T H E JOURNAL OF THE AMERICAN O I L C H E M I S T S ' SOCIETY, SEPTEMBER, 1 9 5 0

proposed by Woolley for lipositol (10). In soybean inositides by contrast sugar appeared only to be " c ar r ied along" rather than to be a component of the molecule. The percentages of phosphorus, nitrogen, and inositol are greater in the fractions c om pr i si ng the large peaks at each edge of the curve than in the center. For example, tube 0 contains 3.6% phosphorus, 1.2.% nitrogen, and 8% inositol, and tube 24 contains 2.7% phosphorus, 1.5% nitrogen, and 9% inositol. In tube 15, which constitutes a small peak at the center of the weight curve, there is only 2.1% phosphorus, 0.27% nitrogen, and 5% inositol. In considering the inositol contents, it should be pointed out that the inositol was estimated by a microbiological assay. This procedure is highly specific for inositol, but the results are considered to be accurate to only about 10%. In the work with soybean phosphatides it appeared that the phosphoinositides cont ai ned two moles of phosphorus for each mole of nitrogen and inositol. However the phosphorus to nitrogen and phosphorus to inositol ratios of the corn inositide fractions vary widely and somewhat i r r e g u l a r l y . Since in most cases the ratios do not approximate whole numbers, it seems unlikely that any fraction contains a single pure compound. However it is observed that in the left hand portion of the curve phosphorus to nitrogen ratios are greater than one while in the right hand portion of the curve the ratio is one or slightly less than one. As can be seen from the curves in Figures 2 and 3, tubes 23 and 24 appear to contain a large amount of material with one mole of phosphorus for each mole of nitrogen and sugar.

Summary Corn phosphatides have been separated into alcohol-soluble and alcohol-insoluble fractions employing

ABSTRACTS 9

Oils and Fats

355

the same procedure previously used with soybean phosphatides. Alcohol-soluble and alcohol-insolubl~' portions have been fractionated by eountercurrent distribution. The alcohol-soluble portion was found to contain lecithin and a small amount of cephalin. In addition to the phosphatides a nitrogen containing compound was concentrated in the 95% methanol-soluble fractions along with a small amount of sugar. As with the corresponding alcohol-insoluble fraction from soybean phosphatides, two major types of phosphoinositides are found to be present, those more soluble in hexane and those more soluble in 95% methanol. In contrast to soybean phosphatides most of the sugar is concentrated in the hexane-soluble fractions. The phosphorus to nitrogen and phosphorus to inositol ratios vary widely and do not approximate two as was the case in the soybean inositides. However the more hexane-soluble fractions seem to be made up largely of material with one mole of phosphorus for each mole of nitrogen and sugar.

Acknowledgment The authors are grateful to J. C. Cowan for his advice and encouragement, to H. It. Hall, and Margaret C. Shekleton for the inositol bioassays and to Mary B. Wiele for the nitrogen and gravimetric phosphorus determinations. 1. Eng. 2. 3. 4.

REFERENCES Atkin, L., Schultz, A. S., Williams, W. L., and Frey, C. N., Ind. Chem., Anal. Ed., 15, 141 (1943). Burmaster, C. F., J. Biol. Chem., 164, 233 (1946). Burmaster, C. F., Ibid., 165, 1 (1946). Craig, I~. C., and Post, 0., Anal. Chem., 21, 500 (1949).

5. Glick, D., J. Biol. Chem., 156, 643 (1944). 6. u ~he corn oil lecithin, Chicago. Refining Unincorporated. 7. Scholfield, C. R., Dutton, It. J., Tanner, F'. W. Jr., and Cowan, J. C., J. ~m. Oil Chem. Soc., $5, 368 (1948). 8. Somegyi, M., 5. Biol. Chem., 160, 61 (1945). 9. Unpublished data Northern Regional Research Laboratory. 10. Wooley, n. w., J. Biol. Chem., 147, 581 (1943). [Received A p r i l 27, 1950]

Don Whyte, Editor I R. A. Reiners,Abstractor

RAPID FAT D]ST]~I~MINATIONIN PLANT CONTROL 0F ~AaAO PlC0])u c T s . F . X. K o b e (Rockwood and Co.). Anal. Chem. 22, 700 (1950). Finely g r o u n d samples are extracted with petroleum ether at room t e m p e r a t u r e and the solids separated f r o m the miseella in a centrifuge. Results are comparable to those obtained by the A.O.A.C. method. I~IC~OI)ETFA~MINATI0:iN r OF UI~SAT~YRATEa) I~'AT'I~Z AOID.S. BY ALKALI ISOMEICIZATION. L. C. Berk, N. Kretchmer, R. T. Holman, and G. O. B u r r (Univ. of M i n n e s o t a ) . Anal. Chem. 22, 718 (1950). The ethylene glycol-potassium hydroxide r e a g e n t normal]y used for alkali isomerization is unsuitable f o r isomerization of snmll (100 m i c r o g r a m ) samples of f a t due to h i g h background absorption. This difficulty is avoided by isomerization in aqueous p o t a s s i u m hydroxide at high t e m p e r a t u r e s (180~ DETt~]~TION OF SOLVENT ICESIDU]~S IN EXTR~CTE]) OROATS. W. Wodsak ( t I y g . I n s t . H a n s e s t a d t , H a m b u r g , Ger.). Z. Lebensm.Untersuch. U. -Forseh. 90, 265-72(1950). Detection of residual solvent in commercial solvent extraction residues was possible by determining the fluorescence of the steam distillate of the isobutyl alcohol-treated sample or by determining the v a p o r pressure of the materials volatile under high vacuum. A 100-g. sample under vacuum w~s heated to 160 ~ and volatile m a t e r i a l was condensed with liquid air. The vapor p r e s s u r e of the condensate at 0 ~ was determined. (Chem. Abs. 44, 6044)

DET]~]I~lV[INATION OF Ni57JTR~L FAT Ibr THB ItIOtt~Y ACID FATS. F. Provvedi (Lab. Chim. Provineiale, Bergamo, I t a l y ) . Olii Minerali, Grassi E Saponi, Colori E Vernici 26, 69-72(1949). Dissolve 5 g. of the f a t in 50 cc. of 95% ethanol, saponify, add It20 to obtain a 50% alcohol solution, decompose the soap with H2SO4, dissolve the f a t t y acids in petroleum ether, evaporate the solvent, and weigh the residue. Determine the acid no. of the f a t t y acids (I~) and t h a t of the original f a t (I~), and calculate the % of the f a t t y acids by the f o r m u l a : X 100 If/I~. The n e u t r a l f a t is: 100 - - X. (Chem. Abs. 44, 5119) THE EST[~ATI0,N OF HORS~-FAT IN" A])MIXTUF~E WITI-I 0,TIIE~ FATS. R. A. Dalley. Analyst 75, 336(1950). The method depends on the presence in horse-fat of 1~% of ]inoleic acid and its relative scarcity in other animal fats. S a t i s f a c t o r y results were obtained on m i x t u r e s containing as little as 5-10% horsef a t admixed with pig, m u t t o n , and beef fat. QUALITATIVE RE~C~'IOI~ FOI~SESAM15 OIL INr 0rrItEK FOOD 0ILS. N. E. Biihrer ( I n s t . Biol., Curitiba, Brazil). Arquiv. Biol. E.

Tecnol., Inst. Biol. E Pasquisas Tecnol., Curitiba, Brazil 3, 57-9(1948). Tests with p u r e and mixed almond and sunflower oils showed t h a t the Villavecchia-Fabris test (0.1 ml. of a 2% solution of f u r f u r a l in the presence of HC]) is reliable. (Chem. Abs. 44, 5492) CI-IROMATOGI~APHI(3 1)ETERIV[INATIOI~ OH VOLATILI~ ~AT~f~y ACID'S II~ SILAGE. E. B r o u w e r and H. J. l~ijkamp (Landb. Hogeschool, W a g e n i n g e n , N e t h e r l a n d s ) . Chem. Week.blad 46, 37-9(1950). C h r o m a t o g r a p h i c examination of 10 samples of grass silage showed t h a t formic acid, propionic acid, and some higher volatile f a t t y acid m a y be present besides acetic and butyric acids. I n silages with low p H the contents of formic and

356

THE J o v ~ 5 0 ~

T H ~ AMERICAN

OIL CHEMISTS'

propionic acids are negligible. I n the higher p H silages the distillation method of Duclaux-Boekhout-Wiegner does not give correct figures f o r the acetic and butyric acids, which is in contrast to the good results with the low pI-I silages. (Chem. Abs. 44, 5495) TH~

