Technical Sessions at Chicago Surpass Previous Records A STAFF R E P O R T Li·: the n u m b e r of technical papers presented at the 113th meeting of the A M E R I C A N C I I K M I C A L S o m e n - a t Chicago, April 10 to 23, did not roach the record set at N e w York last fall, the Chicago meeting did establish a record for the n u m b e r of sessions held. In other words, there were fewer papers given at Chicago, but it took the speakers longer to present them. A total of SOI technical papers were presented in 111 sessions in Chicago as against S09 and 110 for N e w York. A total of 1,338 authors were represented. Another record of sorts was broken b y last day registration at Chicago where 10 registered o n Friday morning. At tendance at the meeting as a whole, however, w a s somewhat less than antici pated. Fi nalfigurewas 8,375. Seventeen of the Society's divisions presented programs at Chicago. T w e l v e started their programs on M o n d a y m o r n ing, but the m a x i m u m number of sessions in progress, 15, c a m e lale in the w e e k — Thursday morning. Fully one third of the sessions were held at the headquarters hotel, the Stevens, but several divisions concen trated their sessions elsewhere. Thus all sessions of the Divisions of Organic and Biological Chemistry were held at the nearby Congress Hotel. Industrial and Engineering Chemistry met at the Palmer House while the agricultural and analytical divisions held their sessions at the L a Salle. T w o divisions main tained headquarters at other hotels— the Division of Paint, Varnish, and Plas tics Chemistry at the Palmer House and the Division of Rubber Chemistry at the Sherman. In all, 23 meeting r o o m s were used.
Three recently formed groups again held special programs—the Chemical Literature Group i η the Division of Chemical Educa tion, (lie Chemical Marketing G r o u p in the Division of industrial and Engineering Chemistry, and the Fermentation Section of the Division of Agricultural and Food Chemistry.
Food arid Dr tig Act
Commemorated
The tenth anniversary of the enactment of the Federal Food, D r u g , and Cosmetics Act was commemorated during the s y m posium o n food quality a n d control which opened the sessions of the Division of Agricultural and Food Chemistry. T h e symposium w a s held in the reconstructed Hotel L a Salle. Ole Salthe, Nutrition Foundation, Inc., w h o presided, reviewed the legislative history of the act, while two legal experts on food control legislation from iCew York, Charles Wesley D u n n a n d James F . Hoge, discussed the law as it affected the food and drug industries, respectively. Paul B . Dunbar, U . S. Commissioner of food and drugs, said that regulatory efforts under the law have been directed toward false claims, "scare copy" in advertising, vague representations as to inadequacy of the American diet, also toward requiring vitamin, a n d mineral-enriched foods to declare the amounts in terms readily understood b y the average consumer. Under the 10-year-old law, some 10,000
seizures of foods and drugs will ha,vu been m a d e and 2,650 criminal actions insti tuted. O n e type of drug control not anti cipated w h e n the law became effective ID 193S was that over insulin, penicillin, and streptomycin. All three of those groups require rigid production controls, and under certain conditions their use could result in fatalities if they were not of the purity and potency required. General divisional sessions which fol lowed heard papers on the irradiation of niacin solutions with x-rays and cathode rays, quality control in the preparation of certain farm products, the use of m o n o sodium glutamate for improving the flavor of meat and foods, the methionine content of alfalfa, properties of p-aminobenzoic acid 'and its sodium salt, two papers devoted to agricultural dusts, the fungus inhibitive properties of certain organic compounds, and heat-treatment of soybean oil meal. B . E . Proctor and S. A . Goldblith. Massachusetts Institute of Technology, reported that recent canning methods in which x-rays, radar, and electron waves are used in place of heat adversely affect vitamin values of the food. Niacin, the antipellagra factor, underwent destruc tion w h e n a concentration of 5 0 micro grams per ml. was subjected to x-radiation of m o r e than 50,000 roentgens. Niacin destruction w a s even more pronounced in the presence of ascorbic acid. T h e entire
The Symposi u m on Food Quality and Control commemorated the tenth anni versary of the enactment of the Food. Drug, ami Cosmetics Act. Speakers were: Charles Wesley Dunn* counsel for various food and drug associations; James F. IWogv, JS'ew York Slate liar Association: Fmil Π. Dunbar, Food and Drug Ad ministration; anil fJle Sal the, IXtttrition Foundation, Inc., who presided
Individually, the Division of Physical and Inorganic Chemistry broke all existing records with 160 papers on 17 sessions. T w o simultaneous sessions were held every day, M o n d a y through Thursday, b y this division with a third session on Thursday morning. Largest of the divi sion's four symposia was that devoted to the transuranium elements, with 34 papers o n three sessions. The s y m p o s i u m record, however, w a s broken b y the Division of Chemical E d u cation, which conducted nine symposia or special sessions and took part in three jointly with other divisions. Runner-up w a s the Division of Biological Chemistry, which held six symposia or special sessions.
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problem of the effect of high energy rays upon vitamins is being; studied at M I T . Food
Flavors
Monosodium glutamate does not con tribute flavor to foods but has the prop erty of accentuating the flavors which characterize them, said a paper by M . J. Blish, International Minerals anil C h e m ical Corp. Flavor is considered to be the combination of both taste and odor, and glutamate by itself is devoid of the former. Sodium glutamate production was ap proximately 6 million pounds in the United States during 1947, yet the average household has yet to utilize its properties. Food flavors in connection with vitamins were also discussed before the Agricultural and Food Chemistry Division by H . A . N a n z and L . C . Cartwright of Foster D . Snell, Inc. A s vitamins have inviting flavors and aromas of their o w n , persons demanding savory foods were on the right nutritional track since research has shown that there is a definite correlation between foods with an appealing taste and those high in nourishment. A child lacking epfficient calcium and vitamin D thus selected foods providing these substances. Vitamin C possesses a pleasant, slightly acid flavor which probably is carried over into the a r o m a of food. It also has the ability to stabilize foods and prevent offflavor. Paprika contains a large amount of ascorbic acid. Vitamin E , or «-tocoph erol, the antisterility factor, also sta bilizesflavorcomponents. Thiamin vita min Bi has an easily detectable odor which is a component of foods containing pork and wheat products. Findings of an inquiry into a large n u m ber of organic compounds which sought to determine their fungus inhibiting proper ties were reported by J. M . Leonard and W . E . W e a v e r of the Naval Research Laboratory. About 130 hydrocarbons and their halides were studied. Aliphatic and alicyclic hydrocarbons had a low order of toxicity, which is augmented b y the introduction of unsaturated linkages. Bromides and iodides possessed varying degrees of toxicity. Methionine levels were found to be in adequate in 17 strains of alfalfa, used extensively in the ration of beef cattle, by E . T . Mertz aad A . F. Kingsley, Purdue University. T h e content varied from 22 to 66 m g . of the amino acid per gram of total nitrogen. Average value was 4 8 m g . of methionine per gram of total nitrogen. As further criteria of purity, the prop erties of p-aminobenzoic acid and its so dium salt were investigated by C . J. Kern, T . Antoshkiw, and M . R . Maiese of the Ives-Cameron C o . , Brooklyn, Ν . Υ . Titra tion of P A B A with a strong base resulted in a sharp end point between p H 6.5 and 8.5, and titration of sodium P A B A with a strong acid yields a useful equivalence point of p H 3.5. T h e use of a boric acid color reaction for the identification of certain flavone
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Spe€tkers al tlie Symposium on Design of Experiment* for Developing Net» Analytical Methods: W. J. Youdcn, Boy ce Thompson Institute for Plant Research; Grant Wernimont, Eastman Kodak C o . , chairman; J. It. David» son9 Merck & Co.; John Hintermaier, Vanity Fair Mills;awid by H a r m o n L . Finston of Ohio Stale consists of precipitating the rhenium a.» sulfide in a hydrofluoric acid solution of the metals, separation of the sulfide and removal of the ΙΙ-ΙΛ», followed by precipitation of tungsten as tungstic acid. Total phosphate, iron, aluminum, and acid-insoluble constituents in phosphate rock can n o w l>o determined in a single sample, according to Charles J. Barton, International \linerals and Chemical Corp. Phosphate is determined b y the phosphovanadiornolybdate method, iron by the (l,10)-plï.enanthroline method and aluminum with sodium alizarinsulfonate, all of these methods being photometric. Accuracy is satisfactory and a threefold cut in time is m a d e over conventional methods. Spec lroph.oloirm.etric Ale I hods Etnpo riant Paul K. AVinter of the General Motor» Corp. proposed a n e w rapid method for the determination of phosphorus, and ao important innovation in testing for caffeine was annoiznced by Ν . Η . Ishlcr of General Foods. This latter method util izes the characteristic absorption of caf feine at 2 7 2 m/tx for rapid spectrophoto metry determination and compares favor ably with the Bailey-Andrew technique in results. N . R . Τ rentier of Merck and C o . de scribed the mass isotope method for the determiiiiit-ion o f the g a m m a isomer of hcxachlorocyclohcxane, or benzene hexachloride. In this very interesting and far reaching technique g a m m a hexadeuterobenzene liexachloridc is used as the tracer molecule, and the extent of isotopic dilu tion in tlie isolated g a m m a isomer mixture is determined b y infrared spectrophoto metry. T h e authors believe the method
