146

TH~ J o u a ~ L

o~ T ~

AMERICAN OIL CHEMISTS'

zene or acetone show the B-spacings o n l y . " I n later studies these workers (5) found one f a t t y acid which gave B- and C-spacings when crystallized f r o m glacial acetic acid. Also these workers found that impurities of f r o m I to 3% were indicated when an aliphatie acid, crystallized f r o m benzene, had both B- and C-spacings. I n view of the data of the present work it appears that the t e m p e r a t u r e at which crystallization of stearic acid f r o m a solvent occurs is the dominant factor with respect to the polymorphic f o r m obtained, and not the type of solvent; i.e., crystallization below the beginning of t r a n s i t i o n at 35.2 ~ C. for the B - f o r m and above the final transition at 52.9~ for the Cform. Either the B- or C-spacing can be obtained from the same solvent with proper t e m p e r a t u r e conditions. F u r t h e r m o r e to use the crystal spacing as a criterion of the p u r i t y of f a t t y acids, it must be known that the conditions of c r y s t a l l i z a t i o n were such as to give the B-spacing only so that a mixture of B- and C-forms will be a valid indication of the degree of purity, and not due to polymorphism. I n crystallographic observations of B-form stearic acid, t e m p e r a t u r e s in the range of the reluctant transition of this acid (35-53~ should be avoided since it is in this range that separation of a mixture of B- and C-forms f r o m the crystallization solvent is possible. Although results have been obtained only for stearic acid, the principles are p r o b a b l y applicable to other even n u m b e r e d n-aliphatic acids, as indicated b y p r e l i m i n a r y results with palmitic acid.

Summary 1. Purified stearic acid ( f r e e z i n g p o i n t 69.20~ melting point 69.5~ when slowly crystallized f r o m benzene at room temperature, yielded t r a n s p a r e n t monoclinic crystals exhibiting an X - r a y diffraction p a t t e r n (long spacing) corresponding to the B-form of the acid. Crystallization of stearic acid f r o m hot glacial acetic acid resulted in a product exhibiting an X - r a y diffraction p a t t e r n (shorter spacing) corresponding to the C-form of the acid. 2. Rapid chilling of a melted sample of Stearic acid likewise yielded a product exhibiting the diffraction p a t t e r n characteristic of the C-forms of the acid.

I ABSTRACTS Oils and Fats THE M ~ r A C ~

.

A. R. Baldwin, Abstractor OF SULrO~AT~DOm AND T ~ D~mNA-

ITS ]~]~IULSIO~q'S. Liu-Chiao F u a n d Chien-Hon Chen. J. Chem. Eng. Chirta 15, 72-80(1948). Good s u l f o n a t e d oil can be prep a r e d f r o m a n y v e g e t a b l e oil except those w i t h h i g h f a t t y acid c o n t e n t or h i g h u n s a t u r a t i o n . S u l f o n a t e d oils o b t a i n e d by sulf o n a t i n g castor, p e a n u t , sesame, a n d cottonseed oils show l i t t l e difference in s u r f a c e t e n s i o n ; the w e t t i n g powers of the s e products decrease in the order named. These sulfonate~l oils are s a t i s f a c t o r y f o r use in the t e x t i l e i n d u s t r y . (Chem. Abs. 44,

353.)

THE Ott~MIS:~ AND 'Ptt~ ~Orf~ONS]~E~ IN:DUSTIlY. W. L. R e t t ~ e r ( B u c k e y e Cotton Oil Co.). Oil Mill Gazetteer 5g ( 7 ) , 34-7 ( 19 50). This p a p e r reviews h i s t o r i c a l l y the d e v e l o p m e n t of the cottonseed p r o c e s s i n g i n d u s t r y .

SOCIETY,

APRIL, 1950

3. The specific volume, expansion in both solid and liquid states, and melting dilation of stearic acid in both B- and C-forms were calculated f r o m dilatometric data. 4. The irreversible transition of stearic acid f r o m the B- to the C-form was r a p i d and visible at 52.9~ but also occurred at 35.2~ when sufficient time was allowed for the transition to occur. 5. The f o r m of stearic acid which was obtained was found to be dependent upon the t e m p e r a t u r e at which crystallization occurred. W h e n crystallization was carried out at t e m p e r a t u r e s below the transition point of the acid, the B-form was obtained, and above the transition point only C-form of the acid was obtained, irrespective of the solvent used for crystallization. 6. The specific heat of stearic acid was determined, and equations developed for expressing the specific heat of the acid in both solid and liquid states. F r o m the calorimetric data, the heat of fusion, and the e n t r o p y of stearic acid were calculated.

Acknowledgment The authors wish to acknowledge the assistance of Mildred M u r r a y , R. T. O'Connor, and M. E. Jefferson, in making the X - r a y diffraction examinations of stearie acid. REFERENCES 1. Normann, W., Chem. Umschau Fette iJle Wachse YIarze, 38, 17-22 (1931). 2. Piper, S. H., Malkin, T., and Austin, H. E., J. Ohom. Soc., 23102318 (1926). 3. Thibaud, Jean, and La Tour, F. nupre, J. de chim. phys., ~9, 153167 (1932). 4. Slagle, F. B., and Ott, E., J. Am. Chem. Soc., 55, 4396-4418 (1933). 5. Francis, F., and Piper, S. H., ft. Am. Chem. Soc., 61, 577-581 (1939). 6. Ralston, A. W., "Fatty A c i d s a n d Their Derivatives," Wiley, 1948, p. 335. 7. Garner, W. E., Madden, F. G., and Rushbrooke, J. E., J. Chem. Soe., 19Z6, 2491-2502. 8. Markley, K. S., "Fatty Acids," Interscience, New York, 1947, p. 94. 9. Bailey, A. E., and Kraemer, E. A., Oil & Soap, gl, 251-253 (1944). 10. Bailey, A. E., Todd, S. S., Singleton, W. S., and Oliver, G. D., Oil & Soap, 21, 293-300 (1944). 11. Bailey, A. E., and Singleton, W. S., Oil & Soap, g2, 265-271 (1945). 12. Gibson, R. E., and Markley, K. S., J. Am. Chem. Soe., 55, 23992406 (1933). 13. Hattiangdi, G. S., ft. Research Natl. Bur. Standards, 4Z, 331. 341 (1949). (Research Paper No. 1972.) 14. Kelley, K. K., Parks, G. S., and Huffman, H. M., J. Phys. Chem., 33, 1802-1805 (1929). 15. Francis, F., Collins, F. J. E., and Piper, S. }/., Proc. Roy. Soe., 158A, 691-718 (1937). [Received D e c e mbe r 5, 1949]

Don Whyte, Editor

I

HYDI~OPROBIO MObTOLAY]~I~S ADSOI~BLI) F1r163 AQUEOU~ SOLU~'IO~S. E. G. S h a f r i n a n d W. A. Z i s m a n ( N a v a l Res ear ch L a b o r a t o r y ) . J. Colloid Sci. 4, 5 7 1 - 9 0 ( 1 9 4 9 ) . E x p e r i m e n t a l m e t h o d s a re d e s c r i b e d f o r t he p r e p a r a t i o n a n d e x a m i n a t i o n of h y d r o p h o b i e m o n o m o l e c u l a r films a d s o r b e d i n t o p l a t i n u m surfa c e s f r o m aqueous s ol ut i ons of p r i m a r y n o r m a l a l k y l amines. The c r i t i c a l l i m i t s to h y d r o p h o b i c film f o r m a t i o n a n d th e de gre e of h y d r o p h o b i c i t y a r e f o u n d to be f u n c t i o n s of th e a m i n e c o n c e n t r a t i o n a n d t h e p i t of t he g e n e r a t i n g solution. A definite c o r r e l a t i o n is e s t a b l i s h e d f o r t h e r e l a t i v e effectiveness of these f a c t o r s a n d t he l e n g t h of t he h y d r o c a r b o n ch ain i n t he a l i p h a t i c p o r t i o n of t he a m i n e molecule. The s h o r t c h a i n a m i n e s (up t h r o u g h dode c yl ) a re f o u n d to be m o s t ads o r p t i v e i n t he a l k a l i n e re gi on, w h e r e a s film f o r m a t i o n of th e h e x a d e c y l a m i n e is l i m i t e d to t he h i g h l y a c i d regions. The i n t e r m e d i a t e t e t r a d e e y l a m i n e evinces a t r a n s i t i o n a l b e h a v i o r , h a v i n g two s e p a r a t e p H r e g i o n s f a v o r a b l e to film f o r m a t i o n . OLE&TE SYSTEIVfS ~O~TAINI~G POTASSIUM ~PdI~ORID~. I~rr. ~LOW PROP]SRTIES AS A FUNCITI0.I'~ OP S.HEA-I~ING STRESS AT 15 ~ AN]) OONSTA]N'T KC[L CK),NC]SNT~ATION. V. VISOOU~ iN]) FXLASTICI BE-

T H E JOUR47AL O1~ THE A M E a l C A N 0 I L C H E M I S T S ' SOCIETY, API~IL, 1 9 5 0 ItAVIOI~ COMPAIZEJ). VI. ELASTI~ FI~OFEI~TIES AS I~UNCT~0,1~ OF KCL ~Olq'CEN'T~ATION; INI~LI]]~NO~O~~ ALCOHOL~ AND FATTY ACID ANIONS O1W ELASTIC Bi~HAVIO~. H. G. B u n g e n b e r g de J o n g and H. J. van den Berg. Proc. Kon. Ned. Akad. Wet. 52, 363-76, 377-88, 465-78(1949). This is a very detailed series of articles describing the properties of oleate solutions. A lengthy abstract may be found in the J. Text. Inst. 40, A417(1949). ELASTIC-VISGOUS STEAI~AT'E SYSTEM. H. J. van den Berg and L. J. de H e e l Proe. Kon. Ned. A/cad. Wet. 52, 457-62(1949). This is a p a p e r describing the stearate system analogous to the oleate systems previously described. [J. Text. Inst. 40, A417 (1949).] OBJECTIVE ~YALUATION Or ODOI~D~TEI~IOI~AT'IONIlXr ORA_NGI~OIL. B. E. P r o c t o r and E. M. K e n y o n (Massachusetts I n s t i t u t e of Technology. Food Technol. 3, 387-92(1949). The development of " t e r p e n c y " odors in citrus oils due to air oxidation was studied by several techniques. A s t a n d a r d W a r b u r g manometric system was used to measure the q u a n t i t y of oxygen absorbed by the oil under controlled conditions. Changes in the i n f r a r e d absorption spectra of the samples were studied, to follow the chemical changes d u r i n g oxidation and to suggest possible reaction products. Calibrated odor panels employing the method of paired comparison gave data On the q u a n t i t y of oxygen necessary to produce " t e r p e n e y " odors. D~rECTION oI~ OLYe~OL BY OONDI~NSATIONWITH ANILIN~ TO QUINOLINE. B. Stempel. Z. anal. Chem. ~29, 232-3(1949). As little as 1 rag. of glycerol will give a positive test. (Chem.

