Systematic Treatment of Reaction Kinetics Can Be Accomplished

Nov 12, 2010 - Publication Date: August 24, 1953 ... of Utah, at the XIIIth International Congress of Pure and Applied Chemistry, held here July 29 to...
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THE CHEMICAL WORLD THIS WEEK

The Svedberg (center), honorary president of the XUIth International Congress of Pure and Applied Chemistry, chats with plenary lecturers Sir Cyril Hinshelwood ( left ) , Oxford University, and Harold C. Urey, University of Chicago. Total attendance at the Stockholm conference was 1200 active members plus 400 passive members, and included 135 members from the United States. Western Germany was represented b y an official delegation to the International Congress for the first time since the war C&EN REPORTS: XUIth I n t e r n a t i o n a l Congress of Pure and Applied Chemistry

Systematic Treatment of Reaction Kinetics Can Be Accomplished Increasing interest noted in f u n d a m e n t a l studies of cellulose a n d commercial utilization of lignin a n d w a s t e w o o d products STOCKHOLM.—No insurmountable difficulties lie in the way of a systematic treatment of reaction kinetics but complications continue to make the process interesting, declared I lenry Eyring, University of Utah, at the XUIth International Congress of Pure and Applied Chemistry, held here July 29 to Aug. 4. It was a meeting of the physical chemistry section, but included a symposium on the chemistry of wood and wood products. In his plenan lecture, Dr. Eyring went on to point out that rate theory is leading to illuminating results in viscosity, plasticity, electrical conductance, isotope effects, and biological processes. Continuing his analysis of current problems of reaction rate theory, he reported that although the difficult task is still unfinished further progress is being made on the calculation of the activation energy for the simplest type of chemical reaction D -f H 2 - » D H + H. "If w e divide the theoretical calculation of reaction rates into ( 1 ) the calcula-

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tion of the potential energy surfaces and ( 2 ) the subsequent statistical mechanical part, we can say that part ( 2 ) is in a comparatively finished state and part ( 1 ) is near its beginning," Dr. Eyring said. Hydrocarbon Decomposition. The thermal decomposition of hydrocarbons offers problems of interest to all types of chemists, said Sir Cyril Hinshelwood, Oxford University. The organic chemistry of the reactions, the kinetics of chain reactions, the way in which inhibitors affect the two

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opposing reactions of an equilibrium system, and theory of unimolecular processes in rather complex molecules are all involved in this study, said the plenary lecturer. The general type of reaction is the formation of a paraffin and an olefin. The saturated paraffin is always the smaller portion from pentane and above, methane being produced in large proportion, ethane in smaller proportion, and propane in smallest proportion. Butane is practically absent, explained Sir Cyril. T h e duality of mechanism, that is by chain reaction and by molecular reaction, is proved by the action of inhibitors, he continued. Nitric oxide' on the one hand or propylene on the other both remove free radicals and reduce the reaction rate. Turning to the theory of unimolecular reactions, Sir Cyril said the available evidence seems to point clearly to the fact that the constant residual reaction (independent of the different inhibitors) which remains when the rate has been reduced to its limiting value b y nitric oxide or by propylene, represents the decomposition of a single molecule directly into simpler molecular payments. Isotope Preparation. In another plenary lecture Klaus Clusius, Zurich, described the work on separation of inactive isotopes as important, even though less in the limelight, as the work on separation of radioactive isotopes. His investigations are leading to a better understanding of vapor pressure, specific heat, and related properties. A thermal diffusion technique involving a heated wire in a glass tube surrounded by a cooling jacket is being used at Zurich. A diffusion chain amounting to a path of as much as 20 meters is used. As an example of the difficulties involved, Prof. Clusius pointed out that for separation of the xenon-136 isotope in a concentration of 97.1%, 8200 steps were required. Krypton and argon isotopes are also being separated. In concentrating the argon isotopes, deuterium chloride is utilized for segregating the desired constituent, he explained. In other plenary lectures Maurice Letort, University of Nancy, discussed the velocity of combustion of carbon, pointing out that at 2000° K. the velocity is approximately 10 times smaller than at 1400° K. S. R. de Groot, University of Utrecht, described the thermodynamics of irreversible processes in physical chemistry. Aldehyde Polymerization. A new interpretation, based on the formation of hydrogen bonds, was proposed to account for the low temperature polymerization of aldehydes. W. C. Schneider, Cambridge University, chose formaldehyde for full discussion but declared that his ideas are readily extendable to the polymers of

