared b y a manufacturing chemical company for medicinal use : dried somewhat. g-Average of four samples of regularly imported Smyrna opium. Table I gives t h e results obtained on analysis. It will be seen t h a t t h e results obtained for t h e morphine total-alkaloids proportions for t h e extracts of raw a n d roasted opium, respectively, closely agree mith t h e figures reported b y Hartwich and Simon (see above), a n d further, t h a t t h e same deductionsv i z . , t h e occurrence of a partial decomposition a n d perhaps a slight volatilization of some of t h e principal by-alkaloids during t h e roasting process-as were expressed by t h e m , may be made. The most noteworthy change, however, taking place in t h e opium as a result of t h e roasting. is t h e practical elimination of codeine, papax-erine and narceine, and t h e reduction in t h e amount of thebaine from a n ordinarily significant percentage t o a mere trace. This change from t h e normal composition of opium is both characteristic and conclusive evidence for t h e recognition
Vol. 8, No. 4
opium (presumably crude) t h a t Aspergillus n i g e r (see fermentation of tschandu above) does not affect morphine b u t attacks both narcotine a n d codeine. Also. Allen says of moist opium t h a t fungoid growths which soon appear gradually diminish a n d destroy t h e aroma, a n d materially reduce t h e alkaloiaal value. T h e identification of a sample as belonging t o t h e third t y p e , i. e . , tschandu or ordinary extract of opium t o which yen shee or its aqueous extract has been added, must, of necessity, be largely dependent upon t h e amount of t h a t material used. A. very high ash percentage, a n unusual alkaloidal composition, or, in cases where yen shee without previous aqueous extraction was used, a considerable water-insoluble residue might indicate t h e presence of yen shee. The ash content of tschandu (smuggled a n d laboratory products) a n d of t h e aqueous extract of opium (U. S. P. product of manufacturing chemists, a n d other extracts prepared from regularly imported Smyrna gum) are approximately t h e same, a n d in t h e various samples examined it has been found t o average in t h e dry material about 6 . 2 2 with a maximum of 7 . 0 9 per cent. Adams a n d Dorman obtained for j samples of smuggled smoking opium an average ash percentage of j . 53 a n d for 13 samples of regularly imported smoking opium a n average of j 98. They
TABLE I No. 2 No. 3 No. 4 h70 5 So. 6 No. 7 KO. DETERMINATION (percentages) n . 4 B A B A n A B A B Extract Residue 8 . . . . . . . . . . . . . 15.90 5.41 14.52 7.81 Moisture . . . . . . . . . . . . . . . . . . . 8.06 8.97 ....................... 17.68 1.53 5.46 6.04 6.80 4.73 4.53 6.04 Ash, dry sample . . . . . . . . . . . . 5.20 5.06 6.15 5.93 3.903.70 7.09 33.38 2.71 . . . . . . . . . . . . . . . 3.03 2.18 Insolublein water, dry sample. 40.00 37.80 ...................... 8.10 20.95 0.0 0.0 1.49 0.0 20.04 8.32 Morphine, dry sample . . . . . . . 13.02 13.54 21.63 21.75 0.0 0.0 20.18 10.01 24.89 12.76 12.75 9.60 1.62 0.38 38.28 Total alkaloids, dry sample.. 27.46 27.98 40.78 40.64 6.01 6.98 24.13 84.17 . . . . . . . . . . 84.38 83.12 92.00 . . . . 52.35 Morphine in total alkaloids.. . 47.41 48.39 53.04 53.52 . . . . . . . 83.63 Morphinetotal-alkaloidsratio 1 : 2.109 1 : 2.066 1 : 1.885 1 : 1.868 , , ,. , . 1: 1.196 1 : 1.188 . . . . . . . . . 1: 1.185 1: 1.203 1: 1.087 . . . 1:1.910 c ? Narcotine(a). . . . . . . . . . . . . . . 4i + t -_ Codeine.. . . . . . . . . . . . . . . . . . Papaverine . . . . . . . . . . . . . . . . . 4 t Narceine.. . . . . . . . . . . . . . . . . . .if i ? T - - ? Thebaine . . . . . . . . . . . . . . . . . . sign. (a)Positive test indicated by f sign. Negative test indicated by
+++ +
+ I+ +
+
I+ +
$
+ 4' + -
1
Yon Scbrader, Avch. f. Ex$. Palhol., 188S, p. 132 Z . physiol. C h e m . . 93 (1914), 276.