Abs. 44, 75.) THE INDEX O~" BE~LIFA~. ITS AFPLICATION TO THE OOI~TROI~0~ ~I)mLE ~ATS. G. E. Brunetti. S. l~ev. Sanidad y asistencia social (Venezuela) ~3, 486-94(1948). The Evers-Bellier method was modified in several ways. The range of values obtained with various oils using this modified method were as follows: p e a n u t oil 39-42.5, olive oil 6-8.5, sunflower oll 19.8-20.7, ses ame seed oil 12-14, and cottonseed oil ]5-17. (Chem. Abs. 44, 349.) SF]~]CTROPI~0ri~0,M~]TKI~ DETE~MlbrATION OF TOTAL NITI~OGE~ IN OILS. C. H. Hale, N. H. Margie, and W. H. J o n e s (Esso Labo ratories). Anal. Chem. 21, 1549-51(1949). A semimicro-Kjel dahl procedure has been devised to use small samples and to allow the determination of very low concentrations of nitrogen. The ammonia is determined by speetrophotometric m e a s u r e m e a t s of the color developed with N e s s l e r ' s reagent. N i t r o g e n compounds can be determined on an average to -4-10% over a concentration r a n g e of 0.002 to 1.0%. The method was developed f o r petroleum products b u t m a y be applicable to glyceride oils. TH~ ESSF_~rTIAL OIL OF Pittospo*um tenuifolium. A. J. Calder and C. L. Carter. J. Soe. Chem. Ind. (London) 68, 355-56 (1949). The oil was f r a c t i o n a t e d and the following constitu ents were isolated and characterized: d-a-pinene 43.2%, d-flpinene 2.2%, myrcene 0.9%, dipentene and d-limonene 0.3%, fl-terpinene 0.4%, a terpene aldehyde 0.3%, /-bornyl acetate 1.4%, u n k n o w n sesquiterpene 8.5%, trieyclie sesquiterpene 11.4%, impure bicyclic sesqniterpene 10.5%, guaiazulene 0.3%, solid paraffins 0.05% and unidentified sesquiterpene alcohols and diterpenes 3.3%. THE ESSERVTIAI, OIL OF Liboeedrus bidwi~lii--~E~v Z~ALAND CE~AIr R. D. B a i t and C. H. tIassell. J. Soe. Chem. Ind. (London) 68, 359(1949). The following fifteen constituents have been separated, l-a-pinene ( 2 4 . 8 % ) ; d-sabinene ( 3 . 3 % ) ; myrcede ( 2 . 7 % ) ; ketone (C~oH~O) ( 3 . 7 % ) ; limonene and dipentene ( 7 . 4 % ) ; p-cymene ( 3 . 4 % ) ; terpinolene ( 0 . 7 % ) ; terpinen-4-ol ( 1 . 2 % ) ; unidentified tricylic sesquiterpene (1.6%) ; unidentified sesquiterpene ( 3 . 7 % ) ; caryophyllene ( 3 . 0 % ) ; 7-curcumene ( 1 8 . 4 % ) ; d-cadinene ( 2 . 7 % ) ; green oil ( 5 . 8 % ) and t a r (including h y d r o c a r b o n ) ( 8 . 2 % ) . ANALYTICAL STANDAR~DMETHODS OF T~STING PATS Ai'ff]) THE~I~ DEI~lVATIVES. G. B. Martinenghi. Olearia 3, 807-810(1949). A critical review of the analytical methods of A.O.C.S. and N . G . D . , p a r t i c u l a r l y in respect to the control of the free acidity of the oil contained in oil-seeds. DETERMINATION OF TH]5 FF~R CENT NFJUTI~AL 0IL Ib; A I~AT. J. Martinez Moreno. Olii minerali, grassi e saponi, colori e verdict 26, 81-82(1949). An equation f o r calculating the a m o u n t of neutral oil present in a f a t based on its constants was developed. SOLUBILITY D I A G P ~ A M USE~D FO!~ THE t~E:MOVAL O,l~ !~RI~ rAX~i~i~ ACIDS I~I~OMI~ISH 0ILS BY EXTRAOTION WITH SOI,VE'NTS. A. RiUs and L. Gutierrez J o d r a . Anales fis. y quire. (Madrid) 45 ( B ) , 245-268(1949). Solubility d i a g r a m s of total f a t t y acids, neutral oil, and solvent were determined f o r coddiver oil and hakeliver oil. The corresponding t e r n a r y d i a g r a m s show t h a t none of the equations proposed in the l i t e r a t u r e - n e i t h e r those for the tie lines, n o r the ones f o r the s a t u r a t i o n i s o t h e r m - - a r e of general validity.

147

STUDIES ON VEO~TA~LE OILS. I I . B~0~[INE ABSOeWT'I0~N BY CAS~Og OIL. J. i~. Velasco and C. Piazza. Anales fis. y quire. (Madrid) 45 ( B ) , 197-206(1949). The speed of addition determined colorimetrically at 10 and 20~ f r o m which an equation covering the reaction can be calculated. E l i O T OIL. I I . B~HAV]Ot~ OF THE OIL ON VACUUM :DIS~ILLATI0~. J. Dominguez and I. Ribas Marques. Anales fis. y quire. (Madrid) 45 ( B ) , 89-110(1949). Vacuum distillation of two e r g o t oils w i t h similar rlcinoleie acid content b u t of a very different hydroxyl value gave neither en~nthole or m~deeilenic acid. F r o m a study of these distillations and those of castor oil and acety]ated castor oil, it is concluded t h a t the acid esterif y i n g the hydroxyl group in ricinoleic acid is removed in the pyrolytic process with f o r m a t i o n of a double bond, thus hindering the pyrolytic f o r m a t i o n of enanthole and undeeilenle acid. ]~I~GOT OIL. I I I . TH~ ~IIGH OPTI~A/~ ACTIVITY OF THE OIL. I. E i b a s Marques and J. Dominguez. Anales fis. y qu~m. (Madrid) 45 ( B ) , 433 440(1949). The optical rotation (a + 10,7) is reduced by saponification. This is due to hydrolysis of the hydroxy ester of ricinoleic acid. OXIDATION

OF

ARI~I~I~

A~ID

-vVITH

I~yPOOHT,OI~I'P~.

I.

PRF~-

ARA.TION 0F .4. DICJHLOI~OABIETICACID. A. Rius and P. Rife. Anales fis. y qulm. (Madrid) 45 ( B ) , 767-784(1949). The reaction between sodium hypochlorite and abietic acid was followed potentiometrically. OXIDATION O1~ ABIETIC ACID WITH HYPOCHLOP~IT~. I I . SAPONIFICATIO~r OF DICHLOICOOIHYDI~OXYABIETIO ACID. A. Rius and P. Rife. Anales fls. y quire. (Madrid) 45 ( B ) , 785-794(1949). An oxide dihydroxide acid (C_.oH~20~) and a tetra-hydroxylated acid isolated fronl the reaction products. THER,MOCHEMISTRY OF THE V~G~TABDI~PATS. I. Ill,AT 0~" BttOMINE ADDITION TO OLIV~ OILS.. J. Oliver Ruiz, Isabel Borrero, and Josefina de ]a Maza. Analcs fis. y quire. (Ma&Hd) 45 ( B ) , 873-892(1949). The thernlal effect of the addition of bromine to different types of olive oil dissolved in carbon tetrachloride was studied. The method was used f o r the m e a s u r e m e n t of the rancidity of the olive oils. STl~ms ON THE W~GETAmm OILS. III. ADSORPTION 0,F HYDRL)GEN BY OLIVE A~YE* ~ASTOI~ OILS. J. R. Yelasco and F. Ramos Ayerbe. Analcs fis. V quire. (Madrid) 45 ( B ) , 207-216(1949). The effect of time and t e m p e r a t u r e on hydrogenation of these ails was studied. HYDaOGENATIOI'r OI~ InAnity OILS. I. FINBAOK WHAL.]~ OII,. R. Miyake. J. Phar.m. Soe. Japan 68, 1-4(1948). I I . SoY~al~~ OIL. Ibid~ 8-10. I I I . S ~ a ) OIL OF Xanthi~em stv~marium. Ibid. 12-13. I V - X I . Svu~Y ov TH~ A(~TIVITI~S O1~'ADKINS~ AND, OTHE~ 0ATALVSTS. Ibid. 14-39. (Chem. Abs. 4d, 352.) THE EFI~E~TS OI~ RADIOAOTIVITYOIq OLEOS3ACID. V. a . B u r t o n (M.!.T., Cambridge, Mass.). J. Am. Chem. Soe. 71, 4117-19 (1949). Purified oleic acid has been b o m b a r d e d with deuterons in a cyclotron. Analysis of the irradiated m a t e r i a l has revealed the f o r m a t i o n of stearie acid, heptadecene, and polymerized acids. I t has been shown t h a t the hydrogen produced by decomposition of an organic molecule under the influence of radioactivity can enter the double bond of a n e i g h b o r i n g molecule. I t has thus been d e m o n s t r a t e d t h a t hydrogen which may be produced by the effects of radioactivity on the organic constituents of a petroleum source sediment could, in p a r t , be removed f r o m the gas phase by reaction with u n s a t u r a t e d components of the sediments. THI~ THERMAL POL~M~IZATION Or ]~0~OLLEa~INIe OO~POU2~rDS. W. F. W h i t m o r e and J. 1~. Gerecht (Polytechnic I n s t . of Brook]yn). J. Am. Chem. Soe. 72, 790-3(1950). A mechanism based on the f o r m a t i o n a n 4 reaction of allylic free radicals has been proposed to explain the t~ermal t r a n s f o r m a t i o n s of simple uns a t u r a t e d compounds. Evidence which s u p p o r t s this allylic radL cal mechanism was obtained f r o m a study of two terminally u n s a t u r a t e d compounds, methyl undecylenate and l-octene. ISOLATION AlXVDST~UC~UI~E OI~ A DII-IYDlCOXYO~TKDE~ADIi~N~)IC~ ACId ~aOM ~ t ~ OIL. S. B. Davis, E. A. Conroy, and N. E. Shakespeare (American C y a n a m i d CO., Stamford, Conn.). J. A.m. Chem. Soc. 72, 124-8(1950). T u n g oil was mixed with an anion-active ion exchange resln and a small f r a c t i o n was recovered by elution of the resin with alkali and extraction of the acidified eluate with carbon tetrachloride. S t o r a g e of this product at 5 ~ resulted in the separation of an oil and a crystalline product. The latter was identified as 9,14-dihydroxy-:10, 12-octadeeadienoic acid: PI~F~PAtCATION- O1~ SALTS 01~ ALIPHATIC AGUDS. E. A. Nikitina and S. N. Makslmova. Zhur. Obshchei Khim, 19, 1108-14(1949). B i s m u t h trioleate, t r l p a h n l t a t e , and trlstearate, and a n t i m o n y monooleate, tripalmitate, tristearate, and trio]eate were prep a r e d by precipitation of the salts f r o m the sodium soaps in alcohol. OSwEoO s o y rLANT. T. G. Luby. Am. Miller and Processor