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acetaldehyde a n d t h e higher aldehydes, glyoxal, chloral, ketene, and related com­ pounds. By virtue of the neighboring carbonyl o x y g e n , aldehydic h y d r o g e n is sufficiently ""positive" t o form strong hydrogen bonds, l i e s a i d . T h e formaldehyde molecule is completely planar in structure and, to illustrate this, Dr. Schneider explained that t h e l o n e pair electrons on the carl?onyl oxygen are described b y two di­ r e c t e d orbitals in t h e plane of the H C = 0 group, making an angle of / 120° with each other and with the C—Ο axis. Formaldehyde can form hydrogen bonds either with itself or w i t h other molecules,„ such as water. Instead of polyoxymethylene structure, Dr. Schneider suggested a completely 'hydrogen-bonded structure for the poly­ mer o f anhydrous formaldehyde. T h e pro­ posed structure, u n d e r favorable condi­ tions of formation, will b e planar, with a repeating ring structure containing four molecules. T h e polymer formed from water solution, he continued, will h a v e varying a m o u n t s of water b o u n d into the structure b y hydrogen bonds. H e w Polyether. A new polyether, capa­ ble o f forming oriented films a n d fibers, has b e e n prepared in the laboratories of Imperial Chemical Industries. I n t h e pres­ ence of electrophilic catalysts, 3:3-bis( chloromethyl ) -oxacyclobutane may b e polymerized. I n t h e paper b y A. C. F a r t h ­ ing and B . J. W . Reynolds, boron trifluoride w a s cited as an acceptable cata­ lyst, but it w a s explained t h a t minute traces of water w e r e also necessary for the polymerization to proceed. T h e re­ sulting polyether, poly-3:3-bis-(chlorornetxiyl)-oxabutene, is an inert, highly crystalline and insoluble polymer, with a melting point of 1 8 0 ° . C h l o r o s u l f o n a t e d Polyethylene Solu­ tions. To study t h e reactions involved in the cross-linking of chlorinated or chlorosulfonated polyethylene, a very sensitive and rapid curing test has b e e n developed. W h e n polyethylene is chlorinated or chlorosulfonated, it produces an elastomer whicli c a n b e cross-linked or cured by a nurriber of different mechanisms. The mechanisms may involve reactions through: (1) the S0 2 C1 groups, ( 2 ) cer­ tain chain chlorine atoms, ( 3 ) unsatu­ rated groups formed b y splitting off HC1 or S 0 2 - h H Cl, or ( 4 ) active methylene groups. E x p l a i n i n g their experimental proce­ dure, W. F. Busse a n d d F . W . Billmeyer, Du Pont, said that potential curing agents were added t o 1 5 % solutions of chloro­ sulfonated polyethylene in tetralin. Vis­ cosity c h a n g e s o r gel formation were noted after the solutions w e r e h e a t e d through t h e various t e m p e r a t u r e cycles u p to 175° C . I t was possible to separate t h e effects o f some of t h e curing reactions b y adding t w o o r more types of curing agents to t h e solution, Mr. Busse said. A l i p h a t i c diamines react very rapidly at room temperature to form sulfonamide V O L U M E

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cross-links. If t h e t e m p e r a t u r e is raised to 150° to 175° C , they m a y also react through the chain chlorine a t o m s , he said. Aromatic diamines can f o r m cross-links through sulfonamide g r o u p s . Ethanolamines form thermoplastic gels involving cross-links t h r o u g h secondary valence forces, h e continued. Many sulfur-containing r u b b e r accelera­ tors, as weM as H2SO.t a n d a q u e o u s K O I I , gel t h e solutions in the t e m p e r a t u r e r a n g e 100° to 150° C. T h e reaction with certain divalent metal oxides is g r e a t l y accelerated b y t h e addition of water or pyridine. Pyridine also accelerates t h e curing rate of certain thixirams and thiourea. T h e D u Pont people feel t h e t e c h n i q u e is rapid enough to study t h e effect of m a n y combinations of chemicals used i n commercial cures and to s t u d y t h e c u r i n g mechanisms of other elastomers. Amylose D e g r a d a t i o n . T h e common methods of starch dispersion lead to sig­ nificant degradation unless oxygen is ex­