1345
to be of great significance from the point of view of absolute analysis of organic substances occurring in complex media and feel that the method must take pre cedence over all other methods as a stand ard for checking other methods since im purities have no effect on its accuracy. Ν . Η . F u r m a n of Princeton in his address at the divisional dinner further' e m p h a sized the importance of this technique. A promising new colorimetric reagent for the determination of copper, mercury, silver, gold, platinum, and palladium, has been found in thio-Michler's ketone, according to Jerome Goldenson of the Chemical Corps Technical C o m m a n d . This compound also seems promising as an internal indicator for volumetric an alysis involving these metals. Of considerable industrial interest and importance was a paper by J a m e s A . Anderson of Humble Oil and Refining Co. on the determination of oxygenated and olefin compound types by infrared spec troscopy. H e showed a number of pro cedures for the quantitative to semiquan titative analysis of individual compound types in complex mixtures by infrared absorption spectroscopy in the liquid phase, analyses being m a d e in m a n y cases where they have not been possible by other means. Design of the Experiment for Developing New Analytical Methods One of the two symposia sponsored by the Division of Analytical a n d Micro Chemistry was a short (four-paper) but important one with the purpose of ac quainting the analytical chemist with sufficient background in statistics to enable him to design experiments which will give with the m i n i m u m a m o u n t of work the m a x i m u m amount of informa tion regarding precision and accuracy. John Hintermaier of the Vanity Fair Mills set the pace in saying that "the literature of today's chemists lacks uni formity in presenting the additional in formation to be extracted from data b y the use of simple statistical methods. Further, and perhaps more serious, au thors are unaware of potential values of their work which additional squeezing will give." H e gave formulas for c o m puting the amount of testing to be done according to preselected probabilities and significance and recommended methods for the statistical approach to experimenta tion. T o avoid false answers, James H . David son of M e r c k & C o . recommended that persons using statistical methods exer cise care in so doing and bear in mind the three factors involved in the development of these methods—the general concepts of the mathematician, the assumption of the statistician, and the reasoning and definitions of the statistical logician. T h e essence of a factorial design, ac cording to W . J. Youden of the Boyce T h o m p s o n Institute for Plant Research,
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is the feature that every analysis is m a d e to furnish several types of information. H e further pointed out that reduction in the n u m b e r of analyses required m a y be brought about b y use of "confounding." This principle utilizes certain compari sons in the data which are known to be insignificant for contrasting effects which are of interest. Of course, the use of statistics should begin in the schools, and Philip J. Elving, chairman of the division, closed the symposium with remarks by himself and M . G u y Mellon o n teaching students h o w to evaluate data. D r . Elving laid stress on the student's acquiring an introduction to the basic concepts which can b e used to evaluate the validity of the data whether obtained in the chemi cal laboratory or elsewhere. H e believes that it is sufficient to acquaint the under graduate with the concepts of the arith metic m e a n and the standard deviation, the relations derived regarding the limite • >f variation of an observed average, and the concepts of confidence limits and quality control charts. Analytical Courses
Examined
Meeting in joint =?ession, the Divrsioa^ of Chemical Education and Analytical and Micro Chemistry presented a s y m posium dealing with the nature of the subject matter which m a y be most profit ably presented in the undergraduate class in quantitative analysis. In introducing the group of speakers Chairman Philip J. Elving of Purdue University pointed out that the symposium had been organized because of the widespread discussion in recent years of the efficacy of the present methods of teaching undergraduate analy sis. S o m e schools have experimented with changing the position of analytical courses to earlier or later parts of the students' course of study. Other educators, repre sented by L . B . Clapp, Brown Univer sity, w h o spoke in another session pre sented b y the Division of Chemical Education, question the gross value of
all or part of the analytical course and have considered eliminating it from the basic course of study. T h e second type of problem brought before the group concerned the nature of the emphasis in present courses. T h e use of instrumental techniques and statistical methods, the inclusion of analysis for organic constituents, and the degree of accuracy to be expected from students were cited as critical considerations in setting up a modern course of study. T h e consensus of the industrial and academic analytical chemists speaking in this symposium w a s that the most valu able contribution to be expected from the undergraduate course in analytical chem istry is its valuable *'exercise in the rigid discipline of scientific reasoning" and the "philosophy of exact analysis.*' For this reason almost all of the speakers recom m e n d e d retention of the * 'classical meth ods" of analysis in the curriculum with che accent on neatness and accuracy. None of the speakers recommended the introduction of more than elementary statistics. T h e speakers also felt that the a m o u n t of instrumental analysis taught in most schools at present is sufficient. A dissent to this latter opinion w a s m a d e by N . Howell F u r m a n of Princeton Univer sity w h o said that most small liberal art* colleges of limited enrollment should in crease the a m o u n t of instrumentation in analytical courses but admitted that the expense of the instruments and the ad vanced theory necessary to understand their operation offered serious deterrents to this trend. I. M . Kolthoff of the Uni versity of Minnesota suggested that in strumental methods of analysis be d e m o n strated by means of slides and motion pictures. Olaf Bergeim of the University of Illi nois Medical School, speaking from the point of view of the needs of the premedical student, also spoke out in favor of increased instrumentation with par ticular emphasis upon the use of the
The Symposium on Amino Acids and Proteins sponsored by the Division of Biological Chemistry featured: F . W. Putnam, University of Chicago; f. R. Spies, U. S. Department of Agriculture; J. T. Edsall, Harvard Medical School, symposium chairman; J. B, Meichior and / . Λ#". Klots, Northwestern University
CHEMICAL
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spectrophotometer, microchemical meth ods, and the use of radioactive tracers. There was little discussion of the nature of the theory to be taught. However, Edward L . Haenisch of Villanova College advocated the omission of the electrochem ical theory of redox equilibria as an un necessary complication. It was generally held that analysis for organic constituents has no part in the basic course in analyti cal chemistry. In speaking for the industiial employer of chemists, George Calingaert of the Ethyl Corp., strongly favored a n accent on basic fundamentals since he said the industrial chemist will learn o n the job the highly specialized field in which he will be engaged if "his college training has been truly basic." Oreatest Analytical Strides N". H . F u r m a n of Princeton w a s the principal speaker at the dinner of the Division of Analytical and Micro Chemis try. President T h o m a s paid tribute to the contributions of the analytical chem ist to the development of atomic energy, and Philip Elving, division chairman, m a d e preliminary announcements of the summer symposium on analytical methods in nuclear chemistry, to be held in Augusl at Northwestern University. D r . F u r m a n spoke o n the impact of the Manhattan Project o n analytical chernis-
Th$> Cover.
try a n d listed some of the analytical areas in which greatest strides were m a d e . These were chromatography, emission spectroscopy, the methods for safe han dling of "hot" material, absorption spec trophotometry,fluorescence,electrochemi cal work, the reinvestigation of volumetric and gravimetric methods, and organic reagents a n d their extraction. Biological
Chemistry
T h e four day session of the Division of Biological Chemistry w a s one of the largest programs ever presented with 81 papers being given. T h e program in cluded a general session and special sessions on microbiology, sterols, metabo lism, amino acids, and proteins. Tn addition t w o symposia covering the field;· of antibiotics a n d metalloporphyrins and heme proteins were sponsored jointly with the Division of Agricultural a n d Food Chemistry. During the M o n d a y morning session 11 papers were presented covering such varied subjects as colloidal aspects of antiseptics, antiglucuronidase, breakdown of barbiturates, Maillard reaction, and surface activity of biotin. In the study on the colloid aspects of antiseptics, H . L . Davis, Alfred Block, and A . A . Stonehill of Johnson and Johnson pointed out that the mechanism of antiseptic action must generally involve
. .