148

T H E JOUI{NAL OF THE AMERICAN 0 I L C H E M I S T S ' SOCIETY, APRIL, 1 9 5 0

78 (2), 27, 46(1950). A brief description is given of the combined expeller and selve~t extraction (basket type) plant. CHEMIOALS I~RO]Y[FATS. R. L. Kenyon, D. V. Stingley, and H. P. Young. Ind. Eng. Chem, #2, 202-13(1950). The manuf a c t u r e of chemicals f r o m f a t s at the A r m o u r and Co. p l a n t in McCook, Illinois, is described. Refining, hydrogenation, and splitting of f a t s produce high grade f a t t y acids f o r use in the p r e p a r a t i o n of nitriles, amines, amine acetates, amides, and q u a t e r n a r y a m m o n i u m salts. WA~ER-I~rSOLU~E ~ATTu ~(:II)S ~NI) ~ u ~ Y ~ i O A O I D I~r C~AM AND B U ~ . F. Hillig, H. A. Lepper, and W. I. Patterson. J. Assoc. Off. Agr. Chem. 33, 731-45(1949). Progressive decomposition experiments on 321 samples of b u t t e r show that, as cream ages and decomposes, the f a t m a y break down forming water-insoluble acids in a m o u n t s f a r in excess of those normally present in sweet cream as well as f o r m i n g b u t y r i c acid, and sometimes propionic acid. SOME

AI)VAN-Cq~S IN

THE

PRO])UCr~ION

Ol~ E~)IBLI~ OILS

AND

rATS. H. S. Mitchell ( S w i f t and Co.). Food Teeh. 4, 50-4 (1950). A review on the processing methods and the perf o r m a n c e requirenients of shortenings. A~MOUR'S STA~. R.. H. P o t t s and G. W. McBride ( A r m o u r and Co.). Chem. Eng. 57 (2), 124-7, 172-5(1950). A description with flow sheet is given for the new McCook P l a n t of A r m o u r and Co. The f a t t r e a t i n g and splitting unit produces mixed glycerine and f a t t y acids f o r use in the distillation, nitrile p r e p a r a t i o n , hydrogenation, and solvent crystallization units. NEW g s E s EOR r A ~ S A N D o i l s . R. G. Gibbs (C. and E. N e w s ) . Chemurgic Dig. 9 (1), 10(1950). The D e p a r t m e n t of Agricult u r e ' s research p r o g r a m to find new uses or expand old uses of f a t s aud oils is summarized. RICE,

TALLOW

NUTS,

AND

GOLDENROD

YIELD

VALUABLE

PROD-

geTS. L. J. Horn. Chemurgic Dig. 9 ( 2 ) , 8-9(1950). A b r i e f descriptio~ of some of the research at the Texas E n g i n e e r i n g E x p e r i m e n t Station. E x p e r i m e n t s have been made to recover oil f r o m gourd seed, orange seed, pecan waste, rice bran, sweet goldenrod, and the Chinese tallow n u t tree. REvIEw o r ANALYTI'CAL CI{]~MISTRY. Anal. Chem. 22, 2-136 (1950). A series of 26 papers on all phases of f u n d a m e n t a l analysis. " L i g h t A b s o r p t i o n S p e c t r o p h o t o m e t r y , " " I n f r a r e d Spectroscopy,' ' ' ' Ultraviolet A b s o r p t i o n S p e c t r o p h o t o n l e t r y , " ' ' X -Ray Diffraction, ' ' ~' C h r o m a t o g r a p h y , ' ' ' ' Distillation, ' ' ' ~E x t r a c t i o n , ' ' and ' ' Biochemical Analysis ' ' are titles which m a y be of interest. D I F F E R F ~ T I A L AITALYSIS W I T H A I ~ E O K M A N SPEC'I~OPHOTOMETEa. R. Bastian, R. Weberling, and F. Palilla (Sylvania Electrical Prod., Inc., N. Y.). Anal. Chem. 22, 160-6(1950). The differential method of colorimetric analysis as applied to the Beckman Model DU spectrophotometer is discussed. Maximum increases in accuracy over the normal method are computed for the entire working r a n g e of the instrument. THERMOGRAPIdlO INVESTIOATIO~ OP LONG-CHAIN ALIPKATIC COMPOUNbS. A. G. Anikin and G. B. Ravich. Doklady Akad. Nau]~ U.S.S.R. 68, 309-11(1949). Triglycerides or h i g h e r a l l phatic acids are crystallized in a thin layer directly in a microthermocouple, made of 0.05-ram. wire and having a loop instead of the usual junction. The couple with the substance, and a similar blank thermocouple, were placed between 2 slides, in a way ensuring m a x i m u m thermal insulation f r o m surrounding objects. This procedure pernfits simultaneous thermal and microscopic examination of samples of the order of a few tenths of a mg. Trilaurin gave heating curves identical with those obtained by macro methods. (Chem. Abs. 44, 898.) THE THIOBAI~B~TURJC ACID REAGENT AS A TEST Felt THE OXII)ATION O~' UNSATUICATEa) FATTY ACIDS ~Y VARIOUS AGEI~'PS. 1~. M. Wilbur, F. Bernheim, and O. W. Shapiro (Duke Univ.). Arch. Biochem. 24, 305-13(1949). Methyl linolenate a f t e r autoxidation or oxidation catalyzed by ascorbie acid, mereapto compounds, or ultraviolet light yields a compound which reacts with t h i o b a r b i t u r i c acid to produce a characteristic color. At p H 6.0 the intensity of the color is a b o u t 16 times greater a f t e r ultraviolet i r r a d i a t i o n than a f t e r catalysis by ascorbic acid or mercapto compounds, and a m o u n t s of the order of 0.2 rig. of methyl linolenate per ml. can be detected a f t e r ultraviolet irradiation. U n d e r the same conditions linoleic acid produces very much less color and this may be due to the presence of smMt a m o u n t s of linolenic acid. Methyl arachidonate produces no color a f t e r incubation with ascorbic acid or mercapto compounds b u t does a f t e r exposure to ultraviolet light. Oleic and stearic acids are inactive, but a crude mixture of C~0 acids gives a color a f t e r incubation with ascorbic acid. Certain aliphatic aldehydes and s u g a r s react with thiob a r b i t u r i c acid to give colors. The color given b y glyoxylic acid a p p r o x i m a t e s most closely t h a t given by linotenic acid.

STALE FLAVOI~ COMPONENTS IN- OldIES) ~VHG~LE MILK. I I .

THE

E X T R A O T I O N O P STALI~ B'UTTEI% OIL P R O M S T A L ~ D!%IED WI-10.LE M I L K B Y OP~GANIC SOLVENTS. R. M c L . W h i t n e y a n d P. ]:[.

Tracy (University of Illinois). J: Dairy Sci. 33, 50-9(1950). Stale flavor was extracted in approximately the same ratio to the f a t as existed in the original stale dried whole milk and was, therefore, considered to be more t h a n 90 per cent extracted. COMBIN~]) DETI~MINA.TION OP TItle] SAPONIrIC!ATIOiWAND KET0I{~RT-~mSSL VALUES. K. T i u f e l . F e t t e u . Seifen 52, 10-11 (1950). Five g r a m s of f a t are saponified and t i t r a t e d as in regular saponification value determination. The soap is freed of alcohol, dissolved in water, and R-M value is determined by the usual method. ADSORPTION Or LO-W M0~L]~GULAR "WEIGHT }CATTY ACIDS BY AN ACTIVATED C:HARC.OAL. ~SE OI~ CI{ROMATOGKAPHy TO OBTAIN ADSOICPTION ISOTHEI~MS. F. H. M. Nestler and H. G. Cassidy (Yale Univ.). J. Am. Chem. Soc. 72, 681-9(1950). Measurement of the adsorption isotherms of the aliphatic f a t t y acids, acetic, propionic and butyric, f r o m aqueous solution and on a commercial activated charcoal, showed each acid to be preferentially adsorbed t h r o u g h o u t the concentration r a n g e of 0-100% by weight. The Freundlieh isotherm equation was applicable over only a n a r r o w concentration range of approximately 0.0050.5%. The technique of f r o n t a l analysis has been used in order to obtain data relating to the adsorption of b i n a r y mixtures of low molecular weight aliphatic f a t t y acids, with a view to an analytical method. DISPLACEMENT ANALYSIS OP LIPIDS. I I . INC~J%F~ASEOS~pARABILITY el~ FATTY AC'IDS BY DEPKI~SSFs SOLUBILITY. L. H a d g a h ] and R. T. H o l m a n (College Station, T e x a s ) . J. Am. Chem. See. 72, 701-5(1950). A d s o r p t i o n isotherms f o r laurie and myristic acids in 95% alcohol on a series of varied adsorbents are given. The depression of solubility of f a t t y acids in alcohol by admixture with water, or by lowering t e m p e r a t u r e increases adsorption and spreads isotherms. The lowered solubility caused by addition of w a t e r increases separability of f a t t y acids as shown in f r o n t a l and displacement analysis. The use of isotherms to predict the character of displacement d i a g r a m s for f a t t y acids has been verified. The best displacer f o u n d thus f a r for a f a t t y acid is its nearest homolog of lower solubility in a solvent which j u s t dissolves the desired concentration of displacer. DISPLACEMEN-T ANALYSIS O!~ LIPIDS. I I I . SZPAP~ATIoN OF NORMAL SATU~.~a~ ~ATTY ACIDS r ~ M rOR~Ir " ~ s ~ r ~ i ~ . . R. T. H o l m a n and L. H a g d a h l (College Station, Texas). J. Biol. Chem. 132, 421-427(1950). Displacement separation of f a t t y acids has been shown to take place f o r all normal saturated acids f r o m 1 to 20 carbon atoms in length by the p r o p e r choice of solvent for each group of acids with Dareo G-60 as adsorbent. THB

SOLUBILITIES

01~ TI-IE N 0 1 % M A L

SATURATED

I~KTTY A0rl]DS

IN ~VATEIZ. D. N. E g g e n b e r g e r et al. J. OrE. Chem. 14, 1108-10 (1949). The solubilities of octanoic, nonanoic, decanoic, and hendeeanoic acids were determined in w a t e r at 30 ~ 40 ~ 50 ~ and 60~ of dodecanoie acid at 40 ~, 50 ~ and 60 ~, and of tetradeeanoie acid at 50 ~ and 60 ~ RELATIVE EFJ~ECTIVENESS OF TWO SYSTEMS Or SELECTION FOR OIL CONTENT O1~ THE CC'I%NKGRhrEL. G. F. S p r a g u e and B, Brimhall ( I o w a Agricultural Exp. S t a t i o n ) . Agronomy J. 42, 83-8 ( 1 9 5 0 ) . T h e recurrent selection procedure at the end of a 5-year period was 2.6 times more efficient than selection during inbreeding. This efficiency would be expected to increase as the time period is increased. REFINING AND HAP.I)ENING Or VEGETABLE OILS. A. Arneil. Chem. and Ind. 20 (1), 3-10(1950). A review of the current practices in refining, bleaching, deodorizing, and h a r d e n i n g technology with specific reference to methods and equipment used in the United States, Germany, and Britain. CHARAeTBI%ISTICS OP GRI~ASES AS REDATEOD TD ANTIrIr BEARING APPLICATIONS. E. S. Carmichael and R. C. Robinson (Soeony-Vacuum Oil Co.). Mech. Eng. 72, 137-41, 43, 44 (1950). The i m p o r t a n t f a c t o r s affecting resistance of a grease are metal component of soap, f a t t y component of soap, mineral oil, reaction of finished grease, additives, bearing design, and operating conditions. FILM TEST. WATER SATURATION VALUES OF ~VATE~-IN-0IL EMULSIONS. Alfred Russ. Seifen-Ole-Fette-Wachse 75, 254-6 (1949). Spreading of water-in-oil emulsions on glass plates shows whether their w a t e r - s a t u r a t i o n value has been reached or whether more w a t e r can be added without b r e a k i n g the emulsion. (Chem. Abs. ~4, 903.) PATENTS LIQUID INJECTABLE OIL-PZC'TIN-DI~UG COMPOSITION. t{. Welch ( U . S . A . ) . U. S. 2,~91,537. A normally liquid oil is combined

