NOVEMBER 1953
On the Chemical World Today
HEADLINES of the Month Events of Interest to Chemists, Chemical Engineers, and Executives
Reviewed by fhe Mifors
September 16. RFC opens nation’s biggest going-out-ofbusiness sale to dispose of holdings, including synthetic rubber plants, a tin smelter, stocks, bonds, notes, mortgages, houses, and factories, by June 30, 1954. b American Cyanamid opens 21,000-square-foot laboratory at Stamford, Conn., for research on fertilizers, insecticides, herbicides, and related chemicals. b USDA and Colorado Agricultural Experiment Station develop reliable 1-hour phosphate availability test adaptable to both acid and alkaline soils.
September 22. Utah-Idaho Sugar starts preproduction runs a t $7,000,000 sugar beet refining plant near Moses Lake, Wash.; this year mill produce 75,000,000 pounds sugar plus molasses and dried beet pulp. b Rayonier develops silvichemieals, series of chemical by-products of sulfite wood pulping. b Industrial Laboratories Publishing schedules publication of Industrial Science and Engineering for advanced technical students, offering technical articles, career information, and professional society news.
September 17.
W. R. Grace buys 180,000 shares of Davison Chemical’s common stock a t $40 per share, bringing total ownership in Davison t o more than 51%. b Nitrogen Division, Allied Chemical & Dye, p h i $5,000,000 plant a t South Point, Ohio, for production of Arcadian 12- 12-12 fertilizer.
September 23. Explosion of cliemical storage tanks kills ten, injures twenty-seven a t Lucidol Division, NovadelAgene, Tonawanda, N. Y. b Monterey Oil and Humble Oil & Refining contract for offshore exploratory drillings near Newport Beach, Calif., is first since passage of Submerged Ilnntls Act.
September 18.
September 24.
Great Britain and France reduce bank discount rates from 4 to 31/2% to cut cost of loans to business and thereby expand production. b International Nickel (Canada) develops process for production of by-product iron ore from low grade nickel ores mined in Sudbury area. Immediate construction of $16,000,000 plant to provide 1,000,000 tons of iron ore per year is planned. b Taylor Oil and Gas puts on stream new 5000-barrelper-stream-day Platformer at Corpus Christi, Tex. b Consolidated Mining & Smelting of Canada starts zinc production a t world’s largest (300 tons per day) electric induction furnace, Trail, B. C.
September 19. Commerce Department announces resignntion of Assistant Secretary Craig R. Sheaffer, following reinstatement of Allen V. Astin as head of NBS ant1 removal of the bureau from Sheaffer’s jurisdiction. September 21.
Abraham Pais, Institute for Advancetl Study, Princeton, K. J., extends usual space-time description of the atom to as many as six dimensioiin in order to explain the large number of particles in the nucleus, not as different forms in,themselves, but as different states of one form. b Du Pont schedules completion of $3,000,000, 100,000ton-per-year plant t o produce ilmenite for early 1955. b American Petroleum Institute withdraws approval of National Standard Petroleum Oil Tables issued in 1936 in favor of tables jointly issued by API, ASTM, and Institute of Petroleum. b Chemical industry in West Germany reports $1.2 billion sales, 10% above first 6 months of 1952. November 1953
St. Maurice Chemicals, owned 1)y Shawinig m Chemicals and Heydeii Chemicals, opens $3,000,000 plant a t Varennes, Que., for production of 30,000,000 pounds fornialdehyde and 3,000,000 pounds pentaerythritol. b Armour Research Foundation, Illinois Institute of Technology, unveils Chem-Dry process for hardening drying oils and resins in 2 to 20 seconds by use of sulfur dichloride vaDor.
September 25. u. S.
Rubber sta1.t~constructioii a t Stints Ana, Calif., of its first foam rubber plant on West Coast. b Quaker Oats plans new central research laboratory a t Barrington, Ill., employing 100 persons. b Dow Corning forms Caiiadian.subsidiary, Dow Corning Silicones. b Oklahoma State Planning and liesources Board engages Blaw-Knox to survey potentials and resources of state.
September 26.
National Science Foundation crcates permanent advisory panel to develop policy on basic research I in minerals discovery and exploration. b Texas City Refining dedicates world’s largest (19,000 liarrels per day) Houdriflow cat cracker. b Goodyear, Gutta Percha, Dominion, Dunlop, and B. F. Goodrich each receive maximum $10,000 fine for operating price-fixing combine since 1936, in violation of Canada’s Combines Act. b Alton Meister, hTationa1 Cancer Institutc of N I H , wins Paul-Lewis Laboratories Award in enzyme chemistry, administered by AMERICAN CHEMICAL Socre~~. b Research teams a t Chas. Pfizer and Lederle Labora-
INDUSTRIAL AND ENGINEERING CHEMISTRY
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package unit, completely engineered plant designed t o produce 2,000,000 t o 15,000,000 pounds per year dried synthetic detergent. b Ben Franklin Refining, Ardmore, Okla., puts on stream 5000-barrel-per-stream-day fluid catalytic cracking unit. w Norwich Pharmacal plans to build $1,500,000 research building a t Xorwich, N. Y., t o house 100 chemical and pharmaceutical investigators. b University of Southern California researchers report hydrocarbons taken from Los Angeles smog produce cancer in mice, possible clue to increasing incidence of human lung cancer. b Standard Oil (California) completes 140-mile. $4,000,000, 15,000-barrel-per-day petroleum products pipeline from Pasco, Wash., t o Spokane.
