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T H E J O t ' H S d L O F I A Y D l - S 7 ' K I . l L .1 S D E S G I S E E R I S G C H E M I S T R Y
alunduin crucible, Tvashed with hot water. t h e crucible heated t o redness and immersed in 95 per cent alcohol. T h e reduction was complete. t h e deposit of metallic copper adhering very firmly t o t h e walls of t h e crucible. 9 number of trials with solutions of known strength gave very accurate results, b u t the shock t o t h e crucibles was too great, many of t h e m cracking after being used t w o or three times. T o avoid t h e breakage of crucibles t h e reduction w a s next tried in t h e vapor of alcohol and with entire success. T h e details of t h e method follow. Collect t h e suboxide of copper on a n alundum filtering crucible, using Spencer's filtering funnels with suction. Thoroughly wash with hot water followed b y alcohol. Heat t h e crucible t o redness a sufficient time t o burn off a n y organic matter t h a t m a y accompany t h e copper oxide. Allow t h e crucible t o cool until t h e redness just begins t o disappear and then immerse it in an atmosphere of alcohol vapor as follows: Bend tlic n-ire ends of a small pipe stem or silica covered triangle so as t o form a tripod support for t h e crucible and set t h e tripod on t h e bottom of a 400 cc. beaker, preferably of metal. P u t into the beaker sufficient strong alcohol (denatured alcohol will answer) t o cover t h e b o t t o m t o t h e depth of about I cm. a n d cover t h e beaker with a watch glass. Heat t h e alcohol t o boiling a n d continue heating until t h e \-apors begin t o condense on t h e under side of t h e cover' glass, then place t h e hot crucible on t h e support above t h e alcohol a n d replace t h e cover glass. If t h e crucible is too hot t h e alcohol m a y t a k e fire b u t t h e flame m a y be readily extinguished b y blowing directly on t o p of t h e cover glass, and no h a r m is done. A4110irt h e alcohol t o continue t o boil a moment after putting in t h e crucible, t h e n remove t h e beaker from the source of heat. T h e heat radiated from t h e crucible will prevent a n y further condensation of alcohol on t h e cover glass. T h e crucible should remain in t h e covered beaker until cooled t o a temperature a little above t h a t of t h e alcohol vapor t o prevent oxidation of t h e copper. About 3 or 4 minutes is sufficient. I t m a y t h e n be t a k e n from the beaker a n d t h e cooling be finished in a desiccator. preliminary t o weighing. If t h e crucible is quite cold when t a k e n from t h e beaker it should be moistened with a little pure alcohol a n d this be burned, holding t h e crucible in an upright position. Xfter t h e alcohol burns off t h e crucible is ready for cooling in t h e desiccator. X porcelain Gooch may he used if preferred. T h e reduction t o metallic copper is almost instantaneous and is complete. T h e results are identical with those b y reduction in hydrogen, closely approximating t h e electrolytic method. This method may be used in copper analysis. t h e separations being made in t h e usual way a n d t h e copper collected in a n y form readily burned t o t h e oxide. If in form of copper sulfide t h e precipitate forms in clots a n d is burned t o t h e oxide with difficulty. I t is preferable t o dry t h e sulfide, roast i t gently, a n d then with a glass rod flattened a t one e n d , crush it t o a powder. T h e rod should be wiped off with a piece of ashless filter paper and t h e paper burned
611
in t h e crucible. The heating may t h e n he continued t o drive off all sulfur and t h e oxide reduced in alcohol vapor. T H E CVEAS-.iMPKICAN SUGAR COMPASY
CESTKAI,"TINGUAKO," PSKICO, CUBA
THE DETERMINATION OF LINT IN COTTONSEEDMEAL By R . S . B R A C K E T T Received January 7 , 1915
