toluene, or with di-?i-propyl sulfide (which is structurally similar). Percolation techniques were used. Here's how the variously modified carbons stack up:
RESEARCH
Potassium Sodium None KOH
% Adsorbed from Percolate Toluene Propyl sulfide 91 69 85 58 25 47-48 23 36
Other alkali metals (except lithium, because of its small atoms), says Mr. McLeod, will probably give similar changes in carbon's adsorption properties.
Reactions at Interfaces
SPREAD PLANES. Chemists at Standard Oil (Ind.) find that the alkali metals sodium and potassium activate carbon more than the usual steam treatment does. The reason: They open small gaps in the carbon planes, William F . Wolff explains to Gordon D. McLeod (left) and Dr. Philip Hill
K, Na Activate Carbon Alkali metal treatment markedly hikes carbon's adsorption properties ACTIVATED
CARBON
(charcoal)
can
be made a lot more active by treating it with sodium or potassium. Already known to improve carbon's inert gas adsorption properties, the alkali metals also help carbon adsorb liquids better. And they don't disturb the carbon's selectivity. Reason: Standard Oil (Ind.) chemists say it's because carbon's pore structure is changed by the alkali metals. According to Gordon D. McLeod, William F. Wolff, and Dr. Philip Hill of Standard's research department, carbon is generally thought to be a series of sheets, one on top of another. Treating with alkali metals causes small gaps to form between the carbon sheets, Mr. McLeod told the chemistry section of the American Association for the Advancement of Science. The new holes, says Mr. McLeod, are probably made when atoms of the metal pry apart the sheets of carbon. The structure then looks like a honeycomb. With the new surfaces, much 38
C&EN JAN.
II,
I960
larger amounts of gases or liquids can be separated. Alkali metal modified carbon is made by stirring molten sodium or potassium with the carbon until the mixture is homogeneous. Carbon was also treated with aqueous potassium hydroxide solution, but this treatment lowers activity. • Potassium Tops. Best separation results, says Mr. McLeod, are obtained with potassium modified carbon because the potassium atom is relatively large. This is followed by sodium modified material, then untreated carbon, and finally by potassium hydroxide modified carbon. Earliest work was in separating inert gases. Using a nitrogen-argon mixture, for example, the alkali activated carbon can adsorb twice as much nitrogen as untreated carbon does. More recent adsorption studies by the Standard group were with liquid mixtures. Typical binary mixtures used: nheptane with either a corresponding seven-carbon aromatic hydrocarbon,
l&EC Christmas Symposium reveals progress in theoretical understanding; more experiments now needed INTERFACES are everywhere, yet they still stubbornly refuse to yield all their secrets to engineers studying them. They are present and play key roles in catalysis, mass and heat transferin fact almost every chemical operation. And each bit of ignorance about them can add to the cost of chemical manufacture. With this spur to their endeavors, some 150 chemical engineers met at the 26th Annual Christmas Symposium of the ACS Division of Industrial and Engineering Chemistry at Johns Hopkins University in Baltimore to discuss mechanisms of reactions at interfaces. • Absorb Two Gases and React. Some parts of interfacial reaction theory have been tested experimentally. Dr. R. L. Pigford and coworkers at University of Delaware have calculated and verified by test what happens when two gases dissolve simultaneously and react either with each other or with a third component already dissolved. Examples: COo and N H 3 dissolving in water and reacting with each other; COo and H 2 S dissolving in alkaline scrubbing solution. His experiments confirm his theoretical calculations, Dr. Pigford says. With the gases reacting with each other, they both dissolve faster than either would without reaction; this increase depends on ratio of solubilities, reaction rate constants, and diffusion coefficients. When the two gases react
MATHESON Compressed Gas Notes