Time 5 24 28 40 30 30

Final D.P. ( from viscosity in M / 2 - N a O H a t 20° ) 1500 600 0 crystals to stand oriented with their long axes perpendicular t o the surface. In the second case, no microscopic crystals could be seen. This explains, according to the Dutch worker, the ease of mechanical and chemical attack in the presence of the optical bleach. The attack may b e by thiosulfate after the chlorine bleach to remove excess chlorine, or by alkali silicates at 80° C. In absolute darkness the weakening effect of the bleaching compounds is absent. Speaking before the same session, a theory was presented by Foster D e e Snell to account for the building properties of polyphosphates in detergency, aside from the sequestering action of the multivalent anions. Snell suggested that soil particles detached from cotton fabric by mechanical action are temporarily prevented from agglomerating and redepositing on the fabric by the surface charge introduced through sorption of the multivalent anions. Those salt anions are subsequently replaced by surfactant anions. However, h e continued, the multivalent anions contribute to the ultimate charge on the surface of the fabric and the suspended soil particles, thus reducing the tendency for soil redeposition. Though only about one salt anion associates for every 100 surfactant anions sorbed, multivalent anions make a substantial contribution to the surface charge density because of neutralization of the charge of the surface anions by the associated gegenions. Coauthor of the paper was Lloyd Osipow. Association Colloid Solutions. Fatty acid soaps, solutions of bile acid salts and similar solutions undergo marked changes in properties within certain "concentration limits." Per Ekwall, Âbo Academy, Finland, in his discussion, related his work to the better known critical micelle concentration ( C M C ) of aqueous associated colloid solutions. At least three concentration limits were recognized in solutions of the bile acid salts. Up to a concentration of about

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0.015 Λί, sodium cholate l>eliaves sts a normal uniunivalent electrolyte, but marked deviations from flu's behavior were observed above this ooncentratioii. Many of the properties of t h e cholate solu­ tions again undergo marked changes when the concentration increases to aîx>ut O.05 M. A third concentration region^ he continued, at which properties of the solutions undergo changes, is 0.10 to 0.12. M. The fatty acid soaps do 3iot behave as normal uniunivalent electrolytes u p to their CMC's, but only to concentrations that are approximately one quarter as strong. At these well defined concentrations, marked changes were observed-,, especially in the behavior of the soaps towards polar-nonpolar substances such as parafBnic alcohols and fatty acids. At higher concentration, changes in the other properties of the solutions were observed, such as in the interaction of the soaps to hydrocarbons and parafBnic alcohols and in their conductances. Three concentration limits were established in solutions of alkyl sulfates, one below and one above the CMC. Glowing Crystals. Glow- curves, useful in studies of stratigraphy, of the geochemistry of uranium and of t h e estimation of age of certain rocks, have been prepared at the University of Wisconsin. Farrington Daniels explained that when certain crystals are exposed to x-ray radiation or radioactivity some electrons are dislodged and become trapped in lattice imperfections. \ATien driven out b>y heating, the electrons emit light at certain temperatures. The glow curves obtained b y plotting light intensity against rise in temperature are characteristics of the crystal, its impurities, its imperfectons, and the radioactivity. Many naturally occurring minerals and rocks contain enough radioactive material in traces to cause the thermal luminescence, Dr. Daniels pointed out. The intensity of thermal luminescence is a measure of the radiation exposure. The glow curves give information concerning the mechanisms of radiation damage, the nature of crystal imperfections, diffusion processes in t h e crystaL and catalysis, he said.

Are you interested in these two new intermediates? Ordinarily w e would use b i g headlines and that sort of t h i n g to announce our products. Our a d v e r t i s i n g a g e n c y h a d trie a d r e a d y , b u t w e felt t h a t w e w e r e n ' t t h a t f a r a l o n g . TRIETHYL ORTHO-ACETATE (CH 3 C(OC 2 H 5 )3) a n d TRIETHYL O R T H O P R O P I O N A T E (CH3CH2C(OC2H5)3) a r e n ' t really available except i n limited r e s e a r c h q u a n t i t i e s . Availability f r o m h e r e o n w i l l d e pend o n you. "We k n o w of p o s s i b i l i t i e s for t h e i r use i n s u b stituted p y r i m i d i n e s . F r o m t h e f o r m u l a s y o u can see that either an alpha-ethoxy-ethylidene o r a n a l p h a - e t h o x y - p r o p y l i d e n e g r o u p is c h e m i c a l l y available. I s there a p o s s i b l e use in plastics? O r dye manufacture? O r p h a r m a c e u t i c a l synthesis? T h i s field i s n o t n e w t o K a y - F r i e s . Y o u ' v e p r o b a b l y s e e n o u r a d s o n TRIETHYL O R T H O FORMATE. W e ' v e b e e n m a n u f a c t u r i n g it f o r a g o o d m a n y y e a r s — m a t t e r o f fact w e r e c e n t l y r e duced the price to b r i n g it into t h e "one-dollar a p o u n d " field of i n t e r m e d i a t e s . W e ' v e a l s o m a d e TRIMETHYL O R T H O FORMATE i n p i l o t plant quantities. At any rate we're interested in o r t h o e s t e r s . If y o u h a v e a n y q u e s t i o n s a b o u t t h e s e o r o t h e r Kay-Fries i n t e r m e d i a t e s , p l e a s e don't hesitate to contact u s .