D]~TE~]YIINATION

OF S Q U A L ~ N ~

IN

Tt~

UNSApONI~IABI~

).[ATTER OF FATS. I. S. Anselmi and R. Monacelli (Ist. Super. Sanita, Rome). l~en. Ist. Super. Sanita (Rome) 12, 358-71 (1949). A sample of olive oil was tested f o r squalene by the method of Filetson as given in A.O.A.C. Methods of Analysis, 6th edition, 1945, and the results showed t h a t the method should be studied to improve its precision and accuracy. (Chem. Abs. 44, 5617) T~ Cq~ITIC~AL POINTS OF FA-TS W I T H ANYLINI5 APPLIEI) TO THE CONTROL OF PURITY O~ C~OA0 FAT. F . Th. Van Voorst ( K e u r i n g s d i e n s t voor Waren, Alkmaar, N e t h e r l a n d s ) . Chem. WeeI~blad 46, 150-1(1950). A method for the determination of the critical points of f a t s with aniline is given, by which the critical point can be determined within 0.1 ~ The critical point of cacao f a t was found to be 42.9. The effect of the presence of b u t t e r f a t on the critical point was studied, and it was found t h a t in the presence of up to 20% b u t t e r f a t there is a decrease of 0.2 ~ of the critical point per percentage of b u t t e r f a t . (Chem. Abs. 44, 5616) A N A L Y S I S O1~ D~ttYDKATli~ CASTOI~ OIL. D . O. Bartl. Chem. L i s t y 37, 90-102, 109-12(1943). Four hundred % excess I B r is required to obtain correct values for the I no. ( H a n u s method). As dehydration of castor oil proceeds, the I no. increases to a constant final value of 148 a f t e r 6-8 hours. The hydroxyl no. decreases gradually. Discrepancies between the 2 numbers are explained by condensation reactions. (Chem. Abs. 44, 5617) TH~

INI~LUE~NCE OF EIq~IR01q-I~ENT U P O N

TH~

C~OMPoSITIOI~ OF

SOCIETY,SEPTENIBER,1950

acids derived f r o m the f a t extracted from the seeds of A m m i visnaga showed s a t u r a t e d acids 5, solid isomer octadecenoic acid 50, liquid isomer octadecenoic acid 32, and octadecadienoic acid 13%. The identities of linoleic, oleic, petroselenic, and palmitic acids were established. (Chem. Abs. 44, 5617) COMI~ON:~*i%T ACIDS AND GLYL-~_,~I])]~S OF DIK& PAT. M . a . M e a r a

and C. B. Patel (Univ. of Liverpool, E n g . ) . J. Sci. Food Agr. 1, ($-51(1950). Dika f a t s are obtained f r o m the seeds of various species of the genus lrvingia. The component f a t acids were capric 2.0, laurie 46.6, myristie 44.1, pa]mitic 5.2, oleic 1.9, and linoleic 0.2 (mole % ) . The chief component glyeerides were trilaurin 7.1, myristodilaurin 32.5, caprolauromyristin 5.2, lauromyristopalmitin !2.1, laurodimyristin 28.7, trimyristin 5.1, and oieolauromyristin 5.1 (mole % ) (Ch.em. Abs. 44, 5617) CULTIVAT]OI~ OF SAF~A)WEI% I N T H ~ GIROITDL REGI017 ( A F I ~ LIMINARY NOTE). G. Sag (Societe Vitex, Bordeaux, F r a n c e ) .

Roy. Intern. Botan. Appl. et. Agr. Trop. 30, 216-22(1950). Safflower varieties from Europe and Morocco were cultivated on soils poor in N and deficient in K. A decrease in the oil content of seeds f r o m 24 to 20% was noted. The oils of European varieties had saponification value 201 and I value 133, while the Moroccan seeds gave oils with saponification value 194 and I value ]22. (Chem. Abs. 44, 5617) RECI~NT A D V A N C E S IN TI-L~ s T U D Y OF C~0'MPON~NT AOIDS A N D COMPONENT G L Y ~ ' R I D B S OF NATURAL FATS. T . P . H J l d i t c h (Univ.

of Liverpool, E n g . ) . Forchr. Chem. OrE. Naturstoff e (Springer VerIag, Vienna, Austria) 5, 74-100(1948). Review with m a n y references. (Chem. Abs. 44, 5617) CONSTITUENT DE SLueD OIL OF Cycus revoluta. S. Ueno, S. Matsuda, and T. K i m u r a . J. Nippon Oil Technol. Soc. 2, No. 5, 10-15(1949). Constants of oil prepared by ether extraction are: yield of oil 20.4%, acid no. 182.2, saponification no. 199.7, I no. 59.8, unsaponifiable substance 4.60%, melting point 44 ~ The f a t acids consist of palmitic, stearic, oleie, and a small amount of behenic. (Chem. Abs, 44, 5618)

suN~-~owgg SEED OILS. I. II~DIVIDUALVARIETIES O1~'SIYNFI~WE~S GROWI'~ IN D I f F E r E N T FAI~TS OF AFKICA. C. Barker and T. P. Hilditch (Univ. of Liverpool). J. Sci. Food Agr. 1, 118(1950). Sunflowers grown from named varieties of seed in Southern Rhodesia, Kenya, and T a n g a n y i k a gave seed oil of somewhat varying composition, but the seed oil from all varieties grown in any one location were practically identical in composition. Seed harvested only two months after p l a n t i n g gave oils of extremely low unsaturation. I L C o ~ [ r O S l ~ O N 0~ TH~ s E ~ OILS o~" S U N ~ % O W B ~ S GRDa~VN

Jeno Becker and P. Ma]iga. Bull. Faculty tlort. Vitieult., Univ. Agr. Sci (Budapest) 10, 86-93(1944) (Pub. 1945). W a l n u t s contained an average of: 4.1% water, 61.2% oil, 19.0% raw protein, and 0.09 mg. % vitamin B1. The oil and protein contents seemed independent of the size of the w a h m t s but were related to each other ; generally a lower content on protein was found with more oil. (Chem. Abs. 44, 5494)

I N E N G L I S H GAR~DENS F~O_~r FIVE S P E C l M ~ q S OlD DI~lW~RE~NT AFRICAN SUNFLOWEI~ SEED. Ibid. 140. Five specimens of sunflower

CATALYTIO

seeds from Africa, the oils in which varied widely in composition (44-72% linoleic acid), were grown in England, and the composition of the resulting English-grown seeds was about the same in all cases. Most of the oils contained, on an average, 68-70% linoleic acid. Varietal factors play little p a r t in determining the composition of sunflower seed oils. The high linoleic content is conditioned by slow development and ripening of the seed. CHANGES IN

COMPOSITION

OF COT'I~NS~]SD DURING DRVEI~p-

~IENT AND aIPENING. D. N. Grindley (Sudan Medical Service, K h a r t o u m ) . J. Svi. Food Agr. 1, 147(1950). Analyses of cottonseed (Gossypium hirsutum) grown in K h a r t o u m , made at different stages of m a t u r i t y after flowering, indicate no appreciable a m o u n t of oil is in the seed until about 35 days a f t e r flowering, after which it increases rapidly. The oil first formed is highly acidic and contains much unsaponifiable m a t t e r alt h o u g h the composition of the f a t t y acids remains practically constant over this period. THE

OOMFON~NT

F&TYy

ACIDS OF v A R I O U s

SUDAN

VE~]~PABLE

OILS. Ibid. ]52. The composition is given of the f a t t y acids present in the f a t s extracted f r o m the following materials:

H y p t i s spicigera, L u f f a eylindrica, Lagenaria vulgaris, Citrullus vuIgaris, Courbonia virgata (husks and kernels), Capparis tomentosa (kernels), and Parinarium curateNi/olia. EDIBLE OILS. W. I-[. Shearon Jr., H. E. Seestrom, and J. P. Hughes. Ind. ~ Eng. Chem. 42, 1266 (1950). Modern methods of processing vegetable oils are reviewed. R~D-B~I~ ~ AND ITS OILS. K. Voituret. Se~/e~-OIeFette-Wachse 76, 115(1950). Both the seed and pulp of the berry of Sambucus raeemosa (red-berried elder) yield a turbid dark oil; the oil from the seed is of disagreeable taste and contains a weakly poisonous irritant. The oil can be refined for alimentary purposes by an absorption process or by treatm e n t with caustic. (Chem. Abs. 44, 6169) EDIBLE SOYBEAN OIL. R . L . Terrill (Soybean Research Council). Soybean Digest 10 (9), 14(1950). The importance of soybean oil in the present f a t and oil picture is discussed.

A m m i vis~aga:

COl~POSITION OF THE FATTY A(~I])S PI~I~S]~NT

IN THE S ~ ) FAT. D. N. Grindley (Sudan Med. Service, Khart o u m ) . J. Sci. Food Agr. 1, 53-6(1950). Analysis of the f a t t y

ON

THE

VALU}~ A N D

Eff]ALUATION OF

SOME

HUNGAKIAN

NUTS.

CATALYTIC OXIDATION OF MOI'~0I~THF~t"~OID ]FATTY ACIDS; THE Ilxr~LUENC'E OF CATIONS OE ~IgTALS OF VH]~ T Y P I C A L AND TI~ANSITIONAL SERIES IN AUTOXIDATION FROCrESSES. J . H .