October 6. General Iron and Metal develop6 chemical washing process for decoating galvanized and enameled scrap prior to steelmaking.
Destruction at Lucidol Division, Novadel-Agene, TonaWanda, N. Y., after a Series of Explosions Which Killed Ten Persons
tories synthesize tetracycline, antibiotic with activity similar t o terramycin.
September 28. Shell Oil awards contract for construction of 50,000-barrel-per-day refinery a t Anacortes, Wash., t o Bechtel. b Joel H. Hildebrand, University of California, receives Willard Gibbs Medal of Chicago Section, AMERICAN CHEMICAL SOCIETY. September 29.
Air Force accelerates production of Boeing B-52 heavy jet bombers and North American F-100 jet fighters. b Chlorophyll producers agree 1953 consumption will total 40,000 pounds, compared to 100,000 pounds in 1952. b Pan-Am Southern breaks ground for fixed-bed hydroforming unit a t El Dorado, Tex.
September 30. Allied Chemical & Dye buys Plaskon Division of Libby-Owens-Ford. b PAD proposes 540,000-barrel-per-day capacity pipeline from Gulf to East Coast. October 1. RFC requires large users of GR-s to place firm orders 3 months in advance of delivery. b Bridgeville, Pa., plant of American Cyanamid resumes operations as %month strike ends. b German Shell and Badische Anilin und Soda Fabrik plan construction of plant a t Ludwigshafen, Germany, for making polyethylene and ethylbenzene. b Victor Chemical Works begins expansion which will double phosphorus oxychloride and trichloride production a t Morrisville, Pa., unit.
October 7. President Eisenhower appoints Everett R . Cook and Leslie R. Rounds t o commission to administer sale of government synthetic rubber plants. b General Electric schedules construction of $1,800,000 combustion research laboratory at Schenectady, N. Y . b Cornell University School of Medicine research team synthesizes oxytocin, pituitary gland hormone. b AEC receives report of Union Electric and Monsanta indicating feasibility of sodium cooled graphite moderated nuclear reactor to produce electric power and plutonium, b Keystone Chemurgic buys chlorophyll manufacturing and research interests of Archer-Daniels-Midland. b Sharp & Dohme develops process t o manufacture whooping cough vaccine by disintegrating whooping cough germs with high-frequency sound ~1 aves. October 8. Charles Phelps Smyth, Princeton University, receives William H. Kichols Medal of New York Section, AMERICAN CHEMICAL SOCIETY. October 9. Union Chemique Belge starts construction of $13,000,000, 50,000-ton-per-year ammonium sulfate fertilizer plant a t Daudkel, Pakistan. b Jonas E. Salk, University of Pittsburgh, announces plans are under x a y to stage nation-wide tests of polio vaccine. October 13. Institute of Textile Technology, Charlottesville, Va., spokesman predicts nevi cyanoethylation process (treating raw cotton with acrylonitrile) will result in new family of textile fibers. October 14. California Standard and Canadian Gulf Oil plan $1,000,000 construction of first portable gas processing plants in western Canada at Edmonton and Calgary, Alberta. b Canada Foods, Kentville, Nova Scotia, schedules 250,000-pound production of carrageenin and sodium alginate in 1954 a t Canada’s first seaweed extraction plant. b Ciba markets combined antihistamine (Pyribenzamine) and penicillin, in oral tablet, t o minimize penicillin sensitivity.
October 5. American Chemical Society charters 143rd local section, Corning Section, to serve Corning, PI‘. Y., October 15. Esso Standard Oil dedicates 24,000-barrel -perarea. day fluid catalytic cracking plant a t Everett, Mass. b Hull Division, Foster D. Snell Research, markets, as 8A INDUSTRIAL AND ENGINEERING CHEMISTRY VOl. 45, No. 1 1
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November 1953
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INDUSTRIAL AND ENGINEERING CHEMISTRY
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used throughout the world for great efficiency with low maintenance
LOUISVILLE DRYING MACHINERY UNIT
GENERAL AMERICAN TRANSPORTATION CORPORATION Dryer Sales Office: 139 S. Fourth Street, Louisville 2, Kentucky General Offices: 135 South LaSalle Street, Chicago 90, Illinois
In Canada: Canadian locomotive Co., Ltd., Kingston, Ontario OFFICES I N ALL PRINCIPAL CITIES
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 45, No. 1I
NOVEMBER 1953
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TechnicaI and CommercIa I DeveIopments A
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GREEN TEE FERTILIZER *
The fertilizer you dream about can be made from ureaformaldehyde condensation products, A full year’s nitrogen supply may be safely applied at one time with controlled availability. According to R. D. Kralovec and TI’. A. Morgan of Du Pont, these products contain about 38% nitrogen, of which three quarters is jn the slowly available form (water-soluble). Fifty to 60y0 of the mater-insoluble nitrogen will nitrify in about 6 monthsin an averagesoil. If you have played golf recently in some parts of Pennsylvania, or in the Baltimore - Washington area, it is possible that you owe that par score to the excellent turf grown with the aid of these fertilizers. Field tests conducted in these localities demonstrate the suitability of U-Fcompounds for this type of long season crop. Kralovec and Morgan report that 4 pounds of nitrogen per 1000 square feet applied in this form will supply an average turf with sufficientnitrogen for one full year of satisfactory growth. From five to ten times this amount of nitrogen can be applied at one time without injury to the turf, they say. The efficiency of a single application equals or exceeds that of multiple applications of the soluble nitrogen fertilizers. For the nongolfer, there are encouraging reports of successful tests on greenhouse floral plants, ornamentals, tobacco, hay, and those crops such as corn, cotton, citrus, and pineapple which are grown in irrigated or heavy rainfall areas. H.WeH*