Gerty T.«»r With the announcement
of this
year's winner of the A M E R I C A N C H E M ICAL S O C I E T Y ' S w o m e n ' s award in
chemistry, Gerty Cori, Washington University School of Medicine, joined the long list of distinguished w o m e n chemists w h o preceded her in winning the award. T h e Francis P . Garvan medal, emblem of the award, goes to Dr. Cori for her varied and extensive research in biochemistry, particularly for her work o n carbohydrate metabo lism and enzymatic reactions. T h e presentation of the gold medal will be made during the fall meetings of the Society. In 1947 D r . Cori shared the Nobel prize in medicine with her husband, Carl F. Cori\ and Bernardo Alberto Houssay of Buenos Aires. T h e Cori s were honored for their work on enzy matic synthesis of glycogen, or animal starch. T h e process by which the body stores sugar in the liver as gly cogen and then recoverts the glycogen to sugar as it is needed was explained by their studies. Gerty Cori w a s born in 1896 in Prague w h e n it w a s part of Austria.
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She attended the G e r m a n University there at the same time as the young scientist w h o m she w a s to marry shortly after their graduation in 1920. For t w o years she w a s an assistant at the Children's Hospital in Vienna, and then she and her husband came to the United States where for nine years they were connected with the N e w Y o r k State Institute for the Study of Malignant Diseases in Buffalo. In 1931 they went to the Washington University School of Medicine where Dr. Cori is n o w a fellow and research associate in pharmacology and bio chemistry. Gerty Cori, w h o has published 73 papers, a n d her husband have earned other joint honors. T w o years ago they received the Midwest A w a r d of the St. Louis Section of the A C S , and they also have received a $5,000 prize of the National Science F u n d of the National A c a d e m y of Sciences for their research o n metabolism. They presented the Harrison H o w e Lecture for 1947. This year Carl Cori has been chosen to receive the Willard Gibbs Medal of the Chicago Section of the A C S .
» MAY
10,
1948
an adsorption of the chemical reagent on the microorganism or u p o n some sub strate in the organism which is poisoned so as to be incapable of catalyzing neces sary life or reproduction processes. This adsorption m a y be so persistent as to exhibit bacteriostatic effects that are falsely interpreted as sterility unless the absorbed antiseptic is neutralized or removed from the organisms by a more effective adsorbant. Studies o n the breakdown of barbitur ates b y surviving tissues b y M . Beiler, Sister Roderick Juhasz, and L . R . Cerecedo of Fordharn University indicated the effect of the diaphragm, liver, and in testine on barbital, amytal, pentobarbital, and pcntothal. Their findings showed that all three tissues affect the breakdown of amytal and pentobarbital. Pentothal is destroyed by the diaphragm, and in testine but not by the liver. Barbital however, is not affected by any of these tissues. During the microbiology session 12 papers were presented in fields relating to the methods of determination of strepto mycin, synthesis of such compounds as £-3-thienylalanine, 0-chloro-a-aminobutyric acid and 6-methylbenzypenillic acids, and microbiological activity of pyridoxyi amino acids. A paper by M . J. Astel and H . N . Jelinek of Case Institute of Technology covering the investigations of the sulfur linkage in bacitracin stated that "early investigators studying the chemical be havior of this c o m p o u n d were led to the conclusion that bacitracin is a polypeptide material. Pursuing this line of thought, bacitracin was hydrolyzed and analyzed for the various amino acids. A J I impor tant result obtained was that cystine is the only sulfur-containing amino acid present." Studies suggested b y this ob servation led to the conclusion that some fractional part of the material in baci tracin is not polypetide. Vitamin Λ Studies A lecithin-tocopherol combination that protects vitamin A from oxidation in air was reported b y Charles J. K e r n , T h o m a s Ajitoshkiv, and Michael R . Maisee of the Ives-Cameron C o . , Brooklyn, Ν . Υ . , before the sterols and nutrition section. Employing s u m m e r temperatures a n d in some cases pure oxygen to test the pro tective action of a number of antioxidants with vitamin A , the investigators reported that a combination of 4 % lecithin and 2 % tocopherol proved m o s t satisfactory. Under conditions in which only 1 0 % of the unprotected vitamin remained, 8 0 % or more was retained when the above mixture w a s used. T h e agents also increase the absorption of vitamin A b y the blood. Emphasizing the global extent of the current vitamin A shortage, the author asserted that this anti oxidant combination should be of real sig nificance in relieving this shortage and in
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An t ibiot ics Sessions Studies on polymyxin, an antibiotic with Gram-negative specificity in contrast to penicillin and the sulfas, were reported by Robert G . Shepherd of the American C3*anamid C o . before the symposium on antibiotics, sponsored jointly by the Division of Biological Chemistry and the Fermentation Section of the Division of Agricultural and Food Chemistry. ΛΥ. II. Peterson of the Uni versity of Wisconsin presided. Although first reported from the American Cyanainid laboratories, polymyxin has been pre pared at the Northern Regional Research Laboratories at Peoria, ill., and has been produced in Kngland under the n a m e "acrosporin." It is isolated from fermentation liquors of Bacillus polymijxa by successive ab sorption on charcoal, elution, and pre W. II. Peterson of the University of IT'isi-onsitt presiiled at the first session of the cipitation followed by hutanol extraction Symposium on Antibiotics at which R. C. Shepherd of the American Cyanamiil and by fractional precipitation of the Co. antl II. E. Carter of the University of Illinois took part, as speakers picrate. D r . Shepherd revealed that poly myxin is a primary amine and contains no free earboxyl or other acidic groups. A Chlorophyll Synthesis protecting the public using vitamin A . number of derivatives have been pre A water-dispersed form of vitamin A During the Thursday morning session a pared. Hydrolysis shows it to be a poly that shows better absorption properties n u m b e r of important new studies on inter peptide. According to the speaker, com than oil-based preparations was reported mediary metabolism were presented. S. mercial preparations of polymyxin con in a paper by B . M e C o o r d , U . A . I'1st com, Graniek of the Rockefeller Institute for tain m a n y active components. Medical Research, in discussing chloro R . H. Tully, F. J. Martin, and A . J. Polymyxin is bactericidal at thera phyll synthesis using chlorella mutants, Keenan of the University of Rochester. peutic levels; it has been used successfully showed for the first time the metabolic C o m p a r e d were ester vitamin A in oil and al in clinical trials on children with severe interrelation between iron protoporphyrin cohol vitamin A in aqueous dispersions pre burns whooping cough, and serious skin and chlorophyll. T h e author stated that pared with sorbitanmonolaurate poly alky 1disease with secondary infection. x-radiation of chlorella produces mutants ene derivative, propylene glycol, etc. A b Studies on the structure of streptomycin which are useful in analyzing the steps eorptionwas better with the aqueous alcohol were the subject of two papers on the of chlorophyll synthesis. A n u m b e r of vitamin, but blood levels of vitamin A symposium. Josef Fried and H o m e r E . mutants have been isolated, some con were maintained longer with the oil·/ Stavely of the Squibb Institute for Medical taining only green pigments or only yellow preparations so that both have certain Research reported that they have estab pigments, some that are colorless, and advantages. In consequence, the authors lished streptomycin Β as a mannopyranoothers that are pink. did not feel that standards for vitamin A side and have renamed it mannosidostrepA pinkish pigment has been isolated requirements should be changed. tomycin. T h e separation of two or more from one of the mutants which lacks Alice L . R o y le and Evangeline Papastreptomycins or other antibiotics from chlorophyll, and the pigment has been george of E m o r y University presented a streptomycin Β b y means of paper parti identified as protoporphyrin 9. tion chromatography was reported by paper discussing the effect of rutin and Walter A . Winstcn and Edward Eigen of ascorbic acid on the autoxidation of epi Selenium Poisoning Mechanism Food Research Laboratories. nephrine. According to the authors the Eventual control of selenium poisoning, inhibition of autoxidation of epinephrine manifest in livestock as "blind staggers" by ascorbic acid and b y substances having An t ibio t ie Nomencla. t u re or "alkali disease,' ' was foreshadowed vitamin Ρ activity has been reported. Pointing out the confusion that is apt in the announcement by I. Gordon Fels Their work has confirmed this report. to result w h e n an antibiotic is n a m e d be and Vernon H . Cheldelin of Oregon T h e inhibition of epinephrine autoxida fore it is definitely identified, Η . Ε . Carter State College that methionine is capable tion w a s slight but reproducible and was of of the University of Illinois discussed the of reversing of toxic effect of selenatc in the s a m e order of magnitude with 0.5 m l . characterization of n e w antibiotic sub yeast. Although the reversal is never of saturated rutin-bufTer solution as with stances. As bad examples of antibiotic; complete (approximately 8 0 to 85%), 0.094 m g . of ascorbic acid. Rutin w a s nomenclature he mentioned one sub the evidence points to the action as being found also to retard the autoxidation of stance to which at least four names have spécifie, they stated. Their findings sugascorbic acid. T h e addition of rutin been assigned: clavacin, clavatin, clavigested that selenatc either destroys further enhanced the antioxidant action formin, and expansin—the latter added methionine, one of the essential amino of the h u m a n serum toward ascorbic even after the investigator recognized his acids, or renders it useless in the body. acid and that of crude rat liver oxidase substance as identical with one already A n in vitro reaction between methionine toward adrenalin. Rutin plus ascorbic known. In another case, the n a m e asperand selenic acid has been found to take acid markedly retarded the rate of autoxi gillin has been given to substances from place readily at room temperature. A dation of epinephrine. five or six different organisms. ciystalline reaction product has been These results support the theory that W h e n to n a m e a substance depends isolated which contains selenium, sulfur, vitamin Ρ «activity involves an effect on upon the relation between the biologist, and nitrogen in organic linkage. T h e epinephrh.., and also indicate the possi and the chemist, asserted D r . Carter. present results indicate that in yeast t he bility that the effect m a y be mediated While it m a y not be practical to wait until primary toxic effect of selenatc is the prethrough ascorbic acid. a pure product is obtained, he urged that vention of methionine utilization in cells.