Hydrogen Chloride, Anhydrous, in the Organic Synthesis Laboratory; Flowmeters and Regulators Hydrogen Chloride, Anhydrous Hydrogen Chloride has many applications in organic synthesis, some of which are discussed below. When there is a choice between gaseous hydrogen chloride and concentrated aqueous hydrochloric acid in chemical operations, chemists have found that hydrogen chloride offers some distinct advantages over aqueous hydrochloric acid. I t is easier to introduce into a reaction because of its high cylinder pressure, thereby eliminating the need for pumps or pressurized carboys, and process operations are simplified. Applications (A) For the preparation of hydrochlorides of amines by treating the amine in an appropriate organic solvent with hydrogen chloride under anhydrous conditions. Products can be obtained free from objectionable odor and moisture. (B) F o r the preparation of esters by using hydrogen chloride in lieu of sulfuric acid as the catalyst. In some cases, the yield is improved and there is less product damage. (C) For the preparation of alkyl chlorides by treating an alkanol with hydrogen chloride in the presence of zinc chloride. (D) For introducing the chloromethyl group (CH2C1) e.g., by introducing hydrogen chloride into a suspension of paraformaldehyde and anhydrous zinc chloride in benzene to obtain benzyl chloride, PhCH2CL. The process may be varied by using methylal or chloromethyl methyl ether in place of paraformaldehyde. (E) For the preparation of aromatic aldehydes by treating aromatic hydrocarbons with a mixture of carbon monoxide and hydrogen chloride in the presence of a metal halide catalyst. (F) For t h e preparation of aromatic aldehydes by passing hydrogen chloride into a suspension of sodium cyanide and aluminum chloride in an excess of the hydrocarbon. A typical analysis of Matheson's Hydrogen Chloride is a s follows:
Hydrogen Chloride Inerts Carbon Dioxide
99.3% 0.2% 0.5%
Hydrogen Chloride, as well as more detailed information on its properties, can be obtained by contacting any of Matheson's plants a t East Rutherford, N. J., Joliet, 111., or Newark, California. The gas is readily available in a range of cylinder sizes from a standard 57 lb. # 1 cylinder to the 8 oz. Lecture Bottle. Our Compressed Gas Catalog gives full details. Write for your copy.
Corrosion Resistant Regulators Matheson has a group of regulators and controls which not only will handle Hydrogen Chloride safely, but will also operate efficiently in controlling and/or reducing pressures of Hydrogen Sulfide, Sulfur Dioxide, Boron Trifluoride, and Nitric Oxide, to name a few. Matheson has developed this type of regulator, see the No. 15 pictured here, by properly employing new corrosion resistant materials that have become available in the last few years. A special plating process is used to coat all surfaces of the regulator, inside and out, with corrosion resistant nickel. The diaphragm and springs are also specially coated. The seat is resilient, inert Kel-F; all gaskets are Teflon. The needle valve on the outlet end is monel. A monel check valve can be supplied too and is recommended for use with the No. 15 series to prevent suck-back of foreign materials into the cylinder. Specifications are included in the Matheson compressed gas catalog.
This catalog deals with many recent innovations in handling corrosive and inert gases with a complete line of Automatic Pressure Regulators, Safety Devices, Flowmeters, Valves, and Manifolds. The catalog listings of our 82 compressed gases also recommend Matheson controls for every available compressed gas.
Flowmeters for Corrosive Gases Matheson Flowmeters can be specially fitted to measure the flow of Hydrogen Chloride and other corrosive gases with complete safety. All of the series 600 flowmeter tubes are made of Pyrex and they are equipped with dual spherical metering floats, one of Pyrex and the other of Stainless Steel. The Single Tube units, Four Tube units, and the 215 series flowmeters can be made available for corrosive service with corrosion resistant end fittings. Our new pamphlet, Matheson Laboratory Flowmeters, gives prices and operating specifications for all of our Flowmeters and their accessories.
Any Questions? Our Technical Department, in East Rutherford, New Jersey, has extensive information on compressed gases and gas handling equipment. We will welcome an opportunity to help solve your problems concerning the use of compressed gas.
The Matheson Company, Inc. Compressed Gases and Regulators
East Rutherford, N. J.
Joliet, 111.
Newark, Calif.
RESEARCH
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C&EN J A N .