THE

JOURNAL

OF THE AMERICAN

w i t h a t h e r a p e u t i c drug, which is r a p i d l y assimilable, a n d pect i n g i v i n g an essentially a n h y d r o u s m i x t u r e which is used f o r t h e r a p e u t i c injections. STABILIZATION OP ORGANI~ COMPOUNDS. ~. B. Thompson. U. S. 2,492,334-6. A method of stabilizing an organic material s u b j e c t to oxidative d e t e r i o r a t i o n comprises a d d i n g a n i n h i b i t o r c o m p r i s i n g a ketone h a v i n g a s u l f u r a t o m a t t a c h e d to t h e carbon a t o m fl to t h e keto group. POLYOXYETI:IYLENE ~STERS IN ~ltOZEW CON!~OTIONS. A. ]~. Steiner a n d A. Miller (Kelco Co.). U. S. 2,.i93,324. A mixture of a n edible colloid a n d p o l y o x y e t h y l e n e ester of stearic acid is a d d e d as a stabilizer in frozen desserts. METHOD AN]) A P P A K A T U S FOE R]ffNDE~INO PAT~. ]~. K o p p i t a n d C. J. Davis, J r . ( A r m o u r a n d Co.). U. S. 2,493,459. P o r k f a t stocks a r e r e n d e r e d w i t h s t e a m to p r o d u c e a m i x t u r e of lard, floaters, t a n k w a t e r , a n d t a n k a g e . A f t e r settling, t h e v a r i o u s s t r a t a are s e p a r a t e d by draw-off a r r a n g e m e n t s in the cooker-tank. PRODUOTION OF ALKYL ESTERS O1~ EATTY ACIDS. F. ,[. Sprules a n d D. P r i c e (Nopco Chem. Co.). U. S. 2,~94,366. T r a n s esterification is first accomplished w i t h a n alkaline c a t a l y s t , t h e n a n acid c a t a l y s t is a d d e d to release f a t t y acids f r o m soap a n d the trans-esterification is c o n t i n u e d to completion. ~YANOETI:[ER ESTEKS OF DIHYDKI~ ALOOHOLS (PLAS%VICrlZE~RS). L. T. Crews ( A r m o u r & Co.). U. S. 2d95,214. A process f o r t h e esterification of a fl-eyanoether of a low molecular w e i g h t a l i p h a t i c dihydric alcohol w i t h a f a t t y acid. A I:I[YDROGENATED SEMIDI~YINO OIL A N D M~THACRYLATI] RESIN MIXTURE AS A LUBKICANT. ~(. A. N a v i k a s ( A r m s t r o n g Cork Co.). U. S. 2,495,277. A n e x t r u d a b l e cork composition comprises cork particles, a binder capable of b e i n g set b y heat, a m i x t u r e of h y d r o g e n a t e d cottonseed oils, a n d b u t y l m e t h a crylate resin. POLYHYDRIC ALCOHOL ]~STFJ~S Ol~ FATTY AC{IDS. A. C. Bell a n d W. G. Alsop ( C o l g a t e - P a l m o l i v e - P e e t Co.). U. S. 2,496,328. P o l y h y d r i c alcohol a n d f a t t y acids are h e a t e d t o g e t h e r w i t h efficient a g i t a t i o n to f o r m a n i n t i m a t e dispersion at 200 ~. The m i x t u r e a f t e r c o m i n g to e q u i l i b r i u m is cooled below 100 ~ when t h e u n r e a c t e d alcohol s e p a r a t e s f r o m t h e esters. PURIFICATION OF OLdie AOID. C. G. Goebel ( E m e r y Inds., I n c . ) . U. S. 2,482,760. S u b j e c t t h e oleic acid to p o l y m e r i z i n g conditions a n d t h e n distill off p u r e oleie acid f r o m t h e polymerized p o l y u n s a t u r a t e d acids. WATER INSOLUBLE LUBRICATING GI~EASE FO,I~ ANTIF~ICVPI0.N RBARIlXrGS. A. J. Morway. U. S. 2,~91,054. A l u b r i c a t i n g composition consists of a dibasic acid ester, a m e t a l soap of a f a t t y acid, a n d a copolymer of s t y r e n e a n d isobutylene. NOI~Y-SPATTE~, ADHESIV~ LUBI%IOATING GI~EASE. A. Beerbower a n d A. J. Morway. U. S. 2,~91,023. A t a c k y l u b r i c a t i n g g r e a s e c o m p o s i t i o n consists of a dibasic acid ester, a l i t h i u m soap, a n d a C~ to C~ a]kyl m e t h a c r y l a t e polymer, t h e p o l y m e r h a v i n g a m o d e r a t e b u t limited solubility in the ester so as to i m p a r t s u b s t a n t i a l t a c k i n e s s a n d s t r i n g i n e s s properties to the composition. ~V[IXED GLYCFII~OLES{T~%S OP FATTY AND IYYDI~OXYACIDS. L . n . Little. U. S. 2,~80,332. T h i s emulsifier comprises t h e glycerol ester of a s a t u r a t e d f a t t y acid h a v i n g at least one free hydroxyl radical on the glyceryl group, t h e l a t t e r b e i n g esterified w i t h lactic acid, t h e m i x e d ester b e i n g free fronl glyeerine-trilactate. PI%EFARATION OF PARTIAL EST]~I~S. H. D. Allen et al. U. S. 2,478,354. Completely esterified polyhydrie alcohol esters of f a t t y acids are couverted into p a r t i a l esters by h e a t i n g t h e esters in the presence of w a t e r b u t in t h e absence of alkaline m a t e r i a l in a n a m o u n t sufficient to serve as a n efficient c a t a l y s t , while the m i x t u r e is u n d e r sufficient p r e s s u r e to keep w a t e r in t h e s y s t e m , r e d u c i n g t h e p r e s s u r e to remove w a t e r f r o m t h e s y s t e m , a n d cooling t h e reaction product. PI%EFARATIOI~ OF ALIPHATIC NITR1LES. W. D. N i e d e r h a u s e r ( R o h m & H a a s Co.). 17. S. 2,493,637. A m m o n i a a n d oleic acid a r e r e a c t e d in the liquid p h a s e at 250-290 ~ i~ t h e presence of a cobalt soap. D I A L K Y L SILANE DE]%IVATIV]5 OF RIOINOLEIC ACID ESTEfi%. ]{. ]~.

Christ (U. S. I n d u s t r i a l C h e m i c a l s ) . U. S. 2,496,335. A t o m p o u n d c o n s i s t i n g of a diether of ricinoleie acid esters a n d dialkyl silane is u s e f u l as a plasticizer for nitrocellulose. TRIAL:KYL SILANE DE~IVATIV~ O1~ R.ICINOL~IC ACID. K . E. :Earh a r t (U. S. I n d u s t r i a l Chemicals, I n c . ) . U. S. 2,496,340. A c o m p o u n d c o n s i s t i n g of a m o n o e t h e r of ricinoleic acid ester a n d trialkyl silane. ~roo~ r H. F. L e u p o l d a n d M. I . Kelley (Nopeo Chem. Co.). U. S. 2,496,631. A f a t t y acid is h e a t e d with an a l k y l a m i n e to f o r m a c o n d e n s a t i o n p r o d u c t which in combina~ tion w i t h a n o n r e s i n i f y i n g oil f o r m s a stable emulsion in water. T h e emulsion is suitable f o r s e l L f u l ] i n g a n d s c o u r i n g of wool.

O I L C H E M I S T S ' SOCIETY, A P R I L , 1 9 5 0

149

SYN~IS~O AN~OXn)XN~S. L. A. Hall (Griffith L a b s . ) . U. S. 2,493,288. Alkyl esters o f gallic acid c a n be a d d e d to f a t t y m a t e r i a l s in a m o u n t s g r e a t e r t h a n are n o r m a l l y soluble b y dissolving t h e ester in a m o l t e n phospholipid. TREATM~-rNT 0F POLY~N-~ 0OMPOffYlq-D~. A. W . R a l s t o n , O. T u r i n s k y a n d L. V a n A k k e r e n ( A r m o u r a n d Co.). U. S. 2r 498,133. A f a t t y polyene c o m p o u n d c o n t a i n i n g u n c o n j u g a t e d double b o n d s is c o n t a c t e d a t a n elevated t e m p e r a t u r e w i t h a h y d r o g e n r e a c t a b l e iodine c o m p o u n d as a c a t a l y s t , to effect a n increase in r e f r a c t i v e i n d e x of t h e c o m p o u n d , a n d t h e iodine is t h e r e a f t e r removed f r o m t h e polyene c o m p o u n d b y t h e use of lead, copper, or silver compounds. The p r o d u c t h a s improved d r y i n g properties. FE~D )'oRTrr D. Melnick ( A s t r o l P r o d u c t s , I n c . ) . U. ~. 2,496,634. F a t - s o l u b l e v i t a m i n s are i n c o r p o r a t e d into a h i g h - m e l t i n g (58 ~ ) physiologically available edible f a t . A prem i x of t h i s m i x t u r e a n d d e f a t t e d e n z y m e - l n a c t i v a t e d soy flour is used f o r fortification of f e e d s t u f f s .