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A plea for better utilization of wood resources was made by Harry F. Lewis, Institute of Paper Chemistry, in his plenary lecture before the symposium on chemistry of wood and wood constituents. Sooner or later, the pulp and lumber industries must break with their old traditions and enter new fields, he saioL The industries would rather make low grade pulps from wood waste and evaporate and burn the liquors than get into t h e business of making alcohol, yeast, lignin ethers, or vanillin. They know the former; they fear the latter—for these require new thinking, new sales foxces, and new VOLUME

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THE CHEMICAL WORLD THIS WEEK development departments, he continued. Lewis drew attention to the fact that any chemical industry derived from wood must face competition from an alert synthetic chemical industry' accustomed to spending sizable percentages of its sales income to support both fundamental and applied research. A few companies in the pulp and paper industry spent only 1 to 1.5% while the chemical industry has spent about 3.5% of its net sales dollar for research. Speculating on possibilities for the future, Lewis said that because conventional wood distillation plants are no longer operating, wood distillation as a process for conversion of wood substances to chemicals is not necessarily finished. The application of the fluidizing process as used by the petroleum industry for the destructive' distillation of sawdust might make possible the recovery of some intermediate products of pyrolysis in high yield; these in turn might be susceptible to hydrogénation or catalytic oxidation with sub-

sequent production of valuable by-products. Another problem of the industry, said Lewis, is its comparative ignorance of the physical and chemical constituents of wood. "We know only in part what lignin is; if we knew its chemical structure we might not even then be able to convert the enormous amounts of lignin available in all of our wastes to a chemical asset, but at least we would work more intelligently toward the ultimate goal, which is to make it a material useful to something else besides the particular plant in while it is formed." Oxidative Changes in Cellulose. A general scheme for the oxidative processes of cellulose under the influence of sodium hypochlorite and hydrogen peroxide was reported by E. D. Kaverzneva, Academy of Science of the U.S.S.R. Dr. Kaverzneva was one of four scientists from the Soviet Union presenting papers before the congress. Although the lectures were all given in Russian, summaries were provided

The Cover .

International Congress Honors Svedberg PWEDISH chemistry and The Svedberg ^ are almost synonymous, so when the Xlllth International Congress of Pure and Applied Chemistry convened in Stockholm in late July, it was natural that Prof. Svedberg be named honorary president of the congress. Svedberg, born in Valbo, Sweden, in 1884, took his academic training and has spent his entire professional career in the University of Uppsala. During the early part of his career, he and his collaborators devoted their attention largely to methods for preparation of inorganic colloids, their kinetic properties, and their behavior in magnetic and electrical fields. But it was while doing a visiting professor stint at the University of Wisconsin in 1923 that Prof. Svedberg constructed the first crude ultracentrifuge, in collaboration with J. B. Nichols, now of Du Pont. The instrument gave a centrifugal field only 100 times gravity, but it established the feasibility of high speed centrifuging as a method for studying colloid particles. It was for his work on the ultracentrifuge that Svedberg received the Nobel Prize in Chemistry in 1926. Since 1931, Svedberg's research has been done at the Institute of Physical Chemistry. Over the years scientists and students from all over the world have taken advantage of the institute's unusual facilities to study the physical chemistry of high molecular compounds, 3464

colloid chemistry, and biochemistry. Both the diffusion method of Lamm and the electrophoresis method of Tiselius, were developed at the institute. Arne Tiselius