Skellon (Acton Tech. College, E n g . ) . J. Soc. Chem. Ind. 69, 116(1950). The oxidation of oleie acid was studied at 120 ~ in the presence of various metal catalysts. The catalytic activity of the metal ions is correlated with their atomic structure and is shown to be a periodic function. AUTOXIDATION OP SATUP~TEiD F A T T y ACIDS. ~ . Faquot and F. de Goursac. Bull. Soc. Chim. France 1950, 172-3. Longchain s a t u r a t e d f a t t y a c i d s and their esters are oxidized by molecular oxygen at 100 ~ and by catalytic use of 1% Ni phthalocyanine or 20% Na and K soaps of the acids used. The principal oxidation products are lower f a t t y acids containing even numbers of C atoms. Lower acids oxidize with more difficulty t h a n acids of high molecular weight. The results indicate t h a t the autoxidatlon of s a t u r a t e d f a t t y acids is effected through fl-oxidation; the isolation of small amounts of lactones in the oxidation product indicates some -y- and 8-oxidation. (Chem. Abs. 44, 5311) OLEIC ACID F'RO~ ~IC~; OIL I~3,R T~XTIL~S. S . Naito a n d T. Tsuchiya. J. Nippon Oil Technol. Soc. 2, No. 6, 13-19(1949). Oleic acid prepared f r o m rice oil h a d I no. 117.3; it cannot be used for textiles without antioxidants. Addition of 0.5% a-naphthol showed, in the M a c K e y test, the rise in temperature to 96 ~ after 173 minutes. (Chem. Abs. 44, 5618) UTILIZATION OF RIDE OIL. ,]-. K a w a i and S. Kinoshita. J. Nippon Oil Teehnol. Soc. 2, No. 6, 33-7(1949). Rice oil having an acid no. 120 is esterifled with ethanol a n d hydrogenation of the product containing 80% ester gave a product m. 33.23.6 ~ with acid no. 2.7 and I no. 6.1. It is suitable as a substitute for cacao fat. (Chem. Abs. 44, 5617) DEOOLORIZATION OF KICE OIL BY HYDlC0OEI'~ I~FJROXIDE. II. J. Kawai. J. Nippon Oil Teehnol Soe. 2, No. 5, 16-19(1949). Use of 2% H_~O~ (29.5%) on oils having high acid no. and subsequent t r e a t m e n t with 4% acid clay or acid clay-activated C gave good results. (Chem. Abs. 44, 5618) EFI~IgCT 0~' ADDITION O F WATER~ O N T H B IL~T/ff OF H Y D R O L Y S I S 01~ PALLS[ 01L IN AUTOC/LAV]~ AVITI~IOUT CATALYST. C. Yanase.

J. Nippon Oil Technol. Soe. 2, No. 6, 7-12(1949). I n hydrolyses of oil at 200 ~ and 284 psi for 15-180 minutes with the ratio

THE JOU~NAL OF

TtIE A M E R I C A N O I L C H E M I S T S ' SOCIETY, S]~FTEMBER, 1 9 5 0

of oil a n d w a t e r a t 1 : 0 . 7 or 1:2.0, t h e r a t e s of h y d r o l y s i s of oil were 1 a n d 1.14. (Chem. Abs. 4 4 , 5617) EI~'PEG~ oF CA.TALY~TS OI~ ~YDROL.YSIS OF F~TS AND OILS IN TH~ AUTOCLAVE. I. THB ]~I~E'C~ OP LIM~. C. Y a n a s e . J. Nippon Oil Technol. Soc. 2, ( 5 ) , 23-32(1949). T h e coefficient of hydrolysis ( p e r c e n t a g e of h y d r o l y s i s w i t h 1 % C u e / p e r c e n t a g e of hydrolysis w i t h o u t CaO) at 160 ~ a n d 31 arm. w a s 27; a t 180 ~ a n d 42 a t m . w a s 2.5; a t 200 ~ a n d 49 arm. w a s 1.7; a n ~ a t 250 ~ a n d 73 a t m . w a s 1.0. I I , E~'~EOT O~ ~AeNgSlA. Ibid. 32-40. I n h y d r o l y s i s a t 180 ~ with initial p r e s s u r e at 284 psi, ZnO gave b e t t e r r e s u l t s t h a n Zn powder or MgO. A d d i t i o n of 1 % e m u l s i f y i n g a g e n t , e.g., t r i e t h a n o l a m i n e or lecithin, resulted in no p a r t i c u l a r benefit. (Chem. Abs. 44, 5615) SODIU/~ 0HLORIT~ IN- TH]~ t'AT INDUSTI~Y. J. ~ o u t o n a n d R. Borezee. Oleagineux 4, 271-280(1949). T h e u s e of NaC102 either alone or in t h e presence of acids, s u c h as ttsPO,, to bleach a n i m a l or v e g e t a b l e f a t s is discussed. (Biol. Abs. Sect. J. 24 [5], 6) SOLVENT EXTR,k(SvPION O1~ VEGETABLE OILS. C. C. M c I n n e s ( A m . M i n e r a l S p i r i t s Co., C h i c a g o ) . Am. Paint J. 34, No. 30, 86-88, 90, 9 2 ( 1 9 5 0 ) . Tables list commercial e x t r a c t i o n solvents, distillation figures on hexane, a n d p r o p e r t i e s of c o m m e r c i a l - g r a d e i s o p e n t a n e , n o r m a l p e n t a n e , isohexaue, cyclohexane, i s o h e p t a n e , a n d isoSctane. (Chem. Abs. 44, 5617) TH~ PEAOTIOAL ~I~EFAEATIO1V OF FATTY AGTDS 01~ 2~ t ~ H D]~GREE O1~ PURITY. I. LAUR~O AOID. P. R a g o n a n d J e a n Belle ( L a b . Central Services Chim. E t a t , P a r i s ) . Mere. Services Chim. E t a t (Paris) 34, 337-41(1948). L a u r i e acid, m.p. 43.60.7 ~ a n d solidification p o i n t 43.4 ~ was p r e p a r e d f r o m t h e e t h y l esters of p a l m oil f a t t y acids by distillation first in a 30-cm. column, t h e n distilling t h e ] a u r a t e f r a c t i o n in a 50-cm. s p i r a l c o l u m n to give a f r a c t i o n , b~ 143-6 ~ m.p. 40-1 ~ T h i s w~s f u r t h e r purified by dissolving 100 g. in 250 ca. alcohol a t 95 ~ n e u t r a l i z i n g w i t h a p p r o x i m a t e l y 250 ca. Of a hot, s a t u r a t e d a q u e o u s L i O H solution, a d d i n g 250 cc. 5 0 % alcohol, a n d c r y s : ta]lizing L i ] a u r a t e by cooling to 15 ~ T h e ' p r e c i p i t a t e w a s recrystallized r e p e a t e d l y f r o m 5 0 % alcohol. T h e acid w a s obt a i n e d b y acidification w i t h HCI. C o n s t a n t s a r e given for v a r i o u s n i t r o g e n derivatives ( a m m o n i a , e t h y l e n e diamine, hexam e t h y l e n e diamine, a n d p i p e r a z i n e ) . (C~hem. Abs. 44, 6168) PU~IFYII~G C!~UD~ GLYOERINE BY I0N gXOHANGE. ~'~. ~I. K a h l e r (Illinois W a t e r T r e a t m e n t Co.). Chem. Eng. 57, 1 0 9 ( 1 9 5 0 ) . T h e steps in t h e ion e x c h a n g e purification of glycerine a r e outlined. I o n e x c h a n g e is claimed to be c h e a p e r t h a n distillation f o r t r a d e s w i t h less t h a n 1 0 % ionized solids a n d f o r s w e e t w a t e r s w i t h less t h a n 2 % ionized m a t e r i a l s . IN-HIBItiON- O1~ BUTTERlVs AUTOXIDATION-. ]~. W i l l s t a e d t a n d A. R e i n a r t . Arkiv. K e m i 1, 319-24(1949). L a c t a r o v i o l i n , a p i g m e n t which is a n u n s a t u r a t e d a l d e h y d e of t h e azulene series, is h i g h l y effective as a n a n t i o x i d a n t f o r b u t t e r f a t . I t is indic a t e d t h a t u n s a t u r a t e d diketones h a v e t h e opposite effect. A review is given of t h e m a j o r classes of a n t i o x i d a n t s . (Chem. Abs. 44, 5491) T ~ g PROP]~RTI]~S O~ N}~'VffZEIALAND BUTT]~%8 Alq~ B UTTT/R~ATS. ii. T H E