II,
I960
with a third component already in the the first application of a general method water, each is absorbed more slowly suggested 12 years ago by Dr. Harrison than it would be if it were the only one Brown, now at California Institute of being absorbed, but faster than would Technology. By comparing the specoccur if there were no chemical re- trum of xenon in the meteorite sample with the spectrum of ordinary, atmosaction with the solute. These results mean, Dr. Pigford pheric xenon, Dr. Reynolds finds an points out, that if you wish to design inordinate excess of the isotope xenona scrubber for a gas stream containing 129 in the meteorite. According to two acid gases, you have to take into Dr. Reynolds, this excess could only be account the competition between the from radioactive decay of the isotope two gases for the alkali or you will end iodine-129, which long ago ceased to up with not enough capacity (assum- exist naturally. This means that the meteorite was ing no safety factor engineered into formed near enough to the time the the system). • More Experiments Needed. But elements were formed that traces of not all phases of interfacial reactions iodine-129 were still in existence. stand on such well-proved grounds. In From the half life of iodine-129 (17 fact, consensus among the listeners million years), Dr. Reynolds calculates (but not shared by all the speakers): that 350 million years elapsed between Theory and mathematics have taken us formation of the elements and formaabout as far as we can go; it is time tion of the meteorite. Since this type to make more measurements of what of meteorite—a chondrite—is generally is actually going on at these inter- considered to be 4600 million years old, he was able to pinpoint the time faces. But this is easier said than done. at which the iodine-129 was last formed How do you measure things which are along with all the other heavy elements occurring in boundary layers that may in our solar system. (Chondrites are be only microns thick and at rates the most common class of stone meteorthat approach instantaneous? How do ites known.) you characterize a surface when the Present methods for dating meteoractive sites on it are smaller than the ites are based on natural radioactivity resolving power of any instrument? of uranium, thorium, potassium, and How do you make sure that you are rubidium. The xenon-iodine method measuring the right thing and are keep- will be useful, says Dr. Reynolds, being out side effects? The only answer cause it is much more sensitive to mentioned at the symposium: "Much changes that occurred in the meteorite extremely careful, precise work is in the time range nearest to the creation needed." of the solar system. In 1954, Dr. Reynolds built the mass spectrometer used in this work specifically for studying rare gas samples. Total amount of xenon in the meteorite Age of Elements Fixed sample was only 42 X 10" 12 gram. A Scientist a t University o f combination of features made the inC a l i f o r n i a figures t h a t solar strument unique when it was first built; it combined principles of modern mass system is 5 billion y e a r s o l d spectrometry with the then newly developed ultra high vacuum techniques. The meteorite sample came from the U S I N G a sensitive mass spectrometer and seven grams of a meteorite which privately owned Nininger Collection of fell 41 years ago in Richardton, N.D., Arizona. Recently, a large portion of a University of California physicist has this collection was sold to the British come up with another estimate of how Museum of Natural History, a move old the elements in our solar system are. that was viewed with great disappointThe answer: 4950 million years, plus ment by Dr. Reynolds. "Right now or minus a piddling 150 million years. we're learning more about the details The figure is a comparatively youthful of the development of the solar system one for the solar system, which until from meteorites than from any other now was thought to be somewhere be- type of research. Every effort should tween 5050 and 7500 million years old. be made to keep valuable collections The finding, by Dr. John H. Reyn- like this one accessible to American olds, associate professor of physics, is scientists," he says.
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From the Rubber Division of the ACS .. .
RESEARCH
Briefs. • •
Introduction to
• National
RUBBER TECHNOLOGY edited by MAURICE MORTON Director, Institute of Rubber Research and Professor of Polymer Chemistry, University of Akron
Science
Foundation
has
revised its indirect cost policy in its support of basic research. Under the new policy, NSF will consider requests for up to 20% of total direct costs as the allowance for indirect costs. This liberalization results from rising administration costs and the resulting hesitance of some researchers to take on contracts at the previous 15% remuneration level, NSF says.
