Dec., 191;
T H E J O U R N A L O F I N D C S T R I A L A Y D ELVGILVEERILVGC H E M I S T R Y
uniform dosage. On t h e other hand, t h e a m o u n t of air-space in t h e containers does not appear t o be a n y factor in t h e deterioration, since some tablets t h a t showed a jo per cent deterioration were stored in securely stoppered tubes which allowed only a very small proportionate air-space, a n d freshly opened tubes showed t h e same deterioration a s had t a k e n place in bottles furnishing a relatively large air-space. ( 2 ) A second possible explanation is f o u n d in t h e t w o forms in which nitroglycerin is known t o exist. K a s t , in 1906,found t h a t solid nitroglycerin is capable of existing in t w o isomeric forms-a labile form melting at 2 . ~ oc. a n d a stable f o r m melting a t 13. j o c. H . Hibbert, in a paper read a t t h e Eighth International Congress of Applied Chemistry, confirmed this, a n d found t h a t freshly prepared llitroglycerin usually crystallizes in t h e labile f o r m ; b u t t h a t on long standing, particularly after having been once frozen, it tends t o change t o t h e stable f o r m ; t h a t the stable form is also promoted b y mixing with wood pulp and sodium nitrate, accompanied b y a trace of moisture; t h a t rubbing x4th a glass rod also promotes t h e change in t h e cold; a n d that the labile isomeride melts a t 2.0' C. a n d t h e stable a t 1 3 . 2 ' C. ' The used in the above tab1ets was O n e lot of paste, purchased in October Igo8, and four lots Of solution, purchased in September 1910,July 1 9 1 1 , February 1 9 1 2 , a n d I I a r c h 1912. T h e y were stored in a small, unheated, and isolated building, in which t h e temperature is always very t o that Of the O u t e r atmosphere. Thus t h e paste had passed through t W o Winters before being used in a n y of t h e series of tablets here reported, while t h e solutions had all passed through one! winter's storage. I n Detroit a temperature Of a feVv7degrees below 0' F. (--IS' C.) occurs in most winters a few times. Hibbert f o u n d that cooling t o -4O' c. stirring 17-ith a glass rod was necessary t o crystallize t h e liquid nitroglycerin, but when t h e liquid was "seeded" with a crystal of the f o r m desired. a temperature of - j o C . Only IVas necessary. He shoWed a marked tento gradually change i n t o t h e dency Of stable f o r m , b u t did not succeed in reversing t h e Process. H e was unable t o change a stabilized f o r m t o labile. H e further showed t h a t liquid nitroglycerin is much more susceptible t o shock-decomposition t h a n t h e solid, b u t t h a t the stabile isomeride seems to persist in t h e liquid condition after i t had been formed, and t h a t slowly-frozen nitroglycerin differs in its properties from rapidly-frozen. Thus i n the paste form, We have in t h e condition most conductive t o forming t h e stable isomeride, e. g., t h e presence of a hard-crystalline body sugar) and Of a trace of moisture; IThile in the alcoholic solution t h e conditions m a y be unfavorable t o t h e formation of t h e stable form. E v e n t h e labile crystals do not form except in t h e presence of some sharp body and rubbing' Hibbert used ground glass and a glass rod t o obtain t h e crystals. T h u s t h e nitroglycerin in those tablets which deteriorated m a y have been in t h e labile condition,
IOjj
with a greater tendency t o decomposition t h a n t h e others. Several tests were made for nitrites in t h e deteriorated tablets, which might show decomposition, b u t none were found. B u t if decomposition occurs, i t is more likely t o be an oxidation process t h a n a reduction, hence a failure t o find nitrites proves nothing. T h e work on t h e isomerides of nitroglycerin is too recent t o prove whether it is a factor in t h e deterioration Of nitroglycerin in tablets or not, b u t three facts are established. I-Tablets containing less t h a n ' / ' I O O grain of nitroglycerin lose strength very markedly on keeping. 11-Tablets made from a n alcoholic solution of nitroglycerin are less stable t h a n those made from a paste, III-It is Probable t h a t a nitroglycerin which has been slowly frozen a n d slowly thawed is better for tablet use t h a n one freshly made. LABORATORY OF P A R K E , DAVIS& C O > l P A N Y DETROIT.~ I I C H I G A N ~.
