CHEMICAL SAFETY - Chemical & Engineering News Archive (ACS

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1155—16th St., N.W., Washington, D.C. 20036 Editor: Michael Heylin Assistant Managing Editors: David M. Kiefer, James H. Krieger, Janice R. Long, Donald J. Soisson, William J. Storck Staff Editor: Ernest L. Carpenter Senior Editors: New York: Earl V. Anderson; Chi­ cago: Joseph Haggin; Washington: Lois R. Ember, Wilbert C. Lepkowski, Rebecca L. Rawls, Howard J. Sanders Associate Editors: Mairin Β. Brennan, Doron Dagani, Bette Hileman, Richard J. Seltzer, Pamela S. Zurer Service Departments Editor: Dolores Miner Editing Services: Joyce A. Richards (Head), Anne Riesberg (Editorial Assistant), Patricia Oates (Ad­ ministrative Assistant) News Bureaus: New York: (212) 697-3223 Ste­ phen C. Stinson (Associate Editor), Marc S. Reisch (Assistant Editor). Chicago: (312) 256-4143 Ward Worthy (Head). Houston: (713) 973-8161 Bruce F. Greek (Head). Washington: (202) 872-4495 David J. Hanson (Associate Editor). West Coast: (415) 653-3630 Rudy M. Baum (Head). Foreign Bureau: London: (01) 540-0414 Dermot A. O'Sullivan (Head), Patricia L. Layman (Associate Editor) Graphics and Production: Leroy Corcoran (Man­ ager). Alan Kahan (Art Director). Barbara Fryer (Production/Art Director). Linda Mattingly (Staff Artist). Diane Kelly (Costing). Business Manager: Arthur Poulos Circulation Development: Cynthia G. Smith ADVISORY BOARD: William J. Bailey, Myron Foveaux, Vincent L. Gregory Jr., John D. Holmfeld, Donald F. Hornig, Isabella Karle, Dorothy Nelkin, Richard Nicholson, Howard A. Schneiderman, Ellen K. Silbergeld, Howard E. Simmons, William P. Slichter, Richard N. Zare Published by AMERICAN CHEMICAL SOCIETY (202) 872-4600; TDD (202) 872-8733 John Κ Crum, Executive Director PUBLISHING BOARD: Barbara G. Wood {Chair­ man); Board of Directors Chairman: Ernest L. Eliel; President: Mary L. Good; E. E. McSweeney; John H. Nelson; Louis D. Quin; and Jean'ne M. Shreeve © Copyright 1987, American Chemical Society Subscription Service: Send all new and renewal subscriptions with payments to: Director, Busi­ ness Management Division, ACS, P.O. Box 57136, Washington, D.C. 20037. Correspondence and telephone calls for changes of address, claims for missing issues, subscription service, status of re­ cords and accounts should be directed to: Manager, Membership & Subscription Services, ACS, P.O. Box 3337, Columbus, Ohio 43210; (614) 421-3776. Changes of Address: Include both old and new addresses with ZIP code numbers and mailing label from a recent issue. Allow four weeks for change to become effective. Claims for missing numbers will not be allowed if loss was due to failure of notice of change of address to be received in the time specified; if claim is dated (a) North America: more than 90 days beyond issue date, (b) all other foreign; more than one year beyond issue date; or if the reason given is "missing from files." Subscription Rates 1987. Printed editions: nonmembers U.S. 1 yr. $44,2 yr. $75, outside U.S. 1 yr. $70, 2 yr. $127. Air freight rates available on re­ quest. Rates above do not apply to nonmember subscribers in Japan, who must enter subscription orders with Maruzen Co. Ltd., 3-10 Nihonbashi 2chome, Chuo-ku, Tokyo 103, Japan. Tel: (03) 2727211. Single copies: Current $6.00. Rates for back ' issues and volumes are available from Microforms & Back Issues Office, ACS, 1155—16th St., N.W., Washington, D.C. 20036. Back and current issues available on microfilm and microfiche. Rates on request from Microform Program, ACS. Chemical & Engineering News (ISSN 00092347) is published weekly except for the last week in December by the American Chemical Society at 1155—16th St., N.W., Washington, D.C. 20036. Second-class postage paid at Washington, D.C, and additional mailing offices. POSTMASTER: Send address changes to Chemical & Engineering News, Membership & Subscription Services, P.O. Box 3337, Columbus, Ohio 43210. ACS assumes no responsibility for the statements and opinions ad­ vanced by the contributors to its publications. Advertising Management CENTCOM LTD. (For list of offices see page 63) 2