R]~LATION 0]8' IIARDNESS 0 ~ N~%~/ Z E A L A N D

OO~:~s

BUTTI~I~ TO O~)X~[POSITION-OP THE BUTTERI~AT. ]~.. ~/~. Dolby ( D a i r y l~esearch Inst., P a l m e r s t o n N o r t h , N e w Z e a l a n d ) . J. Dairy 1r search 16, 336-47(1949). H a r d n e s s d e t e r m i n a t i o n s were m a d e on m o n t h l y s a m p l e s of b u t t e r froni 9 f a c t o r i e s in N e w Z e a l a n d over t h e course of 3 years. The iodine value a n d s o f t e n i n g p o i n t of t h e f a t was correlated w i t h t h e h a r d n e s s of t h e b u t t e r . T h e increase in iodine value w a s a c c o m p a n i e d b y a c o m p e n s a t o r y c h a n g e in t h e p r o p o r t i o n s of t h e lower s a t u r a t e d acids so t h a t t h e a v e r a g e m.p. of t h e f a t r e m a i n e d t h e same. T h e s o f t e n i n g p o i n t is d e p e n d e n t on the glyceride s t r u c t u r e r a t h e r t h a n t h e p r o p o r t i o n s of t h e i n d i v i d u a l f a t t y acids. (Chem. Abs. 44, 549D POSSIBILITY OF 0OLOUESN-GVA~NASPATIWITH RATANJOq TO PR~V N N T ITS USE AS AN- ADULTERANT IN GtlE]~. K o t h a v a l l ( I n d i a n D a i r y Res. Inst., B a n g a l o r e ) . Indian Jour. Vet. Sci. and Animal Husbandry 17 ( 3 ) , 171-176(1947). I t is s u g g e s t e d t h a t t h e r e d dye o b t a i n e d f r o m t h e roots of r a t a n j o t (Onosma echiodes--Boraglnaceae) be u s e d to color h y d r o g e n a t e d veget a b l e oils to p r e v e n t t h e i r u s e f o r t h e a d u l t e r a t i o n of ghee. (Biol. Abs. Sect. G., 24, 32) EI~FgOT OF HE~T ON- TH]~ O H E M I C A L C'OMPOS.ITION- OF GHE~. J. N. Trivedy, G. K . M u r t h y , S. M. K u k a d e , a n d N. N. D a s t u r ( I n d i a n D a i r y Res. Inst., B a n g a l o r e ) . Indian Jowr. Dairy Sei. 1 (3), 69-77(1948). The chemical c o n s t a n t s of cow a n d b u f falo ghee (clarified b u t t e r f a t ) h e a t e d u p to 250 ~ f o r 5 to 45 m i n u t e s are given. S a m p l e s h e a t e d over 125 ~ give b u r n t a n d tallowy flavor. T h e peroxide value of s a m p l e s i n c r e a s e d r a p i d l y TM

357

a t 175 ~. N e a r l y 7 9 % of color in cow ghee w a s d e s t r o y e d at 175 ~ (BioL Abs. Sect. G., 24, 33) FAOTOES IN~LUENOING THE KEE~ING Q U A L I T Y OF' OlIE~. D . P . P e r s a i a n d 0. R. B a r n i c o a t ( M a s s e y A g r . Coll., P a l m e r s t o n N o r t h , N e w Z e a l a n d ) . J. Dairy l~esea~h 16, 356-62(1949). Of t h e f o u r m a i n f a c t o r s c o m m o n l y r e g a r d e d as i n f l u e n c i n g k e e p i n g p r o p e r t i e s of ghee ( m o i s t u r e content, acidity, heatt r e a t m e n t , a n d t y p e of b a c t e r i a l culture used in s o u r i n g ) t h e h e a t - t r e a t m e n t w a s t h e m o s t i m p o r t a n t . The h i g h e r the final t e m p e r a t u r e (110 ~ a n d h i g h e r ) a t t a i n e d d u r i n g evaporation, t h e b e t t e r were t h e k e e p i n g qualities of t h e product, provided t h e b u t t e r h a d been h e a t e d in c o n t a c t with t h e curd, boiled as r a p i d l y aS possible, a n d g i v e n a m i n i m u m a m o u n t o f s t i r r i n g . T h e h n p r o v e d k e e p i n g p r o p e r t i e s c o n f e r r e d on t h e e h e a t e d to 110-150 ~ were due to a n t i o x i d a n t s ( a p p a r e n t l y p h o s p h o l i p i d s ) e x t r a c t e d f r o m t h e curd d u r i n g cooking. I n i t i a l a c i d i t y a n d m o i s t u r e c o n t e n t s h a d no effect on s t o r a g e life of t h e e a t 38 ~. S o u r i n g milk to 2.5 to 3.0% lactic acid did n o t d e t r a c t f r o m t h e k e e p i n g q u a l i t y of t h e ghee m a d e f r o m it. S t o r a g e li~e of ghee a t 38 ~ could be p r e d i c t e d with f a i r a c c u r a c y f r o m its r a t e of o x i d a t i o n a t 100 ~ (Chem. Abs. 44, 5491) PRESEI~VATION ely ]LAW TALLOW. M. T. F r a n c o i s a n d A. S e r g e n t (:Lab. Chevreul, P a r i s ) . Bull. Meus. Iterg. 4, 151-3 (1950). L o w q u a l i t y tallow w a s w a s h e d w i t h w a t e r t h o r o u g h l y a n d t h e n stored u n d e r a s o d i u m acetate-acetic acid buffer ( p H 3.15) f o r 15 d a y s at 30 ~ S u b s t a n t i a l l y no h y d r o l y s i s of t h e f a t occurred d u r i n g this period. (Chem. Abs. 44, 6171) STORAG~ o~ GHE~E iiq" DI~FT]RE~NT TYP]~S ~F C~NTAINERS. T . M . P a u l , V. R. B h a l e r a o , a n d C. P. A n a n t a k r i s h n a n ( I n d i a n D a i r y Res. Inst., B a n g a l o r e ) . Indian Jour. Dairy Sei. 2 ( 1 ) , 7-11(1949). Cow a n d buffalo b u t t e r f a t s were stored in v a r i o u s c o n t a i n e r s f o r 6 m o n t h s . B u t t e r f a t s stored in m u d , brass, a n d bronze c o n t a i n e r s quickly became rancid. S a m p l e s k e p t well in glass, porcelain, a l u m i n u m , a n d tinned-iron. (Biol. Abs. Sect. G., 24, 32) PATENTS EXTaAOTION Pt~OC;ESS AND APPARATUS. B. B. B e e s o n ( F r e n c h Oil Mill Maeh. Co.). U. S. 2,512,71,0. A process is disclosed f o r t h e solvent e x t r a c t i o n of f a t s f r o m f a t b e a r i n g m a t e r i a l s in w h i c h t h e d r a i n a g e of t h e solvent t h r o u g h t h e m a t e r i a l is increased by vibrating the material. PRO0]~S~ FOI~ S~ABIXJIZING EDIBLE I~AT~Y 0IL. F. A. L i n d s e y J r . a n d W. T. Maxwell ( S o u t h e r n Cotton Oil Co.). U. S. 2,513,948. A f a t t y oil is stabilized b y a d d i n g citric acid a n d h e a t i n g t h e m i x t u r e to 120-190 ~ u n t i l a s u b s t a n t i a l p a r t of t h e citric acid is converted to aconitie acid or aconitie a n h y dride acid. T h e t r e a t m e n t is s t o p p e d before a n y appreciable a m o u n t of itaconic a n h y d r i d e is f o r m e d . PROOES8 OF PEE~]]~NTING R A N O I D I T Y OF 000KINO FATS. E. B. Doolin. U. S. 2,514,479. T h e f o r m a t i o n of peroxides a n d t h e d e v e l o p m e n t of r a n c i d i t y are i n h i b i t e d d u r i n g the s t o r a g e of u s e d cooking f a t s b y p o u r i n g the h o t f a t ( a t least 3 3 0 ~ into a c o n t a i n e r u n t i l t h e c o n t a i n e r is full a n d t h e n s e a l i n g t h e c o n t a i n e r so t h a t it is a i r - t i g h t . M~THOD OP S~PARATIlCG GLYGE~ID~S. V. J . M u c k e r h e i d e ( E m ery I n d u s t r i e s I n c . ) . U. 8. 2,514,608. T r i g l y c e r i d e s a r e dissolved in isopropyl acetate, ethyl acetate, or m e t h y l isobutyl ketone, t h e solution r a p i d l y chilled to p r e c i p i t a t e t h e m o r e solid triglycerides, a n d t h e solids removed f r o m solution. DES~mCOLATm17. K . C. D. /-Iickman ( E a s t m a n K o d a k Co.). U. S. 2,515;041. Oil c o n c e n t r a t e s are dissolved in m e t h a n o l or ethylene glycol (1-10% solution) a n d t h e p r e c i p i t a t e d sterols collected.