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PAPER 2,
DIVISION O F F E R T I L I Z E R
A N D SOIL C H E M I S T R Y
P
LETHAL FATTY ACIDS For years, a lively controversy has raged over whether soaps-that is, ordinary sodium salts of fatty acids-actually kill bacteria. Various early workers insisted that soaps were definitely effective as germ killers. Recent findings, however, indicate that some misleading results in early tests possibly stemmed from the presence of free fatty acids caused by the not-too-careful control of pH during soap manufacture. This is in line with the discovery made some years ago that the fungistatic principle in human hair consists of fatty acids in the Ci-C13 range and that the acids in the Cs-C12 range are especially potent in the inhibition of mold growth. J. V. Karabinos and H. J. Ferlin of Blockson Chemical Co. report that several fatty acids, particularly those containing 9 to 12 carbon atoms, shorn unusually high germicidal activity in acid medium. For example, in solutions at pH 3, the 11November 1953
carbon acid, undecylic acid, is able to kill the common bacterium. Stmhulococcus aureus. at dilutions of 1 Dart in 88.000. Of all the ia&y acids studied, undecylic acid shows far and away the maximum bactericidal activity. At pH 3, t h e killing dilution for pelargonic acid is only 1 to 12,000, while for capric acid it is 1 to 65,000 and for lauric, 1 to 48,000. As the pH is raised, the bactericidal activity drops off markedly. For example, when the pH is increased from 3 to 6, the killing dilution for capric acid drops from 1 to 65,000 to 1 to 13,000. Significantly, the germicidal action of Cg t o Cl2 fatty acids in acidic medium has been found to be of the same order of magnitude as that of the commonly used quateinary ammonium germicides in alkaline solution. Obviously, a major question is: How do fatty arids go about killing bacteria? Present indications are that a bacterium is destroyed as the fatty acid groups attach themselves to the protein molecules and cause a form of suffocation, either by preventing the bacteiium from excreting its water-soluble toxic metabolic products or possibly by cutting off its oxygen supply. Of practical significance, Karabinos and Ferlin suggest that, in any cleaning operation that can be rayried out in acid solution, the C9 to C12fatty acids, even in eatremely low concentrations, might be used effectively as gerniicides. Aqueous solutions of these fatty acids might be prepared for direct external or even internal germicidd application. Furthermore, the bactericidal activity of fatty acids might serve as the basis for a biological method of determining micro quantities of these acids. H.J.S.
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PAPER
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DIVISION
BIOLOCilOAL
ROCKING ALONG W I T H PHASE EQUILIBRIA
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Studying phase equilibria at above-atmospheric pressui es usually means rocking sealed-glass tubes in variable temperature furnaces. This in turn means that tube mortality, especially a t high temperatures, is apt to be somewhat distressing. W. L. Marshall and coworkers at Oak Ridge National Laboratory have designed a unit which they say reduces tube explosions to an insignificant minimum, permits rapid determinations, and is simple and inexpensive. Backbone of the apparatus is a cylindrical heating block of aluminum (or graphite) 30 em. long and 5 cm. in diameter. An 8-mm. hole in the center of the long axis holds the sample tube, and samples are viewed through a window drilled perpendicular to the sample tube hole (a telescope and lamp give good observation). Heat is by resistance wire wrapped in grooves around the outside of the block. Sample tubes may be made of 4-inch lengths of borosilicate glass of 1-mm. inside diameter and 3-mm. outside diameter. For temperatures above 320’ C., Marshall suggests silica tubes of the same outside diameter but with a slightly smaller inside (Continued on page IS A )
INDUSTRIAL AND ENGINEERING CHEMISTRY
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0 Pfizer Fumaric Acid is easy to handle because it is free-flowing and non-hygroscopic. It is non-volatile, odorless, noncorroding and non-toxic-actually lower in toxicity than some food acids. These iin p o r t a n t cha r a ct e r i s t i c s a r e making Pfizer Fumaric Acid the preferred acid in the coatings industry. Write for sample and prices.
CHAS. PFIZER & CO., INC. 630 Flushing Ave., Brooklyn 6, N. Y. Branch Offices: Chicago, Ill.; San Francisco, Calif.; Vernon, Calif.; Atlanta, Go.