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concerning the chemistry υί the degrada tion of the porphyrins in the animal organism. Nothing was known until re cently concerning the precursors and mechanism of synthesis of h e m e . T h e y have found, using the heavy isotope of nitrogen (X 1 5 ), that glycine is the nitro genous precursor of tie protoporphyrin of heme in both the human and the rat. Neither proline nor glutamic acid, pre viously suspected of participating in pyrrole formation, are directly involved in the formation of the pyrrole nucleus. Glycine w a s suhsecjuently synthesized with C 1 4 in the carboxyl group and fed to rats in order to establish definitely the position of glycine in the porphyrin. From model experiments of Fischer and Fink it would appear that the glycine carboxyl carbon atom is the methine carbon of the porphyrin while the acarbon atom is in t he alpha position iu the pyrrole. The feeding of labeled glycine results therefore in the formation of labeled heme which in turn labels the red blood cell. This affords a means of studying some aspects of the dynamics of hemoglobin formation and breakdown and the life span of the h u m a n erythrocyte, both in the normal and in certain well-defined pathologic states.
before naming, tiie work be pushed to a point where there is only a 1:100 chance that the substance will be identical with a k n o w n antibiotic. Several of the papers on the afternoon session of the antibiotics symposium, over which Robert D . Coghill of Abbott Laboratories presided, were devoted to penicillin analysis. In addition, the de velopment and use of a 5-gallon bottle fermenter for research in antibiotics was described in a paper by Bruce S. Lane and D o n Collingsworth of the Upjohn C o . Agitators, packing glands, top clamping device, and pumping connections were dis cussed as well as equipment for tempera ture control and for sterilization and measurement of the air used for aeration.
Symposium on iMetalloporphyrins and Heme Proteins A major symposium on metal loporphyrins and heme proteins was held on Wednesday under the joint sponsorship of the Division of Biological Chemistry and the Division of Agricultural and Food Chemistry. Presiding at the meeting w a s W . Mansfield Clark, Johns Hopkins University, w h o also presented a survey of his fundamental studies on coordination of metalloporphyrin and nitrogenous bases. David Shemin of Columbia University presented his studies on the biological synthesis of h e m e using the heavy isotope of nitrogen, N 1 5 , which reveals the impor tance of glycine in this process. Accord ing to the author there is some information
Itittlogical Model
Systems
Synthetic chelate compounds as models of biologically important substances were discussed b y M . Calvin of the University of California. The author discussed the
Left. C. W. Tusker, McCill University; \V. F. Fowler, Jr., Eu s I r ri a η fondu k Co.; and C. H. Portly ce, Eitsltnan Ko dak, chairman of Cellulose Division. Iteloto. Elisha H. Lewis, Univ. of Kentucky (s tangling"),spcttkingat round table discussion on analyti cal fnethc*€lsf€»r cellulose
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M A Y
10,
1948
oxygen-carrying synthetic chelate c o m pounds from ti.. point of view of the relationship between their molecular and crystal structure and their oxygencarrying capacities, both in the solid state and in solution. Dean Burk of the National Institute of Health discussed the remarkable group of recently described cobalt compounds such as eobaltodihistidinc which combine reversibly with oxygen in a manner which m a y illuminate the nature of the ironoxygen linkage in hemoglobin. Dr. Burk stated that the ability to combine with oxygen gas reversibly and stably under physiological conditions demonstrated so far for hemoglobin, myoglobin, hemocyanin, and oxidases like Atmugsftrmcnt, all iron or copper proteinp of high molecular weight, has also been found with various simple cobaltousaniino acid complexes, including cobaltou? c o m p o u n d s of histidine/1-methylhistidine, 3-methylhistidinc, benzylhistidine, dibenzylhistidine, as party lhistidine, carnosine, anserine, histamine, lysine, arginine, tryptophan, proline, ornithine, serine, asparagine, glutamine, glutamate, gly cine, and glycyl-glycine (though not with cysteine, methionine, asparatate, putreecin or a- or β-alaninc). He added that the oxygen affinity con stants of the reversibly oxygenated c o m plexes m a y vary b y several orders of m a g nitude with different amino acids.
Cell·ε lose l'rogra m T h e program of the Division of Cellulose Chemistry was shorter than usual, with four papers presented o n a morning session and a n afternoon devoted to a round-table discussion on analytical methods for cellu lose. T h e program opened with a paper on bemicelluloses from maple holocellulose by CJeorgc J. Hitter and a report on wood cellulose hydrolysis by Elwin K . Harris, both of the Forest Products Laboratory. Madison, Wis. Reporting studies on the properties of cellulose oxidized b y nitrogen dioxide, W F . Fowler of Eastman K o d a k C o . asserted that ketone groups are the most probable source of alkali solubility of the celluronic acids produced. Such groups are believed to enolize, he continued, the ene-dioh· splitting as in simple carbohydrates, the adjacent glucoside linkages hydrolyzing. and an extensive alkaline degradation set u p which continues along the chain to produce reducing and acidic substances. In thefinalpaper, Clinton W . Tasker of McGill University discussed the appli cation of the tosylation-halogenation reac tion to a hydroxyethyl cellulose. H e indi cated that iodination is capable of over estimating the n u m b e r of primary hydroxyl groups and that cyclization m a y re sult from the linkage of glucose unit> through the tosylated hydroxyethyl groups. Presiding at the round table was Divi-
1349
si on Chairman Charles It. Fordyee, East m a n K o d a k C o . , w h o pointed out that while 20 analytical procedures are under consideration, very little w o r k has been done on them since early in the war. Lead ing the discussion in the absence of Fred Olsen, originally scheduled, w a s Peter Van W y c k of Hercules P o w d e r C o . , chairman of the subcommittee on vis cosity. During the discussion, the in clusion of molecular weight distribution in viscosity methods and officiai recogni tion of the relative term "intrinsic vis cosity" were advocated. Unprintetl
Curricula
O n e of the largest divisional programs of the meeting was that presented by the Division of Chemical Education. More than 1 0 % of the total number of papers presented in Chicago w a s sponsored either solely or jointly b y this group. Luncheon speaker Franklin B . Snyder, president of Northwestern University, key noted a problem discussed in various aspects in most of the purely educational sessions w h e n he spoke on " W h a t Is This Thing Called Education?" H e spoke of the value of what he called "the imprinted curricula" which will form the social and professional attitudes of the graduate and m a y have more value in the long run than the collection of facts which he m a y or m a y not remember. T h e significance of these intangibles w a s pointed out fre quently by technical session speakers throughout the four days of the meeting and particularly in the symposium on edu cation for professional responsibilities. In the extended discussion periods which characterized this meeting the col lege chemistry faculties were subjected to m u c h stinging criticism. However, their rebuttal stressed the overcrowded conditions prevailing on all campuses at present which necessitated m u c h recourse to methods of expediency.
It was pointed out that industry too has a responsibility to develop the profes sional caliber of its professional employ ees. In the s y m p o s i u m mentioned ab>ovc and the one which preceded it o n place ment of chemists a n d chemical engineers two speakers defined certai η areas of this responsibility.