9 Biology and Nutrition A. R. Baldwin, Abstractor THE ABSOLUTION AND DISPOSITION OF ORALLY ADMINIST~CED Ilal-LABELED I~UTrR,AL FAT IN !~Al~. M. M. S t a n l e y a n d S. J. T h a n n h a u s e r . J. Lab. ~ Clin. Med. 34, 1634-9(1949). Characteristic curves of a b s o r p t i o n a n d u t i l i z a t i o n of physiologic a m o u n t s of lipid t a k e n b y m o u t h b y s u b j e c t s on a m i x e d diet were d e m o n s t r a t e d b y t h e use of u n s a t u r a t e d f a t s iodinated with Ix~x. T h e p r o p o r t i o n of t h e a d m i n i s t e r e d r a d i o a c t i v e I which w a s .collected by t h e t h y r o i d a n d excreted in t h e urine, as well as the m a g n i t u d e o f t h e water-soluble p o r t i o n in the serum, i n d i c a t e d t h e e x t e n t of b r e a k d o w n of t h e labeled f a t . U n d e r t h e s e c i r c u m s t a n c e s in n o r m a l s u b j e c t s , d e g r a d a t i o n of f r o m 50-73% of t h e orally a d m i n i s t e r e d i o d i n a t e d f a t took place w i t h i n 24 hours. S u b j e c t s with " I d i o p a t h i c " hyperlipemia a n d the n e p h r o t i e s y n d r o m e utilized t h e labeled lipid m u c h m o r e slowly. POLY~THEN'OID ~ATTY ACID METABOLISM. IX. Dm'0SIWON OF POLYUNSATI)-RATFD FATTY ACIDS IN- FAT-DEFICIENT RATS UPON SINOLE FAT~mJ{ ACRID SUPFLEMEI%YTATION. C. W i d m e r a n d R. T. H o l m a n (College S t a t i o n , T e x a s ) . Arch. Biochem. 25, 1-12 (1950). S u p p l e m e n t s of 0.05 ml. of E t s t e a r a t e , oleate, Iinoleate, a n d linolenate p e r d a y were f e d to each of 4 g r o u p s of f a t - s t a r v e d r a t s f o r a period of 8 weeks. S p e c t r o p h o t o m e t r i c a n a l y s i s of t h e alkali-isomerized s a m p l e s of f a t t y acids ext r a c t e d f r o m t h e v a r i o u s t i s s u e s w a s made. R a t s f e d a n o r m a l stock r a t i o n showed deposition of p o l y u n s a t u r a t e d f a t t y acids in t h e h e a r t , liver, brain, kidney, blood, a n d skeletal muscle, a r r a n g e d in order of d e c r e a s i n g concentration. Negligible a m o u n t s were f o u n d to be p r e s e n t in adipose tissue. The r a t was s h o w n to s y n t h e s i z e arachidonic acid f r o m linoleic acid b u t n o t f r o m linolenic acid. The r a t was shown to synthesize hexaenoic acid f r o m linolenic acid b u t n o t f r o m linoleic acid. SYNTI=[I~SIS 01~ EN'AlqTIOMERSO a-I~ClTHIikrS. E. B a e r a n d M. K a t e s (Univ. of T o r o n t o ) . J. Am. Chem. Soc. 72, 942-9(1950). B o t h e n u n t i o m e r i c f o r m s of f u l l y s a t u r a t e d a-lecithins of a s s u r e d c o n s t i t u t i o n a l a n d configurational p u r i t y have been synthesized. T h r e e homologous a - l e c i t h i n s of t h e L - s e r i e s , n a m e l y , distearoyl-, dipahnitoyl-, a n d dimyristoyl-leeithin were prepared. X=ray diffraction p a t t e r n s , solubilities, a n d other physical d a t a of t h e p u r e crystalline lecithins are given. The s y n t h e t i c L-a-dlpalmitoyl-lecithin a n d n a t u r a l dipalmitoy]-lecit h i n were f o u n d to be identical. HISTOOHE~ICAL LOOALIZATION OF TRIY]~ LIPASE. G. Gomori (Univ. C h i c a g o ) . ProP. Soc. Exptl. Biol. & Med. 72, 697-700 (1949). W a t e r - s o l u b l e u n s a t u r a t e d f a t t y acid esters are hydrolyzed a l m o s t exclusively by t h e p a n c r e a t i c t y p e of esterase ( t r u e lipase) while similar esters of s a t u r a t e d f a t t y acids are readily a t t a c k e d b y esterases of both t h e h e p a t i c a n d p a n c r e a t i c type. LIPOXYDAS~. Win. F r a n k e . Fette u. Seifen 52, 11-19(1950). A comprehensive review f r o m 110 references. PAR]~NTERAL lq-IYTRITION. X. OBSEI~VATIOi%rS O N THE USE OF A FAN ~ I m S l O N FOlt I~I~VE~OUS ~V~ITION IN ]dAiS. S . W . Gorens et al. J. Lab. # Clin. Med. 34, 1627-33(1949). Observ a t i o n s are reported on t h e i n t r a v e n o u s a d m i n i s t r a t i o n of a 15% f a t emulsion to 11 patiengs r e p r e s e n t i n g a v a r i e t y of comm o n illnesses. The emulsiou was effective as i n d i c a t e d by f a v o r a b l e clinical response, t h e p r e v e n t i o n of w e i g h t loss, a n d t h e m a i n t e n a n c e of positive n i t r o g e n a n d p o t a s s i u m balance. S u b s e q u e n t p o s t m o r t e m e x a m i n a t i o n of 3 of these p a t i e n t s

150

T H E J O U R N A L OF THE A M E R I C A N 0 I L

revealed t h a t t h e f a t emulsions h a d p r o d u c e d no p a t h o l o g i c changes, either gross or microscopic. ~EOYIA1VIS~ O~ I~AT ABS:OI~PTION AS EVII)RNCF~D BY OHYLOMIOKOGI~APttlC S~o-DI]~]S. H. C. Tidwell ( S o u t h w e s t e r n Medical College). J. Biol. Chem. I8Z, 405-14(1950). The a b s o r p t i o n o f n e u t r a l f a t , or t h e f r e e f a t t y acids p r e p a r e d f r o m it gave a similar s y s t e m i c lipemia in r a t s a n d m a n . This does n o t a g r e e w i t h t h e s u g g e s t i o n of different p a t h w a y s f o r these subs t a n c e s a f t e r a b s o r p t i o n . A n e m u l s i f y i n g s y s t e m , f a t t y acids w i t h monoglyeeride, did n o t cause t h e i n c r e a s e d n u m b e r of chylomicrons in t h e blood w h e n i n g e s t e d with either m i n e r a l oil or a diether of glycerol. A n i n c r e a s e d r a t e of f a t absorption followed t h e i n g e s t i o n of f a t w i t h a d d e d lecithin or of m o a o g l y c e r i d e alone. T h e f a c t t h a t choline g i v e n a l o n g with t h e f a t h a d a s i m i l a r effect s u g g e s t s t h a t t h i s ihcreased rate of a b s o r p t i o n c a n n o t be exclusively t h e result of a n increased emulsification of the f a t in the intestine. INTRAVenOUS IN~'USION-S OF CON-O~r~A~'~-.~) COMBIN-F~ FAT EMULSIONS IN-~O HUMAN s t m z ~ c ~ s . B. G. P. Shafiroff, J. H. Mulholland, a n d E. Roth ( N . Y. U n i v . ) . Prec. Soc. Exptl. Biol. # Med. 72, 543-7(1949). Two t y p e s of c o m b i n e d f a t emulsions, one c o n t a i n i n g 1 5 % f a t a n d t h e other 2 0 % f a t , were i n f u s e d into 25 h u m a n s u b j e c t s i n t r a v e n o u s l y . T h e incidence of c o n s t i t u t i o n a l r e a c t i o n s w a s 27%. THE THIOBARBITUIr ACID TEST APPI,IF~ TO TISSUES FROM RATS TiCkleD ~N VARIOUS W&~S, S. K . D o n n a n ( D u k e U n i v . ) . J. Biol. Chem. 182, 415-19(1950). T h e a m o u n t of oxidized linolenie acid, either free or combined, in t h e phopholipide molecule is m e a s u r e d by t h e T B A test. T h e oxidation produ c t is in all p r o b a b i l i t y a peroxide. Ascorbic acid is a n excellent c a t a l y s t for this oxidation. T i s s u e s i n c u b a t e d w i t h a n excess of ascorbic acid give a value b y t h e T B A t e s t which denotes t h e a m o u n t of linolenic acid a n d possibly c e r t a i n C~o acids, oxidizable by ascorbic acid. T h e r e s u l t s o b t a i n e d b y t h e t h i o b a r b i t u r i c acid t e s t parallel t h o s e b y t h e m o r e conv e n t i o n a l methods. ARTERIOSCLEROSIS IN RELATION TO lnAT METABOLISm. A n o n . Nutrition Roy. 8, 6 1 - 2 ( I 9 5 0 ) . A b r i e f review of t h e s u b j e c t i n d i c a t e s t h a t t h e r e is a m a r k e d c h a n g e in f a t m e t a b o l i s m in t h e aged. T h i s results in p r o l o n g e d e h y l o m i c r o n e m i a a f t e r f a t i n g e s t i o n a n d a relationship is s u g g e s t e d b e t w e e n c o n t i n u e d c h y l o m i c r o n e m i a a n d the genesis of arteriosclerosis. THE ROLE O~" LIPIDS AN-D DIPOPROTEIN-S IN A~'kimF~OS(~-%EPA)SIS~ J. W. G e r m a n , F. L i n d g r e n , H. Elliott, W. M a n t z , ft. H e w i t t , B. Strisower, V. H e r r i n g , a n d T. P. L y o n ( U n i v e r s i t y of Calif o r n i a , B e r k e l e y ) . Science 111, 166-71, 1 8 6 ( 1 9 5 0 ) . T h e mecha n i s m of cholesterol t r a n s p o r t in t h e s e r u m of r a b b i t s a n d h u m a n s v i a g i a n t lipid a n d l i p o p r o t e i n molecules of low densi t y h a s been characterized. I n b o t h species t h e r e exist classes of molecules of h i g h e r S( r a t e a n d lower d e n s i t y t h a n the m a j o r g r o u p of cholesterol-bearing lipoproteins. Evidence imp l i c a t i n g t h e cholesterol-bearing molecules of t h e S~ 10-30 class in t h e p r o d u c t i o n of cholesterol-induced atherosc!erosis in the r a b b i t h a s been presented. A s t u d y of 104 p a t i e n t s w i t h proved m y o c a r d i a l i n f a r c t i o n s reveals an a l m o s t u n i v e r s a l occurrence of cholesterol-bearing molecules of t h e S~ 10-20 class ( a class of molecules similar in m a n y respects to t h e Sr 10-30 class in r a b b i t s ) , a t f a i r l y h i g h levels in t h e blood. All categories of n o r m a l h u m a n s s t u d i e d show a lower f r e q u e n c y of occurrence of m e a s u r a b l e c o n c e n t r a t i o n s of S~ 10-20 molecules t h a n do t h e m y o c a r d i a l i n f a r c t i o n p a t i e n t s w i t h c o r o n a r y a r t e r y atherosclerosis. E ~ P ~ O T o~ OI~OLIN-E AS A LIPOTR~PIO AG~N~ IN- THE TREATMENT O~ I-IUMAI~ A~ m. M. Morrison a n d W. F. Gonzales (Los A n g e l e s C o u n t y Gen. H o s p . ) . Prec. Soc. Exptl. Biol and Med. 73, 37-8(1950). Choline was effective in r e d u c i n g t h e m o r t a l i t y r a t e due to r e c u r r e n t c o r o n a r y - t h r o m bosis w i t h m y o c a r d i a l i n f a r c t i o n in 115 p a t i e n t s . STUDIES OR]"]*]TH[ON-IN'E. I I . T I ~ INTL'R~I~NC~ WITH LIPIDE I~im'ABOLIS~. E. F a r b e r , M. V. S i m p s o n , a n d H. T a r v e r (University of California, B e r k e l e y ) . J. Biol. Chem. 182, 91-9 (1950). E t h i o n i n e is c a p a b l e of i n d u c i n g f a t t y livers in f a s t e d f e m a l e r a t s in 12 hours. M e t h i o n i n e is t h e only a m i n o acid capable of c o u n t e r a c t i n g this effect. Choline a n d other known lipotropic a g e n t s h a v e little or no effect. C a r b o h y d r a t e in l a r g e doses p r e v e n t s or cures t h i s t y p e of f a t t y liver. TlCIE EF~]~C~ O~ SOYBF~AN-GI~OWTtI I~I~IBI~OI~ ON- rffHl~AVAILALienr, H. Specter, H. L. Fevold, a n d G. H. B e r r y m a n ( T h e Q. M. F o o d a n d C o n t a i n e r I n s t . ) . Arch. Bioehem. 24, 299~304 (1949). T h e presence of m e t h i o n i n e a t effective levels of 600, 1000, ]500, a n d 2500 rag. % in a low-choline, ] 2 . 5 % p r o t e i n diet c o n t a i n i n g r a w or autoclaved s o y b e a n m e a l caused a p r o g r e s s i v e decrease in liver lipids of w e a n l i n g rats. Differences in p r o t e i n efficiency were n o t parallel to t h e c h a n g e s