Ame Tiselius, president of the International Union of Pure and Applied Chemistry, was born in Stockholm in 1902. From 1925 to 1932, he served as a research assistant in physical chemistry at Uppsala, where he received his doctorate in 1931. His thesis was on the electrophoresis of proteins, the field in which he later made his most impressive scientific contributions. In fact, his work on electrophoresis and his parallel development of the Tiselius apparatus for electrophoretic study of colloids were primarily responsible for his receiving the Nobel Prize in Chemistry in 1948. During World War II, he and his associates, particularly Ingelman and Gronwall, conducted their pioneering work on the bacterial production of dextran from sugar. Thanks in large measure to their continuing efforts, Swedish manufacture of this blood plasma expander has attained full-scale commercial status. Likewise, the development of blood fractionation techniques owe much to Arne Tiselius. Today, he devotes a great deal of his time to research on peptides, amino acids, and viruses. CHEMICAL

in English and, in some cases, full texts in other languages were available. The presence of keto groups in the oxycellulose has been proved by t h e preparation of oximes and their reduction t o amino derivatives at the Moscow academy. Some of these groups are a.-oximonoketonic, which follows from the fact that a positive endiolic reaction is obtained with phosphor ic-arsenic-wolframie acid and oxycelluloses prepared in an alkaline solution, she explained. In oxycelluloses obtained by hypochlorite oxidation in acid medium the Russians have observed the formation of very small amounts of carbonic acid esters, ^which are easily hydrolyzed with the evolution of COs by even a brief treatment with 0.025 ZV NaOH. By measuring the decrease in viscosity of cellulose solutions in cuprammonium reagent during the stepwise addition of increasing amounts of oxygen, t h e importance of very small traces of oxygen for the oxidative splitting of cellulose in alkaline medium could be shown, she said. The addition of easily oxidized substances (oxidation inhibitors) retarded the splitting reaction and almost completely stopped the decrease in viscosity. The fundamental cause for the decrease in viscosity on oxidizing cellulose in alkaline medium is the presence of not only aldehydic but also of ketonic groups which lead to the weakening of the allcali resistance of the glucociddic bonds, declared Dr. Kaverzneva. Cellulose Degradation. Degradation curves and limit D. P. (degree of polymerization) values have been detennined in cotton and wood pulp cellulose from sedimentation and diffusion experiments in copper ethylene diamine solutions, carried out at the Swedish Institute for Textile Research by Jan Linderot and Nils Gralen. Cellulose precipitated from these solutions had a high amount of amorphous substance, but had a molecular weight equal to that of the original material. The degradation curves and limit D.P. values of the precipitated substances, however, differed very much from those of the original samples, and the Swedes suggested that the limit D.P. values depend on supermolecular structure rather than molecular structure. The absolute crystallinity values determined by Hermans' quantitative x-ray method for the natural samples agreed with values from the sorption ratios for the substances. The regenerated samples, however, showed a considerable difference. Linderot and Gralen suggested that the samples contain amorphous substances inaccessible to sorption and hydrolytic attack. Another paper on the crystallinity of cellulose "was presented by Olli Ant-V/uorinen, State Institute for Technical Research, Finland. When regenerated cellulose is subjected to a pressure of 15,000 AND

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THE CHEMICAL WORLD THIS WEEK kilograms p e r square centimeter it under­ goes a rearrangement b y which t h e crystallinity of the pressed sample is in­ creased. This rearrangement takes place only if t h e ion exchanging carboxyl groups of cellulose have been liberated before pressing, said Ant-Wuorinen. N e w possibilities of bleaching cellulosic materials with hypobromite and hypochlorite-bromide mixtures were pointed out in a paper by Menachem Lewin, R e ­ search Council of Israel. The rates of oxi­ dation of bleached wood pulp, bleached cotton, bleached flax, and viscose yarns increase with rising p H , contrary to oxida­ tions with hypochlorite, he said. Discuss­ ing t h e properties of hypobromite oxycelluloses, h e said t h e viscosities in cuprammonium solution increase with decreas­ ing p H of t h e oxidation runs a n d the socalled "dangerous zone" known in t h e hypochlorite oxidations at pH 7 is n o t observed. T h e maximum of reducing groups was found a t ρ Η 8 to 9. A decrease in t h e reducing group at higher p H values, accompanied b y a cor­ responding increase in carboxyl groups, suggested that the reducing groups w e r e formed through the action of hypobromous acid, whereas the carboxyl groups were formed through the action of hypobromite ions. Lignin. At the Swedish Forest Products Research Laboratory t h e occurrence of free or etherified α-carbonol groups in Brauns' native lignin has been demon­ strated. T h e methylation of native lignin w i t h methanolic hydrochloric acid cannot b e d u e to acetal formation but h a s to b e interpreted as an etherification of t h e free α-carbonol groups, or a rèetherifîcation of t h e etherified α-carbonol group, declared Erich Adler and Joseph Gierer. N e w compounds of lignin with small amounts of sulfur and also with cresols h a v e been made u n d e r pressure at 200° to 260° C. Louis G . Ricciardi a n d Donald