Seq uences for Undergradua te Che mis try A n e w sequence for the presentation of the material traditionally presented to- the undergraduate student in chemistry was suggested by L . B . Clapp in a paper pre sented before the general session of the Division of Chemical Education. Dr. Clapp introduced his suggestion b y point ing out the rapid breakdown of the iikterdepartmental categories in the practice of chemistry. T h e modern approach to chemistry would suggest that the coxirse in physical chemistry should be the first taught. However, the freshman student lacks sufficient physics and mathematics to m a k e this course practicable. A s a second best, the chemistry depart ment at B r o w n University, represented by Clapp, has introduced a full year coxirsc in organic taught at a freshman level. This assumes that the student has fc>cen successfully exposed to basic general chieniistry in high school and no attempt is roade to review this material. This particular procedure of not repeating the high scliool work has the gratuitous advantage o f a greatly increased student morale. In the second year the chemistry nxajoi is required to take two semesters of physi cal and one semester of inorganic, hairing been provided in previous year with basic college physios and calculus. Xhus grounded, the student is permittee! to specialize somewhat in the upper aromatic hydrocarbons wc©e given by D . A . H o w e s of the AngloIranian Oil C o . , including a number of physical constants which were presented
2 6, N O . 19 . . » » M A Y 10,
1948
for thefirsttime. Wayne Proell and C . E . A d a m s of the Standard Oil C o . (Indiana) reported that alkane-sulfonic acids ap pear to be particularly suitable as catalysts for the study of polymerization and alkylation because side reactions are essentially absent. In a detailed discussion of past and re cent research into the origin of petroleums and natural gas, Β . Τ . Brooks, well-known consultant, deprecated theories of high temperature and of radioactivity in the formation of petroleum a n d emphasized a theory of a two-stage formation in which a first stage formed transition products by chemical and bacterial action a n d in a second stage catalytic clays reacted be low 250° F. with these transition products to form petroleums as we k n o w them. Modern Motor Fuels T h e symposium on modern motor fuels held by the Division of Petroleum Chemistry was opened by the chairman of the division, Gustav Egloff, with a re view of recent developments, a discussion of present legislation and government work in thefield,a n d s o m e predictions as to the future. With the great interest that is being taken today in increasing the efficiency of motor fuels, both in themselves and in the manner in which they are utilized and the possible widespread development of high compression-ratio engines, more attention is being paid to octane n u m b e r and to fuels of high "sensitivity" or dif ference between the motor octane and research octane numbers. Therefore the paper delivered by D . P . Heath of the Socony-Vacuum Laboratories which re ported an extensive program of research into the determination of octane numbers of blended gasolines was especially timely. TJhere has been some publicity given re cently tofluidalumina catalysts for use in cracking, reforming, and other processes as compared with conventional silica and silica-alumina catalysts, a n d the paper introducing the results of still another catalyst, a synthetic silica-magnesia mate rial, was of much interest- R . W . Rich ardson, associate director of the Esso Laboratories, presented data to show that this new material gives greater gasoline yield when used in cracking than do the other catalysts mentioned although the gasoline is lower in octane n u m b e r than that produced with silica-alumina. Less fresh catalyst replacement seems to be indicated, and the use of such a catalyst in fluid catalytic cracking seems to be war ranted, especially where high liquid prod uct yield is desirable and yields of low boiling unsaturates, such as butane-butene, are not of prime importance. Petroleum
Dinner
T h e dinner of the Division of Petroleum Chemistry was mainly entertainment, as usual, but a very pleasant addition was a short summary of the division's history 1361
The Symposium, on Modern Motor Fuels featured: John Anderson, Shell Development Co.; Roger Richardson, Esso Laboratories ; E. L. Walters, Shell Development Co.; Gu&tav Eglojf, Universal Oil Products, division chairman; and D. P . Heath, F. L. Nelson, and J. W. Brooks of Socony- Vacuum Oil Co· during the past 2 5 years b y Robert E. Wilson, chairman of the board, Standard of Indiana, one of the founders of the division. D r . Wilson emphasized that the growth of the division from less than 350 in the 1920's to 1,557 in 1948 paralleled the petroleum industry a n d remarked that 9 5 % of the increase in energy requirements in the past 2 5 years w a s due to petroleum. ideal Behavior T h e Division of Physical a n d Inorganic Chemistry presented its usual large program that included symposia sponsored either jointly or solely by the division. T h e topics of these S3rniposia included transuranium elements, galvanic cells and batteries, organorcietallic compounds, and aerosols. T h e highlight of the division's social program was reached in its dinner meeting at which Joel Hildcbrand of the University of California was the main speaker. Henry Eyring, of the University of Utah a n d chairman of the division, presided at the dinner meeting. Before introducing the principal speaker, D r . E y ring drew the gathering's attention to a symposium which will be held under the division's sponsorship at Syracuse University, June 28 to 30. H e revealed that under the chairmanship of Martin Kilpatrick of the Illinois Institute of Technology the symposium conirnmittee has planned a program that will include sessions on the thermodynamic properties of inorganic compounds, new industrial developments, and the inorganic chemistry of sulfur, phosphorous, nitrogen, and the halogens. "Deviations from Ideal Behavior" was the title of the informally presented talk by Hildebrand. In it, the speaker attempted to draw analogies between ideal cases in the liquid state and those in hum a n conduct and affairs. T h e result was a pleasing discussion that stimulated the thinking of all w h o heard it. Just as in the case of chemistry, Professor Hildebrand declared, ideal behavior in h u m a n affairs is never attained but al-
1361
w a y s asymptotically approached. E n tropy in science can be likened to confusion in social conduct, and negative deviations such as low energy are represented in h u m a n affairs by the characteristic of low imagination. High energy and high entropy on the other hand, Professor Hildebrand contended, can be as confusing in the social thinking of the scientist as well as in his scientific deliberations. Scientists must always be prepared to m a k e the difficult but necessary choice between working for their o w n ideals and those in the best interests of society, two not alw a y s compatible aims. Professor Hildebrand concluded b y saying that scientists must keep the s a m e integrity of thinking outside the laboratory as in their daily work. W h e n they fail to do this, he warned, they face the prospect of losing influence in social affairs. Uranium
Hexafltioridc
Conductivity
A description of the measurements of the thermal conductivity of uranium hexafluoride in gaseous form was presented in the paper by P . A . Argron of Alexander Smith and Sons and A . H . Taylor of the Air Reduction C o . T h e two authors accomplished the work described in the paper during their employment at C o l u m bia University's laboratories working on the Manhattan Project. It w a s revealed that hot wire measurements were used in the determination, the conductivity being determined at t w o different temperatures. T h e actual technique consisted of heating by electrical means a wire enclosed in a cell containing gaseous uranium hexafluoride. B y noting the additional electrical energy required to heat the wire to a slightly higher temperature the constants for the thermal conductivity w a s calculated. During the course of the work the walls of the cell were kept at constant temperature. A t first, d u e to the corrosive nature of the material being measured, the cell characteristics changed rapidly. Eventually these characteristics leveled off and it became possible to m a k e precise c o m -
CHEMICAL
parisons with other gases. T h e thermal conductivity of uranium hexafluoride was then obtained by graphical comparison with the data of k n o w n gases. T h e effect of high frequency sound waves on several liquids w a s reported in the paper by Alfred Weissler of the Naval Research Laboratory. T h e author revealed that experiments had been carried out o n some 2 0 substances with the use of a 3 million cycle ultrasonic interferometer. T h e results of the studies have indicated that the so-called "silent sound" measurements provide a good m e a n s of c o m p o u n d identification superior in m a n y ways to the m o r e conventional refractive index type of measurement. T h e ultrasonic production of iodine from an aqueous solution of potassium iodide in contact with s o m e carbon tetrachloride was discussed in a subsequent paper by D r . Weissler. H e revealed that the a m o u n t of iodine liberated during a five-minute irradiation is almost independent of the normality of the potassium iodide or the a m o u n t of carbon tetrachloride used except at very low concentrations. T h e dimensions and material of the container, however, did have an effect on the iodine yield. Polythene, porcelain, metal, a n d glass containers were used, and glass seemed to be the most suitable from the point of yield of iodine obtained. T h e diameters of the various glass tubes did not seem to be as critical as the wall thickness.
