they could be easily synthesized and be cause deuterium labels possible points of attack in the oxidative process. According to Khan, the autoxidation of deuterated compounds formed by replac ing hydrogen atoms on the double bond has given concrete experimental evidence for a number of phenomena of autoxida tion reactions: (1) initial attack of oxy gen at the double bond and the inherent induction; (2) the propagation of autoxi dation by attack on the methylenic group, alpha to the double bond during the steady state; (3) the presence of resonance in free radicals formed and consequent shift ing of the double bond; and (4) the loca tion of hydrogen atoms contributed to the formation of the major portion of the water. The experiments have established four definite and distinct stages of autoxi dation, said Kahn, and the results have lent support to the theories proposed by the Britisher, E. II. Farmer. Water formation in autoxidation, Kahn continued, was shown to be the outcome of the primary decomposition of peroxides, mainly hydroperoxides, and the formation of organic volatile products to be that of the secondary decomposition at a later stage. New Method for Hydroxylating. A new method for hydroxylating long-chain unsaturated fatty acids, esters, alcohols, and hydrocarbons was described in a pa per by H. B. Knight, R. E. Koos, and Daniel Swern, all of the Eastern Regional Research Laboratory. Formic acid at its boiling point at atmospheric pressure adds readily to the double bonds of oleic, elaidic, and linoleic acids, methyl oleate, oleyl alcohol, 1-hexene, and glycerides, yielding the corresponding formate esters, explained Knight. By using perchloric acid in small amounts as catalyst, the reaction time can be reduced from 24 hours to about 10 minutes. Acetic acid catalyzed by per chloric acid also adds to the double bond, but at a slower rate than formic acid, he said. By means of these reactions, oleic and elaidic acids can be converted to monohydroxystearic acids in good yields, ac cording to Knight. He went on to explain that linoleic acid yields a mixture of monohydroxyoctadecenoic and dihydroxystearic acids, and oleyl alcohol yields a glycol. Wax Works. Using a chromatographic method, Κ. Ε. Murray, Commonwealth Scientific Industrial Research Organiza tion, Melbourne, Australia, found the pro portion of normal acids among the acids of carnauba wax to be 38 r /r. Murray sepa rated the nonnal acid mixture into its components by amplified distillation of the methyl esters and by this technique re vealed the presence of the acids of even carbon numbers from C» to Cat». Melting points, long crystal spacings, and crystal habit were used to identify the various acids. From the experimental work, Murray estimated the relative amounts as follows: Cu,, $%-t Cao, 11.5*7c; CM, 9 % ; Cut 30%; CM, 12%; G», 16.5'', ; and Cm», 77t. V O L U M E
3 0,
NO.
C&EN REPORTS: Packaging Institute
Handling Long-Lived Isotopes A Serious Atomic-Age Problem Shooting isotopes permanent solution NEW YORK.-The long-lived isotopes, with half-lives in t h e thousands and mil lions of years, present one of the most im portant problems of the atomic age, ac cording to Paul Colsmann, Brookhaven National Laboratory. Mr. Colsmann told the 14th annual forum of the Packaging Institute here Oct. 20 to 22 that there is no present means of disposal which will guarantee future safety other than con trolled storage. Even sealing t h e material in metal, which is then embedded in cement and dumped into a shale-forming deposit in the ocean, does not guarantee that the ma terial will not become a hazard a hundred or a thousand years from now. Shooting such long-lived radioactive waste mate rials into space seems to be t h e most permanent solution but will probably never be economically feasible, he contin ued. It is absolutely necessary that the use
into
space
would
provide
ot radioactive materials be controlled and supervised somewhere along the line from supplier to user, Mr. Colsmann empha sized. Radioactive materials can be bene ficial to mankind in the hands of a com petent trained physician, but the nature of these materials makes them dangerous in the hands of the uninitiated. The ideal situation would be to never receive any exposure, yet everyone is being exposed to cosmic radiation and natural radioactivity in the air. Certain levels of radiation may be received by the body continuously without noticeable harm. Those who work at Brookhaven and in the atomic field in general are limited to a daily exposure of 50 milliroentgens a day. The average radiation received by a citizen is about 0.1 milliroentgens (mr. ) per hour so that in a day one receives 2.5 mr. or Vaut h of the Brookhaven tolerance. A wristwatch with a radium dial gives ex posure of 10 mr. daily to the wrist. An
U s e α CARBIDE Ester . . . . in Your Lacquer The high purity and uniformity of Carbide's ester sol vents a r e important considerations in maintaining high standards o f quality in the manufacture of lacquers. B. P ^ G CEUOSOiVE A c e t a t e
156.4
M e t h y l A m y ! Acetate
146.3
Butyl A c e t a t e
126.3
h o p r o p y ! A c e t a t e is an efficient,
stable,
low - boiling
lacquer
solvent with a toluener dilution r a t i o of 2.9 Ethyl A c e t a t e
44» « N O V E M B E R
77.1
CARBIDE AND CAUBÛN ί CHEMICALS COMPANY
\
A Division of
Cellosolve" is a registered trade-mark of Union Carbide and Carbon Corporation.