Its Properties Rate High with Coatings Manufacturers Pf izer 0
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Manufacturing Chemistsf o r Over 100 Years
12h
I N D U S T R I A L AND E N G I N E E R I N G CHEMISTRY
Vol. 45, No. 11
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diameter. A borosilicate-glass liner in the block assures a snug fit. Tube preparation, including filling, sealing, and inserting in the apparatus requires about 2 minutes. Rocking would not give good mixing in such small-diameter tubes. A bell buzzer, therefore, is used to impart back-andforth motion to the sample tubes. Tubes are linked to the buzzer arm, and a timer gives automatic on-off vibration. Some of the advantages: small samples required, rapid tube preparation, rapid temperature changes, tubes can be put in or taken out a t any temperature, explosions practically eliminated a t pressures to about 3200 pounds per square inch. G.H.B. PAPER 2 4 ,
DIVISION OF PHYSICAL A N D INORGANIC C H E M I S T R Y
FLAME-OUT FOR RESINS Glass fiber-reinforced polyester resins have hit the materials of construction field, but not as hard as they might if their flammability were less. Phthalic anhydride-based materials are particularly disconcerting. They are no more flammable than wood of equal thickness, but because of superior mechanical strength unusually slender construction members may be made with them, and their flammability increases sharply as thickness is reduced. Flammability reduction has been attempted by adding flameproofing compounds as plasticizers or extenders. Doubtful permanence and a weakening of the resins have put these in the unsuccessful category. The approach, then, has been to completely new bases. Hooker Electrochemical Co. has come up with onbintroduction of chlorinated compounds. It has found that the diene adduct (now commercially available) of hexachlorocyclopentadiene with maleic acid can be a major constituent (up to 500/0) in synthesizing unsaturated polyester resins. The new resins, in the form of 1/8-inch laminates, burn only one twelfth as fast as either wood or phthalic-based laminates
HET polyester
of the same thickness. When 3% antimony oxide is added, these sheets do not even ignite under standard ASTM tests.
R.G.G. PAPER 2 0 , D I V I S I O N O F P A I N T . PRINTING I N K CHEMISTRY
PLASTICS,
AND
VINYL SHORT CUT Use of acetylene to produce vinyl chloride may take the low dilution road. Newer processes for acetylene production from light hydrocarbons-the Wulff thermal cracking, Sasche partial oxidation, and Schoch electric discharge processesall form product gases containing only about 10 moleyo acetglene, the remainder being primarily hydrogen and methane. Concentration and purification of the acetylene is one of the more difficult steps in any of these processes. An interesting angle is the process for making vinyl chloride monomer direct from this dilute product gas, recently developed by R. E. Lynn, Jr., and K. A. Kobe a t the University of Texas. Hydrogen chloride requirements are manufactured right in the process stream by adding chlorine to react with the hydrogen already there. Reaction is initiated by a glowing nichrome wire; by introducing enough chlorine to produce hydrogen chloride in excess of that required to react with the acetylene, sufficient heat results from the exothermic reaction to form an additional 2 to 3y0acetylene by pyrolysis of some of the unreacted methane left in the stream. Conversion of acetylene and hydrogen chloride to vinyl monomer is catalyzed by a mercuric chloride-barium chloride complex salt supported on activated carbon. Activity of the catalyst is decreased by the presence of higher acetylenes and amyl mercaptans. so these materials should be removed from the reaction stream. Nearly all of the acetyIene in the gas stream is converted to a satisfactorily pure and reactive vinyl chloride. T;CTork at Texas U. was carried out in a pilot plant (Continued on page 16 A )
Phthalic polyester
Hickory wood
One Minute after Bringing i n t o Contact with Hot Bar a t 900' to 100O'C.
November 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
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TURBO=MIXER,
a division of
GENERAL AMERICAN TRANSPORTATION C O R P O R A T I O N
Turbo Hydrogenators a t General Mills Plant, Kankakee, Ill.
Turbo-FLotution Conditioners a t Duual Sulfur & Potash Plant.
Turbo flotation cells at Noralyn p l a n t of International Minerals & Chemical Corp.
AT WORK These and many more leading chemical processing companies use Turbo-Mixers to handle their more difficult jobs of mixing liquids, solids or gases. You’re invited to visit
11s
at the 24th Exposition
of Chemical Industries in Philadelphia, November 30 -December 5. Booths #42 and #44, Commercial Museum C Convention Hall. Turbo-Mixers i n causticizing operatian a t Brown Paper Co.
Turbo-Mixers used in antibiotics f e r mentation a t Upjohn Company Plant.
Turbo aerators a n d floaters on phenolic treatment a t G A T C car washingplant.
Reichhold Chemicals, Inc. Resin Cooker w i t h Turbo-Mixer.
SALES OFFICE: 3 8 0 M A D I S O N A V E N U E , NEW Y O R K 17, N E W Y O R K General ofices: 1 3 5 S. La Salle St., Chicago 90, Illinois Offices i n all principal cities ERAL WMEWlCAN k ERS TOWERS TA
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-DRYERS EVAPORATORS RS PRESSURE VESSELS
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 45, No. 11
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operating on Schoch arc discharge process gas, but addition of carbon monoxide to the process stream to simulate gas from thermal cracking or partial oxidation processes did not affect the results, The plant operated at temperatures of 150" C. to produce 45 pounds of vinyl chloride per day. Aside from the economic advantage of using cheap dilute acetylene, no localized overheating and subsequent sublimation and deactivation of the catalyst take place during operation. One disadvantage is the need of moving relatively large amounts of gas per pound of vinyl output. Recovery of the monomer is also expected to be a problem, because it is present in the output with a low partial pressure. The latter difficulty, it is hoped, will be overcome by adsorbing the product on active carbon or by use of some organic solvent suitable for extraction. Prospects look bright enough for the Fluor Corp. of Los Angeles, and it is planning to make the process available on a commercial scale. D.M.K. PAPER 7.