Biology and Nutrition R. A . D~ST~BUV~ON O~ ~ r ~ a ~

Reiners, Abstractor

CA~0.~r A~ONO r ~ E UPmS or T~E

ALaA Scenedesmus pURINa B~ZE~ PItOTOS.YNTHE'I~C EXPOSUI~S. K. A. C l e n d e n n i n g (Univ. of C h i c a g o ) . Arch. Biochem. 27, 75 (1950). T h e t r a c e r c a r b o n f o u n d in t h e b e n z e n e - s o l u b l e fraction of Scenedesm~s obliquus a f t e r 40-second e x p o s u r e s to Ca*O= is i n c o r p o r a t e d in nonvolatile w a t e r - i n s o l u b l e c o m p o u n d s . A f t e r saponification t h e t r a c e r c a r b o n w a s f o u n d to be quite unif o r m l y d i s t r i b u t e d b e t w e e n unsaponifiables, f a t t y acid, a n d w a t e r soluble saponification p r o d u c t s . A p p r o x i m a t e l y equal a m o u n t s of t r a c e r were recovered in t h e s a t u r a t e d a n d u n s a t u r a t e d f a t t y acid f r a c t i o n s . SUNs OF BIOLOGIO~klJ I~An2 SYNT]=IESIS. M. A n g e r m a i r . Seifen-Ole-Fette-Wachse 76, 24-5, 45-6, 68-9(1950). Review on f a t s y n t h e s i s in a n i m a l s a n d p l a n t s i n c l u d i n g m i c r o o r g a n i s m s is given. T h e technology, composition, a n d possible u s e s of t h e f a t s a r e discussed, (Chem. Abs. 44, 6167)

358

T H E J O U R N A L OF THE A M E R I C A N O I L C H E M I S T S ' SOCIETY, SEPTEMBER, ] 9 5 0

PAgTITION IIYPOTI-I]~SIS FOR IN~STINAL ABSOgPTION OP rAT. I. B. B e r r y a n d A. C. I v y ( U n i v . of Illinois). Am. Jour. Physiology 162, 8 0 ( 1 9 5 0 ) . S a m p l e s of emulsified m i n e r a l oil r a n g i n g in particle size f r o m 200 to 0.2 ~ were i n t r o d u c e d into t h e a l i m e n t a r y t r a c t of dogs. No evidence w a s f o u n d t h a t even t h e m o s t finely dispersed oil was a b s o r b e d in significant a m o u n t s ; t h e r e was no chemically detectable loss of m i n e r a l oil f r o m t h e l u m e n of the intestine, a n d t h e r e w a s no increase in non-saponifiable m a t e r i a l in t h e thoracic duct lymph. THE UNSATU~A:YION Or ~ATS IN WOODS. ~. Desnuelle. Inds. Agr. et Aliment. (Paris) 66, 365-71(1949). A review. I n t h e g r o w i n g rat, deficiencies of linoleic a n d a r a c h i d o n i e acids cause skin t r o u b l e s a n d stop growth. Vaeeenie acid m a y have biological properties. (Chem. Abs. 44, 5974) TH~ IN~'LU]~NCE 01r TIIE INTAKE 0 r COCONUT OIL a N ~AL,C~U~s BAr,ANOE. V. S a d a s i v a n ( I n d i a n R e s e a r c h F u n d Assoc., Coon e a r ) . Current Sci. (india) 19, 2 8 ( 1 9 5 0 ) . A d u l t r a t s showed a positive Ca b a l a n c e w i t h coconut oil as diet f a t . T h e r a t ' s a s s i m i l a t i o n of N, Ca, a n d P w a s s i m i l a r w h e t h e r clarified b u t t e r or coconut oil was t h e diet f a t . (Chem. Abs. 44, 5446) THE OONO~'rTRATIDN Or TOOOP~[~OhS rl~OM NAI~O~L SOVl~CES BY MOLBOUI~F; DISTILr,A~ON. J. Green a n d P . l~. W a t t (Vitam i n s Lts. L a b s . ) . J. Sei. Food Agr. 1, 1 5 7 ( 1 9 5 0 ) . Tocopherol c o n c e n t r a t e s were p r e p a r e d directly f r o m v a r i o u s seed oils b y t h e use of a l a b o r a t o r y model cyclic falling-film m o l e c u l a r still. F r o m 80-94% of t h e tocopherols in s o y b e a n a n d cottonseed oils were recovered in t h e distillate, which h a d a p o t e n c y f r o m 14 to 30 rag. tocopherol per g. INPLL~NOE

OF TOCOpIIE~OL O N ]~EPOSITION Or V I T A M I N

A. P.

Dubouloz, P. Pistone, a n d R. Marville (Univ. Marseille, F r a n c e ) . Bull. Sac. Chim. Biol. 31, 1273-8(1949). I n a d u l t r a t s t h e q u a n t i t y of v i t a m i n A deposited in t h e liver a f t e r i n g e s t i o n of a single n m s s i v e dose a v e r a g e d 2 2 % of t h e q u a n t i t y disapp e a r i n g front t h e digestive t r a c t when t h e v i t a m i n was accomp a n i e d by n a t u r a l a n t i o x i d a n t s or a d d e d tocopherol. I t fell to a p p r o x i m a t e l y 24% w h e n the v i t a m i n was given in oil f r e e of all a n t i o x i d a n t s . (Chem. Abs. 44, 5971) TH~ ESTIMATION Or VITAMIN A IN nv~. A CBI~Ie'AL Sa~OI)Y or ~m,I~ODS. A. K. R. McDowell ( D a i r y R e s e a r c h Inst., P a l m e r s t o n N o r t h , N e w Z e a l a n d ) . J. Dairy Research 16, 348-55 (1949). The L o v i b o n d T i n t o m e t e r was f o u n d m o r e reliable t h a n either t h e P u l f r i c h p h o t o m e t e r or the Spekker a b s o r p t i o m e t e r f o r the a s s e s s m e n t of t h e blue color f r o m the C a r r - P r i c e test on b u t t e r f a t . B y use of a B e c k m a n s p e c t r o p h o t o m e t e r v i t a m i n A in b u t t e r f a t w a s also e s t i m a t e d by a b s o r p t i o n at 324 m~. F r o m s p e c t r o p h o t o m e t r i c r e a d i n g s a t this wave l e n g t h a n d at 450 m ~ t h e a b s o r p t i o n due to carotenoids a n d n o n c a r o t e n o i d s c a n be calculated. C o m p a r i s o n of t h e b u t t e r f a t s a m p l e s b y t h e C a r t - P r i c e t e s t a n d b y t h e direct s p e c t r o p h o t o m e t r i c m e t h o d shows a r e a s o n a b l y good a g r e e m e n t . (Chem. Abs. 44, 5490) E S T I M A T I O N OF V I T A M I ~ A IN T H Z PRES~b~C~ Or INTF_atF~RINO MATEI~IAr,S. W . A. McGillivray (Univ. N. Zealand, P M m e r s t o n North). Anal. Chem. 22, 494(1950). Extinction coefficients are

d e t e r m i n e d s p e c t r o p h o t o m e t r i c a l l y at 325 ( m a x i m u m absorpt i o n ) , 310, a n d 340 m m A n equation is developed which perm i t s calculation of t h e extinction coefficient for v i t a m i n A alone, provided t h e p o i n t s on t h e curve c o r r e s p o n d i n g to t h e i n t e r f e r i n g s u b s t a n c e s alone lie in a s t r a i g h t line. T h i s proviso g e n e r a l l y applies over t h e n a r r o w wave b a n d considered. T h e wave l e n g t h at w h i c h r e a d i n g s are t a k e n a n d t h e i r i n t e r p r e t a t i o n will d e p e n d on t h e solvent a n d on w h e t h e r t h e v i t a m i n A is esterified or not. (Chem. Abs. 44, 5423) MIOI~ODETERMINATION O1~ VITAMIN A BY M~ANS 0~ TI~IOHLO~O.ACETIO AOID RE~OE~T. G. N o g r a d y . Magyar Orvosi Arch. 45, 135-46(1944). T h e micro m e t h o d described is b a s e d on t h e Carr-Price reaction. Trichloroacetic acid is used in place of SbCh. T h i s reaction is more specific a n d less sensitive to water, a n d its blue color shows only a slow decrease of i n t e n s i t y . (Chem. Abs. 44, 5415) DETERMINATION 0~" POLYUNSATURATED rAq~PY ACIDS IN BLd)OD. P. W. O ' C o n n e l l a n d B. F. D a u b e r t (Univ. of P i t t s b u r g h , P i t t s b u r g h , P a . ) . Arch. Bioehem. 25, 444-6(1950). L i n o l e a t e in b e e f p l a s m a was d e t e r m i n e d b y e x t r a c t i n g t h e t o t a l lipid of the p l a s m a , s a p o n i f y i n g it, s u b j e c t i n g it to alkali isomerization, a n d r e a d i n g a b s o r p t i o n at 233 m # in a b s o l u t e m e t h a n o l . Corrections f o r o t h e r lipids m u s t be made. (Chem. Abs. 44, 5945) ~=ATUI~]~ Or END LACTATION" MIr,K I~AT. T. M. P a u l a n d C. P. A n a n t a k r i s h n a n ( I n d i a n D a i r y Res. Inst., B a n g a l o r e ) . Indian Jour. Dairy Sei. 2 ( 2 ) , 58-64 (1949). S a m o l e s of b u t t e r f a t were collected f r o m a n i m a l s in a n a d v a n c e d s t a g e of pregn a n c y a n d classified as " d r y . " The f a t % of milk s a m p l e s varied f r o m 2.3 to 16. A g r a d u a l decrease in t h e Reichert a n d saponification values a n d a n increase in t h e iodine value oc-

e u r r e d w i t h t h e a d v a n c e in p r e g n a n c y . No c o n s i s t e n t c h a n g e s were noted in t h e P o l e n s k e values. (Biol. Abs. Sect. G., 24, 32) TIIE ADI~IATIC Eff~ASMOBI%ANOHIALIV]~ OILS. I V . BIOCHEMICAr. S T U D Y O1~ OILS ~ItOM THE LIVE~ A E ~ F ~ O S 0~ C'~NTKINA SALWIANL S. Cmelik ( I n s t . O c e a n o g r a f . I R i b a r s t v o U Splitu, J u g o s l a v i j e ) . Aeta AdriaL 4, 3 - 2 3 ( 1 9 4 9 ) . L i v e r oils f r o m t h i s species were c o m p a r e d as to p h y s i c a l a n d chemical properties, as were oils f r o m fertilized a n d u n f e r t i l i z e d eggs. Chemical p r o p e r t i e s of f a t acids f r o m all these sources were quite similar. C h r o m a t o g r a p h i c a b s o r p t i o n on A12Oz was p a r t i a l l y s u c c e s s f u l in s e p a r a t i n g c m n p o n e n t s of t h e unsaponifiable m a t e r i a l , cholesterol, selachyl, butyl, a n d c h i m y l alcohols b e i n g identified. The unsaponified p o r t i o n of e g g oil c o n t a i n s m u c h m o r e cholesterol t h a n does t h e liver oil. T h e oil f r o m fertilized e g g s shows g r e a t decrease in p e r c e n t a g e of unsaponifiables, f r e e f a t acids, t o t a l f a t acids, saponification no., a n d I no. f r o m t h a t of u n f e r t i l i z e d eggs. (Chem. Abs. 44, 5619)