F . Othmer, Polytechnic Institute of Brook­ lyn, declared t h e new compounds a r e strong, hard, water-resistant, and resistant to termites, insects, and rodents. If t h e lignin is first methylated to fill its func­ tional groups, a much poorer reaction a n d lower strength results, the authors pointed out. T h e y cited the possibility of the p r o ­ duction of wallboard from sawdust or shavings in an entirely dry process which requires no synthetic resins or binders since t h e modified lignin acts as an autogeneous resin with both thermosetting a n d thermoplastic properties. A minimum of extractives in the wood is advantageous. A lignin content in t h e wood greater than about 3 0 % is adequate but to those species with a lower amount, lignin obtained from pulping or acid h y ­ drolysis of wood may b e added. T h e authors explained that optimum results were obtained by varying time, tempera­ ture, a n d pressure, amounts of a d d e d lignin, amounts of sulfur or cresol, a n d other factors. Americans A t t e n d i n g X I H t h I n t e r n a t i o n a l Congress of Pure a n d A p p l i e d Chemistry

Adams, Mabelle, London, England Adams, R. R., Battelle Institut, Frankfurt, Germany Adams, Roger, University of Illinois Adkins, A. L., American Embassy, London Anderson, A. B., University of California Anderson, Bjorn, Maplewood, N . J. Bain, J. P., Glidden Co. Baldwin, R. L., Oxford University Berend, Gertrude, Hoffmann-La Roche, Inc. Bigeleisen, Jacob, Brookhaven National Laboratory Blume, R. C., E . I. d u Pont d e Nemours and Co. BlumenthaL \L. M., Washington, D . C. Boyd, G. E . , Oak Ridge National Laboratory Brauns, F . E . , Appleton, W i s . Broida, H . P., National Bureau of Standards Buchdahl, Rolf, Monsanto Chemical Co.

T h r e e of t h e some 135 Americans attending the International Congress in Stockholm relax b e t w e e n sessions. Left to right: Ε . Η . Volwiler, Abbott Laboratories; Roger Adams, University of Illinois; a n d E m i l Ott, Hercules Powder C o .

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Busse, W . F . , E . I. d u P o n t de Nemours and C o . Capell, L . T., Ohio State University Carter, H . E., University of Illinois Chesley, K. G., Crossett L u m b e r Co. Coppick, Sydney, American Viscose C o r p . Curtiss, L. F., Garrett Park, Md. Daniels, Farrington, University of Wisconsin Edsall, J. T., H a r v a r d University Eyring, Henry, University of Utah Ferry, J. D., University of Wisconsin Fisher, C. H., Southern Regional Research Laboratory Flory, P . J., Cornell University Fuguitt, R. E., Glidden C o . Fuoss, R. M., Yale University Gilbert, E . C , Oregon State College Gilbert, J. W., International Paper C o . Gillette, R. H., Brussels, Belgium Glattfeld, J. W . E., Argonne National Laboratory Goldschmid, Otto, Rayonier, Inc. Green, A. D., Esso Research Center Green, Charlotte, Carlsberg Laboratorium, Copenhagen Gregor, H. P., Polytechnic Institute of Brooklyn Harris, Milton, Harris Research Laboratories Hedberg, Kenneth, University Kjemiske Institut, Blindern, N o r w a y Holzer, W . F., Crown Zellerbach Corp. Horton, A. W., University of Cincinnati Inskeep, Gordon, NEERING N E W S

C H E M I C A L AND E N G I ­

Inskeep, Cora, London, England J aim, E . C , State University of N e w York Johnson, W . C , University of Chicago Julian, P . L., Glidden Co. Kilpatrick, Martin, Illinois Institute of Technology Kilpatrick, Mary, Illinois Institute of Technology Kirkwood, J. G., Yale University Kline, G. M., National Bureau of Standards Kolthoff, I. M., University of Minnesota Kornblum, Nathan, University College, London Laitinen, Η. Α., University of Illinois La Mer, Victor, Columbia University Latimer, W . M., University of California Lewinson, V. Α., Mellon Institute Lewis, H . F . , Institute of Paper Chemistry Lovell, E . L., Rayonier, I n c . Luck, J. M., Stanford University Lundgren, H. P . , Western Regional Research Laboratory Malm, C . J., Rochester, Ν . Υ. Mark, Herman, Polytechnic Institute of Brooklyn Martin, A. F., Hercules Powder Co. McBurney, L. F . , Hercules Powder C o . McMeekin, T. L., Eastern Regional Research Laboratory Moore, Stanford, Rockefeller Institute Morawetz, Herbert, Polytechnic Institute of Brooklyn Myers, W . G., Ohio State University Nadelman, A. H . , Western Michigan College Nichols, J. B., E . I. d u P o n t de Nemours and C o . Nord, F . F., F o r d h a m University Nutting, H. S., D o w Chemical Co. Oncley, J. L., H a r v a r d Univei^ity Othmer, D . F . , Polytechnic Institute of Brooklyn Ott, Emil, Hercules Powder Co. Pauling, Linus, California Institute of Technology Pew, J. C , Forest Products Laboratory Pickels, E . G., Atherton, Calif. Pitzer, K. S., University of California Prosen, E . J., National Bureau of Standards