_ _
+
I
++ -- --- -
of t h e material. It is also of interest t o t h e smoker, since i t is said t h a t thebaine is t h e most poisonous (Allen, p. 361) a n d narceine t h e most strongly narcotic' of all t h e opium alkaloids. Attention should be called t o t h e very considerable amount of alkaloidal reacting bodies (exclusive of some free narcotine which is also present) remaining i n t h e water-insoluble roasted cake left after t h e preparation of t h e tschandu. These unnamed alkaloids or decomposition products were identified as such b y their behavior towards solvents a n d towards t h e general alkaloidal precipitants, Mayer's reagent, etc., a n d also b y their forming salts b y direct union of t h e base with a n acid. I n this connection a s t a t e m e n t made b y Browne (reference above), t h a t ching ko "contains no opium" (supposedly meaning usual opium alkaloids), is t o be noted as strengthening t h e conclusion t h a t t h e alkaloidal bodies found in t h e exhausted roasted cake exist in a physical s t a t e which renders them, entirely insoluble in water. N o a t t e m p t was made t o study t h e possible changes t h a t might occur during fermentation of tschandu. Hartwich a n d Simon found no apparent alteration in t h e alkaloidal constituents, b u t t h a t there may be a change is indicated by t h e in\-estigation of' C. v. Friederichs? n.ho found of 2
I
-
_ _
_ _
++
No. 9 18.97 5.97 38.50 13.09 27.88 46.95 1:2.130
++t +i-
mention also two samples manufactured in t h e United States which contain very high percentages, viz., 9 . 4 3 a n d I O . 48, respectively, b u t do not s t a t e whether or not t h e addition of yen shee was suspected. I n another sample, manufactured also in t h e United States, t h e y found t h e per cent ash t o be b u t 4 . 6 1 . T h e ash content of t h e very few samples of yen shee examined b y t h e author varied from I 2 t o I j per cent for t h e whole dry material, a n d from I j t o 2 2 per cent for its dry aqueous extract. T h e high degree of solubility in water of t h e opium ash, which is composed mainly of t h e sulfates and phosphates of lime a n d magnesium, may serve t o distinguish it from many of t h e mineral adulterants commonly used for sophistication. T h e alkaloidal composition of yen shee. naturally, is somewhat similar t o t h a t of tschandu; it should vary, however, from t h e ordinary extract even more markedly t h a n t h e latter, because of t h e higher temperature t o which it has been subjected. Moissan' states t h a t t h e temperature of pure tschandu in the pipe a t t h e moment fumes are given off is about Z j o " . This temperature, howe.i-er. lasting as it does b u t a few seconds, neither decomposes nor volatilizes all of t h e morphine, b u t does decompose most of t h e principal by-alkaloids. Volatilization of morphine in t h e pipe has been both affirmed and denied; however, t h e ' Compl. Tend., 1892, p 988
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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 CHEMISTRY
majority of investigators incline t o t h e belief t h a t no undecomposed morphine passes off i n t h e opium smoke. Should t h e whole pipe scrapings, instead of its aqueous extract, be used for adulteration, a large a m o u n t of water-insoluble residue (consisting chiefly of carbon, a n d yielding b u t little a s h ) , found in conjunction with t h e indications above, would point t o t h e addition of t h a t material t o t h e smoking opium. Lack af opportunity a n d material prevented t h e writer from determining b y experiment t h e possibility of detecting signifiqnt amounts of yen shee in tschandu or in t h e ordinary extract, a n d also from obtaining sufficient d a t a t o be able t o give entirely satisfactory constants for it. T h e foregoing facts, therefore, can serve only as suggestions t o those who may have occasion t o investigate t h e matter. No especial s t u d y of samples bf t h e fourth t y p e was made. An indication of foreign adulteration is ordinarily shown b y a n abnormal ash or a n unusual water-insoluble residue of t h e material under examination. Among t h e adulterants said t o h a v e been used m a y be mentioned starch, glucose, gums, ext r a c t of poppy plants, Chinese lily buds, chalk, gypsum. litharge, ashes, etc. M E T H O D S OF