9 Waxes E. H. McMullen, Abstractor PHYSICAL AND T~OHNICAL FI%OPEI%TIEg O1~ HYDI%O,CAI%BOI~WAXES, THI~]IP~ C~ASSIrIOArlvION, -&NI) NOMENOT~AT*UI~E. K a r l It, Grodde (Deut. E r d J l A.-G., Chem. Abt. M a r i e n d o r f , B e r l i n ) . E r d 6 l u. Kohle 3, 61-72(1950). F o r m u l a s a r e g i v e n f o r t h e calculation of t h e molecular w e i g h t of paraffins as a f u n c t i o n of solidification point, density, r e f r a c t i v e index, viscosity ( W a l t h e r ' s e x p r e s s i o n ) , b o i l i n g point, a n d f o r t h e c a l c u l a t i o n of v a p o r pressures. B y s u b s t i t u t i n g c, a s y m m e t r y ' ' a n d ' ' r i n g " values, t h e above f o r m u l a s can be a p p l i e d to iso- a n d r i n g paraffins ( c e r e s i n ) . The a p p l i c a t i o n of t h e s e f o r m u l a s to w a x e s of diss i m i l a r c o m p o s i t i o n is discussed w i t h p a r t i c u l a r r e f e r e n c e to b e h a v i o r of t h e solidification point. A p r a c t i c a l m e a s u r e of composition is f o u n d to be t h e m e a n slope of t h e d i s t r i b u t i o n curve versus solidification point. D i c h l o r o e t h a n e is u s e d f o r f r a c t i o n a t i o n , a n d d a t a show t h e influence of dilution on separation. F o r h i g h - m e l t i n g w a x e s a " t u r b i d i t y p o i n t " is u s e d as criterion f o r d e t e r m i n i n g composition. T h e oxidizability in air of paraffins a n d isoparaffins is t h e s a m e ; however ceresins are m u c h more r e s i s t a n t t o w a r d s oxidation. A classification a n d n o m e n c l a t u r e f o r waxes a r e p r e s e n t e d a n d t h e a n a l y t i c a l procedures f o r t h e classification described (Chem. Abs. 44, 5573) SYNT~ETIO WXXES. I I I . E. E. Halls. Food 19, 108-10(1950). G r o u p s of s y n t h e t i c waxes of i n t e r e s t to t h e food i n d u s t r y a r e described, a n d t h e i r p h y s i c a l a n d chemical p r o p e r t i e s a r e t a b u lated. (Chem. Abs. 44, 5485) PATENTS EXTrACtION Or UNSAPONII~I~ImS rROM WOOL OREaSE. A r e h i e B. P o r t e r ( N O P C O Chemical CO.). U. S. 2,499,877. Wool g r e a s e ( s o l v e n t - e x t r a c t e d or acid-cracked g r a d e ) is saponified w i t h a 4-200% excess of alcoholic alkali, the saponified m a s s is p a r t i a l l y n e u t r a l i z e d w i t h m i n e r a l acid to a p H of 8.5-11.0, a n d t h e m i x t u r e is e x t r a c t e d w i t h a h a l o g e n a t e d h y d r o c a r b o n solvent, p r e f e r a b l y dichloroethane. Sterols a n d o t h e r u n s a p o n i fiables are recovered q u a n t i t a t i v e l y . (Chem. Abs. 44, 6176) EMUL~ION~ OP "I~HEKMOPLASTIC~ I~]~SIRVS,, W&XES, AN'/) OILS. J a m e s K . D i x o n a n d Russell L. M o r g a n ( A m e r i c a n C y a n a m i d Co.). U. S. 2,500,122. E m u l s i o n s of resins, waxes, a n d f a t t y oils are p r e p a r e d in a q u e o u s o r g a n i c solvent m i x t u r e s b y use of a cationic a m i d o c o m p o u n d as e m u l s i f y i n g a g e n t . E x a m p l e s of resins are alkyds, b u t y l a t e d m e l a m i n e - f o r m a l d e h y d e condensates, b u t y l a t e d u r e a - f o r m a l d e h y d e , a n d r o s i n - f m n a r i c acid a d d u c t . E x a m p l e s of w a x e s are c a r n a u b a w a x a n d paraffin. E x a m p l e s of e m u l s i f y i n g a g e n t s a r e ( 3 - s t e a r o y l a m i n o p r o p y l ) - , (3-1auroylaminopropyl)-, and (3-oleoylaminopropyl(dimethyl( 2 - h y d r o x y - e t h y l ) a m m o n i u m chloride, ( 3 - s t e a r o y l a m i n o p r o p y l ) d i m e t h y l ( 2 , 3 - d i h y d r o x y p r o p y l ) a m m o n i u m chloride, a n d t h e rea c t i o n p r o d u c t of ( 3 - s t e a r o y l a m i n o p r o p y l ) d i m e t h y l - a m m o n i u m chloride w i t h 20 molecules of ethylene oxide. (Chem. Abs. 44, 6176) POr,YETHYLFrNE WAX COMPOSITIONS. F r e d e r i c k It. M a e L a r e n a n d J o h n A. A n d e r s o n ( S t a n d a r d Oil Co. o f I n d i a n a ) . U . S . 2,504,270. I n c r e a s e d tensile s t r e n g t h is g i v e n to p e t r o l e u m w a x b y t h e a d d i t i o n of very s m a l l a m o u n t s of h i g h - m o l e c u l a r ethylene polymers. (Chem. Abs. 44, 6114) POLYZT~Yr,~g WAXgS. Michael E r c h a k J r . (Allied Chemical a n d Dye C a r p ) . U. S. 2,504,r Synthetic hard, hlgh-melting w a x of t h e f o r m u l a M e ( C ~ H ~ ) , C ( O H ) M e ~ is p r e p a r e d b y polym e r i z i n g ethylene of at l e a s t 9 0 % p u r i t y c o n t a i n i n g less t h a n 0.01% b y w e i g h t o x y g e n a t 140-200 ~ a n d 6,500 lb./sq, in. p r e s s u r e in t h e presence of 0.1-2.0% h y d r o g e n peroxide a n d a n

TI~E JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, SEPTE:MBER, 1 9 5 0 amount of isopropanol corresponding to 5-10% of the volume of the reaction zone. The wax produced has penetration of 1 to 3 at 22~ under a load of 200 g r a m s ; the melting point ranges f r o m 105 ~ to 115 ~ depending on the reaction conditions. Temperatures above 165 ~ and high hydrogen peroxide concentration favor production of softer wax while the w a x obtained at lower temperatures a n d hydrogen peroxide concentration and high isopropanol concentration is hard. (Che~r~. Abs. 44, 5622) AQUEOus WAX EMITLSION. A. F. B u c k m a n Jr., and M a r g a r e t M. Rendall (S. C. Johnson and Son Inc.). U. S. 2,504,920. A n aqueous wax emulsion suitable for making asbestos-cement building boards water-repellent is prepared by h e a t i n g to 190~ a mixture of stearic acid 24.1, yellow c a r n a u b a wax 2.8, polybutene (molecular weight 940) 10, morpholine 3.5, 26 ~ B6., a m m o n i u m hydroxide 4 parts, and enough water to bring the water content to 94 parts. For t r e a t m e n t of the boards, 1 p a r t aqueous emulsion is mixed with t i t a n i u m dioxide 0.25, and water 24 parts. Polybutene of higher and lower molecular weight can also be used. (Chem. Abs. 44, 5622).

9 Drying Oils Robert E. Beal, Abstractor FOI~ATION

01~ BODI]~I) L I N S I ~

OIL.

M.

Kronstein,

M.

M.