AND ENGINEERING

NEWS

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'>. t / . reagents are fine for laboratoryuse, b u t they can get you into trouble. They often lead you to overlook the impurities i n the chemicals of commerce, which may upset carefully calculated reaction rates and yields. There is at least one chemical—glycerine—where you can forget this problem. The manufacturers now can supply a C.P. grade in tank cars. T h e y do it b y pass­ ing crude glycerine through a series of A M B E R L I T E ® cation and anion exchangers, and it comes out essen­

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tially pure. Concentration by simple makes it ready for shipment.

evaporation

A M B E R L I T E ion exchange seeks jobs like this. I t has found them in processing glycerine, sorbitol, sugar, syrups, arabic acid, formic acid, acetone, formalde­ hyde, metals, and milk. If your process is hampered by trace quantities of chemical impurities, investigate A M B E R L I T E ion exchange as a means of dis­ posing of them. a bi-monthly report is available on request.

AMBER-HI-LITES,

exchange,

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R E S I N O U S

PRODUCT'S

D I V I S I O N

P H I L A D E L P H I A

5 ,

P E N N S Y L V A N I A

Do You Need a Building Site with Good Water? Is your business one that needs pure, soft water? You see, we used to need water, too. HBoiler water. We were very fussy about the kind of water we gave our locomotives. Because of greater use of Diesels, we are retiring a number of wells, pumping plants, tanks and softening plants. Some of these installations are on. large, level plots along our railway with access to good highways as well as rail sidings. For instance, w e h a v e two good locations near Columbus, O. One of them 16 miles nortfci, near Dela-

ware, O., has a plot of 45 acres with adjoining property that can be acquired; and another 30 miles south at Circleville, O., has 90 acres. Others are available in Indiana, Michigan, Virginia, West Virginia and Ontario. Tell us how much land you want and where you want it. We'll offer you a complete installation for much under its reproduction cost. For further details, write to Chesapeake and Ohio Railway, Cleveland 1, Ohio, Detroit, Michigan, Huntington, West Virginia.

Chesapeake and Ohio Railway SERVING: V I R G I N I A · WEST V I R G I N I A · KENTUCKY · O H I O INDIANA 3468

· MICHIGAN

New Text

· SOUTHERM O N T A R I O CHEMICAL

AND

ENGINEERING

NEWS

THE C H E M I C A L W O R L D THIS WEEK Putnam, F. W . , Cambridge University Rabinowitch, Eugen, University o£ Illinois Ramsey, J. B . , University of California Ranz, W . Ε., Cambridge, England Rasmussen, J. O., Nbbelinstitutet for Fyaik, Stockholm Reichel, F. EL, Villanova Reyerson, L. H., University of Minnesota Richter, G. Α . , Eastman Kodak Co. Riegel, Byron, G. D . Searle & Co. Rossini, F. EX, Carnegie Institute of Technology Rowen, J. W\, Carlsberg Laboratorium Copenhagen Salvesen, J. H., Marathon Corp. Schachman, Η . Κ., University of California Schantz, E. J., Chemical Corps Schellman, J. Α., Carlsberg Laboratorium, Copenhagen Scheraga, Η. Α., Cornell University Seaton, E. EL, Paris, France Silverman, Alexander, University of Pittsburgh Simons, J. H . , University of Florida Smith, E. R., National Bureau of Standards Snell, Cornelia, Foster D . Snell, Inc. Snell, Foster, Foster D. Snell, Inc. Sobel, A. E.9 Jewish Hospital of Brooklyn Sparks, W. J., Standard Oil Development Co. Strange, J. G-, Institute of Paper Chemistry Sumner, J. B . , Ithaca, Ν. Υ. Swanson, W. H., Kimberly-Clark Corp. Swenson, KL Α., Svenska Trâforskningsinstitutet, Stockholm Szasz, G. J., American Embassy, London Trenner, Nelson, Uppsala Turkevich, John, Princeton University Van Rysselberghe, Pierre, University of Oregon Vaslow, Fred, Carbsberg Laboratorium, Copenhagen Vickery, Η. Β., Connecticut Agricultural Experiment Station Volwiler, Ε. Η., Abbott Laboratories Waddington, Guy, U . S. Bureau of Mines Ward, Kyle, Jr., Institute of Paper Chemistry Whistler, R. L., Purdue University White, Blanche, Celanese Research Laboratories Wiley, A. J., Sulphite Pulp Manufacturers Research L e a g u e Wilson, R. E . , Standard Oil Co. of Indiana Wolfrom, M . L., Ohio State Universitv Zelikoff, Murray, U . S. Air Force