C H E M I S T S ' SOCIETY, A F R I L , ] 9 5 0 in liver lipids described above. T h e g r o w t h - p r o m o t i n g value of diets c o n t a i n i n g r a w s o y b e a n meal was consistently less t h a n similar diets c o n t a i n i n g autoclaved s o y b e a n meal. HEXADEOENOIO AOID AS A GROWTH lCACTOIr FOI~ L&(FI~IO ACID BAOTEaIA. J . B. H a s s i n e n , G. T. D u r b i n , a n d F. W. B e r n h a r t ( W y e t h , I n c . ) . Arch. Biochem. 25, 9 1 - 6 ( 1 9 5 0 ) . P a l m i t o l e i c acid (9-hexadecenoic acid) s u p p o r t s good acid p r o d u c t i o n of a m u t a n t s t r a i n of L. bifidu, at lower levels of concentration, a n d i n h i b i t s at h i g h e r levels, in c o n t r a s t to oleic acid which s u p p o r t s acid p r o d u c t i o n at b o t h h i g h a n d low levels o f addition. W i t h L. arabinosus hexadecenoic acid, in a m e d i u m cont a i n i n g no biotin, s t i m u l a t e s acid p r o d u c t i o n in a m a n n e r similar to oleic acid. A s y n e r g i s t i c effect of s a t u r a t e d f a t t y acids a n d oleic acid on t h e g r o w t h of a m u t a n t s t r a i n of L. bifid~s h a s b e e n d e m o n s t r a t e d . W i t h L, arabinosus, the g r o w t h s t i m u l a t i o n caused b y oleic acid is s l i g h t l y inhibited by p a l m i t i c a n d stearic acids. AOETATE AND OLE&TE R.EQUII~EI~]~NTS OF THE' LACTIC GROUP OF STREP'rOC~CCI. E. B. Collins, F. E. Nelson, a n d C. E. P a r m e lee ( I o w a Agr. Exp. S t a . ) . J. Bact. 59, 69-74(1950). A chemically defined m e d i u m m a d e b y a d d i n g s o d i u m a c e t a t e a n d s o r b i t a n moaooleate to the m e d i u m of N i v e n (1944) p e r m i t t e d t h e g r o w t h of all t e s t e d s t r a i n s of t h e lactic group of streptococci t h a t did n o t grow in t h e u n s u p p l e m e n t e d m e d i u m . STEROLS AN]) FATTy ACIDS IN THE NUTKITION O1~ ]ffNT~Z0'IO A~OEBAE i~r C~JL~mES. A. M. Griffin a n d W. G. M e C a r t e n (Gee. W a s h i n g t o n U n i v e r s i t y ) . Prec. Soc. Exp?l. Biol. and Meal. 72, 645-8(1949). Cholesterol in a d e q u a t e a m o u n t s can be s u b s t i t u t e d f o r s e r u m in liver i n f u s i o n m e d i a for culture of entozoic amoebae. Oleic acid in o p t i m u m c o n c e n t r a t i o n s reinforces t h e a c t i o n of cholesterol. THE >ION" OF STRE~PTOMYCIN. IV. FATTY ACID OXlDATI01V BY Myeobactevium ~uberculosis, AVIAN-'TYPE. E. L. Oginsky, P. H. Smith, a n d M. Solotorovsky (Merck I n s t i t u t e for Therapeutic R e s e a r c h ) . J. Bact. 59, 29-44(1950). A s t u d y of f a t t y acid o x i d a t i o n by Micobacterium tuberculosis, a v i a n type, s t r a i n K i r e h b e r g , showed t h a t t h e o x i d a t i o n of t h e h i g h e r f a t t y acids was p a r t i a l l y i n h i b i t e d b y s t r e p t o m y c i n . S t r e p t o m y c i n a p p a r ently i n h i b i t e d t h e o x i d a t i o n of the b r e a k d o w n p r o d u c t s of t h e f a t t y acids r a t h e r t h a n t h e o x i d a t i o n of t h e c h a i n itself. The r e s i s t a n t s t r a i n derived f r o m t h i s o r g a n i s m also oxidized t h e f a t t y acids, b u t w i t h o u t c o m p a r a b l e s t r e p t o m y c i n inhibition. S i m i l a r i n h i b i t i o n b y this antibiotic of s t e a r a t e oxidation by Escherichia cell was also observed. S t r e p t o m y c i n - r e s i s t a n t E. cell h a d lost the m a j o r p o r t i o n of t h e oxidative m e c h a n i s m f o r h i g h e r f a t t y acids. TRE OXIDATION O~ fl-CAROTE~. N. L. Wendler, C. Rosenblum, a n d M. T i s h l e r (Merck & Co.). J. Am. Chem. See. 72, 234-9(1950). The o x i d a t i o n of fl-carotene w i t h h y d r o g e n peroxide-osmium tetroxide h a s yielded v i t a m i n A aldehyde, fli o n y l i d e n e a e e t a l d e h y d e a n d 2,7-dimethyloctatriendial. V i t a m i n A aldehyde w a s f o u n d to posses a biological a c t i v i t y approachi n g t h a t of v i t a m i n A. I t h a s been converted to v i t a m i n A by reduction with l i t h i u m a l u m i n u m hydride. ELEOTKOPHORETIC ANALYSIS OF PEANUT AND COTTON'SEE[DMF~AL PRO~'m~S. M. L. A a r o n , M. E. A d a m s , a n d A. M. A l t s c h u l (South. Reg. Res. L a b s . U . S . D . A . ) . J. Phys. and Colloid Chem. 54, 56-66(1950). P e a n u t p r o t e i n h a s been f o u n d to consist of two m a j o r a n d several m i n o r components. Cottonseed meal protein h a s two m a j o r a n d two m i n o r c o m p o n e n t s . ~URTH]ha STUDINS ON THE IV~ETABOLISM IN- VITRO el ~ I~AD~0,ACTIVE TRILAU~Ibr AN]) SODIUM OUTAI~O&TE. R. P. Geyer, L. W. Mathews, a n d F. J. S t a t e ( H a r v a r d U n i v . ) . J. Biol. Chem. 182, 101-8(1950). T h e a m o u n t of r a d i o a c t i v e carbon dioxide derived f r o m carboxyl-labeled lipids i n c u b a t e d with t i s s u e slices was i n c r e a s e d b y t h e a d d i t i o n of f u m a r a t e , ma]eate, oxalacerate, p y r u v a t e , a n d a - k e t o g l u t a r a t e . M a l o n a t e decreased t h e activity of t h e respired c a r b o n dioxide in such a w a y t h a t t h e concurrent a d d i t i o n of a n y of t h e above c o m p o u n d s h a d little effect on t h e m a l o n a t e inhibition. THE INPLUENCE O1~ SOME QUINONE I~E~IVATIV]~S 0'N- TH:~ LIPID F0]~MATION IN- YEASt. O. H o f f m a n - O s t e n h o f a n d E. Ariz. Arch. Bioehem. 24, 459-61(1949). Some qulnones caused i n h i b i t i o n of f a t f o r m a t i o n in y e a s t while in other cases t h e r e was either no effect or a n a c t i v a t i o n took place. W i t h c e r t a i n concentrations of all quinones, t h e r e w a s a r e m a r k a b l e increase of the sterol p o r t i o n in t h e total lipids. STUDIES ON- STEKOID ]t~]hTABOLIS.I~i. ~V~II. ID~ENTIFIOATIO.N-AN]) CHAI%AOTERIZATION Ot~ ADDITIONAL KF~TOSTEI~OIDS ISOLATED I~I~OM U~INE OP H~ALTI{Y AN]) DISF~&S~F~DPEltSO'NS. S. L i e b e r m a n , D. K. Fukushima and K. Dobriner (Sloan-Kettcring Institute for Cancer Res.). J. Biol. C'hem. i82, 299-315 (1950). Seven steroids h a v e beeu isolated f r o m h u m a n u r i n e for t h e first t i m e a n d f o u r u r i n a r y steroids which were p a r t l y c h a r a c t e r i z e d previously have been identified.

T H E JOURNAL OF T H E

AMERICAN 0 I L CHEMISTS' SOCIETY, APRIL, 1 9 5 0

STUDIES IN STEROID XIETABOLISIM. VIII. DEa~gOTION A N D L O O A T I O N O[~ ETI~I-YLENIC D O U B L E B O N D S IN STEROIDS B Y INIWKA-

I%EID SPEOTKOMEtTI%Y. ]{. N. Jones, P. Humphries, E. Packard, and K. Dobriner (Sloan-Kettering I n s t i t u t e for Cancer Research, N. Y.). J. Am. Chem. Soc. 72, 86-91(1950). The infrared absorption spectra of u n s a t u r a t e d steroids have been examined. A comparative study of steroids containing ethylenic linkage at different positions has shown t h a t the frequency of the m a x i m u m in the region of the C = G stretching vibration (1580-1680 cm. -~) is specific for a given location of the bond in the steroid molecule. I n conjugated dienes, a, f l - u n s a t u r a t e d ketones and the estrogens these bands are in~ense. In steroids containing non-conjugated ethylenic double bonds the bands, although weak, can generally be observed. S~3])IES I~ S ~ O I D M~ABOLIS2~. IX. FUI%THE~% OBSE~W~TlOl~rS ON THE IN~AiCE~ ABSOI~PTION SPE(~TRA OF KETOSTn2KOIDS

ANn ST~OID E S ~ S . R. N. Jones, P. ttumphries, and K. Dobriner (S]oan-IKettering Inst. for Cancer Res.). J. Am. Chem. Soc. 72, 956-61(1956). Measurements of the position of the carbonyl stretching vibration in the i n f r a r e d spectra of carbon disulfide solutions of an additional 180 steroids are reported.