TT'hile a t first sight i t might appear an easy m a t t e r t o determine t h e amount of lint in cottonseed-meal b y purely mechanical means, it has been found impracticable t o do so with any degree of accuracy. T h e following chemical method of estimating t h e lint was worked out and found t o give x-ery satisfactory results: As preliminary t o t h e work i t was first ascertained t h a t alkali a n d acid of I , z j per cent strength, as used for crude fiber' determinations, was practically without action on lint. X sufficient amount of cottonseed was t h e n freed from lint b y first picking a n d finally singeing t h e last. portions carefully t o avoid injury t o t h e seed. T h e seeds were t h e n cut open a n d t h e meats remox-ed completely from t h e hulls. Crude fiber2 was prepared from both the hulls anti t h e meats, b y t h e method above referred t o . T h e crude fiber t h u s prepared was treated, in 0 .z-gram portions side b y side with t h e same weight of lint, on a boiling water b a t h , with z j cc. of a solution of zinc chloride for three minutes, the time required t o dissolve the lint. In this way t h e action of t h e zinc chloride3 solution on t h e crude fiber was determined, a n d t h e necessary correction made in carrying out a determination of lint in ordinary cottonseed-meal. T h e zinc chloride solution was prepared b y dissolving metallic zinc in concentrated hydrochloric acid, concentrating until t h e solution solidified on cooling, a n d t h e n adding twice t h e weight of 40 per cent hydrochloric acid. On treating t h e crude fiber and lint with t h e zinc solution, t h e contents of t h e beakers x e r e stirred vigorously during t h e three minutes nece t o dissolve t h e lint, a n d filtered hot through weighed porcelain Gooch crucibles with asbestos m a t s ; t h e residues in t h e case of t h e fibers were washed with z j cc. of t h e zinc solution. then with water a n d finally with a little 9j per cent alcohol dried and weighed. E X . ~ M P L E - - ~ ~treating 0 . 2-gm. portions of ( ( i ) crude fiber from hulls. ( b ) crude fiber from meats. and ( c ) "crude fiber" from a cottonseecl-meal! ivith z j cc. of a zinc chloride solution for three minutes, the amount dissolyed was as folloivs: ( a ) 0 . 0 6 8 ; g . . ( b ) 0 . 0 6 ; 8 g. a n d (c) 0 . 1000 g . T h e correction was. therefore, 0 . 0 6 8 2 5 gram. Hence t h e amounL of lint in t h e "crude fiber" from t h e cott,onseetl-meal was 0.1000- 0.0682j = 0 . 0 3 1 7 j g r a m . B u t t h e hlethods of Analysis, A. 0 . .4.C., Bull. 107, revised. p. 5 6 This crude fiber includes ash ingredients of the fiber. The ;irh i i . honevei, so small in amount as to be negligible, unless I large prolitirtion of hulls is contained in the cottonseed-meal. Only in the latter c d i r ~volild it be necessary to take the ash of the fiber into account i n calculating thc amount of lint in the meal. "Cross-Brvan'sMethod for Cellulose"--Cohn'~ ''Tt..I>.rrid R e x x e . i t ~ , ' ' p. 5 2 . 1
2
* 61 2
T H E J O U R - V A L O F I L V D C S T R I A L . 4 S D ELVGIiYEERIL\'G
meal, on a.nalysis, gave I O per cent of "crude fiber,'! which gives I . j8jj a s t h e per cent of lint in t h e cottonseed-meal, since 2 grams of t h e cottonseed-meal contained .o. 031 j j g r a m lint. T o f u r t h e r test t h e method t h e following mixtures mere m a d e : ( a ) I gm. of cottonseed-meal with 0 . I g r a m of lint. ( b ) I gm. of cottonseed-meal with 0 . 2 gram of lint. T h e crude fiber a n d lint amounted in ( a ) t o 0 . 2 0 0 1 g r a m a n d i n ( b ) t o 0.3032 gram. T h e factor for a new zinc chloride solution based on t h e use of j o cc. for three minutes was o.oj12j gram. Crude fiber and l i n t . . . . . . . . . . . . . . . . . . . Crude fiber residue.. . . . . . . . . . . . . . . . . . . Correction. . . . . . . . . . . . . . . . . . . . . . . . . . . .
(a) 0 . 2 0 0 1 g. 0.0393
-~ 0 . I608 0 . 0 5 125 _
L i n t . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hence, per cent lint in mixture.. . . . . . . . . Calculated oer cent lint in mixture. . . . . .
(b) 0.3032 g. 0.0323
_
0.10955 9.96 10.53
0.2709 0.05125 _
_
_
.
0.21963 18.30 17.99
T h e method a s given was worked o u t under t h e immediate direction of Assistant Professor J. H. Mitchell b y t w o s t u d e n t s of t h e last senior class, a s a thesis. With more careful work a n d experience, no d o u b t much more accurate results could be obtained. A t t h e commencement of t h e work Schweitzer's reagent ( a n ammoniacal solution of copper hydroxide) was tried, b u t t h e solution as prepared b y t h e stud e n t s failed t o dissolve lint. Acknowledgments are due Mr. Mitchell for supervising t h e work, a n d t o hfessrs. J. M. McIntosh a n d E. R. Gilmore, t h e t w o students, for their careful a n d faithful prosecution of t h e work. CLEMSON AGRICULTURAL COLLEGE S. . C CLEMSON COLLEGE.