CHEMICALS AND INTERMEDIATES TO MEET YOUR REQUIREMENTS CH,

o-Toluidine Technical DESCRIPTIVE I N F O R M A T I O N i&^uiéi^iÛ

T h i s i n t e r m e d i a t e is a c l e a r , l i g h t y e l l o w o i l w h i c h m a y d a r k e n o n s t o r a g e . I t is c o m p l e t e l y s o l u b l e i n 1 0 % h y d r o c h l o r i c a c i d , s o l u b l e in e t h e r a n d a l c o h o l , a n d s p a r i n g l y s o l u b l e in w a t e r . T r a c e s of n i t r o t o l u enes a n d isomers m a y b e present a s impurities. o-Toluid i n e T e c h n i c a l is a v a i l a b l e i n c o m m e r c i a l q u a n t i t i e s . SPECIFICATIONS I o - T o l u i d i n e T e c h n i c a l is p r o d u c e d t o t h e s e s p e c i f i c a tions: Purity . . . 99.5 % m i n i m u m

.&'>

Distillation R a n g e . . . It shall distill 5 t o 9 5 cc b e t w e e n 1.0°C, including the t e m perature 2 0 0 . 2 ° C , corrected t o 760 m m . SUGGESTED USES

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O p p o r t u n i t i e s for u s e o f o - T o l u i d i n e T e c h n i c a l i n c l u d e application as an intermediate i n t h e synthesis o f rubber chemicals, dyes a n d pharmaceuticals. I t m a y b e i n t e r e s t i n g a s a n a b s o r b e n t for S O 2 a n d S O 3 w a s t e gases.

DO YOU NEED A SPECSFIC INTERMEDIATE? A WIDE VARIETY of chemical i n t e r m e d i a t e s is n o w available from t h e D u P o n t Organic C h e m i c a l s D e p a r t m e n t . I t will p a y y o u t o e v a l u a t e t h e s e p r o d u c t s for y o u r m a n u f a c t u r i n g processes. A NEW INTERMEDIATE? W e h a v e the facilities t o p r o d u c e specific intermediates . perhaps o n e t h a t w i l l m e e t y o u r e x a c t requirem e n t s . Our technical m e n w i l l be glad t o s t u d y y o u r p r o b l e m s and work w i t h y o u in product d e v e l o p m e n t .

Morton Research Laboratories Planned f o r Woodstock, III.

A REQUEST o n y o u r c o m p a n y letterhead will bring c o m p l e t e inform a t i o n . J u s t w r i t e t o E. I . du P o n t d e N e m o u r s & C o . (Inc.), Organic C h e m i c a l s D e p t . , C h e m i c a l s D i v . , W i l m i n g t o n 9 8 , D e l .

Construction will begin this fall on a n e w research laboratory at Woodstock, 111. This installation will house the principal research activities of Morton Salt. In the n e w facilities, experimental research will be conducted o n b o t h laboratory and pilot unit scale i n t h e fields of inorganic, or­ ganic, and catalytic chemistry. It is prob­ able that initial personnel requirements will include 3 5 to 4 0 chemists in addition to other staff and office personnel. T h e building, o f contemporary design, will have enclosed space of approximately 400,000 cu-bic feet. T h e building will comprise t w o stories and basement, and will b e of brick construction "with stone 3 1,

NO.

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NHL

M.W. 107.2

INDUSTRY

V Ο LUME

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AUGUST

iPÔHï BETTER THINGS FOR BETTER LIVING . . . THROUGH CHEMISTRY

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1953

DERARTMÊIÎÎÎ: 3469