DIVISION O F I N D U S T R I A L A N D E N G I N E E R I N 5 c"HEM1STRY
ENZYME INHIBITORS
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Ammoniated dentifrices proved so popular some years ago t h a t by 1950 these types had captured 15y0of the market. I n 1951, however, a n odor- and bacteria-conscious public transferred its allegiance to toothpastes containing chlorophyll, and now these products appear to have reached the crest of popularity for the time being. One reason is the successful introduction of still another product for oral hygiene, a dentifrice containing the antienzyme factors Nlauroyl sarcosinate and sodium dehydroacetate. These are reported after rather extended research to inhibit the formation of decay acids in the mouth, for as long as 12 to 24 hours, Meanwhile, consumer dollar purchases of dentifrices in the past few years have increased four times, the volume H.S. last year amounting to $145,000,000. P A P E R 13,
DIVISION O F C H E M I C A L M A R K E T I N G A N D ECONOMICS
FRACTIONATE WITH AMMONIA
1
This crude product was subjected to a series of extractions in lvhich the salt concentration and pH of the liquid ammonia were precisely varied. Five fractions were obtained, later to be tested in the analytical ultracentrifuge. Three of these fractions proved of special interest. Each of the three was found to contain a high concentration of a single and different protein having a molecular weight of either about 6000 or 12,000. This represents perhaps the first isolation of a relatively small protein molecule from the pancreas. The biological inertiiess of this protein, having a molecular weight of about 6000, strongly suggests that the minimum molecular weight of insulin may be 12,000.
When the biochemist is looking around for a nice, classical method for fractionating a complex mixture of proteins, he is apt to select a procedure calling for aqueous solutions of ethyl alcohol or of some other organic solvent. T o bring about the required separation, he can introduce a number of variables into these systems to take advantage of the differing physical and chemical properties of the protein components, I n all of this work, solvents with low dielectric constants are definitely a t a premium. Since the dielectric constant of alcohol solutions is relatively high, the application of suitable nonaqueous solvents in protein fractionation is being thoroughly explored. Research by Eric Ellenbogen of the University of Pittsburgh has centered around the use of liquid ammonia. This solvent not only has a low dielectric constant but can also be readily handled in ordinary laboratory apparatus. To determine the effectiveness of liquid ammonia as a fractionator of proteins, Dr. Ellenbogen investigated the protein most fully characterized-insulin. Preliminary tests showed that, despite prolonged exposure of crystalline zinc insulin to liquid ammonia, the biological, physical, and chemical properties of the protein remained completely unchanged. I n Dr. Ellenbogen's research, a crude insulin preparation from beef pancreas was selected as the starting material. November 1953
With a Nonaqueous Solvent, Purified Proteins
I n any ideal fractionation, one of the overriding requirements is that the physical properties of the individual constituents in no way be permanently altered in the separation process. According to Dr. Ellenbogen, liquid ammonia fractionation can be entirely satisfactory in this respect. Thus this work may very well point the way to the eventual widespread use of liquid ammonia as a fractionator of biological products. H.J.S. PAPER 49.
DIVISION O F B I O L O 5 I C A L C H E M I S T R Y
UNSIMPLE SIRUPS . . . . the product of the synthesis possesses an infrared
spectrum identical to that of sucrose octaacetate measured under the same conditions. . . . This unequivocal proof of the first authentic chemical synthesis of sucrose spelled success for Raymond U. Lemieux and George Huber in their long search for the answer to this classic problem in carbohydrate chemistry. Lemieux and Huber, engaged in fundamental research on the chemical properties of sugar at the National Research Foundation of Canada, accomplished a reproducible synthesis by reacting a sirupy 1,3,4,6-tetra-O-acetyl-~fructofuranose with Brigl's anhydride at 100' C., followed b y acetylation and extraction of the material from a benzene solution. The synthesis of sugar represents a significant advance in knowledge of the chemical properties of glucose and
INDUSTRIAL AND ENGINEERING CHEMISTRY
(Confinued on page 17 A ) 1SA
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provides a basic pattern for synthesizing many other complicated substances. It is possible also that, as a result of this work, biochemists may be able to prepare sugar molecules labeled a t specific positions for use in tracing the path of the sugar molecule in life processes. 2-Desoxy-~-ribose has remained for years a rare and unobtainable sugar in spite of a lively interest in the nucleic acids and their relationship to such important phenomena as the mechanism of inheritance, growth and development, and normal versus abnormal growth. Several synthetic routes to 2-desoxyribose have been recorded, but the methods have been tedious and expensive, and it has been difficult to obtain even experimental quantities of the sugar. John W. Sowden, Washington University, St. Louis, Mo., reports a simple and economical synthesis by alkaline isomerization of D-glucose and degradation of the resulting metasaccharinic acids. From 100 grams of glucose and using nothing larger than a 2-liter flask, he has obtained as much as 5 grams of the pure R.C. desoxy sugar. PAPERS 48 AND
molded article on immersion in boiling water. Dishes molded from styrene and methylstyrene were subjected to immersion in boiling water for 15 and 60 minutes, respectively. Styrene in the shorter period showed considerable warpage; methylstyrene treated four times as long showed no effects of deformation. The heat distortion temperature of mixed methylstyrenes was shown to be nearly a linear function of the values of the pure monomers from which they are made up. Suggestion is t h a t the o-methylstyrene is responsible for an increase in heat distortion temperature when added to the para, and that the meta isomer causes a lowering of the softening point of the para. Since the process for preparation appears economical and the polymeric properties of the methylstyrenes are attractive, their use in plastics, rubber, and resins appears imminent. W.Q.H. PAPER 84.
