O i l Chemists' Meeting HARRY W. STENERSON, Assist Editor WARTIME supply problems and the use of substitute materials have greatly complicated the work of fat and oil technologists, and more than 400 attended the 18th fail meeting of the American Oil Chemists' Society staged last month in the Hotel La Salle, Chicago, t o hear and discuss the new problems which are disturbing the industry. Papers were read on new analytical methods, problems in soap and glycerin processing, antioxidants, and general fat and oil technology. T h e four-day meeting was called to order b y Klare S. Markley, chief of the Oil, Fat, and Protein Division, Southern Regional Research Laboratory, U. S. Department of Agriculture. Synergy has been part of t h e chemist's nomenclature for a long time, b u t it is only recently that he has been making industrial use of this phenomenon. I t is defined as the "opposite of antagonism". It is noted when a chemical substance is introduced into a compound or mixture and when this is followed by a marked increase in activity of the whole, although the components separately may be partly or wholly inefficient in effectiveness. As expressed more simply by P a t Macaluso in Industrial and Engineering Chemistry (Vol. 36, No. 11), synergy is that force by which "two and two make five". A paper read by H. A. Mattill, University of Iowa, showed that synergists have a marked effect in the antioxygenic action on fatty acids. With few exceptions, substances which exert such action, notably oxalic acid, are diphenolic a n d polyphen o l s compounds possessing similar electronic configuration. They are antioxygenic, it was said, because they can release hydrogen or electrons o r both, and thereby prevent the formation and accumulation of peroxides. T h e release of hydrogen is a two-step process; the first
reversible, the second irreversible, resulting in the formation of quinones. All other substances which have antioxygenic action in fats may properly be called "synergists", the paper stated, because they merely reinforce the effect of the phenolic compounds and have little or no activity apart from them. Ascorbic acid efficiency in this connection was attributed to the fact that it is practically a reservoir of hydrogen.
Monoglyceride Determination Swift and Co. chemists described a method for the determination of monoglycerides in fats and oils. W. D . Pohle, V. C. Mehlenbacher, and J. H. Cook said the procedure was based on the oxidation of the monoglyceride with periodic acid, followed by measurement of the oxidizing reagent consumed. Analyses of pure monoglycerides, triglycerides, mixtures of pure monoglycerides and triglycerides, commercial product, fats and oils were reported. Among the antioxidants essentially unaffected in their effects by moisture in tests with lard, said a paper prepared by representatives of the Research Laboratory of the American Meat Institute, Chicago, are gum guaiac, tocopherols, agerite resin, and nordihydroguaiiiretic acid. T h e "active oxygen" method was employed for the lard studies and no antioxidant had been added previously, yet the yields gave the same stability figures whether or not the air stream was passed through a drying tower after being scrubbed, said Julius Nagy, B. W. Beadle, and H. R. Kraybill, of the AMI research staff. The paper, read by Buell W. Beadle, said that lard showed much higher stability in the presence of moist air than, dry air when d-isoascorbyl palmitate, ascorbic acid, triethanolamine, or certain aether £ÏÏ&»
terials are added. Storage tests also indicated that data obtained through the use of dried air were more reliable as an indication of storage behavior. H. E . Longenecker and B. F. Daubert,. University of Pittsburgh, discussing an approach to the molecular structure-of glycerides in drying oils, said that satisfactory methods are not yet at hand for the complete determination of exact glyceride configurations of the natural drying oils. While such methods are under development, it is desirable that studies bemade on the physical properties of glycerides whose structure has been established! by reliable methods of synthesis. A number of unsaturated glyceride series have been prepared, therefore, and these have been accorded physical measurements such as x-ray diffraction, rates of oxidation,, spectrophotometric analysis, solubility,, thermometric techniques, and surface film phenomena in connection with glycerideconfigurations. These series contain both linolenic and linoleic acids, and the University of Pittsburgh workers felt that the projection of these studies into additional known synthetic glyceride structures might provide in a material way a basic understanding of" naturally occurring drying oils.