ON CONSTITUENTS OF OIL OF CASSIA' By FRANCIS D. DODGEA K D ALFREDE. SHERXDAL Received Ma$ 28, 1915
T h e essential oil of cassia, obtained i n China by s t e a m distillation of the bark and leaves of Cinnamo?num cassia, is commercially one of the most important oils, yet its composition does not Seem t o have been thorougllly investigated, T h e chief constituentis t h e fi-ell-known cinnamic aldehyde, t h e amount of which, in per cent. pure oils, appears t o \-ary frorn 7 j t o t h e last f r a c t i o n s of the oil, a crystalliIle compound has, at times, been noted: i t was designated steroptene" by Rochleder who first observed i t , a n d \%,as later identified as t h e methyl ether of orthocoumaric aldehyde by Bertram and Kursten2 who also synthesized the compound by t h e condensation of methyl salicylic aldehyde Tvith acetaldehyde, In 1889, Schimmel a n d C o . isolated cinnamyl acetate as a constituent, and t h e presence of phenyl-propyl acetate indicated b y the boiling point of the alcohols obtained b y saponification of t h e esters present, Cinnamic acid also occurs in small a m o u n t s , undoubtedly resulting f r o m oxidation of t h e cinnamic aldehyde. In commercial oils, mineral oil a n d rosin are found, eTidence of t h e gross adulteration so long practiced, Apparently pure oils generally show a slight rot a t i o n , in t h e polarimeter, b u t to this is d u e , has not yet been ascertained,
In the course of a n examination of a sample of oil of cassia, it as found that lTvhen t h e alkaline solution obtained by shaking the oil dilute sodium hydroxide was acidified a n d distilled with steam, t h e distillate gave an intense purple coloration 7h-ithferric chloride, this reaction could n o t be due to any of the heretofore recognized constituents of t h e oil, t h e test was applied to' various samples of commercial oils, to determine if it were perhaps due to the presence of a n accidental impurity. Fifteen cc. of oil were per cent sodium shaken with an equal volume of Society' N e w l ~ ~ ~ n ~ ~: ~e ~&p a$ ~e ~c ~~ :the ~ ~ lAmerican ~ f 2 J . p y a k l . Chem., [21 61, 316.
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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'
hydroxide a n d t h e mixture allowed t o s t a n d until t h e s u p e r n a t a n t liquid was clear. T h e l a t t e r was t h e n decanted, acidified, a n d distilled with steam. The first 5 cc. of distillate, which contained a little oil, a n d h a d t h e characteristic odor of salicylic aldehyde, gave, in every case, strong indications of t h e presence of phenolic compounds. I n order t o identify t h e compound responsible for this reaction, a n d t o determine approximately t h e a m o u n t present in t h e oil, 5 0 0 grams of a freshly redistilled oil, of undoubted purity, were worked u p . T h e oil h a d t h e specific gravity 1 . 0 5 0 a t 2 j ', rotation + 0 . 3 2 ' , a n d showed 88 per cent cinnamic aldehyde, b y t h e usual method. It was extracted twice with 500 cc. portions of 2 per cent sodium hydroxide, t h e clear alkaline solution acidified, a n d extracted with ether. T h e ether solution was t h e n extracted with I O per cent sodium bisulfite solution, t h e l a t t e r neutralized with soda, distilled with s t e a m , a n d t h e distillate again extracted with ether. T h e ether solution, on evaporation, left a colorless oil, weighing 1.66 grams, showing t h e characteristic properties of salicylic aldehyde, a n d yielding a crystalline semicarbazone, melting a t 2 2 8 ', with decomposition. T h e first ether solution, after extraction with bisulfite, was washed with sodium bicarbonate solution t o remove acids, a n d t h e n evaporated. An oily residue, weighing 0.53 g., was obtained, which crystallized on standing, a n d was identified as coumarin (melting point, after crystallization from hot water, 6 7 ' ) . F r o m t h e bicarbonate washings a small a m o u n t of crystalline acid was isolated, which melted, n o t very sharply, a t 123'-I z 8 ' , a n d showed, on titration, a n acid value of 3 7 9 (calc. for cinnamic acid, 3 7 8 . 3 ; for benzoic acid, 4 5 9 ) . T h e experiment indicated, t h e n , t h e presence of a b o u t 0.4 per cent salicylic aldehyde a n d about 0 . 2 per cent coumarin in t h e oil. T h e a m o u n t of t h e l a t t e r in t h e original material m u s t , however, be considerably more, since coumarin is not readily volatile with s t e a m . I n addition t o t h e compounds mentioned, we found indications of other substances, in small a m o u n t , so t h a t a n examination of a larger q u a n t i t y of oil seemed advisable. F r o m 600 lbs. of oil we obtained a n alkalisoluble portion amounting t o 3 lbs. Of this, a b o u t 2 5 per cent was readily volatile i n s t e a m , a n d consisted
I
By
JAMES
H. PAYNB
Received October 18, 1915
I n a n article written for THISJ O U R X A L a b o u t a year ago* t h e writer dealt with this subject i n a n introductory manner, tracing roughly t h e s t a t e of t h e a r t a n d deducing, b y methods of comparison with similar operations in lime a n d cement practice, what t h e fuel consumption a n d operating costs should be. F r o m data covering t h e performance of several lime recovery plants which t h e writer has h a d t h e privilege of observing for a period of a year or ni.ore, it is now 1
THIS JOURXAL.