3,
1952
4615
THE CHEMICAL WORLD THIS WEEK airplane pilot confronting the many radium dialed instruments is exposed to 1 to 10 nir. per hour, hence one airplane used by Hrookha\en lor high altitude cosmic ray measurements had such instruments replaced to reduce the background radiation. New Uses. Among the newer uses for radiation products are static eliminators. Also, they are Ining used for activation of phosphors now done by radium and polonium, Colsmann observed. The use of radioisotopes in fluorescent tubes or in instruments containing radiation sources would be relatively new, he» said. Industrial radiography is a very large field in which suitably-packaged radioisotopes have a future in competing with \-ray and radium. Cold sterilization of drugs and food has tremendous possibilities. Standard Drums and Pails. The 18gage, 55-gallon drum and the 5-gulIon pail are the bread-and-butter items of the steel shipping container industry, representing about 65'r of the number of containers produced, said William I. Hanrahan, United States Steel Products. The petroleum industry now purchases about 65'< of the drums currently made*. There are now 45 manufacturers with 60 plants making drums and pails, and 25 other manufacturers with 60 plants making only shipping pails, he said. Most drum-making equipment turns out 300 drums per hour, but the more modern equipment does 600 hourly. Only one worker on the line actually touches the material, inserting heads and bottoms. Production time from flat sheet to railroad car is only 15 minutes. Government specifications call for drums that are grease- and dirt-free, scale-free, and rustinhibited. This has been achieved, after fabricating, by spray cleaning, followed by rust-inhibiting treatment with a watersoluble zinc phosphate coating, 150 to 200 milligrams per square foot. It is necessary to use the treatments after fabrication and not in the flat condition. Food Caking. Principal causes of food caking are pressure, temperature, and moisture, arranged in the order of their increasing importance, said R. A. Morck, chief chemist, R. B. Davis Co. Moisture, the principal cause of caking, has led to economic loss that is probably astonishingly large. What is actually the cause is the evaporation of moisture. Where moisture is the primary caking cause there are eight precautions: Start with a dry product. Eliminate or reduce soluble impurities that lower the product's equilibrium relative humidity. Keep particles large and uniform in size, since fine particles dissolve more readily. Agitate the product during drying to break u p the cohesion of the cementing material. Cool the product, d o not pack while hot until moisture-free, and pack only in airtight container. K^ep the packing room atmosphere dry. Add inert material to prevent caking, such as starch in powdered sugar. Prevent access of moisture into the product after packaging.
4616
Good housekeeping is important. E. O. Burroughs, Jr., F. S. Royster Guano Co., employs drawings to illustrate hazards of sloppy housekeeping in a fertilizer plant C & E N REPORTS: N a t i o n a l S a f e t y Congress and Exposition
Maintenance Work Is Greatest Hazard to Chemical Plant Safety Maintenance workers should be training in protection from hazards C U I C A G O . - W h e n the first cooperative safety congress was held in Milwaukee in 1912, one hotel easily accommodated all the n* 'ctings and exhibits, as well as the 250 delegates who participated. In the years that have passed since, the congress has grown; the 40th National Safety Congress and Exposition held last week in Chicago filled five of the city's largest hotels. The growth of the national safety movement has produced highly desirable results, said Ned H. Dearborn, president of the National Safety Council. In the past 40 years there have been 500,000 fewer accidental deaths in the United States than would have occurred had the death rate continued at the 1912 level. Still, he admonished, there can he no satisfaction with "an accident experience "which, in 1952, will result in 100,000 deaths in the United States and nearly 10 million nonfatal injuries." The chemical processing industries, which have played a leading role in the reduction of over-all accident rates in recent years, were well represented at the Chicago sessions, and the safety consciousness they displayed did much to explain the industry's enviable—though far from perfect—record. Safety must be given more than ordinary attention in the chemical industry, since in ' the public mind chemistry tends to b e associated with explosives and poisons—far fetched as this may be in most instances. In order t o retain good community relations a chemical
CHEMICAL
given
special
plant, more than any other, must earn a reputation as a safe place to work. Maintenance Workers. In the papers presented before the chemical section of the 40th Safety Congress, it was not the production worker who got most of the attention, but the maintenance man. Injuries are far more prevalent among maintenance workers than production personnel in this industry, said D . W . Gibson of Columbia Chemical Division. A production worker, doing highly repetitive work, becomes thoroughly familiar with his department, his task, and the equipment he uses. Maintenance workers, however, must work in all departments, with a variety of conditions, equipment, machinery, and methods. Lack of familiarity with the chemical operation is hazardous, Gibson said, and requires that attention to safety be a part of every maintenance job. Going a step further, E. G. Volz of Monsanto declared that the maintenance man has the most hazardous job in all industrial operations. Because of the poisonous or corrosive nature of many chemicals, he said, maintenance work in the chemical industry is particularly dangerous, and workers must b e given special training and equipment to protect them from all hazards. Maintenance craftsmen cannot be expected to be entirely familiar with all facets of the industry, and care must therefore be exercised by others to protect them. As an example of specific maintenance problems in the chemical industry. Earl R. Wallace of Eastman Kodak cited in-
AND
ENGINEERING
NEWS