Transuranium
Elements
T h e symposium on the transuranium elements opened with a historical review of the newcomers to the periodic table by Glenn T . Seaborg of the University of California, w h o presided at thefirstsession. D r . Seaborg pointed out that although neptunium, plutonium, americium, and curium have all been discovered within the past eight years, their chemistry has been well explored and considerable information has been unearthed about them. At first these investigations had to be m a d e on tracer amounts by radiochemical methods. M o r e recently, D r . Seaborg declared, it has been possible to isolate these m a terials in weighable amounts, a n d macroscopic techniques have been employed. These various studies have shown, the speaker claimed, that not only the transuranium elements but several of the heaviest of the natural elements and a number of undiscovered transcurium elements as well are all related to each other in that they form a transition series. For this reason, Seaborg explained, the program of the symposium w a s designed to include papers o n actinium, thorium, protactinium, and uranium. Actinium
isolatetl
T h e successful production of actinium by the b o m b a r d m e n t of radium in a uranium pile w a s announced b y French
AND
ENGINEERING
NEWS
H a g e m a n of the Argonne National Laboratory in the paper he presented to the symposium about the isolation of the element and the preparation of seme of its compounds. T h e author declared that the element, number 89 in the periodic table, is probably the last naturally occurring element which can be isolated in visible amounts. After the irradiation, H a g e m a n explained it was necessary to separate the actinium from radium and the "daughter" elements of radium and actinium—thorium, polonium, lead, and bismuth. Because of the extreme radioactivity of the materials it was necessary to effect this separation by remote control. T h e preparation and identification of several pure compounds of actinium were also revealed in the H a g e m a n paper. A m o n g these, which were determined by x-ray methods, were thefluoride,chloride, bromide, oxychloride, oxybromide, oxide, sulfide, and phosphate. The x-ray identifications were extremely difficult because of actinium's penetrating radiations which tended to fog the plate. T h e only way such measurements were m a d e possible was b y using very small material samples within 24 hours after separation before "hard" radiation could develop. Samples of carnotite, fergusonite and hatchettolite were examined in a search for plutonium and neptunium as described in a paper by C . S. Garner of the University of California, N . A . Bonner of Washington University, and Seaborg. The searches were instituted to find out whether these elements existed in nature to a degree that would m a k e their recovery from ores directly a worthwhile and economical process. N o evidence was found, however, that appreciable amounts of either element were obtainable. The actual concentrations found were of the upper limit order of one part in 1010 of carnotite, one part in 109 of fergusonite and hatchettolite. T h e isolation and chemical properties of protactinium w a s the topic of the paper b y R . C . T h o m p s o n , now at the University of Texas but formerly with the Metallurgical Laboratory of the University of Chicago. T h e author revealed thai the studies on the chemistry of protactinium have been carried on in three main categories : tracer scale studies of coprecipitation, adsorption, and solvent extraction, the development and application of procedures for the extraction of milligram amounts of protactinium from natural sources, and some milligram adsorption, solvent extraction, and solubility studies. T h e likelihood that absorption phenomena are chiefly involved seems indicated by the coprecipitation studies, the author declared. A cation exchange resin is capable of adsorbing protactinium from acid solution, the element probably being in the colloidal form. A n anion exchange resin functions in a like manner in the case of hydrofluoric acid solutions of pro·
VOLUME
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tactinium. In this case, the adsorption is probably in the form of the P a F 7 ion. Organic solvents are capable of extracting protactinium nitrates and chlorides from aqueous solutions. S o m e studies in the dry chemistry of plutonium fluorides were presented in the paper b y Sherman Fried and N o r m a n R . Davidson formerly of the Argonne N a tional Laboratory and n o w with the California Institute of Technology. T h e authors said that although plutonium tetrafluoride does not react with dry oxygen at temperatures up to 600 °C. the tri fluoride will undergo a reaction to form the tetrafluoride and the oxide at this temperature. A t 900 °C. the tetrafluoride will decompose to form the trifluorideand presumably fluorine. This latter reaction has been observed to take place in containers m a d e of platinum, beryllium oxide, and calcium fluoride, and so the idea that the reaction is one that takes place with the materials of the containing vessel is somewhat precluded, the authors explained. The absorption spectra of transuranium salts seem to consist for the most part of lines comparable in sharpness with those of the alkal ine earths, according to Simon Fried and Fred Leitz of the Clinton N a tional Laboratory, but their intensities are considerably greater. It would appear, the authors declared, that the analogies so often drawn between the transuranium elements and the rare earths g o beyond the electronic configurations of the basic states and extend to the electronic configurations of the activated states as well.
N O . 19 · · » .
Aerosols A discussion of the aging process in disperse systems of solids in still a n d turbulent air was presented in the paper b y G . 0 . Langstroth, T . Gillespie, and R . M . Pearce of the University of Alberta. T h e authors revealed that in studies o n the aging of systems in still air the practice has been to interpret the slope of the particular volume versus the time curve as the coagulation constant. This method has led to values for the constant that are three or four times as great, as that predicted b y theory.
Studies of the particle n u m b e r and mass concentration changes in a m m o n i u m chloride smokes both in still and moving air has brought about a different method of interpretation of data. In these cases, the differential equation for the rate of change of particle number has added to it a term to take into account any loss to surfaces. This results in the volume versus time curve having a constant descriptive of the rate of loss as well as the desired coagulation constant. T h e additional advantage is found in that the latter constant finds comfortable agreement with that predicted b y theory. Recent progress in the use of aerosols to disseminate insecticides on a large scale was discussed in the paper presented by Victor K . L a M e r and Seymour Hockberg of Columbia University. T h e authors revealed that although the most immediate applications will be in tropical and subtropical climates, there are several instances in the temperate regions, such as the fight against black flies, where aerosol dissemination methods will be of great consequence. T h e importance of the proper droplet size was stressed in the paper. In one actual case the authors presented, in which a generator capable of producing particle sizes of 2 to 40 micron diameter was used, kill on the wing of mosquitoes was achieved at 6,000 feet, and larval control at distances of 8,000 feet downwind w a s noted. Perhaps more important, the authors declared, w a s the fact that this was accomplished at surprisingly low area dosages of the insecticide used,
DDT. T h e n o w familiar high pressure type aerosol insecticide b o m b will gradually be replaced b y low or moderate pressure containers which will result in a saving to the consumer, according to Lyie Goodhue of the Phillips Petroleum C o . T h e reason for the economy is twofold, according to the author of a paper on the subject presented at the aerosol symposium. T h e container for the lower pressure materials will be less expensive than that for the high pressure materials, and an added advantage is found in the fact that the low pressure propellants
On the program of the Division of Physical and Inorganic Chemistry were: IP. M . Manning, Argonne National Laboratory; Bruce Longtin, Illinois Institute of Technology; and Jacob Bigeleisen, olso of the Argonne National Laboratory
M A Y 10, 1 9 4 8
1363
are generally better solvents than those used in the high pressure devices. Galvanic
Cells and Batteries
The gaps of knowledge that exist about the behavior of physical and inorganic systems at extremely high and low tem peratures and about the problems involved in the mechanism and construction of miniature cells with high potential energy were pointed out in the opening remarks of Walter J. H a m e r of the National Bureau of Standards. D r . H a m e r , w h o presided at the opening session of the symposium on galvanic cells and batteries, said that this lack of knowledge has accentuated the problem of battery manufacturers to find suitable substitutes for battery materials, which are gradually becoming scarce. T h e conventional approach to battery design m a y have to be abandoned, D r . H a m e r declared. Renewed interest in reserve-type batteries or those activated at the time of use has broadened the ap proach to the subject of cells. Batteries activated either mechanically, b y water, by shock, or b y heat should store indefi nitely without deterioration. It is not nec essary to think in terms of reversibility, ehelf life, or chemical side reactions w h e n dealing with batteries of this type. Sulfuric acid solutions, the electrolyte of the lead-acid storage cell, was the topic of a paper presented b y T . F . Y o u n g of the University of Chicago. T h e dissociation constants of sulfuric acid have a range of values that m a k e possible the investiga tion of solutions in which the solute is completely dissociated, others in which it is mainly hydrogen ion and bisulfate ion, and others, extremely concentrated, in which it is hardly possible to perceive a first dissociation at all. T h e results of recent investigations of the temperature coefficient of the second dissociation constant and the properties of ternary mixtures of electrolytes have m a d e it possible to calculate the heat of dilution curve for very dilute solutions. This theoretical curve agrees very well with observed experimental data. A method to evaluate the depolarizing characteristics of manganese dioxide de polarizers w a s described in the paper by G . A . Marsh and H . J. M c D o n a l d of Illi nois Institute of Technology. The authors pointed out that the conventional means of accomplishing this evaluation has been by the construction of test cells and meas uring the e.m.f. and capacity of the cells. T h e n e w method m a k e s use of a pulse polarizer, a device often used to study rates of corrosdbn of metals under certain condi tions. This high voltage pulse mechanism polarizes an electrode surface with a pulse of electricity, and a sensitive detector and recorder reveal the depolarization behavior of the test electrode under study. Organ ownetallic
Compounds
T h e fascinating field of organometallic compounds was well explored in the s y m
1364
posium on the subject. A . A . Morton of the Massachusetts Institute of Technol ogy pointed out in his paper o n organosodium compounds some of the limitations on the preparation of these materials. It has been k n o w n for s o m e time that these organosodium compounds are capable of undergoing acid-salt interchange reac tions and reactions including addition to carbonyl and certain olefin systems, cleav age of ethers, and polymerization of dienes. More recent developments in their use are along two general lines ; the metalation of olefins and certain aromatic compounds and the catalytic polymerization of dienes to high molecular weight materials by use of Alfin catalysts. The organic compounds of arsenic were the subject of a paper by C . K . Banks of Parke, Davis & C o . T h e author ex plained that these materials are hybrid substances having properties like their inorganic counterparts intermediate be tween the organolithiums and organozincs on one hand and the distinctly nonmetal-" lie sulfonic and phosphonic acids and ni trogen and halogen derivatives on the other. Arsenic is unique in that it will form compounds having one to five carbon residues attached to the arsenic atom, which though sufficiently stable under ordinary conditions can be caused to disproportionate. D u e to the variety of linkages and struc ture organic arsenicals can be classified into about 10 major categories having some 35 subgroupings. Because of this great variation arsenic lends itself to a host of medicinal uses where it is necessary to control the relative toxicities of the drug to both host and infectious organism. The formation of complex alkyl com pounds by the reaction of the alkyls of strongly electropositive elements such as the alkali metals with the alkyls of ac ceptor elements such as aluminum and boron was discussed in the paper b y D . T . Hurd of the General Electric C o . A s an example of this type of synthesis the au thor used the case of the addition of excess aluminum tri methyl to lithium methyl in ether solution which after evaporation yields lithium aluminum tetramethyl as a white crystalline solid stable in dry air at room temperature. If boron trimethyl is used instead of the aluminum compound, lithium boron tetramethyl is formed. This material is soluble in water to form a strongly acid solution with strong reduc ing properties. W h e n acidified this solu tion releases large volumes of spontane ously flammable boron trimethyl. A n interesting comparison was m a d e be tween pseudo-organic behavior of the boron-nitrogen unit and the carbon-carbon bond of conventional organic chemistry in the paper b y A - B . Burg and C . L . R a n dolph of the University of California at Los Angeles. T h e authors used as ex amples the benaene-structure of B^NaHt, the neopentane-analog ( C H 3 ) 3 N B H 3 and the butane-pattern of H 3 B N H 2 B H 2 N H 3 .