6 (1914), 937.
12
principally of salicylic aldehyde; t h e last portion of t h e steam distillate was separated, b y means of sodium carbonate solution, into a n insoluble p a r t , mostly coumarin, a n d a n oily acid, which dissolved. T h e latter, when isolated in t h e usual manner, showed a molecular weight of a b o u t I 7 5 b y titration (assumed monobasic), a n d seemed t o be unsaturated, a s it readily reduced permanganate solution. A larger q u a n t i t y of this acid, or acid mixture, was isolated from t h e portion of oil not easily volatile with s t e a m , which was worked u p as follows: Crystals of coumarin which h a d separated on standing were filtered off; on washing t h e oil with sodium carbonate solution, more coumarin crystallized o u t , a n d was separated. F r o m t h e alkaline solution, b y acidifying, a mixture of cinnamic acid a n d oil was obtained. T h e l a t t e r , on chilling, yielded more coumarin, a n d a n oily acid mixture, which was distilled in vacuo. About 60 per cent of i t came over between 1 4 5 ' a n d 2 0 0 ' ( 2 9 m m . ) , a n d t h e yellow distillate crystallized on chilling. T h e crystals were found t o be salicylic acid. T h e liquid portion of t h e distillate, which appeared t o be t h e oily acid mentioned above, was esterified with ethyl alcohol, a n d yielded a n ester mixture, boiling between 2 2 0 ' a n d 2 8 5 O , a n d having t h e odor characteristic of t h e esters of t h e higher f a t t y acids. On fractioning this t h e first portion was lighter t h a n water; t h e last, heavier, a n d apparently contained ethyl benzoate. T h e small Quantity of substance prevented a further examination. T o s u m u p , t h e results of o u r examination showed t h a t t h e oil of cassia contained at least 0 . j per cent soluble in dilute alkali, consisting of a mixture of about 2 5 per cent salicylic aldehyde, 6 0 per cent coumarin, 8-10 per cent cinnamic acid, a n d small amounts of salicylic acid, benzoic acid a n d a volatile liquid acid, not identified. N o phenol, other t h a n salicylic aldehyde, could be detected. Although present in small proportion, salicylic aldehyde a n d coumarin undoubtedly contribute to t h e composite aroma of t h e oil. I n fact, t h e presence of t h e former can be often detected b y odor, in t h e first fraction of a redistilled oil, a n d i t seems remarkable t h a t these familiar compounds should so long have escaped observation. LABORATORY OF THE DODGE A N D OLCOTTCOMPANY B A Y Q K S E , N E W JERSEY
LABORATORY AND PLANT
I LIME RECOVERY FROM SPENT CAUSTICIZlNG M U D
Vol. 7 , No.
1
possible t o deal with t h e subject more in detail, a n d also t o suggest further improvements in design. Every soda pulp mill, alkali works, and t h e larger soap works, carries on t h e causticizing operation a n d produces daily large quantities of spent lime mud. Miscellaneous chemical industries also produce quantities of t h i s material. M u d of similar character is produced b y t h e Steffen process of de-sugarizing molasses a n d in t h e manufacture of magnesia, acetone, etc., b u t in these cases t h e mud contains no caustic a n d is often of coarser grain a n d hence more easily freed from water. I n almost every case t h e removal a n d disposal of