DIVISION O F PETROLEUM
CHEMISTRY
38. D I V I S I O N O F CARBOHYDRATE C H E M I S T R Y
IRONING OUT WOOD DIFFICULTIES SANS BENZENE Brought about as a result of the widespread, successful use of styrene in plastics and synthetic rubber and the indication that vinyl monomers of closely related chemical structure might be of interest in the same applications, postwar studies of the properties of methylstyrenes show a good possibility that the materials will develop into commercial products of great importance. A process recently developed by American Cyanamid uses toluene and acetylene, or xylene and acetaldehyde, to produce 1,l-diarylethanes, which are then cracked catalytically in the vapor phase to produce the methylstyrenes. The process is of particular interest inasmuch as benzene, critically scarce in recent years, is not required.
x
Polymethylstyrene boiled 60 minutes
Polystyrene boiled 15 minutes
Keeping I t Straight
Several properties of the polymethylstyrenes offer advantages over styrene. One of importance in many plastic applications is heat distortion temperature. A comparison shows the following extrapolated heat distortion temperatures for some of the products: Heat F t o r t i o n ,
C.
Monomer Stvrene Methylstyrene (67% para, 37% ortho) Dimethylstyrene (90% 2,4and 10% 3,4)
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108
118
The advantage of high heat distortion temperature was illustrated by comparing the resistance to deformation of a November 1953
Familiar with the havoc a rusting pin can play with a piece of fabric? Or maybe you've seen what rusty grommets can do to a canvas tent. Does the same thing happen to wood? Yes, says Eduard Farber of the Timber Engineering Go., who has been tackling a problem to which little thought has been previously given. Old railroad cross ties, removed from tracks after many years of service, show deterioration under the tie plate which cannot be entirely explained as mechanical damage. Farber has found this is due to changes in chemical composition of the wood, catalyzed by iron salts. For old cross ties the portion of wood dissolved by boiling with dilute hydrochloric acid was generally more than normal for the same species of wood, and the amount of reducing sugars in the solutions was below normal, indicating a loss in carbohydrate content of the wood. Lignin solubility was less. Ratios between wood's principal components, hemicelluloses, cellulose, and lignin, differed greatly from those of normal wood. Similar changes were found in accelerated tests using iron filings and thin veneer in water-vapor saturated atmosphere a t 140" F. for 10 weeks, with complete immersion in water for 4 hours each day. Much needs to be learned about this deterioration-perhaps by measuring the degree of polymerization of the carbohydrates and the solubilities of the lignin components. I n the meantime Dr. Farber suggests that this decomposition is very slow and modern protective coatings will reduce it greatly for most applications. For those such as cross ties, however, he advocates addition of calcium carbonate, 1% by weight on dry wood basis, either in dust or slurry form, or using an impregnant or coating as a carrier as an effective method of suppressing the amount of iron picked up by the wood. W.H.S. PAPER 32. D I V I S I O N
O F I N D U S T R I A L AND E N G I N E E R I N G
CHEMISTRY
KNOCK, KNOCK, WHAT'S THERE? What's there may be a number of carbonyl compounds, formed before ignition from the gasoline hydrocarbons charged into an automobile cylinder. A combination of heat and pressure, caused by the compression stroke of the piston, may partially oxidize such hydrocarbons as propane, propene, n-
INDUSTRIAL AND ENGINEERING CHEMISTRY
(Continued on page 18 A )
17 A
This NEW METHOD DRIES AIR
NIAGARA CONTROLLED HUMIDITY AIR CONDITIONING This method removes moisture from air by contact with a liquid in a small spray chamber. The liquid spray contact temperature and the absorbent concentration, factors that are easily and positively controlled, determine exactly the amount of moisture remaining in the leaving air. Heating or cooling is done as a separate function.