Synthetic Detergents Lawrence H. Flett, National AnilineDivision, Allied Chemical & D y e Corp.,. and 1943 Schoellkopf Medalist, took upone of the newer angles of synthetic detergents research in his paper in discussing the antibiotic and antiseptic properties of surface-active agents. Under proper conditions, all such agents exert considerable control over the growth of bacteria and fungi, and, including soap, they all work a destructive action on insects as well as on microorganisms and vegetation. These effects vary, the speaker said.
H . R. Kraybill, American Meat Institute; J. J. Vollertsen, Armour and Co.; Bruce P. Neil, General Mills, Inc.; and Nat Sugarman, Georgia· School of Technology 2006
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D. C. Spice, The Drackett Co., and Theresa Johnston, American Red Cross
K. S. Mark ley. Southern Regional Research Laboratory, and president of American O i l Chemists' Society,· h i . L. Roschen, Swift and C o .
Mrs. Govan and W . J . G o v a n , Jr., chemical engineer, Chicago
Alfred Left.
F. Kapecki, Wurster and Sanger, Inc., and . M r s . Kapecki W . B. Hendrey, Edwal Laboratories, and Mrs. Lucy Hawkins, assistant editor, 0 / 7 a n d Soap
Mrs. Clara Noreen (secretary to J . P. Harris), and P. R. W y l i e , both of Industrial Chemical Sales Division, West Virginia Pulp and Paper Co., M r s . E. W . Recroît, American Red Cross, and B. P. N e i l , General Mills, I n c .
A . C. H o v e y and R. H . M a n l c y , both o i General M i l l s , Inc.; R. O . Brown, Pillsbury M i l l s , Carl S. M i n e r , Miner Laboratories, J. W . Bodman, Lever Bros. Co., and C. W . Lenth, consultant, Chicago V O L U M E
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H . H . St. Cyr, Darling and C o . / A . E. W e l l s , S. F. Lawrason C o . , L t d . /
H . A . M a t t i l l , University of Iowa/ H . A . Schmidt, Lever Brothers C o .
ft*gjfft»wfV Joseph Eichberg, A m e r i c a n Lecithin C o . ; H . G . H o u l t o n , Girdler Corp.; R. W . Cornell, Pittsburgh Plate Glass C o . / and G . N . W a l k e r , Minnesota Linseed O i l Paint C o .
The synthetic detergent Nacconol N R has been found to b e an effective bactericide in acid solution, b u t relatively ineffective in alkaline liquors. T h e antiseptic action i s slow, and using the standard test of the U. S. Department of Agriculture, the detergent shows no phenol coefficient except i n certain acid solutions. For example, cultures of Staphylococcus aureus are treated in solution with 0.1 per cent of the synthetic detergent, and a decrease follows in bacteria numbers during the first hour. Complete bactericidal action requires from 24 t o 72 hours. Solutions of ordinary washing strength retard t h e growth of yeast. T w o outstanding properties are nonvolatility and absence of toxicity. A s insecticides, the detergents are effective as repellents, stomach poisons, and contact poisons. Oil chemists are going beyond glycerols and glycerin in t h e formulation of paints and varnishes from polyhydric alcohols. J. C. Konen, E . T . Clocker, and R. P. Cox, of Archer-Daniels-Midland Co., Minneapolis, discussing t h e esterification of unsaturated fatty acids, presented data obtained in the esterification of linseed and soybean fatty acids w i t h sorbitol, pentaerythritol, and other polyhydric alcohols. Their discussion also touched on catalysts, both acid and alkaline; alcoholysis, arid ester interchange reactions.
2008
The fatty acid contents of various t o bacco seeds have been determined at t h e Eastern Regional Research Laboratory, employing the thiocyanometric method, and h a v e been found remarkably uniform in composition. T h e paper, prepared b y R . W. Riemenschneider, R. M . Speck, and E . G. Beinhart of the Philadelphia laboratory, disclosed that the tobacco oils contained on an average 75 per cent linoleic acid, 15 per cent oleic acid, and 10 per cent saturated acids. T h e same uniformity was noted also in analytical constants, such as refractive index and iodine number. I n the investigation of the fatty acid constituents of one oil, palmitic a n d stearic acids constituted about 7 per cent and 3 per cent, respectively, of t h e total fatty acids. I t also contained 0.043 per cent tocopherol. High linoleic acid content and a low content of the more highly unsaturated acids made i t highly suitable for t h e manufacture of nonyellowing alkyds or the preparation of linoleic acid concentrates.