1959, 553 pages, $10.00 This book represents one of the many traditional activities of the American Chemical Society's Division of Rubber Chemistry. It is also the direct result of the growing educational activities of the various active Rubber Groups in the United States. With the advent of the synthetic rubbers and allied synthetic polymers, the rubber industry found itself more and more involved in "chemical" fields. There resulted a growing demand on the part of the technologist as well as from others in the sales, service, and purchasing activities for more technical information about these expanding fields. Hence various Rubber Groups in all parts of the country began sponsoring lecture series on rubber technology for the benefit of their members and the industry as a whole. This book is a compilation of selected lectures that introduces new members of the rubber industry to the basic aspects of rubber technology. The selection of contributors and articles indicates that this book has accomplished a broad coverage of a rapidly growing technology. CONTENTS: History and Summary of Rubber Technology; Introduction to Polymer Chemistry; Natural Rubber; Vulcanization; Accelerators of Vulcanization; Antioxidants and Antiozonants; Rubber Plasticizers, Softeners and Extenders; Carbon Black; NonBlack Compounding Ingredients; ButadieneStyrene Rubbers; Nitrile and Polyacrylate Rubbers; Butyl Rubbers; Neoprene; Hypalon; Polysulfide Polymers; Silicone Rubbers; Reclaimed Rubbers; Latex, Sponge and Foam; Physical Testing; Processing Equipment for the Rubber Industry.
Examine It Free for 10 Days MAIL THIS COUPON TODAY REINHOLD PUBLISHING CORPORATION Dept. M-579, 430 Park Avenue New York 22, N.Y.
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42
C&EN
JAN. I I ,
I960
• Applications
for
federal
• Research on sulfite pulping byproducts gets another vote of confidence, as trustees for Sulphite Pulp Manufacturers' Research League okay a 1960 budget of $163,500, up 6.4% from 1959. The league's years of research are paying off, the trustees heard at their annual meeting. The amount of spent liquor processed for by-products has grown steadily for several years. In 1959, mills with about 20% of the U.S. sulfite pulping capacity could process their sulfite wastes. And next year, this figure will rise to 25%.
aid in
building or modernizing graduate research laboratories must be in by March 1, 1960, or face a six-month delay, the National Science Foundation warns. NSF plans to consider the proposals late this spring, will announce its decisions in late summer. Applications received after March 1 will be reviewed after the next cutoff date, September 1, 1960. The program requires at least 50% nonfederal funds and a graduate course leading to the Ph.D. degree. • Hypernuclei, ordinary atomic nuclei in which a neutral lambda hyperon particle replaces one of the neutrons, are being studied by Dr. Martin M. Block, head of Duke University's high energy nuclear physics group. Dr. Block is concentrating on the lambda helium-4 hypernucleus, is studying it in his liquid helium bubble chamber. He has sent his data to several laboratories around the world for analysis. • Iron oxide powder in the 200 to 1000 A. range has been made in sample quantities at Vitro Laboratories, West Orange, N.J. Iron oxide was part of a program that has produced many finely divided metals and metal oxides with a high intensity electric arc. • New grants totaling $340,000 will go to 11 university research labs from the Nutrition Foundation. Earmarked for basic research in nutritional science, these awards raise the total given since 1941 to more than $5.5 million. Much of the new work sponsored by the foundation will be in the field of fat metabolism, with emphasis on dietary balance between saturated and unsaturated fats. Research on proteins, minerals, vitamins, and sugars is also a part of the program.
• British scientists have isolated cephalosporin C, one of a new group of antibiotics under study in England, and are attempting to identify its structure. The compound is closely related to penicillin both chemically and biologically. But unlike penicillin, it resists destruction by penicillinase. The research end of the project is under Sir Howard Flory, with the support of Glaxo Laboratories and National Research Development Corp. • Cryogenic thermometry will get more attention at the National Bureau of Standards. NBS aims to provide more precise temperature calibrations from 90° K. to 20° K. and to provide a calibration service from 20° K. to 2° K. The bureau will also take steps to extend the international temperature scale below 90° K., where no international agreement now exists. • Smog fighters will soon have help from General Electric meteorologists at Hanford. A research program there aims to determine air patterns which prevail at night, when most temperature inversions occur. GE scientists plan to release nonradioactive test materials from the plant's 410-ft. meteorological tower, will sample the air at 800 stations scattered over a 16-mile radius. Results will be applicable to other areas with similar wind conditions, GE says. • Ford Foundation has made a grant of half a million dollars to the European Organization for Nuclear Research (CERN) to enable physicists from nonmember states to work in CERN's laboratories. The world's largest particle accelerator—the 28-billion-electron-volt synchrotron—is part of the facilities at the Geneva research center.