heptane, and n-pentane to formaldehyde, acetaldehyde, propionaldehgde, and acrolein. These compounds, and the alkyl hydroperoxides mhich are found along with them, could be the villains that make the vaporized gasoline explode, rather than burn nith a smooth “Cadillac-type” flame. Acetone, crotonaldehyde, and slight amounts of polyfunctional materials, 1-2-dicarbonyl compounds, and nionocarbonyl conipounds of four or more carbon atoms are also produced in the preflame reactions. Of the materials studied by E. V. Malmberg and his associates a t Ohio State, n-heptane (zero on the octane scale) released more than 5% of its heating value in these partial oxidation reactions, J3-hile isooctane (100 on the scale) \\Tasted consideiably less energy. Isolation of the carbonyl intermediates posed quite a problem, A “motored engine” was used, driven by an electric motor, so that spark ignition mas not necessary. Samples were n-ithdrawn from the combustion chamber through a sampling valve, TT hich remained open about 1.1 milliseconds, or 6’ of rotation of the engine crankshaft a t the speed used. This valve was opposite the spark plug, so that samples of unburned gas could be extracted ahead of the flame front even when the engine was firing. An ionization plug narned of the approach of the flame t o the sampling valve. A reduction in the motoring power required to rotate the unfired engine, and an increase in cylinder pressures are evidence of energy release and chemical reaction during the compression stroke. As gasoline octane requirements become higher and higher. and as the compression ratios of modern engines continue to be increased, these preflanie carbonyls may supply the key to the no-knock gasoline of the futuie. 1‘LJ.R. P A P E R 68,
DIVISION O F ORGANIC CHEMISTRY
The Niagara’s Controlled Humidity Method using HYGROL moisture-absorbent liquid is
. .. it removes moisture
as a separate function from cooling or heating and so gives a precise result constantly and always. Niagara machines using liquid contact means of drying air have given over 20 years o f service. Best and most effective because
. ..
Most reliable because the absorbent is continuously reconcentrated automatically. No moisture-sensitive instruments are required to control your conditions.
.. .
Most flexible because you can obtain any condition at will and hold it as long as you wish in either continuous production, testing or storage.
...
Easiest to take care of because the apparatus is simple, parts are accessible, controls are trustworthy. Most compact,
taking less space for installation.
.
n o re-heat is needed to obtain the relative humidity you wish in normal temperature ranges and frequently no refrigeration is used to remove moisture. Inexpensive to operate because..
The cleanest because..
.n o solids, salts or solutions of solids
are used and there are n o corrosive or reactive substances. For complete information write
NIAGARA BLOWER COMPANY Over 35 Years of Service in Industrial A i r Engineering N e w York 17, N. Y , Dept. EC, 405 Lexington Ave.
V I A THE SHORT ROUTE There have been two disadvantages t o the quartz tube combustion method, widely used in the petroleum industry for the determination of sulfur and halogens in organic materials: The attention of the operator is constantly required and determinations are often lost as a result of incomplete cornbustion. A team of scientists a t Shell Development Co. has devised a method that allows more rapid combustion and facilitates the combustion of volatile materials. These workers observed that if the sample is vaporized in a stream of nitrogen (instead of air in the conventional process) and the vapors are mixed with oxygen within the heated zone of the combustion tube, an intense flame results in the zone of admixture of oxygen and sample vapors. %’hy not use the flame temperature as a measure of the rate of sample vaporization? A direct relationship was found between the flame temperature and sample vaporization rate. This suggested that the temperature could be used as the basis for automatic control of the rate of vaporization. Further work led to the development of completely automatic combustion apparatus which controls the rate of combustion to compensate for the characteristics of a wide variety of sample types. Control is obtained by placing a thermocouple in the flame which occurs a t the entrance to the combustion furnace. The rate of sample vaporization is controlled by the temperature of this thermocouple. The thermocouple, by means of a n amplifier and relay circuit, switches the sample heater off and turns on a cooling air blast or switches
Sales Engineers in Principal Cities of U. 5. and Canada 18 A
INDUSTRIAL AND ENGINEERING CHEMISTRY
(Continued on page 20 A ) Vol, 45, No. 11
The greatest adva
in resin-cement chemistry in ten years
c
‘
PENNSALT F U R A N CEMENT 3
A Fura-Tone, Product
Combines a//the advantages of ordinary furan-type cements with many new ones yet costs no more I
-
Now Pennsalt, original producer of quicksetting silicates and resin-type cements, offers an entirely new and exclusive furan cement-far superior to anything on the market today! It supersedes other products as the most versatile, generalpurpose cement for bonding acid-proof brick or tile in the construction of corrosion - resistant linings; floors, and trenches.
I
cements now on the market! To give speedy service to customers, Pennsalt is stocking this new product at many points throughout the nation. Pennsalt Corrosion Engineers are ready to advise users on the proper application of new Pennsalt Furan Cement. For further information about this outstanding product or its use, just write: Corrosion Engineering Dept ., Pennsylvania Salt Manufacturing Co., 454 Widener Bldg., Philadelphia 7, Pa. I
-
The new Pennsalt Furan Cement is based on a furfural-ketone resin, completely different from furfural-alcohol types now in common use. It has all the important virtues of other furan cements as well as many it alone can claim (see list at right). Perhaps the most startling fact about new Pennsalt Furan Cement is this: even considering its many advantages, i t costs no more than ordinary furan
Properties of new Pennsalt Furan Cement The important advaqtages common to furan cements:
1. 2.
Stable-store it indefinitely Does not cause dermatitis
Plus ail there poinlr of clear superiority:
3. Actual, workable 2-to-1 4.
5. 6. 7. 8. 9.
