rine concentration attainable in their present system—about 30%—Adcock's group is not able to replace all 12 hydrogens in neopentane to any large extent using the gradient reactor alone. (The major product in the optimum isomer distribution contains only 10 fluorines.) They are, however, able to force replacement of all J12 hydrogens. They accomplish this by sending the effluent stream from the gradient reactor through a special photochemical stage containing a 550-watt ultraviolet lamp. This additional—almost magical—stage increases the amount of perfluoroneopentane from 9% to 90% of the total distribution. Perfluoroisobutane, the fragmentation product, is formed in only 4% yield. With perhaps justified optimism, Adcock predicts that the use of the photochemical stage "may very well make direct fluorination practical." The key to its success is the photoactivation of fluorine, which makes the reaction "go all the way." At the other extreme, Adcock is able to achieve intermediate degrees of fluorine substitution merely by controlling the stoichiometry of fluorine and hydrocarbon. It even may be possible to limit fluorine replacement to only one or two hydrogens by controlling carefully the amount of fluorine present in the reactor, he says. They haven't tried it yet, but he says, "I see no practical reason why it couldn't be done." The aerosol process is a further advance over the "low-temperature, gradient (LTG) fluorination" technique that Adcock helped develop in the early 1970's with Richard J. Lagow and Norma J. Maraschin at Massachusetts Institute of Technology. In that system, a stream of helium carried hydrocarbon vapor into a four-zone reactor where the hydrocarbon was condensed on dry icecooled turnings. Reaction with gaseous fluorine occurred on this surface, after which the more volatile, more highly fluorinated products were desorbed by allowing the temperature to rise in a particular zone of the reactor. Less highly fluorinated intermediates were subjected to higher temperatures and higher fluorine concentrations until the desired extent of fluorination was attained. Typically, such "batch" reactions took from three to seven days to complete. With the aerosol reactor, these long reaction times have been reduced drastically because of its continuous, flow-through nature. In the old LTG process, says Adcock, it took 10 days to produce 20 millimoles of a product. With the aerosol reactor, that yield now can be achieved in 10 hours.
Adcock and his colleagues only recently have begun to use the aerosol reactor to investigate the fluorination of other compounds, such as benzene, cyclohexane, 1,4-dioxane, and 2,2dimethyl-l,3-dioxolane. Their preliminary results indicate that esters, ketals, amides, and other groups that are solvolytically unstable to hydrogen fluoride can be fluorinated without fear of cleavage. Adcock hopes that aerosol fluorination may one day prove to be commercially feasible, if only for the production of special research chemicals. The aerosol method is simpler and more general than any fluorination technique now being used industrially. "Our reactor deals totally with flows and gradients and all are maintained without a single moving part in the reactor itself," he points out. Although there were some problems in the early stages of the reactor's development, he notes, these were solved by simplifying the system, not by making it more complex. Now, having recently crowned his aerosol fluorinator with the photochemical stage, Adcock says that his research group is "definitely on the road to perfluorination." •
EPA's water quality criteria under attack
Chemical Congress The Environmental Protection Agency's proposed criteria for acceptable water quality have come under attack from two eminent biologists. Arthur L. Buikema Jr. and John Cairns Jr. of the biology department at Virginia Polytechnic Institute & State University are concerned about improper collection of data, subsequent improper manipulation of the data, and attempts to extrapolate ecosystem behavior from single-species data. Intense effort has gone into EPA's three drafts of water quality criteria, and there is great pressure to meet legal deadlines for them (C&EN, July 14, page 24). However, Buikema and Cairns don't believe the current third draft is anywhere near what is needed to provide clean water. The blame for this situation
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I
Dissident Soviet polymer scientist arrives in U.S. Soviet polymer scientist Yuriy Yarim-Agaev visited Washington, D.C., last month, where he met with, among others, staff members of the American Chemical Society. Here, talking with him at ACS headquarters are, from left, Maria A. Snow of the ACS Office of International Activities; Yarim-Agaev's wife Yulia; Robert E. Henze, director of the ACS Membership Division; Hugh Simon of the U.S. Department of State's Regional Human Rights Office for Europe; and Gordon Bixler, manager of the ACS Office of International Activities (far right). Yarim-Agaev arrived in the U.S. in July, having been granted permission by the Soviet government to leave the Soviet Union. A member of the Moscow Helsinki Group, he was dismissed from his position in the polymer department of the Institute of Chemical Physics in Moscow as a result of his activities in defense of dissident Soviet scientists Yuri Orlov, Anatoly Scharansky, and Alexander Ginzburg. In June, at the direction of the ACS Board of Directors, ACS president James D. D'lanni sent letters to Soviet officials expressing the society's concern for Yarim-Agaev's welfare and requesting that he be allowed to emigrate if he so wished. Western scientists had in 1979 learned of Yarim-Agaev's situation, and he had received offers of positions in several laboratories, including that of Stanford University chemistry professor Paul J. Flory.