ANALYSIS 1-20 g. of t h e d r y pulverized sample are mixed with sand a n d exhausted with I per cent tartaric acid solution. T h e mixture is filtered a n d washed' with water until t h e washings no longer give a test with Mayer's reagent. Evaporate filtrate a n d washings on steam b a t h t o dryness; t a k e u p t h e a,lkaloidal salts with alcohol, make alkaline, a n d again evaporate t o dryness. From this residue extract t h e now free alkaloids with isobutyl alcohol, a n d evaporate t h e solvent in uacuo on a sand b a t h ; or, if no vacuum evaporating a p p a r a t u s be a t hand, extract t h e free alkaloids with successive exhaustions b y ether, acetic ether, a n d a mixture of I O per cent alcohol in chloroform, a n d evaporate these combined solvents t o dryness in t h e ordinary way. Treat t h e residue with I per cent hydrochloric acid which dissolves t h e alkaloids as salts; filter, if necessary, a n d wash t h e residue with water. Concentrate t h e solution of t h e alkaloidal salts (or t h e combined filtrate a n d washings as t h e case may be) t o a small volume, a n d a d d a n excess of a I O per cent caustic soda solution. This precipit a t e s (A) t h e narcotine. papaverine. thebaine, laudanosine, protopine, hydrocotarnine a n d some of t h e cryptopine, etc., while i n solution ( B ) remain t h e morphine, codeine, narceine, lanthopine, laudanine, codamine, meconidine, a p a r t of the cryptopine, etc. Filter a n d wash t h e precipitate with a small amount of water, a n d t r e a t as follows: (A)-Digest t h e Precipitate in dilute alcohol, render faintly acid (to litmus) with acetic acid, a n d a d d 3 volumes of boiling water. This precipitates t h e narcotine a n d papaverine, which are filtered out, washed with a little water a n d dissolved in a minimum of dilute hydrochloric acid. Dilute t h e liquid until it contains not more t h a n 11/400 of narcotine, when potassium ferricyanide is added which precipi-
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tates t h e whole of t h e papaverine. Filter after standing 24 hrs., a n d either weigh t h e precipitate as papaverine ferricyanide, or wash i t with a little water, decompose with dilute caustic soda, a n d dissolve t h e liberated alkaloid in dilute hydrochloric acid, a n d reprecipitate with ammonia. The narcotine is determined in t h e filtrate from t h e precipitate produced b y ferricyanide, b y precipitation with ammonia; or, b y making t h e filtrate alkaline with caustic soda, shaking out with ether a n d crystallizing t h e extracted narcotine from a definite amount of go per cent alcohol, a n d weighing. The filtrate obtained from t h e acetic acid a n d water precipitate is concentrated t o a small volume, made exactly neutral a n d t h e n mixed with a 2 0 per cent solution of sodium salicylate. After 2 4 hrs. t h e separated crystalline precipitate of thebaine salicylate is collected on a tared filter, washed with a little water, dried a t 100' and weighed. T o obtain t h e pure thebaine, t r e a t t h e precipitate on t h e filter with dilute caustic soda until t h e washings, after evaporation, n o longer give a test with ferric chloride for salicylic acid. The mother liquor, from which papaverine, narcotine a n d thebaine have been separated, is acidified with hydrochloric acid which precipitates most of t h e salicylic acid. This is filtered off, a n d t h e filtrate shaken with chloroform t o remove t h e last traces of t h e salicylic acid. T h e acid filtrate ( I ) , now free from salicylic acid, is set aside t o be mixed with solution ( 2 ) . (B)-The original alkaline filtrate containing morphine, codeine, narceine, etc., is acidulated with dilute hydrochloric acid, concentrated on t h e steam b a t h , a n d t h e n mixed with a slight excess of 2 per cent ammonia water. This precipitates t h e larger a m o u n t of morphine which, after standing several hours in t h e cold, is filtered a n d washed with cold water. T h e filtrate a n d washings are, after concentrating, acidulated with hydrochloric acid, a n d again supersaturated with ammonia water. If some additional morphine should separate, t h e process is repeated in t h e same manner, a n d t h e morphine collected on t h e same filter. T h e total morphine may t h e n be determined b y titration, using methyl red as indicator. T