9 Wclxes E. H. McMullen, Abstractor LATEST CAt~N~UBA WAX S~m)Y. Charles J. Marsel (New York Univ.). Chem. Ind. 66, 2 1 6 - 1 8 ( 1 9 4 9 ) . Physical constants, including dirt and moisture Content, flash point, melti n g point, acid number, saponification number, iodine number, and emulsifiability, were determined on 56 samples (4 types) of carnauba wax. No con'elation between emulsifiability and any of the physical constants could be found. A n improved me,hod for acid number determination was developed using a mixture of isopropyl alcohol, n-amyl alcohol, and toluene as the solvent and a phenolphthalein indicator with methylene blue as a m a s k i n g agent to give a sharp end-point. POLYESTERAMIDES

]N P A I N T M E D I A FO1% APPLICATION' TO* N A T U -

I~AL I~UBBEg. H. G. White. J. Oil ,~ Co'our Chemists' Assoc. 32, 461-71(1949). A hard wax is obtained by h e a t i n g together adipic acid, ethylene glycol, and monoethanolamine until a molecular weight of 5,000-10,000 is reached. This product can be treated with a more reactive monomer containing two reactive groups to form a polymer with molecular weight in the 100,000-500,000 region. This product shows rubber-like properties and is useful in the preparation of varnishes and lacquers for rubber goods. A METHO]) O~' I%]~SOLVING OIL-PII~LO-WAST15']~MULSIONS.. ~. W. H o m e and J. Wade Watkins. Bur. of Mines pamphlet, 47 pp., 23 figs. Supt. of Documents. Describes study undertaken to recover microcrystalline (high-melting-polnt) waxes (from pitwaste emulsions). Method of resolving such emulsions and thereby recovering the oil and wax was developed and perfected in a field pilot plant. Discusses laboratory tests and analyses t h a t differ from s t a n d a r d methods. (Bur. of Mines, List 417, Jan., 1950.) NEVVV 2dEq%IOn O1~ I>~t/vE~MINING SAPONIFICAT'IO'lq NUMBEI~, PARTICULAaLY O1~ WAXES. Werner Zolhler. Farben, Lacke, Anstriehsto~% 19~9, 385-90. The new ( " H e z e l " ) method of determining the saponification number consists in heating to 130 ~ for two hours 3-5 g. of wax or f a t with 40-50 ml. of approximately 0.5 2( potassium hydroxide solution in ethylene glycol in a covered flask placed inside an oven; a little xylene can be added to make the mixture fully soluble. A f t e r saponification, the mixture is t r a n s f e r r e d into a beaker, washed with ethylene glycol, and titrated with 0.5 N hydrochloric acid, first to thymolphthalein, then at a boil with bromophenol blue (blue-yellow); the l a t t e r amount is equal to the saponified f a t t y acids. Saponification numbers by the I n t e r n a t i o n a l Commission method (6 hrs.) and by the Hezel ulethod follow: Beeswax, bleached, 84.7, 92.2; carnauba wax, 73.7, 81.6. The Hezel method requires no blank, no reflux or water bath, only two hours of heating, and only one quantitative solution. (Chem. Abs. 44, 1724.) PATENTS WAX DISPlgl~SIONS. G. B. ttoltzclan and J. E. Clemens ( S t a n d a r d Oil Development Co.). U. S. 2,311,338. A method for producing a highly dispersed colloidal solution of a crystalline high-molecular weight ester wax is described. TWO-STAGE PI~OC~SS I~OR THE SYNTHESIS O]~ HYDROaAIgBONS. Clinton H. Holder ( S t a n d a r d Oil Development Co.). U. S. 2,~33,771. Liquid hydrocarbons are produced by means of bring-

151

ing the synthesis gas mixture of carbon monoxide and hydrogen into contact with a dense bed of fluidized alkali metal salt promoted iron synthesis catalyst. The product stream containing partially spent very fine catalyst particles is scrubbed with a high-boiling hydrocarbon oil. The catalyst particle slurry thus formed is introduced into a second reaction zone where a synthesis gas containing 3 to 7 parts of hydrogen to 1 part carbon monoxide is brought into contact with the slurry at a pressure between 306 and 750 lb./sq, in. at a temperature of 350-500~ to produce a product containing a s u b s t a n t i a l amount of high-melting wax. (Chem. Abs. 44, 1673.) SOLVENT

EXTRA~TIOIN- OF

OILS, FATS, ~V2~X]gS, CUrtIS, I%ESINS,

~TC. Charles R. i i n c a i d e . U. S. 2,~91,115. The a p p a r a t u s is designed to extract a wide variety of oils, fats, waxes, gums, and resins from their solids. Discoloration and decomposition are reduced to a m i n i m u m by employing a short solvent contact with the solid, clarification of the raffinate by filtration and chenfical treatment, and by flash evaporation at atmospheric pressure of the clarified rafflnate. (Chem. Abs. 44,

17273

FLAME-R~SISTANT IvII~ISHES. (The British Thomson-Houston Co., Ltd.) B. P. 593,414. Wax-like materials t h a t are suitable for coating a n d / o r i m p r e g n a t i n g materials such as asbestos, cotton and glass fibers, and lead wire are obtained by the reaction between a chlorinated aromatic acid or acid chloride and an aliphatic diamine containing from 2-6 carbon atoms. A f t e r application, the finishes arc heated to about 170~ giving smooth dry fihns t h a t are flexible and abrasion-resistant, and are claimed to have a high degree of flame resistance. (Paint Technology 15, No. 169, 31-32, 1950.)

9

Drying Oils Robert E. Beol, Abstractor

SA~LOWE~ OIL. L. M . Christensen (Western Solvents, Inc., Longmont, Colo.). Am. Paint J. 34, No. 20, 54, 56, 58, 60, 62, 63(1950). The composition and properties of the oll are reviewed. At 585~ the oil bleached f r o m 10 to 2 (Gardner) in a few minutes and on continued heating it bodied at about 75% the rate of linseed oil b u t developed less acidity t h a n the latter. THE OIL 0F TI-IE COTIA C'HESNUT. II. EXTI%AC'I~ION, PHYSIOAL AND OHEMIOAL CHAI%AC~TFA%ISTIC~S. M. da C. P. B. Cavalcanti. Rev. qulm. ind. (Rio de Janeiro) 16, No. 180, 16-8(1947). The oil proved equal to olticica and t u n g oils in drying tests and had the following characteristics: color (Lovibond) 3 yellow, 0:8 red, absolute viscosity 1.4 poise at 25 ~ acidity 1.63% as oleie, ester nmnber 184.2, aeetyl number 139.9. (Chem. Abs. 43, 8700.) SYNTHESIS 01~ LINOLEI(~ ACID. R. A. Raphael and F. Sondheimer ( h n p e r i a l College of Science and Technol., London). Nature 165, No. 4189, 235(1950). The acid has been synthesized by partial hydrogenation of 9,1Loetadecadiyneoie acid. The latter was obtained by condensing oetyne-2-oI-1 methane snlfonate with the Grlgnard complex of ~-chlorooctyned, replacing chlorine in the product with iodine, and condensing the iodo-derivative with sodlomalonic ester. The synthetic linoleic acid gave a tetrabromlde, m.p. 112-113 ~ and could be hydrogenated to stearic acid. THE 0ONSTITUrglON A N D PROpI~i%TIES OF A CONhUGATE~ DIF/NE AOID PaESENT IN STILLIN'GIA OIL. A Orossley and T. P. Hilditeh (Univ. o f Liverpool). J. Chem. Soc. 1949, 3353-7. About 5% of n-deca-2:4-dienole acid was recovered from carefully saponifled sti]lingia oil. The acid was characterized t h r o u g h its methyl ester by ultimate analysis, saponification equivalent (171.8), melting point of the hydrogenated product and its derivatives, a , d melting point of the p e r m a n g a n a t e oxidation product. The absorption spectrum of the pure acid bad a peak at 260 mtL. Half-hydrogenation of the methyl ester with Baney nickel at 110 ~ produced about 15% unchanged ester, 15% completely hydrogenated ester, 40% methyl dec-3-enoate, and 30% of the isomeric A'-'- and ~-monoethylenic esters. REACTIONS O1~ UNSATURA'I'E~ DIBASI(? ACIDS. WITH" LINSE:ED O~L. C. Cosgrove and K. E a r h a r t . Ind. Eng. Chem. 4t, 1492-6 (1949). Maleic anhydride adducts with cyclopentadiene and substituted cyelopentadiene react with linseed oil and glycerol at 260 ~ in a m a n n e r similar to maleic and fumarie acids alone, to f o r m alkyds. Maleic anhydride adduets with butadiene, :isoprene, 2-methylbutadiene, and piperylene do not react w i t h linseed oil under shnilar conditions. The d a t a indicate that the drying oil double bonds do not conjugate before the addition of an u n s a t u r a t e d acid. (Chem. Abs. 43, 8700.)

152

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, A P R I L , 1 9 5 0

DRYING C A T A L y s T s ~ I ~ L I N S E E D OIL. D. P a g a n i . Congr. teeh. intern, ind. peintures inds. assoc. 1, 369-74(1947). T h e

d r y i n g action of the m a n g a n e s e s a l t s of t h e f a t acids of oiticiea oil, chinawood oil, perilla oil, a n d g r a p e s e e d oil on linseed oil fell in t h e order g i v e n ( 0 . 6 % m a n g a n e s e o p t i m u m ) . T h e dryi n g time f o r linseed oil with lead a b i e t a t e s a n d r e s i n a t e s a r e given. Of 18 linoleate driers tested t h e calcium s a l t w a s t h e best a n d gave t h e lowest w a t e r v a p o r p e r m e a b i l i t y f o r linseed oil films. (Chem. Abs. 43, 8699.) T H E CATALYTIC E~ECT Old V I N O L E A T E S O ~ THE DI~YING OF LINSEEO OIL. D. P a g a n i . Congr. tech. intern, ind. peintures inds. assoc, i, 364-8(1947). L e a d vindicate (lead salt of grape. seed oil f a t acids) c o m p a r e d f a v o r a b l y w i t h lead resinate as a drier f o r linseed oil. T h e o p t i m u m drier c o n c e n t r a t i o n a n d d r y i n g time for other metallic vinoleates are given. (Chem. Abs. 43, 8699.) T H E ACTION O1~ MODERN DRYERS O17 T O B A C C O AN]) SUNFLOWER SEre) OILS. C. Castorina. Olearia 3, 801-806(1949). T h e dryi n g qualities of tobacco-seed, sunflower-seed a n d linseed oils w h e n h e a t e d w i t h equal a m o u n t s of " s o l i g e n " or t h e m o r e m o d e r n c, h e x o g e n " d r y e r s were c o m p a r e d a n d t h e l a t t e r f o u n d to be p r e f e r a b l e . I f a n oil w h i c h h a s been h e a t e d w i t h lead a n d cobalt is m i x e d w i t h a like q u a n t i t y of oH which h a s been h e a t e d w i t h lead a n d m a n g a n e s e , d r y i n g is m o r e r a p i d t h a n would be t h e case with t h e s a m e oil which w a s h e a t e d with all t h r e e driers at once. ALtVI VAICNISH. 5. D. yon Mikusch. Farben, Lavke, Austrichstoffe 3, 232-3(1949). A n e w a i r - d r y i n g exterior e n a m e l b a s e d on a 3 : 1 : 1 r a t i o of linseed, chinawood, a n d oiticica oils p l u s a n " o i l - s a v i n g " s y n t h e t i c resin, is described. (Chem. Abs. 43, 8701.) LAC-LINS]~m) OIL VAKNISHES. II1. LAO-LINSE~I) OIL-LIME. Y. S a n k a r a n a r a y a n a n . J. Sci. Ind. Research (India) 8B, 87-8 (1949). L a e c a n be i n c o r p o r a t e d in linseed oil into which calcium h y d r o x i d e ( 5 % ) , calcium linoleate or s t e a r a t e , zinc s t e a r a t e , or p o t a s s i u m linoleate h a v e been added. P a r t i a l r e p l a c e m e n t of calcium h y d r o x i d e b y P b O i m p r o v e s t h e dryi n g characteristics. (Chem. Abs. 43, 8701.) T ~ E LnqOXYlq GEL lit LINOLEUM MANIY~AO~W/I~. M. R. ~ l l s . P a i n t Teehnol. 14, No. 167, 487 93 a n d No. 168, 535-41(1949). T h e gel is p r o d u c e d b y r e p e a t e d l y flooding sheets of eotton s u s p e n d e d vertically, w i t h boiled linseed oil c o n t a i n i n g lead drier ( I ) , by blowing t h e oil w i t h air or o x y g e n in a j a c k e t e d d r u m equipped with beaters, a t a b o u t 60 ~ u n t i l t h i c k a n d t h e n h e a t i n g in open t r a y s at 40 ~ u n t i l solid ( I I ) , or b y b l o w i n g t h e oil at 250 ~ f o r several h o u r s u n t i l thick, in a n open kettle, h e a t i n g i n small kettles at 290 ~ until gelled, a n d t h e n d u m p i n g in cooling t r o u g h s ( I I I ) . I requires several m o n t h s , I I requires several days, a n d I I I requires a b o u t one day. The l i n o x y n gel is fluxed w i t h m o l t e n rosin a n d a f t e r t h e a d d i t i o n of powdered resins it is h e a t e d at 140~ ~ u n t i l it a g a i n gels. T h i s gel is m a s t i c a t e d a n d m i x e d w i t h p i g m e n t s a n d fillers a n d t h e n calendered or p r e s s e d into a suitable b a c k i n g a n d h e a t e d at a b o u t 55 ~ u n t i l h a r d . I I is m o s t widely used because it is f a s t e r t h a n I a n d gives a more s a t i s f a c t o r y p r o d u c t t h a n I I I . M e c h a n i c a l o x i d a t i o n ( I I ) produces a f r a c t i o n ( 6 0 % ) insoluble in hexane, believed to be a n i n t e r m o l e c u l a r p o l y m e r considerably larger t h a n dimers. F i n a l h e a t i n g to g e l a t i o n gives a n ether-insoluble f r a c t i o n p r o b a b l y f o r m e d f r o m t h e hexane-insoluble f r a c t i o n a n d r e s u l t s in a mlcellar structure. F l u x i n g w i t h rosin proba b l y c h a n g e s t h e gel s t r u c t u r e into long c h a i n p o l y m e r s which cross-link d u r i n g the final h a r d e n i n g of t h e linoleum. PATENTS PAIN~