February 16, 1987 C&EN

LETTERS

CHEMICAL SAFETY Explosion hazard in the synthesis of titanium iodides SIR: I attempted the synthesis of about I of the reaction mixture in the copper 5g of Til 4 from the elements, by solidtube to ensure uniform heating. The state reaction under unreactive atmo­ temperature of the reaction mixture was sphere. Stoichiometric amounts of io­ slowly raised in this water bath. dine and titanium powder were weighed As the temperature of the bath and mixed together, in a glove box, un­ reached about 90 °C, a violent explosion der dry nitrogen. Exact stoichiometry is occurred, splitting the copper tube hard to achieve because of the volatility open, shattering the beaker, and splash­ of iodine. ing iodine all over the fume hood where the reaction was being carried out. We The mixture was loaded inside a cop­ repeated the experiment at a much per tube that had been sealed at one end smaller scale (about 500 mg Til 4 ), under by flattening and bending four times. the same conditions, hoping for maybe a The tube was about a quarter filled with vigorous but hopefully nonexplosive the reagents. The other end of the tube reaction. However, again at around 90 was temporarily sealed inside the glove °C, an explosion occurred, so violent box to keep the reagents under dry ni­ that the top end of the copper tube that trogen while final sealing was per­ was bent four times, unbent and split formed outside the glove box, also by open; the reaction mixture was thrown flattening and bending four times. We out, splashing the fume hood, and the have successfully used this technique beaker broke. At this point, it was obvi­ many times for solid-state reactions of ous that even small amounts of reaction fluorides up to 800 °C; leaks were never mixtures were very dangerous and no observed below 400 °C. In the synthesis further attempt to control the reaction of Til 4 , the copper tube was held almost was done. vertical in a narrow beaker that con­ tained enough water to have about half Georges Denes of the tube immersed; i.e. the water lev­ Concordia University el in the beaker was well above the level I Montreal, Que., Canada

The DDT problem SIR: J. Gordon Edwards and I. W. Tucker (C&EN, Sept. 29,1986, page 5) requested facts in their letter to support truth about DDT and supplied none. In 1949, DDT was sprayed irresponsi­ bly in Illinois to control phloem necro­ sis of elms, supposedly transmitted by a leaf hopper. This nectar could not be found there. No elms were saved; many birds died. Authorities blamed the jit­ ters and mortality on bird malaria, but they failed to find the organism. Without funds or support, I chal­ lenged this diagnosis. Self-limiting con­ centrations of DDT were found in bird brains. It was biologically accumulated through leaf litter and earthworms. I was advised to keep quiet or be an un­ employed inert toxicologist. Neverthe­ less, I submitted the data for publication and was rebuffed with "We don't pub­ lish negative data." The data were even­ tually published in 1958 in the Journal of Wildlife Management (Vol. 22, page 269).

Similar findings have been published by others on modest budgets. There is some truth in "Silent Spring." I knew Rachael Carson. She was against the misuse, not the use, of insecticides. Some of the data to support the safety of DDT to humans resulted from my daily ingestion of DDT and biopsies from my buttocks. The importance of concentrations of toxins in assessing long-range biologi­ cal effects continues to be a valid con­ cern despite censorship. Roy J. Barker Tucson

Beyond oil SIR: I would like to make a few com­ ments on your interesting review of the book "Beyond Oil" (C&EN, Dec. 1,1986, page 25). On behalf of economists, the use of price, capital, and labor as key factors in economic calculations is a device for es-

tablishing a common ground. One might substitute resources, technology, and society but it would merely be a question of semantics. Cost, price, and value would again intrude. However, the absence of any questioning of the derivation and validity of gross national product is more serious. For example, while the national output of private swimming pools and bottled water may augment the GNP considerably, they may be indicators of a deteriorated ecology, such as polluted lakes, ponds, and rivers. Also, it seems that the concept of renewable resources may become something of a fetish. The farmers and herdsmen of the Sahel depend completely on renewable resources and consequently are at the mercy of the elements. Leonard H. Clapp Wilmington, Del.