h e filtrate is made acid with hydrochloric acid, evaporated until it measures 7 5 cc., made alkaline with 2 per cent ammonia water, a n d shaken out with benzol, which takes u p t h e codeine only. The benzol is separated a n d evaporated, and t h e residue (codeine) estimated either gravimetrically or volumetricallyif t h e latter, use cochineal a s indicator. The alkaline liquid f r o m t h e benzol extraction is acidulated with hydrochloric acid, a n d shaken out with chloroform. The chloroform is separated a n d evaporated, and t h e residue (narceine) determined b y titration, using methyl red as indicator. The acid solution ( 2 ) , still containing rare alkaloids of t h e original alkaline filtrate ( B ) , is mixed with t h e acid solution ( I ) , which contains t h e rare alkaloids of t h e original caustic soda precipit a t e ( A ) , a n d , after adding a good excess of magnesium oxide, t h e combined liquids are evaporated t o dryness on t h e steam bath. The total free alkaloids t h u s formed are dissolved in a suitable solvent or sol-
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vents, the solvent evaporated t o dryness, and t h e residue dissolved in an excess of N I i o o hydrochloric acid, and titrated with N / I O O alkali, using methyl red as indicator--1 cc. A 7 1 1 0 0 acid equals 0.003jj g. alkaloids (estimated factor). The above process, which may be open t o some criticism for lack of exact accuracy in the final determination of some individual alkaloid (due t o its imperfect purification), has given very satisfactory results in this laboratory, a n d , considering the difficulties obtaining in t h e quantitative separation of t h e principal alkaloids in a single sample of opium, is t o be recommended for its comparative accuracy a n d ease of manipulation. I n t h e process are embodied parts of t h e schemes employed for t h e estimation of single alkaloids b y a number of ins7estigators.l The manipulations, however, are somewhat modified, and t h e whole is so arranged as t o be fairly well adapted t o t h e estimation of t h e principal alkaloids in a single sample. 11-As a corroborative method €or t h e determination of t h e morphine total-alkaloids proportions, in which, however, only t h e morphine is individually separated (the by-alkaloids being estimated as a whole), advantage was taken of the very accurate and rapid process devised by t h e U. S. Bureau of Chemistry ( D e p t . of Agriculture) and modified b y Dohme and Englehardt, for t h e determination of morphine in opium. T h e procedure, with directions for t h e collection and estimation of the by-alkaloids as used in this laboratory, is as follows: One gram of t h e sample is extracted and the alkaloids are obtained in solution as hydrochlorides in just t h e same manner as in the preceding process. Then add t o the concentrated solution caustic potash solution until a distinct alkaline reaction is obtained. The entire volume should not exceed 40-4j cc. Shake out with various portions of ether t o remove by-alkaloids; separate, and evaporate t h e ethereal liquid t o dryness, Dissolve t h e residue in dilute hydrochloric acid, and set aside. T h e alkaline aqueous liquid is slightly acidified with hydrochloric acid, a n d in t h e mixture about 13 t o 14 g. of powdered sodium chloride are dissolved. T h e mixture is then made slightly, b u t distinctly, alkaline with ammonia, and t h e morphine is shaken out with a mixture of 8 t o I O cc. of alcohol and 3 0 cc. of chloroform. T h e shaking should be continued for z min. The chloroform is drawn off and filtered through 3 or 4 in. of cotton, evenly packed in the stem of a funnel and wetted with chloroform. T h e shaking out of t h e aqueous liquid is then continued with j more portions of 2 j, 20, 20. 2 0 , 2 0 cc. of chloroform containing j t o 7 cc. of alcohol. The chloroform solutions are filtered through t h e same funnel, t h e chloroform is evaporated and t h e residue taken u p in a n excess of standardized acid, and t h e excess titraD. B. Dott, Allen’s “Com. 1 Hartwich and Simon, reference above. Org. .4nal.,” 4th Ed., 6 (1912), 372. Hesse, I b i d . Plugge, Analysl, 12 (1887), 197. Andrews, I b i d . , 36 (1911). 489. Caspari. Pharm. Review, 1904, p. 348. Van der Wielen, Bull. Sci. Pkarm., 17 (19101, 5 9 ; Pkarm. Zeit., 10 (1903),267.