Analytical Equipment Better control procedure for hydrogenated and standard t y p e shortenings was outlined before the meeting b y B . S . Harrington, Major P . B . Crist, A. A. Kiess, and W . A. Jacob of the Chemical Research and Development Division, Armour a n d
CHEMICAL
Co. I t is called t h e " C " number analytical machine, a n d because i t is mechanical it has enabled t h e researcher to eliminate certain subjective errors involved i n other analytical methods. D a t a o n experiments with detergents in low solution concentrations were supplied b y J a y C. Harris and Earl L . Brown of the Monsanto Chemical Co., D a y t o n , Ohio. T e s t s made w i t h Santomerse N o . 1 or N o . 3 with T S P P a t 0.05 per cent (in synthetic sea water) indicated optimum soil removal for combinations of 8 0 per cent T S P P and 20 per cent Santomerse, a n d a t this solution concentration the T S P P - a l o n e appeared t o remove more soil. Detergëntesting conducted with a number of alkat line soap builders indicated relatively high rates of soil removal at l o w solution concentrations i n comparison with Santomerse N o . 1, a n d accounted for improved déiergency of i t s mixtures with alkali. T h e Nation's synthetic rubber program stimulated development of a comparatively simple process for t h e conversion of butanediol to butadiene, said A . J. Liebmann, Schenley Research Institute, Lawrenceburg, I n d . T h e process consists of four major steps: (1) Conversion of carbohydrates from grain, molasses, or corn sugar mashes by means of bacterial fermentation into 2 , 3 butanediol.
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a n increase in membership. T h e report rendered a t t h e Chicago meeting said t h a t agreement could not be obtained as be tween various laboratories in an effort to d e t e r m i n e if thiocyanogen constants, stoichiometrically calculated from fatty acids to giycerides, could be used with satis factory accuracy. Samples wrere sent o u t a n d reagents supplied from two sources; all laboratories used identical materials. R e s u l t s in closer agreement now were o b t a i n e d for regular and special cottonseed oils, p e a n u t oil, a n d soybean oil· I t wras found t h a t some samples, notably t h e higher melting point fats, are not com pletely soluble in t h e reagent, b u t their solubility was improved through the addi tion of carbon tetrachloride, purified b y a m e t h o d supplied b y one of the committee m e m b e r s , a n d which involved treatments w i t h H2SO4, a n d washings with K O H . I n t h i s method, all traces of moisture in car b o n tetrachloride are removed after sev eral t r e a t m e n t s with phosphoric a n h y dride. W i t h regard to insoluble bromide, t h e r e p o r t said t h a t this t e s t h a d stimulated m o r e t h a n ordinary interest this year be cause of its application to the evaluation of soaps intended for use in t h e production of synthetic rubber. A t t e m p t s made pre viously t o make t h e test quantitative were found to be unsatisfactory after thorough investigation b y members, some of whom a r e connected with the Southern Regional
O i l Chemists' Meeting (CONTINTED FROM PAGE 2 0 0 8 )
(2) Separation of butanediol from t h e mash a n d its purification. (3) Esterification of butanediol into the diacetate ester. (4) Pyrolysis of t h e diacetate ester into butadiene. While butanediol is a new industrial chemical not y e t available a t a low price, and cannot compete with petroleum or al cohol for t h e production of butadiene, two microorganisms h a v e been developed for t h e industrial application of the process. T h e yields (pounds per bushel) obtained are as follows: Aerobacter Aerogenes Aerobacillus Polymyxa
Butanediol
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The d a t a were obtained during t h e operation of a pilot p l a n t of approximately 200 bushels of grain per d a y capacity. D r . Liebmann suggested t h e industrial use of butanediol as a desirable material, and as a n intermediate in t h e production of com mercially valuable organic derivativesWater Softening Properties Ε. Ε . Rauff of Lever Brothers Co., Cambridge, Mass., discussed t h e watersoftening characteristics of tallow, soy bean, a n d coconut oils, a n d rosin soaps, using w a t e r s of varying ratios of calcium t o magnesium a t a level of 50 p.p.m. hardness. I t w a s ascertained t h a t sodium soybean oil soap is slightly m o r e effective than s o d i u m tallow soap in softening water a t all r a t i o s of calcium t o magnesium, and t h e a m o u n t of soap required increases as t h e r a t i o of calcium t o magnesium de creases. T h e p a p e r said t h a t i t requires five t i m e s as m u c h p u r e rosin soap to· soften 50 p.p.m. w a t e r as tallow soap. Sodium coconut oil soap is materially less effective than either sodium tallow soap or sodium soybean soap i n softening water, b u t appears more effective in calcium hard water t h a n in m a g n e s i u m .