Bioorganic chemistry SIR: I would like to voice a need for ACS (and other publishing entities) to acknowledge bioorganic chemistry as an integral part of organic chemistry, and to make whatever administrative decisions are necessary to encourage the publication of bioorganic articles in ACS journals other than the Journal of the American Chemical Society (JACS). Here is the status quo. If an organic chemist completes a project currently viewed as interdisciplinary between biochemistry and organic chemistry, the natural first choice is JACS. However, publishing articles in JACS is a function of several variables, one of which is the quality of the work. If an article is not accepted for publication by JACS (as is often the case these days, mainly for space reasons), our fictional organic chemist does not, at present, have viable alternatives among the other ACS publications. It must be "biochemical" enough for Biochemistry or "organic" enough for The Journal of Organic Chemistry (JOC), which may be hard to establish with various camps steeped in the traditions of their respective disciplines. For example, I cite a recent reviewer's comment: "[Journal name] is the wrong journal for this type material. Organic chemists will not read it and the biochemists who might be interested will not see it." In this case, the author felt it was precisely organic chemists who should have seen the

work; who was right is not the issue, but the fact that the scenario occurs so frequently is cause for concern. This situation will be especially aggravated in the coming years. One cannot help but note that many (perhaps most) of the new organic faculty around the U.S. are bioorganic chemists. If bioorganic chemistry is not an integral part of organic chemistry by definition, then organic chemistry faces an enormous defection in the near future. Furthermore, funding initiatives like those generated at the National Science Foundation that specifically seek to establish cross-fertilized projects point to an increasing role of organic chemists in nonclassical areas. My personal view is that we should not create yet another journal, but rather should encourage bioorganic chemists to stay close to their roots by specifically soliciting and reserving space for bioorganic articles in JOC. If the size of JOC is to be maintained, then we must acknowledge that emphases in organic research are changing from the traditional, and adjust the contents of the journal accordingly. Anthony W. Czarnik Assistant Professor of Chemistry Ohio State University, Columbus Editor of Biochemistry replies: With regard to Prof. Czarnik's letter on the publication of bioorganic papers in ACS journals, I shall let the organic chemists speak for themselves. High quality of the work is, of course, an overriding criterion for the acceptance of publications iri Biochemistry, as it is for all primary journals published by ACS. I assume therefore, that Czarnik's comments relate only to bioorganic papers of high quality. A manuscript should also address a problem of timely interest and importance since the science of yesterday usually does not advance a discipline, be it organic or biological chemistry. I am not aware that Biochemistry has. declined out of hand manuscripts in bioorganic chemistry that meet the above criteria. If that were the case, we would have had to decline manuscripts dealing with enzymic reaction mechanisms or with the organic synthesis of biologically important peptides, proteins, or polynucleotides, just to mention a few. In 'fact, we would be delighted to have the opportunity to consider more manuscripts of that category provided, of course, they

are of high quality, and address a problem of biochemical significance. I agree that scientific journals must adjust their contents to the changes from the traditional in order to stay current and survive, and the creation of yet another journal would not solve this problem; it would merely replace existing journals and accelerate their obsolescence. Hans Neurath Editor of Biochemistry

Plastic bottles SIR: Donald Clemens (C&EN, Dec. 15, 1986, page 2) reports that plastic bottles containing 30% H 2 0 2 became dangerously brittle upon standing for one year. His concern, reinforced by the accompanying editor's note, is with the deterioration of the bottle. I believe that another concern is possibly serious contamination of the contained H 2 0 2 by plasticizer extracted from the plastic, with consequent embrittlement. A determination of nonvolatile residue in a sample of old H 2 0 2 , or a UV spectrophotometry examination, might prove informative. Arthur Cherkin Research Direct or-GRECC VA Medical Center Sepulveda, Calif.

Binary chemical weapons SIR: I refer to R. J. Saxton's letter (C&EN, Sept. 1, 1986, page 2) urging ACS to adopt a stance on the production of chemical weapons. There is no reason why ACS should not urge all nations to stop the production of weapons of war whether they are chemical, mechanical, nuclear, et al. However, please do not condemn the Reagan Administration for funding the production of chemical weapons that may give the U.S. an advantage in case of war. War is dreadful to contemplate, but the use of chemical weapons is far more advantageous to a nation at war than having its healthy young citizens killed by rifle bullets or bombs. Warfare is not a game played by a set of rules and there is no "humane" method of killing each other. The object is to overcome the enemy as quickly as possible and minimize death and destruction, or preferably deter any potentially offending nation from starting a war. Harold Reintjes ACS Member Emeritus Green Village, N.J. February 16, 1987 C&EN

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