Ward, S. S. Morris, and D. Mishkind (New York Univ., New York, N. Y.). New York Univ. Coll. Eng., Symposiur on Varnish and Paint Chem. 1948, 77-88. Diffraction x-ray spect r a and ultraviolet spectrographic tests will reveal approaching gelation. The latter shows a rapid s h i f t i n g between wave lengths of 310-265 millimierons as the raw oil is bodied. (Chem. Abs. 44, 5609) MALEATE OILS---MODIfiCATIONS O~ DI~YIN~ OILS WITI:I ~IAL~I0 ACID ~m~IVATIV~S:. C. P. A. Kappelmeier, J. H. van der Neut, a n d W. R. V a n Goor. Kunststoffe 40, 81-7(1950). I n the reaction of maleie acid with simple olefins a '~substituent addit i o n " takes place at the a-methylene group which leads to the formation of alkenyl-suecinic acid anhydrides. I f several double bonds exist in the molecule, conjugation tends to occur. Maleate oils body f a s t at high temperatures, and their films through-dry well and are water- and weather-resistant. (Chem. Abs. 44, 5609) ISOMBIClZ&TION OP DI~YII~G O'ILS~. M. C. deWilde. I~d. Chain. belge 15, 72-9(1950). A review with 40 references. I M P I % O V I N G D K Y I N G PI~OP]~F~TIES o!~ soFq ~ OILS. 12[. L. ICiee. Paint Vaxnish Production 30, No. 2, 13, 15-17(1950). Copolymerization of domestic oils with heat-reactlve " C a r b i c " anhydride resins gives products which are fast-bodying, dry rapidly, through-dry well, improve the hardness of phthallie alkyds, and m a y replace China wood oil. The use of polyhydric alcohols of higher functionality t h a n glycerol to improve domestic oils is reviewed. (Chem. Abs. 44, 5116) MODI~I~]) oILS. H. A. Boekenoogen. Verfl~ronie~r 23, 77-80 (1950). Improvement of n a t u r a l drying oils by the removal of antloxidants, coloring matter, and other undesirable materials is reviewed. A new process of isomerization which gives 50% conjugation with linseed oil is described. The oil polymerizes in 6% of the time f o r ordinary linseed oil and gives films which show no after-tack. (Chem. Abs. 44, 5609) Olq TI-~E DI~YING O~ LINSE~a) O~L. t~. Dooper. Verfkronielc 23, 84(1950). The chemical and physical properties of samples of poor drying and samples of good drying linseed oil were determined, but no differences were detected other t h a n in drying time. EXPE~IM]~XTS IN TH~ DI~YING OF QI~AI~HI~ COLDI~S. l{. Beuerle and M. H a r t m a n n . Angew. Chem. 62, i43-4(1950). Light, especially ultraviolet, and O accelerate the drying of linseed oil, with and without the use of driers. Drying in the presence of carbon dioxide or moisture is slower. (Chem. Abs. 44, 5608) SoI~B PRACTiCAl, amsws wI~H Iso~t~IZEI) oILS.. 12[. W. Talen. Verfkroniek 23, 80-2(1950). The properties of linseed oil isomerized by a new process are compared with ordinary linseed oil and t u n g oil both bodied a n d unbodied. The isomerized oil has better water resistance and lies between linseed and t u n g oils in drying time, chalking, and in scorch tests. (Chem. Abs. 44, 5610) APPLICATIOIXI

6~i~ INIV~AKED

SPE(3~ROS~0'PY

TO, TH]~ S T U D Y

Ol~

DI~YING OILS AN]) O~ICTAIN PLASTICS. M. Kronstein. New York Univ. Coll. Eng., Symposium on Varnish and Paint Chemistry 1948, 13-40. W i t h this method the most noticeabl e change when linseed oll was converted to an insoluble, infusible substance was in the region between 1000 and 1150 em, -~ and it shows t h a t the insoluble product is still oil substance. Similar changes were noted with other oils. Although the spectra of monomeric

359

styrene and linseed oil were completely different, those of solid polystyrene and of the polymer produced f r o m ]iquefed gelled linseed oil and styrene at 50 ~ showed t h a t similar i n f r a r e d shirtings had occurred. The insoluble f o r m appears to have its own spectral, chemical, and physical properties. (Chem. Abs. 44, 5608) ANALYSIS Ola D~IIYI>I~ATED OAST0,1~ OIL. D. O. Bartl. Chem. Listy 37, 98-102, 109-12(1943). Correct values for the I value ( H a n u s ) require 400% excess IBr. As dehydration proceeds, the I value increases to a constant final value of 148 after 6-8 hours and the hydroxyl number decreases gradually. The diserepancy is explained by condensation reactions. (Chem. Abs. 44, 5617) SYST]~MATIC FI~ACTIONATION OP BODI'EI> LINSgEJ) 0'IL (STANDOIL). J. Petit (French P a i n t and Varnish Research Lab., P a r i s ) . New Yor~ Univ. CoN. Eng., Symposium on Varnish and Paint Chem. 1948, 71-6. Fraetionation with alcohols of v a r y i n g molecular weights gives evidence of the heterogeneity of bodied oils. (Chem. Abs. 44, 5609) TURKISI~ T0~AOCO-S~EO OIL. S. L. Alpar and S. Esin (Univ. I s t a n b u l ) . l~ev. faculte sea. univ. Istanbul 14A, 65-71(1949). The oil had I value of 140, saponification value of 187, unsaponifiable content of 2.1% solid f a t t y acids 8.0%, liquid f a t acids 82%, and linoleie acid content of 68.5%. The oil films dried within 5-8 days in sunlight and in 1-2 days when mixed with red lead. (Chem. Abs. 44, 5619) PATENTS TKEATMENT

O1~ H Y D K O C A P ~ B O N DKYII~G TYP],3 DICYING OILS T O I~IpP~0"q~I]~NT IX T1~]~II% I)RYING QUALITIES. E. ~/~.

]~]~ECT AN Geiser (Universal Oil Products Co.). U. S. 2,513,558. A hydrocarbon drying oil boiling below 250 ~ recovered from polymerization sludge, is contacted at reaction conditions which m a i n t a i n the reactants in liquid phase, with BFz hydrate or with a BFa complex with an O-containing organic compound, and an improved drying oil is recovered f r o m the sludge thus formed. COATING C'0MPGSITIONS. D. S. Breslow (Hercules Powder Co.). U. S. 2,515,290. The cojalposition comprises a pentaerythritol ester of a dehydroabietyl N-substituted carbamic acid and a drying oil. P I ~ O O E S S F01~ O B T A I N I N G

B O D I E D ])KYING AN]) SElVLIDRYING 0$LS.

B. C. P r a t t (E. I. d u P o n t deNemours and Co.). U. S. 2,516,590. A catalyst used in amounts of 0.1-2.0% for bodying drying oils at 250-350 ~ consists of a resin which is the reaction product of sulfur dioxide and an organic compound containing a carbon to carbon double bond. M~HOD OY ~F.ATING TALL O~L. 3-. J. Smereehniak and G. W. Barlow (American Cyanamid Co.). U. S. 2,515,739. The color and odor of tall oil f a t t y acids are improved by heating them with 0.1-2.5% of metallic Zn at 150-275 ~ CONTINUOUS PRGC~SS )'OI~ ~H]~ D~,~Y]>~OXYI~ION 0~' OAS~OI~ OIL. S. B. Radlove (The M a y t a g Co.). U. S. 2,515,797. The oil is mixed with 0.1-1.0% of 70-90% sulfuric acid and allowed to flow by g r a v i t y in a thin film over a heated surface where it is heated to 240-400 ~ and continuously subjected to a vacuum for the removal of volatile material.

9 Detergents Lenore Petchaft, Abstractor SOLUBILIZATION 01~ pROTF~IIq-I~Y]~PI~]~CIPITAT]~S. 3-. C. Perrone (Inst. nacl. technol., ]~io de J a n e i r o ) . Rev. brazil, biol. g, 425-6(1949) (in E n g l i s h ) . The precipitates formed upon addition of various cationic dyes to a slightly alkaline solution of egg albumin redlssolve when a soap or an anionic alkyl sulfate detergent is added. Cationic and nonionie detergents have no such action. The soaps and anionic detergents f o r m soluble nondialyzable complexes with the dyes. (Chem. Abs. 44, 4525) TH-Z AGIX(~ O~ C~OII)S. W. Kopaczerski. Chimie # industrie 63, 27-33 (1950). The changes in the properties of colloidal systems with time are attributed to the degree of dispersion, which determines the stability. The stability of the system in t u r n depends on its sensitivity to light, its oxidation-reduction tendency, its catalytic Character, its degree of transparency, and its chromogen properties. The theory is applied to the aging characteristics of glass, gelatin, gums, soaps, greases, and other industrial products. The possible importance of the electrical potential of the air, cosmic rays, and m a g n e t i c storms is indicated. (40 references.) (Chem. Abs. 44, 4751) I~PORTANC~ O~ AN~IYDROUS PHO~PI~AT~S FOI~ T~I~ SOAP AND n L ~ G ~ r ~ INI)USTItY. K u r t Lindner (Beflin-Lichterfelde-Ost, GEL). Seifen-Ole-Fette-Wachse 76) 133-6(1950). Review on the

360

T H E JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, SEPTEMBER, 1 9 5 0

chemistry of anhydrous phosphates, their influence on water hardness, their practical importance, and the influence of N a hexametaphosphate on surface activity. (Chem. Abs. 44, 617]) W A T F ~ - S O L U B L E CELLULOSE E T H E l ' S AS EMULSII~YING AGEINTS~.