SOME IMPORTANT CONSTITUENTS IN THE FRUIT OF THE OSAGE ORANGE B y J. S. MCHARGUE Received February 8, 1915
T h e Osage orange ( M e c l u r a pomiferum) is a small tree which, when first discovered, was g r o w h g wild i n t h e southwestern portion of t h e United S t a t e s between t h e Arkansas a n d hIissouri rivers. This particular section of t h e c o u n t r y was for m a n y years t h e home a n d h u n t i n g grounds of t h e Osage Indians. T o t h e m t h i s tree was of economic importance for t w o reasons-from t h e t r u n k t h e y made bows which possessed superior elasticity, a n d from i t s fruit t h e y obtained a juice which possessed all t h e necessary adhesive properties for making their war paint. On account of t h i s association with this tribe of Indians a n d from t h e resemblance of t h e fruit t o t h a t of t h e t r u e orange, t h e tree has received t h e popular n a m e of Osage orange, although there is no botanical relation between t h e t w o plants. T h e chief source of value of t h i s plant t o t h e white m a n has been, first, for growing rural hedges, a n d secondly, for a crude yellow dye which is obtained from t h e roots. Owing t o i t s adaptability t o t h e climatic conditions existing in t h e Mississippi valley it m a y be found growing in almost a n y p a r t of this area t o d a y , although i t s use a s a hedge is being abandoned. Through Central K e n t u c k y m a n y farmers ha\-e
CHEMISTRY
YOI. 7 . NO. 7
allowed their hedges t o go untrimmed or permitted t h e plant t o grow in out-of-the-way nooks until no small area is covered with t h i s tree. T h e young tree grows rapidly on good land a n d t h e female trees begin bearing large quantities of fruit a t from six t o t e n years of age. .it m a t u r i t y t h e fruit has a greenish yellow color, a n average diameter of 3 1 / 2 inches a n d a n average weight of one t o one a n d a half pounds. T h e fruit. or hedge balls, as t h e y are commonly called, consists of a dense pear-shaped core a t t h e center from which radiate rather long, irregular sized cells t h a t t e r m i n a t e in a n enlarged or club f o r m , t h u s making an irregular surface. T h e cells are made u p of t w o p a r t s , t h e milk sacks a n d t h e seed sacks. T h e milk sacks form about two-thirds of t h e entire length of t h e cell a n d e s t e n d t o t h e surface. T h e seed sacks lie beneath t h e milk sacks a n d are a t t a c h e d t o t h e core a t their base. T h e milk sacks contain a milky, mucilaginous fluid which in t h e ripe fruit is neutral t o litmus, reacts only slightly with a tincture of guaiacum for oxidases, has a n insipid t a s t e a n d a n odor similar t o t h a t emitted b y t h e crushed twigs of cedar. I n 1912 considerable interest was aroused through newspaper dispatches e m a n a t i n g from Professors E m erson a n d Roess of t h e University of Kansas, who s t a t e d t h a t t h e y h a d discovered in t h e fruit of t h e Osage orange a new a n d cheap source of India r u b b e r . This announcement, according t o Fox,' crea t e d considerable interest among t h e rubber factories generally a n d perhaps more in particular among those a t Akron, Ohio. Accordingly, Fox read a report of his previous investigations on t h e Osage orange before T h e E i g h t h International Congress of Applied Chemistry, a t New York, i n 1912. His investigations show t h a t t h e Osage orange does not contain rubber of a n y commercial importance. So f a r as t h e literature shows, t h e above summarizes t h e work t h a t has t h u s f a r been done o n t h e Osage orange from a n y s t a n d p o i n t . Recently there appeared. in one of our leading f a r m journals, a n inquiry a s t o t h e chemical composition of t h e Osage orange. This paper also s t a t e d t h a t certain farmers in Illinois h a d been feeding t h e oranges t o their stock a n d found t h a t t h e y a t e t h e m with considerable relish. I n order t o find o u t more definitely concerning t h e composition of this fruit, a number of oranges were collected in November of 1914 a n d analyzed (see Tables I a n d 11). T h e oranges were prepared for analysis a s follows: t h e outside milky cells were pared off t o t h e seeds; t h e p a r t containing t h e seeds was pared off t o t h e core, a n d each portion dried a n d kept separately. After drying, t h e milky portion was ground fine for analysis. T h e acetone extract is a brownish, semi-solid resin. a t ordinary t e m p e r a t u r e . T h e oranges contain a r a t h e r large a m o u n t of ovalshaped seeds, t h e kernels of which are approximately '8 in. long a n d in. thick. T h e y are easily separated from t h e hulls when d r y . Kernels were separated from t h e hulls a n d dried a t 100' C . 1
Orig. Comm. 8th Inter Cong. A p p . Chem., Appendix, pp. 593--,597