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ted back with standard alkali: using methyl red as t h e indicator. The alkaline (ammonia) liquid left is now made slightly acid with hydrochloric acid, and then mixed with the acid solution of the ether residue set aside before. The combined solutions are treated with a good excess of magnesium oxide and evaporated on t h e steam b a t h t o dryness. The free alkaloids are extracted from t h e residue and estimated by titration in t h e usual manner. I n this case, however, assume I cc. A I I O acid equal t o 0 . 0 3 9 3 g. byalkaloids. Q U.4 L I T A TIV E T E S T S
The following color tests for t h e principal alkaloids are t o be recommended as giving very characteristic and delicate reactions: MORPHINE-OliVeT’S test (Chem. and DIZLg, 85 (I9I4), 249). Add a few cc. of hydrogen peroxide and a small amount of strong ammonia water t o a solution of morphine or its salts. Stir with a copper wire: gas is evolved and a deep port wine color is produced. Any blue color, due to the copper, may be destroyed with a few drops of potassium cyanide. NARcoTIsE-Treat solution of alkaloid in hydrochloric acid with bromine: a yellow precipitate forms which dissolves on heating. On adding gradually bromine water and boiling, a rose color is produced which is destroyed by an excess of bromine. (Allen, p. 402.) CODEIXE-LafOn‘S reagent ( I g. ammonium selenite in 20 cc. strong sulfuric acid) gives a fine green color with even traces of codeine. PAPAVERINE-\Vam!n’S recently published test (/. A m . Chew. Soc., 37 (1g15), 2 4 0 2 ) . Treat papaverine ferricyanide with Marquis’ reagent (sulfuric acid containing a small amount of formaldehyde) : a blue color is produced which changes to violet, to green, and finally to a dirty brown. ,SARCEINE-PlUgge’S test ( J . Chem. SOC., 5 2 (1888), 8 7 0 ) . Evaporate the solution of the alkaloid with dilute sulfuric acid a t rooo. When the acid is sufficiently concentrated a violetred color is produced, changing to cherry-red by continued heating. After cooling, the addition of a trace of nitric acid causes bluish violet streaks to appear in the red liquid. THEBAINE-The alkaloid when heated with dilute sulfuric acid gives a red color, changing t o yellow and finally to violet. (Hartn-ich and Simon, reference above.) SUMNARY
To determine whether samples of T y p e I were manufactured for medicinal use or prepared solely €or smoking purposes, dependence must be placed upon t h e water content, which. while its line of demarcation between t h e two classes is very faint, still can afford t h e basis for comparatively reliable judgment. I n the case of “moonshine” extract of opium, however! a decided variation of the morphine content from the 20 per cent requirement of t h e Pharmacopoeia should be valuable circumstantial evidence in support of an opinion. Samples of T y p e I1 are partly demonstrated b y t h e proportion of morphine found in t h e total alkaloids, and may be conclusively identified by t h e practical absence of codeine, papaverine and narceine and the diminished amount of thebaine in the smoking opium under examination. The morphine totalalkaloids ratio for tschandu should lie between I : I. I I
Apr., 1916
T H E JOCRAVAL O F IiVDlrSI'RI.1L
and I : I . ~ O >a n d t h e amount Qf morphine should never be less t h a n two-thirds of t h e entire alkaloidal content. For t h e extract of t h e unroasted opium t h e ratio should vary between I : I . jo and I : z + , a n d t h e proportion of morphine should naturally be t h e reverse of t h a t for tschandu. Samples of T y p e I11 will show a n abnormal alkaloidal composition similar t o t h a t of tschandu; this, however, may be moderated or exaggerated, depending on whether yen shee was added t o the ordi-
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nary extract or t o tschandu. Suspicion will also be directed towards a sample when its ash percentage exceeds 8 . 0 , or its water-insoluble residue (consisting largely of carbon) exceeds 5 . 0 in t h e dry material. T h e peculiar and characteristic odor of yen shee may also furnish a clue if noticed in t h e smoking opium. Samples of T y p e ITr may be identified b y t h e usual physical, chemical and microscopical tests. U S. CUSTOMS LABORATORY BALTIMORE, MARYLAID
LABORATORY AND PLANT T H E MANUFACTURE OF GASOLINE AND BENZENETOLUENE FROM PETROLEUM AND OTHER HYDROCARBONS By W. F. RITTMAN, C. B. DUTTON AND E. W. D E A N Received March 6 , 1916