CHEMICAL
Division of Rubber
Chemistry
The twenty-ninth meeting of the Divi sion of Rubber Chemistry at Chicago con vened on Wednesday of the general meet ing for three days and was unusually well attended. T h e division dinner was held Thursday evening, at which tinictlie first award of the Charles Good3rear Medal was m a d e to George Oenslager, of Akron, for his historic development of organic accelerators and other notable contribu tions to rubber processing technology. The technical sessions of the division as well as the dinner were held in the Hotel Sherman, with Harry E . Outcault of St. Joseph Lead C o . and chairman of the division presiding. Papers at the first session were given over to problems of polymerization, cyclorubber, alkyl phenol antioxidants, the vulcanization of and the effect of light on neoprene. L . H . Perry, Union Bay State Chemical C o . , described work done at the Newport Industries laboratory o n tertbutyl hydroperoxide and derivatives as catalysts for low molecular weight polyisoprene. Technologists from the U . S. Rubber C o . laboratory at Naugatuck, Conn., described the effect of low poly merization temperatures on G E - S -vulcanizates, and three chemists from Firestone Tire and Rubber C o . offered a paper out lining results of polymerization work with various monomers in the b u n a S-3 system. On the two succeeding days speakers accorded attention to a number of aspects in compounding rubber with furnace blacks, to the tackiness of butyl a n d na tural rubber, aging effects o f scrap, and the results of recent strain tests for evalu ating rubber compounds. The properties of a high abrasion black, Philblack O , were compared witli other types by technical workers from the Phillips Petroleum C o . The curing and scorcbing properties of furnace blacks, and an ex trusion shrinkage test for judging process ing properties, were discussed by Ε . Μ . Dannenberg and C . A . Stokes of O o d frey L . Cabot, Boston. Means of reducing scorch when afinefurnace black is used as replacement for channel black in tire tread stocks, were presented in a paper by O . H . McCollum of the D u Pont, rubber laboratory. Other talks on the technical program dealt with the effect of pigments on the hardness of natural and synthetic rub bers, high-styrcne resins in compounding, the effect of high processing temperatures on accelerator stability, and compounding practices employing petroleum products. There was also a separate discussion by H . A . Winkelmann of D r y d e n Rubber Co. and R . E . Elliott, Standard Oil of Indiana, on the effect of a· petroleum-type plasticizer on various furnace blacks in natural rubber. T h e medal dinner of the Hubber Divi sion was one of the best attended events of the Chicago meeting. There were 42
A N D ENGINEERING
NEWS
George Oenslager is congratiilatetl by Harry E, Outcau.lt, St. Joseph Lead Co,9 chairman of the Division of Rubber Chem istry, on his receipt of the first Cliarles Goodyear Medal, guests of honor at the head table, and the grand ballroom of the Sherman w a s filled to capacity when Division Chairman Outcaul t rose to introduce D r . Oenslager as "the m a n w h o had brought employment to our industry." In addition to the medal and certificate, D r . Oenslager w a s given a token check for $200 by the division members in recog nition of his contributions, which prob ably rank second only to those of Charles Goodyear, discoverer of vulcanization. Dr. Outcault formally presented the awards to the medalist following an ad dress on Ocnslager's scientific accomplish ments given by H . E . S i m m o n s , president of the University of Akron. A n account of George Oenslager, his contributions to rubber chemistry and his personal side, w a s published in C H E M I C A L A N D ENGINEERING N E W S , March 29, 1948. On the following morning, the division honored four past Goodyear lecturers by presenting them with medals and certifi cates of award similar to those given D r . Oenslager. These Goodyear medalists are Ira Williams, J. M . Hubcr Corp.; Waldo L . Semon, B . F . Goodrich C o . ; and Lorin B . Sebrell, Goodyear Tire and Rubber C o . A medal and certificate also were awarded to the first m a n to be selected for this honor, David Spence of Pacific Grove, Calif., w h o could not c o m e to Chi cago. Presentation will be m a d e to h i m during the July meeting of the rubber division in Los Angeles. Molasses
Prices to
Drop
A prediction that the price of black strap molasses will fall to 10 cents a gal lon from its present level of 34 cents w a s voiced b y Robert S. Aries of the Poly technic Institute of Brooklyn, speaking before the Division of Sugar Chemistry and Technology. T o back his statement, D r . Aries pointed out that the whole world is planting sugar. There is already a sugar glut in the dollar countries, he asserted, and there soon will be in others. Molasses will be forced d o w n , he pre
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NO.
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Right. H, E, Simmons, president of Akron University9 and H. I, Cramer, chairman-elect of the division. Dr. Simmons discussed the metlalisfs contributions to rubber chemistry
dicts, by synthetic and by-product alco hol with molasses from w o o d hydrolysis providing a coiling to prices. But dis agreeing with others w h o cite costs of 7 to 10 cents per gallon for molasses from this source, h e has arrived at a more prob able range of 16 to 18 cents. Broken d o w n , his figures arc based on the following al lowances: depreciation, 2 cents per gallon; labor, 5 cents; chemicals, 1 cent; steam, 2 cents; w o o d , 5 to 7 cents; maintenance, 1 cent. As for the effect of ion exchange methods in sugar refining, which while increasing sugar yields would lower molasses pro duction, D r . Aries does not feel that this will be a serious factor for the next decade. At the s a m e session, at which W . W . Pigm a n of the Institute of Paper Chemistry presided, the recovery of 180 tons of aconitic acid from a 190,000-ton sugar crop at a single plant at Raceland, L a . , last year w a s reported in a paper by R . J. Furse and Leon Godchaux II of Godchaux Sugars, Inc. T h e Louisiana sugar crop could supply more than 4 million pounds of this product annually, they stated. Aconitic acid, a nonsugar impurity in molasses, is useful in synthetic detergents and as a softening agent for plastics and rubber. Aconitic acid is removed continuously as the calcium magnesium salt by the addition of lime and calcium chloride to w a r m Β molasses. Centrifuges are e m ployed for concentration, separation, and washing. Β molasses averaged 4 . 2 % aconitic acid content on solids during the 1947 crop, the authors stated, with an average removal of 2.3% o n solids. While the occurrence of aconitic acid in sugar cane juices has long been k n o w n , its quan tity has been underestimated until re cently, they added. T h e isolation from enzyme-hydrolyzed sugar beet pulp of ferulic acid, supposedly derived from coniferin, w a s reported by Elizabeth R o b o z of the N e w York State Agricultural Experiment Station, Cornell University.