R. I. Morrison and B. Campbell (Imperial Chem. Inds. Ltd., Stevenston, Aryshire, Scot.). J. Soc. Chem. Ind. (London) 68, 333-6(1949). Methylethylcellulose ( I ) is a more effective emulsifier in a lower concentration t h a n N a earboxymethylcellulose ( I I ) . A mixture of both is better t h a n either alone. The presence of a high-viscoslty I I reduced the tendency of I to foam. I reduced the interfacial tension between H~O and liquid paraffin much more t h a n did II. I n a concentration of 0.5%, I showed 25.3 and I I 47.5 dynes/cm. I caunot be used over 40 ~ since its solubility is much reduced with increase in temperature. However an emulsion first made was stable at 45 ~. Emulsions made with I were stable over the range of p H 2-10 whereas at an acid p H emulsions with I I break down. (Chem. Abe. 44, 6662) TI-I~ IIVPLUEN-CE 0~' S O D I U ~ CARBOXYMETHYL Ok-~LLULOSE ON T H E SUSPENDING P O W E ~ O~ B*UILT SOAP SOLUTIONS. C'. t~. Bayley

and A. S. W e a t h e r b u r n (National Research Labs., Ottawa, ~anada). Textile Research J. 20, 510-13(1950). The influence of sodium carboxymethyl celhilose (CMC) on the ability of soap solutions to prevent the deposition of carbon black on fabric during the detergent process has been studied. I t was found t h a t the presence of alkaline builders (sodium carbonate, modified soda, sodium metasilicate, and sodium orthosilicate) resalted in a decrease in the suspending power of soap solutions. The addition of CMC to such built soap solutions compensated to a considerable extent for this reduction in suspending power caused by the builder although in no case did the suspending power equal t h a t of the unbuilt soap. The m a x i m u m improvem e n t in suspending power was obtained with a CMC concentration of 0.005% e.g., 5% of the weight of soap used. I n general, those builders which caused the greatest depression in the suspending power of the soap solution also showed the greatest improvement in suspending power on the addition of CMC. SO~E PHYSICAL-OHEMICAL A S P E O T S O~ COTTOIkT I)~]VE~G~N6~Y. CATIO~,YIO A D S O R P T I O N A N D E X C T I A N G ~ A S S H O W N B ~ P~ADIOCAL-

oIUM TgAOm~ STUDIES. J. M. L a m b e r t (General Aniline and Film Corp., Easton, P a . ) . lnd. Eng. C%em. 42, 1394-8(1950). Some of the physical-chemical properties of cotton responsible for the complex interactions in practical detergency have been reviewed. The accessibility and acidic characteristics of cotton appear to be of particular importance. The role of adsorption as an i m p o r t a n t factor in detergency is illustrated by experim e n t a l adsorption d a t a of surface-active agents on cotton. Radioisotope tracer methods are described for m e a s u r i n g the adsorption and exchange of calcium on cotton as it occurs in laboratory wash tests simulating hard water laundering. Results are presented which were obtained with several cotton detergents in multicycle wash tests. V a r y i n g a m o u n t s of calcium are adsorbed depending on the detergent and on the condition of the cloth (new or used cotton). A tentative interpretation of these effects is offered as well as a discussion of possible extensions of the method. M E T H O D S OP ~VALUATING DETER~]ENTS. Cornelia T. Snell (Foster D. Snell Inc., New York, N. Y.). Am. Dyestuff Reptr., 39, 485-7(1950). General review article covering types of detergents and the methods available for evaluating their efficiency. Methods include: surface tension measurement, interfacial tension measurement, m e a s u r e m e n t of dispersing power, measurement of wetting power, and washing tests. CO
soap and detergent builders including hydrolysis, sequestering power, surface activity, f o a m i n g ability, and effect on the soap or detergent in question. Emphasis is placed on care of choosing proper builder for particular conditions so t h a t detergency is enhanced and soil redeposition is prevented. Requirements and formulas are given for such products as household soaps, h a n d dishwashing compounds, automatic dishwashing compounds, floor cleaners, dairy detergents, bottle washing compounds, a n d metal cleaners. STRUCTUR]~ OF AQUEOUS SOLUTION'S OF SOAFLIKE SUBSTAI'~CFS.

G. S. Hartly. Ann. Repts. Progress Chem. (Chem. SOP., London) 45, 33-51(1948). Review with m a n y references. (Chem. Abs. 44, 5681) F O A M S T F D I ~ S W I T H SOAPS A N D T E X ~ I L E AUXILIARIES. E r n s t Gotte. Melliand Textilber. 29, 65-9, ]05-8(1948). The physics of f r o t h i n g and techniques for m e a s u r i n g , f o a m i n g power are discussed. Measurements were made with a jacketed, graduated glass cylinder. Air was introduced through fine openings in the bottom of the cylinder, a n d a means for a g i t a t i n g the liquid was provided. A study was made of homologous series of the types RSOdNa, RSO~Na, and RCOONa. The m i n i m u m concentration for f o a m f o r m a t i o n is independent of temperature but decreases as the chain length increases. The f o a m i n g rate increases with temperature. For each material there is an optimum concentration f o r f o a m formation which is dependent upon the chain length. The half-life of the f o a m increases with chain length to a m a x i m u m at C,7. The f o a m i n g power of the RSO~Na series is superior to the other two types. (Chem. Abs. 44, 6660) APPLICATION" OF N E ~ r F~KpEI%I]~f]~q~A~L METHOI)S TO T H E STUDY

O1~ SUR]~A(~E-AOTIV~]C~)MPOI)-NDS. Madeleine Raison and Raphael Matalon. Mere. services chim. etat (Paris) 34, 353-71(1948). Some industrial chemicals were studied to determine their activity at the interfaces. Tension measurements were made with a wire loop and wettability was determined by s t u d y i n g drops on a surface. The measure of wettability is given in the coefficient of spreading S/V. This coefficient gets larger as the surface tension is lowered, increasing abruptly at the concentration t h a t gives m i n i m u m surface tension. F o a m i n g was studied with the laminometer and is produced at concentrations much lower t h a n those that give m i n i m u m tension. The volume of f o a m increases sharply at m i n i m u m surface tension. The f o a m i n g power is related to the molecular constitution of the molecules of the detergents. (Chem. Abs. 44, 5678) T t t E p~EPAB~TIOI~ O1~ L I l l E - AND AC~I)-P~SISTAIqT ~ A S H I N G , DISPE~SIN~G, ANI~ W~T'I'IIqO AGENTS FOR T H E T E X T I L E INDUSTRY.

Walter Riess. Seifen-Ole-Fette-Wachse 76, ]03-4(]950). Secondary alcohols are prepared f r o m the ketones obtained by the distillation of low-molecular weight f a t t y acids (butyric, caprolc, and caprylie acids) over catalysts. These alcohols are condensed with benzene, naphthalene or phenol, and oleum or C1SO,H at 30-40 ~ to yield true sulfonic acids. (Chem. Abs. 44,

617~) SFLPHAT~]D P R I M L Y

FATTY A L C O H O L S .

A.

R.

Keast.

Per-

fumery Esseut. Oil t~ecord 41, 223-6(1950).

Review article covering methods of producing f a t t y alcohols, production of the sulphate useful as a detergent, s u m m a r y of such properties as detergency, f o a m i n g power and "emulsifying power, and a survey of the various uses of these f a t t y alcohol sulfates. USES o~ s ~ c u z AS A SOAP PmLE~. P a u l I. Smith. Am. Perf u m e r Essen~. Oil trey. 56, 51-2(]950). Up to 20% starch m a y be used as a soap filler. It does not affect detergency and produces a smooth bar and shiny lather. I t is possible t h a t the beneficial action of starch can be attributed to its colloidal and gel-formlng character. Starch helps m a s k alkalinity and prevent rancidity b u t m a y tend to discolor white soap. ANAnYSIs ov S(~AP STO~KS. J. P. Wolff. Bull. mens. ITEI~G 4, 165-8(1950). A mixture of 67% dioxane and 33% of 1:[~O is an excellent solvent which prevents emulsions upon extraetion of the neutral f a t with petroleum ether and eliminates the danger of a possible hydrolysis if, previous to the determination of total f a t , HC1, is used for the decomposition. Volumetric methods are discussed b u t recommended only for very pure soap stocks. (Chem. Abs. 44, 6171) DET]~I~IINATIOI~ OF SILICATES IN- L A U I q D F ~ N G

C~k~[POUNI~S. W .

Gottschaldt. Fette u. Seifen 51, 432(1944). For a speedy gravimetric determination of SIP2, a 2-g. sample is mixed with 1.5-2.0 g. NH~C1, 15 ml. concentrated HCI is added slowly, the mixture is heated l0 min. on the steam bath, diluted with 50 ml. boiling H~O, filtered, a n d the precipitate ignited. I n the absence of phosphates a colorlmetric method using the color reaction with ammonium molybdate is suggested. (Chem. Abs. 44, 6662)