T h e U. S. Bureau of Mines has just published Bulletin 114,bearing t h e above title. I n view of t h e wide-spread interest in t h e processes described in this publication, t h e authors have, upon request, prepared t h e following abstract, including supplementary information acquired since t h e completion of t h e original manuscript.- [EDITOR. ] T h e bulletin deals with t h e cracking of petroleum and other hydrocarbons a n d the productions thereby of gasoline or of benzene a n d toluene. T h e first part is devoted t o a discussion of t h e principles involved. T h e second deals with t h e large-scale development of both processes. The latter section is of primary interest t o readers of THIS J O U R N A L , as t h e matters discussed in t h e forepart of t h e bulletin have been covered generally b y articles previously published.' PURPOSE O F EXPERIMENTS
In connection with t h e description of and comment on t h e large-scale development of t h e benzene-toluene process which follows, it should b e kept in mind t h a t the object in, view was t o demonstrate t h e commercial feasibility of t h e process. Certain refinements in mechanical equipment were out of t h e question a t t h e outset since such devices were not suited t o minute s t u d y of each step in t h e process, but could be installed at a n y time after t h e commercial possibilities of t h e process had been demonstrated; e . g., such obvious improvements as feeding t h e oil b y a single p u m p through a common header, or t h e use of one large condenser for all t h e tubes in place of individual condensers for each tube, were set aside in favor of less desirable mechanical arrangements b y which each tube could be kept as a separate unit and its products analyzed a p a r t from those of t h e remaining tubes. I t will be recognized readily t h a t it was first necessary t o prove t h a t t h e process would work as well on a commercial basis as in t h e laboratory. This could be done only a t t h e sacrifice of a very considerable percentage of t h e product formed. Elimination of THIS JOURNAL, 6 (19141, 383, 472; 7 (1915), 945, 1014, 1019; 8 (1916), 20; M e t . and Chem. E m . , 13 (1915). 682.
this loss was regarded as a mere matter of course, t o be taken u p a t will. These losses continued, however, throughout t h e period covered b y the d a t a published. L A R G E - S C A L E D E V E L O P M E N T 0 F B E S ZE S E - T0 L C E N E
PROCESS
Under t h e terms of t h e agreement with t h e Aetna Explosives Co., t h e work incident t o t h e development of the benzene-toluene process on a scale of commercial magnitude was begun a t Pittsburgh, P a . il plant was acquired and t h e experimentation was begun which was t o result in t h e successful working out of t h e process on a commercial scale. E X P E R I M E N T S WITH V A R I O U S S I Z E S O F T U B E S
The original apparatus used in the laboratory experiments consisted of a tube 1 1 / ~ in. in diameter by 3 it. in length. When the development work was undertaken, a small number of experiments with a tube of the same internal diameter, but 41/2 ft. in length, sufficed t o show that the longer tube gave the same general results. A second tube z1/2 in. in diameter and 4 ft. long gave equal11 satisfactory results, and was, therefore, promptly abandoned in favor of a tube 4l/2 in. in diameter and 6 f t . long which was found to give results comparable with those obtained with the original small tube. Some half dozen or more runs were made at varying temperatures and rates of feed, a t a pressure of 2 5 0 lbs. per sq. in. A t a temperature of 600' C. and a rate of feed of 8 gal. per hour an oil of 0.94 specific gravity was recovered, which on distillation in the laboratory gave a benzene yield of 1 2 per cent and a toluene yield of 8 per cent, on the basis of recovered oil. Thus sufficiently favorable results were obtained with this apparatus to justify its abandonment in favor of one of still larger size. In the next series of experiments the length of the tube was increased from 6 to I O ft., the diameter remaining the same. It was found that operations at comparable temperatures and pressures with those used in the shorter tubes gave the same relative yields of aromatic hydrocarbons. The increased length, however, which exposed the gases for a longer period of time to the influence of temperature and pressure, made it possible to increase the rate of feed from 8 to I O gal. per hour. This change illustrates one of the important means of controlling the time element in a gaseous hydrocarbon reaction. The results obtained with the single 41/2-in.tube were of such a character as to justify experiments to determine whether or not satisfactory yields could be obtained by encasing I O tubes in a single combustion chamber. Accordingly, a furnace containing a battery of I O tubes, 4l/2 in. in diameter by I O ft. in length, was constructed. Experience with this installation proved that the 41/2-in. tube was of too small diameter t o give efficient results. I t