10.
powder-solutionratio Increased acid resistance Increased alkali resistance Increased resistance to most solvents Longer working life Easier handling characteristics-less “temperamental” or “hot” Choice of owders-Powder C (carbon filler) and f’owder S (siliceous filler) Economical to buy and use
I
Furs-Tone is a Trademark OF lwineton Varnish & Insulator Division of Mlnncsota Mining & Manufacturing Company
November 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
19 A
the heater on and turns off the air blast as the flame temperature goes above or below the control point. Thus the oper% tor need only press a button and return a t the sound of a buzzer which signals the completion of the combustion, How do results compare with samples containing known amounts of sulfur? Tests shown below, along with others, indicate that an accuracy of 99% or better may be expected for materials containing more than 5% sulfur or halogen and, in the lower concentrations, the results indicate that sulfur or halogen can generally be determined to &0.03%.
Here showing "Aircomatic"
welding on Aluminum shell
of a 5 4 " 0.d. x 10' flxed tube sheet Heat Exchanger. Inset shows the completed job of one of three such units on the order.
% Sulfur or Halogen Present Found 92.2 92.0 17.3 17.3 100 0 98 9
Material Carbon tetrachloride Monochlorinated paraffin wax Flowers of sulfur Phenyl sulfoxide
15.9
Benzyl disulfide
26.0
99 1-
16.0 16.0 26.1
An operator can complete from 15 to 25 determinations in an 8-hour working day. Productivity is further increased in comparison with manually operated apparatus because no determinations are lost with the automatic apparatus as a result of incomplete combustion. M7.Q .H . PAPER 30. DIVISION O F
PETROLEUM C H E M I S T R Y
TRENDS I N BOILER WATER TREATMENT
experienced craftsmanship . . , yes, let DOWNINGTOWN's experience and research in the fabrication of various grades of Carbon Steel, Stainless Steels, Nickel-Clad, Stainless-Clad, MonelClad, Cupro-Nickel, Aluminum, etc., be of help to you. W e are equipped with the most modern facilities to handle complete jobs, within our limitations, in the correct alloys and methods of fabrication required to assure maximum operating efficiency.
DOWNINGTOWN's Heat Transfer Division is under the direction and supervision of men thoroughly trained and experienced in this field. O u r Engineering Consultation is at your service to aid you in preparation of plans and specifications for definite jobs. Useful literature gladly sent upon request. Remember: "your needs are our specialty!"
We,
along with our parent company, would be very glad to greet you a t our booth #714, Chemical lndustries Exposition, N o v . 30th-Dec. sth, Philadelphia. N e w York Office: 30 Church St.
I
DOWNINGTOWN DOWNINOTOWN-PINNA. ,LA" -
20 A
IASRICAIION AND M U 1
Here is what a panel discussion a t the Chicago meeting brought out on new developments in boiler water chemistry and chemical engineering : New acid inhibitors stable up to 190" F. permit higher temperatures during acid treatment to remove boiler deposits. Two-bed ion exchange is more popular than mixed-bed ion exchange for silica removal demineralizing. Use of ion-permeable membranes to treat boiler waters is sound theoretically, but considerable engineering development will be needed before it is practical for large scale use in boiler plants. Three out of four companies are now controlling pH of feedwater chemically; most use ammonia or amines, while the balance use caustic or recirculation of boiler water. Sodium sulfite has been almost universally accepted for controlling dissolved oxygen in boiler feed water, and hydrazine is a possible newcomer for removing traces of dissolved oxygen and G.H.B. also elevating the p H of feedwater. PAPERS B TO 14. CHEMISTRY
OF
WATER,
SEWACIE,
AN0
SANITATION
WATCH THAT FOREST Look not always to coded punched cards for the solutions to problems of locating chemical information. Indexers a t American Cyanamid Co. put information on cards (a special typewriter is used) and file it in a Kardex installation. No other special equipment is used, I n a search for all compounds containing only one KO2 group and one OH, all other functional and heterocyclic systems excluded, 11 such compounds out of a total 10,000in the file (there is room for 23,000) were located in 7 . 5 minutes. Estimated time for a mechanically sorted, punched card operation is 10 minutes. Key to the system is an empirical formula arrangement of compounds based on functionality and a new order of precedence related to the periodic table. Filing is strictly alphabetical and numerical. J.H.K. PAPER 6 ,
INDUSTRIAL AND ENG
DlVlSlON
D I V I S I O N 07 C H E M I C A L
NEERING CHEMISTRY
LITERATURE
Vol. 45, No. 11
In 5 great markets General American offers you complete bulk liquid storage terminal facilities with no capital investment on your part.
You use modern facilities, pipelines, manifolds, blending equipment. You have complete privacy. All methods of bulk liquid transportation
At the Ports of New York and New Orleans there is high-speed canning, drumming and barrelling equipment-yours to use.
use General American’dyor lease” facilities at Corpus Christi Export bulk liquid traffic is big business at Corpus Christi. Outward bound tankers carried 1,124,950 tons of all types of bulk liquids in 1952-making Corpus Christi one of the nation’s key bulk liquid distribution centers.
TANK STORAGE TERMINALS in Important Marketing Centers Port of N e w
York
(Carterot,
N. J.)
Potl of N e w Orleans (Goodhope, la.)
Ct&do?t
6 Houston Corpus Christi
06 General American transportation Corporation 135 South La Salle Street, Chicago 90, Illinois