· · • MAY
10, 1948
Strep ta mine
Synlhesixetl
Turning to the scientific papers on the sugar program, the configuration of streptidine and a synthesis of strcptamine were announced b y M . L . Wolfram a n d S. M . Olin of Ohio State University at the opening session of the division, at which D r . Wolfram presided. This con stitutes the first synthesis of the cyclotol portion of streptomycin; it w a s derived basically from glucose. Streptidine w a s concluded to be configurationally all trans. In another paper from Ohio State, D r . Wolfram and F . A . H . Rice revealed that it has been found possible to dissolve sulfated sugars and polysaccharides in absolute sulfuric acid at —15° wibhout decomposition; addition of five volumes of acetic anhydride leads to simultaneous desulfation and acetylation of the sugar or polysaccharide. Other esters of inorganic acids, such as nitrates and phosphates, m a y similarly be removed from carbohy drates. A m o n g other papers, a new method of analytically separating amylose from amylopectin by differences in the solu bility of their carbanilates in ethyl acetate was reported by Louis Sattler of Brooklyn College and F . W . Zerban of the N e w York Sugar Trade Laboratory. T h e syn thesis of a n u m b e r of iodo-sugar deriva tives to examine their utility as x-ray contrast agents was reported b y Albert L . R a y m o n d a n d Elmer F . Schrocder of G . D . Searie and C o . While some of the water-soluble derivatives give satisfac tory x-ray visualization in the kidneys, a region not heretofore reached safely b y this type of treatment, they are relatively unstable, splitting off H I , and will re quire further investigation before clinical use. Blue
Babies
A newly discovered water-borne disease that turns babies blue was reported before the Division of Water, Sewage, and Sani tation Chemistry by chemists of the Illi nois Department of Public Health. These
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T. it. I\Tetvkirk9 Corn Protittcts Rejining Co.; Elisabeth Roboz, Cornell University; and J. ÏJ*/. Crecrt* institute of Paper Chemistry, spoke o n the sugur chemistry program "blue babies" are the progeny of drinking water contaminated by excessive nitrogen in the shallow wells of rural areas in the Midwest and other parts of the world, according to the authors, James G . AVcart and C . W . Klassen. W h e n water from a contaminated well is used in preparing a baby's formula or as a supplement to breast feeding, excessive nitrogen in the form of nitrate m a y i m pede the blood's delivery of oxygen to body tissues, producing a bluish or cyanotic condition of the skin, they pointed out. The toxic effect results from the conversion of nitrate into nitrite b\· bacterial action in the intestine. O n absorption into the blood, nitrite converts hemoglobin to methemoglobin, which is incapable of transport ing oxygen. Blue babies resemble those suffering from pneumonia or congenital heart malformations. In severe cases, death or serious d a m a g e can result. During the past year in Illinois alone, the authors revealed, 33 cases, includingfivedeaths, were reported. Although swift recovery can often b e assured merely by substituting satisfactory water, the problem persists because in countless instances n o other water is available, and there is no practical method of removing the nitrate, they stated. Aside from changing the water, other treatments have been developed which involve methylene blue or ascorbic acid. " T h e prompt recovery following the use of either of these two substances is reported to be very dramatic/' they added. Discussing the source of ground-water nitrates, Weart and Klassen indicated that they must c o m e from soil h u m u s . N i trates are so readily liberated from the soil by moderate leaching that they are not found in surface soil except in minute quantities. H e a v y rainfall tends to wash nitrates into the lower soil depths and a w a y from plant action. T h e concentration of nitrate is attributed to the geology and water distribution of the area. T h e mineral quality of high nitrate waters is generally abnormal from the standpoint of domestic use, the authors
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continued, indicat ing that they are normal as to alka linity but contain sulfate and chloride in rather large amounts. T h e waters are generally free from a m m o n i a , iron, a n d fluorides and are sparkling clear. N o correla tion has been found between the presence of largo amounts of nitrate and the sanitary quality of the water. It w a s proposed that a m a x i m u m
safe limit of 10 p . p . m . of nitrate nitrogen be established for all water used in infant feedingr T h e authors found that at least 2br,'c of farm wells furnish-water with more than 100 |).p.m. of nitrate nitrogen. T h e conditions which permit these high con centrations of nitrates exist in m a n y other parts of the world, particularly in the richer agricultural areas of Kurope and Asia. High nitrates waters have already been reported from Iowa, Kansas, N e braska, Michigan, Illinois, Minnesota, M i s souri, Belgium, and England. Cosmic Radiocarbon T h e isolation 6f cosmic radiocarbon from sewage gas w a s announced by Aris tide V . Crosse of the Jloudry laboratories in reporting work done in cooperation with Willard F. Libby o f the Institute of N u clear Studies, Chicago. Exploring the theory that a naturally occurring radioac tive carbon m a y be formed from nitrogen by neutrons produced from cosmic radia tion, the co-workers searched for radioac tivity in petroleum methane and in m e t h ane from sewage gas. Assuming the cosmic ray origin of the expected isotope, C 1 4 , and considering that its half-life is 4,800 years, it would be expected to occur in all "living" carbon, or carbon on the surface of the earth in con tact with the atmosphere, while geologi cally old or "dead" carbon, such as in coal, peat, or petroleum, should be free from it. These suppositions were confirmed when petroleum methane failed to show any activity, and methane from Baltimore sewage gas, after isotopic concentration in Clusius-Dickcl columns, showed the existence of natural C 1 4 in amounts of 0.95 X 10"12 grams of Cu per gram of carbon, or equal to 10.5 disintegrations per minute and per gram of carbon. T h e effect of vanadium on B . O . D . de terminations was revealed in a paper by VI. Gladys Swope and Anne Gearing of Allegheny C o u n t y Sanitary Authority (Pennsylvania). Encountering vanadium in the course of a n investigation of the treatment and handling of industrial wastes, the authors suspected that it
CHEMICAL
might hinder biological action, inasmuch a s vanadium salts have been r e c o m m e n d e d as antiseptics. It w a s found that as little as 0.25 p . p . m . had a noticeable effect. Other papers on the general program of the Division of Water, Sewage, and Sanita tion Chemistry, over which Miss S w o p e presided, included discussions of water analysis, anion-active resins, and biologi cal oxygen d e m a n d of sewage. In addition a symposium on the industrial application of ion exchange w a s conducted jointly with the Division of Industrial and Engi neering Chemistry. Also a part of the pro g r a m were inspection trips to the Chicago South District water filtration plant a n d the Southwest plant of the Chicago Sani tary District. ion. Exchit η ge
Application.
T e n papers were presented on the s y m posium o n industrial applications of ion exchange, with A . S. B c h r m a n of Chicago presiding. Topics covered included aspects and applications of ion exchange in water treatment, silica removal,waste treatment, the pharmaceutical field, milk products, agriculture, and sugar refining. T h e application and economics of ion exchangers in water treatment were dis cussed b y II. B . Gustafson of Infilco C o . w h o stated that ion exchangers are con venient and versatile tools of considerable usefulness in the art of water treatment In one application ion exchangers m a y compete against precipitation methods of treatment, in another against distillation, in a third against an alternative ion ex change procedure, and in a fourth m a y complement another method or methods of treatment. Occasionally, ion exchang ers are used as filters to remove suspended matter, but such a n application is nol generally sound or practicable. Ion ex changers have been given an increased a m o u n t of attention in the past few years. This expanded interest seems due largely to the discovery of synthetic organic ex changers which apparently captured the imagination of resin manufacturers as it opened a new field for resin application. instrumentation for Ion. Exchange Processes Instrumentation in the control of ion exchange processes w a s discussed by W . N . Greer a n d G . A . Perley of Leeds a n d Northrup C o . Regarding the need for this instrumentation, the authors stated that numerous papers have been p u b lished recently on the use of ion exchangers in various processes, but little mention has been m a d e of instruments used as a guide either in pilot plant or full plant operation, or of the use of recording or automatic control equipment. With the .trend in sonne cases toward continuous processing through a series of exchangers, the value of instrumentation becomes increasingly m o r e important. T h e m o d e of operation and the material being processed largely determines the instrumentation required.
AND
ENGINEERING
NEWS