Report of Analysis Committee The committee o n Analysis of Commer cial F a t s a n d Oils, h e a d e d b y V. C. Mehlenbacher, Swift & Co., Chicago, submitted a 16-page r e p o r t on thiocyanogen values, a fat stability t e s t , o n insoluble bromides (hexabromide t e s t ) , unsaponifiable matter, t h e congeal point, along with a table of F.A.C. Color S t a n d a r d s . T h i s committee is a cooperative effort between t h e AMERICAN
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American Oil C h e m i s t s ' Society, a n d ren ders r e p o r t s to b o t h organizations. 11 also works with the A S T M a n d w i t h the U. S. Referee on Oils, F a t s , a n d Waxes forthe As sociation of Official Agricultural Chemists. The work of t h e ACS-AOCS group h a s broadened in recent m o n t h s , necessitating
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Research L a b o r a t o r y Interest therefore has b e e n centered in the qualitative as pects of the hexabromide test. I n this procedure, a sample of a fatty acid is a d d e d to a m i x t u r e of acetic acid a n d ethyl ether, and if n o precipitate forms, bromine is introduced from a dropping bottle, pref erably under a hood. When cooled to 0 ° to 5° C , t h e mixture is held in this range for 4 h o u r s a n d examined. If a h e a v y pre cipitate has formed, report t h e t e s t " P o s i t i v e " ; if the solution is clean a n d brilliant, r e p o r t " N e g a t i v e " . T h e committee has conducted consider able w o r k in an a t t e m p t t o standardize some m e t h o d for t h e congeal point, as those employed in industry varied in de tail. Details therefore were s t a n d a r d ized a n d t h e method in general was as follows: T h e temperatures, a p p a r a t u s , and lighting were standardized a n d a definite q u a n t i t y of sample was stirred t o the clouding point in a water-cooled b a t h . T h e s a m p l e wras then transferred t o an aircooled b a t h , t h e thermometer fixed in one position, and left stationary until t h e tem p e r a t u r e increased t o a m a x i m u m . An exhibit of technical laboratory equip ment was held in conjunction w i t h the meeting in t h e American R o o m of t h e LaSalle. A complimentary s t a g smoker and an informal dinner followed b y dancing highlighted t h e entertainment program. A luncheon a n d card p a r t y were t h e fea tures of the ladies' program.
ALPHABETICAL LIST OF ADVERTISERS I "Ace Glass, Inc 2041 Alberene Stone Corp. of V a . . . . . . . 2051 American Cyanamid & Chemical Corp 1978-1979 H American I n s t r u m e n t Co 2072 I American Platinum Works 2019 Becco Sales Corp Bemis B r o . B a g Co 1 B e r k & Co., Inc., F . W I Blaw-Knox Co Buffalo Electro-Chemical Co., Inc.
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Carbide & Carbon Chemicals Corp.. O.F.C. Chicaero Float Works, I n c 2018 Co^ ie Corp 2034 C o W i a n & Bell Co., I n c 2048 1 Columbia Chemical Division 2043 I Combustion Engineering Co., Inc.. 2045 I Commercial Solvents C o r p 2022-2023 Croll-Reynolds Co 2050 D o w Chemical Co D u r a l o y Co E d w a l Laboratories, I n c 1 E d w a r d s Brothers, Inc E i m e r & Amend
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