C O M P O S I T I O N S I~ILOM 0 A T A L Y T I C A L L Y

CONJUGATEJI) OILS.

A. J. Lewis a n d J. C. Cowan. U. S. 2,49~i,565. A p a i n t mixt u r e consists essentially of basic c a r b o n a t e white lead pigm e n t ; soy b e a n oil t h a t h a s been c o n j u g a t e d b y t r e a t m e n t in t h e presence of nickel-carbon c a t a l y s t , p a i n t drier, a n d calcium oxide. P R o c e s s o r MODIFYING ~'ATTY OILS. S. B. Radlove ( M a y t a g Co.), U. S. 2,497,689. A n oll h a v i n g at l e a s t 2 0 % o f f a t acids w i t h 3 n o n - c o n j u g a t e d double bonds is selectively h y d r o g e n a t e d to s a t u r a t e all b u t two of t h e double b o n d s in t h e acid. A t least 50% of t h e two r e m a i n i n g double b o n d s a n d those origin a l l y p r e s e n t are isomerized in the presence of t h e h y d r o g e n a tion c a t a l y s t to produce a n oil of i m p r o v e d c o a t i n g properties. DI~YINO OILS. P. K a s s a n d J. Nichols ( I n t e r c h e m i c a l Corp.). U. S. 2,497,890. The d r y i n g p r o p e r t i e s of m i x t u r e s of t u n g oil w i t h other d r y i n g oils a r e i m p r o v e d b y reflu~:ing t h e m i • with acetic a n h y d r i d e a t ]60-180 ~ a n d r e m o v i n g t h e anhydride. Mom~'IE~) ~)~ING OILS. J. Nichols ( I n t e r c h e m i e a l Corp.). U. S. 2,497,904. T h e d r y i n g qualities of t u n g oil are i m p r o v e d by r e f l u x i n g t h e oil w i t h acetic a n h y d r i d e at 160-180 ~ a n d removing the anhydride.

P R O O E S S OFf MAKIb[G A POLyESTEr. ]). W . Y o u n g a n d J. P. Rocea ( S t a n d a r d Oil D e v e l o p m e n t Co.). U. S. 2,4.97,968. Subs t a n t i a l l y p u r e m e t h y l dilinoleate is r e a c t e d w i t h deeamethylene glycol in t h e presence of a b o u t 1.0% of Zn dilinoleate h a v i n g a molecular weight of a b o u t 1000, a t 180-220 ~ f o r a sufficient reaction t i m e to produce a h i g h molecular w e i g h t polyester.

9 Detergents kenore THE

Petchoft, Abstractor

ACTIVITY OOE~PI~ICal~T OF SURI~A6~-AOTIVE MATEI~IALS IN

AQUEOUS SOLUTIONS. fy~. M. Scholberg. J. Phys. ~ Coffoid Chem. 54, 107-114(1950). T h e e x p e r i m e n t s are a n a t t e m p t to show t h a t s u r f a c e t e n s i o n m e a s u r e m e n t s c a n be u s e d to d e t e r m i n e the activity coefficients of s u r f a c e - a c t i v e materials. The m e t h o d allows a considerable increase in accuracy, for it is in the very dilute r e g i o n s t h a t s u r f a c e t e n s i o n m e a s u r e m e n t s show t h e g r e a t e s t c h a n g e s . S u r f a c e p r e s s u r e m e a s u r e m e n t s provide a good m e t h o d f o r the d e t e r m i n a t i o n of the critical point c o r r e s p o n d i n g to t h e b e g i n n i n g of micelle f o r m a tion. T h e c h a n g e in t h e a b s o r p t i o n s p e e t r u m of a c y a n i n e dye also gives good results. SURfACE-ACtiVE AGENTS. B. J. G a r c e a u (Arnold, H o f f m a n & Co., Inc., Providence, R. L ) . Am. Dyestuff Reptr. 39, 87-90 (1950). A g e n e r a l review article g i v i n g f u n d a m e n t a l s of detergency a n d d e s c r i b i n g anionic, cationic, a n d non-ionic surface-actlve a g e n t s . ANALYSIS

0F W A S H I N G

AND

6*I, EANS~NG

AQE~TS.

I. GR~VI-

METRIC DETEi~MllqATION OF SILICIO AOID. R i c h a r d Neu. Seifendle-Fctte-Waehse 75, 215-16(1949). The m e t h o d of conversion to silica with a m i x t u r e of 3 p a r t s of a m m o n i u m chloride a n d I p a r t a m m o n i u m s u l f a t e followed b y e v a p o r a t i o n with hydrofluoric acid gives good r e s u l t s with w a s h i n g powders c o n t a i n i n g silicates as fillers, a n d c a n also be applied to liquids c o n t a i n i n g soluble silicates. I I . DETERMINATION" O~ (~AI~ONIC ACID BY VOLUME DISPLACEMENT. Ibid. 473-4. The m e t h o d a n d a p p a r a t u s of R a u s c h e r (Pharm. Zentva~haffc 88, 362(]1947) f o r t h e d e t e r m i n a t i o n of c a r b o n dioxide in b a k i n g powders gives s a t i s f a c t o r y r e s u l t s with w a s h i n g powders. (Chem. Abs. 44, 1725.) MEASURING DETFfg~ENT POWER. K . T o m l i n s o n . Mfg. Chemist 20, 477-80(1949). Laboratory m e t h o d s f o r d e t e r m i n i n g w e t t i n g p o w e r - - s u r f a c e tension, loosening p o w e r - - - i n t e r r a c i a l tension, e m u l s i f y i n g a n d s u s p e n d i n g power, a n d l a t h e r are described. However, it is e m p h a s i z e d t h a t the only real test of a d e t e r g e n t is u n d e r full-scale w a s h i n g tests. L I M I T I N G OONC'ENTKATION OP ELEOTI%OLYTES IN C O N C E N T R A T E D (SOAP) SOLUTION. K . Loffi. Seifen-61e-Fe~e-Wachse 75, 471-2 (1949). The m a x i m u m allowable c o n c e n t r a t i o n s of electrolytes f o r solutions of v a r i o u s t y p e s of soap, w i t h o u t occurrence of layer s e p a r a t i o n are discussed. (Chem. Abs. 44, 1269.) CLAI%IPIGATION 0P TH~ ~/O1%K Olq SOAP FOAMS IN AQUEOUS SOLUTIONS. E. Otero Aenlle a n d S. Garela F e r n a n d e z . A n a l e s fls. y quire. ( M a d r i d ) 4 5 ( B ) , 217-224(1949). S t u d i e d t h e s e p a r a t i o n a n d c o n c e n t r a t i o n of f a t t y acids b y t h e t e c h n i q u e of f o a m i n g , f r o m a n a q u e o u s solution of t h e i r alkaline salts. M~CI=[ANrS[M Olg FOI%MATIOI% r OF ~MULSIONSo 1~. J. D v o r e t s k a y a . KolYoid, Zhur. 11, 311-13 (1949). W h e n air w a s b u b b l e d t h r o u g h a m i x t u r e of 1 volume of w a t e r in 1 vohlme oil (kerosene) t h e emulsion f o r m e d w a s of t h e oil-in-water t y p e if t h e vessel was of glass well wetted with water, a n d of t h e water-in-oil t y p e if t h e vessel was of a plastic n o n w e t t e d b y water. E m u l sifiers such as oleic acid, calcium oleate, a n d calcium n a p h t h e n ate were u s e d at 0.01-0.03 N concentrations. T H E I~OKMATION A N D SUP~AO~ A0[PIVITY OF A MIX~iI~ MIC'E~uLE. L o u i s Desalbres. Bull. soe. chim. France 1949, 591-3. There is a n a c c e n t u a t i o n of t h e m i n i m u m in s u r f a c e t e n s i o n as a f u n c t i o n of c o n c e n t r a t i o n of f a t t y acid salt in a q u e o u s solution w h e n a polar s u b s t a n c e is present. The p H of t h e solution is also i m p o r t a n t in a c c e n t u a t i n g t h e m i n i m u m . A d i s t i n c t m i n i m u m is observed w i t h 0.00066 M s o d i m n oleate a n d w i t h 0.0024 M s o d i u m l a u r a t e wben a-terpineol is a d d e d w i t h t h e soaps to w a t e r a d j u s t e d to p H 9. The a c c e n t u a t i o n is caused by t h e f o r m a t i o n in basic solution of a m i x e d micelle cont a i n i n g t h e alcohol a n d soap which is very stable a n d less s u r f a c e - a c t i v e t h a n a p u r e soap micelle. A m a x i m u m in surface t e n s i o n is observed when t h e soap is a d d e d to a satur a t e d solution of a-terpineol in water. T h i s is because of a c h a n g e in t h e s u r f a c e c o m p o s i t i o n caused b y t h e s a l t i n g out of t h e alcohol by t h e soap. W h e n t h e m e d i u m is u m d e alkaline, this m a x i m u m d i s a p p e a r s . (Chem. Abs. 44, 906.)