The numerous studies that have doesn't rest entirely with EPA, they told the Division of Petroleum been devoted to sublethal effects of Chemistry. Industry, the scientific toxicants have seldom been of much community, and various kinds of en- use in establishing water quality crivironmental advocates, they believe, teria, Buikema says. Many of the studies were carried out for the wrong are equally at fault. According to Buikema and Cairns, reasons, such as developing confifew toxicity data have been published dence in the techniques and apparain peer-reviewed literature. The data tus, without much concern over suitthat do appear are often improperly ability of the resulting data in precollected, primarily because the dicting real-world effects. Another problem that disturbs biology of the test organisms hasn't been considered in test design. Those Buikema and Cairns is that the apdata that are available suggest that plication rate of toxicants during a. organisms in unnatural systems are toxicity test is often inappropriate. more sensitive to toxicants than they Usually tests require continuous exposure to a fixed level of toxicant for are in natural systems. Until the biological parameters are 48 hours or more. However, most incorporated into the design of tox- chemicals in the environment vary icity tests, the Virginia scientists considerably in concentration over maintain, those tests will be subject time. Time-dose dependency of organto severe scientific criticism. There have been some advances in acute test ism tolerance and resistance has been methods in recent years but most of studied by physiologists for years, but them have been directed toward im- this concept has rarely and only reproving the toxicant delivery system cently been applied to toxicity testso that pollutant concentrations were ing. Buikema and Cairns say that constant rather than intermittent. because natural organisms are very The basic acute test methods have seldom exposed to stable concentraremained almost unchanged for 125 tions for long periods of time, toxicity testing should include some proceyears.
dures for a recovery period in toxicant-free water. The two scientists also believe that toxicity tests with pure compounds are of limited value because most compounds, except for spills or accidents, are not expected to enter the environment unaccompanied by other compounds. For most organisms, other compounds may add or subtract from the effects of exposure to the pure compounds. It all boils down to the fact that the ability to predict biological effects accurately from test data is inadequate. If the data being used to develop EPA's criteria are questionable, Buikema and Cairns don't think manipulation of the data is any better. Some of the proposed criteria, they say, were based on data manipulation that was improper and, in at least one case, led to minimum estimation errors of as much as 165%. Despite considerable professional criticism of the procedures used by EPA, Buikema and Cairns don't believe that the most recent third draft benefited much thereby. They maintain that close reading of the rule for criteria development shows that unpublished and/or nonpeer-reviewed data can be used. Also admissible are data that do not meet acceptability requirements—for example, unmeasured toxicant concentrations. A feature particularly irksome to Buikema and Cairns is that EPA permits combination of data for different life stages, for EC50 and LC50 concentrations, for lethal and sublethal effects, for salt- and freshwater, and for algal and vascular plants. The method of calculating the average 24-hour exposure is also suspect. The desire to protect 95% of all species present may result in criteria that are overprotective and for which no biological benefit can be demonstrated. And the criteria also may be unachievable physically by industry under any conditions. Even if all these problems didn't exist, Buikema and Cairns believe that EPA's criteria would be of little value for other reasons. The criteria are based on single-species tests, Buikema says, with no consideration for natural biotic and abiotic interactions and no validation in field or microcosm studies. The application of single species toxicity data assumes that the ecosystems are merely collections of species. Furthermore, the criteria documents assume that the ecosystems do not recover after episodic events. This, say Buikema and Cairns, is simply not true. Ecosystems can recover rapidly. The presently proposed criteria are
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A general presentation of the subject is supplemented by illustrations of how to solve practical problems, with frequent citing of industrial examples. The course focuses on the interaction of chemical engineering with chemical phenomena and processes and covers such examples as non-isothermal batch reactors, flow reactor scale-ups, combined adsorption, and chemical reactions. Comparisons between the chemical engineering treatments of fluid flow, heat transfer, and mass transfer are made. Although the course is not highly mathematical, some knowledge of calculus is required. FACULTY: Dr. Richard G. Griskey, Professor, College of Engineering and Applied Science, University of WisconsinMilwaukee. FEE: ACS Members, $325.00; Nonmembers, $385.00. DATES: November 13-14,1980
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pictured by Buikema and Cairns as virtually a no-win prescription, but, they say, EPA isn't solely responsible. Ecologists and toxicologists have provided neither suitable methods for carrying out ecosystem tests nor a reliable data base. Industry has spent most of its time and money in reacting defensively to regulatory pressures. The advocates and promoters have done little more than create more confusion. •
was careful not to publicize it. We, however, are active coconspirators in plans for extermination of tens of millions." I believe, with great regret, that Grey is right in one respect. The U.S. scientific community remains simply uninformed about what nuclear war on U.S. territory is going to mean. Hence it appears much less concerned about heading off such a nuclear war than our Soviet scientific colleagues. It is incumbent on scientific societies at least to remove that ignorance by "writing in detail about the unwritten about." Rustum Roy Director, Materials Research Laboratory, Pennsylvania State University
Letters Continued from page 3 ness of the "literature" on the other side. I wonder if they are familiar with the work of Ellul, of Heilbroner, Mumford, Roszak, von Weizsacker, or Weisskopf. If not, then I suggest that it is this very narrowness (which is, of course, fundamentally at the core of science) that we are being criticized for. We cannot respond to criticism on our terms, on our turf, any longer. What's good for science may, or may not, be good for society. We must recognize that neither GM nor science can expect that anymore. That ball game is over. Science is a human enterprise to be on tap for, not on top of, human values and aspirations. It is Grey, who for all his protestations about not relegating nuclear war to the realm of the unthinkable, appears to have done precisely that. The Boston physicians talked chapter and verse on numbers killed, availability of health services, etc. I did not find Grey replying by citing the Office of Technology Assessment study on the "Effects of Nuclear War," saying that after all only 4 million would be killed promptly in the minimum 2-megaton attack on Philadelphia, or the lethal 1000-rem fallout level over several thousand square miles of the Midwest after a hundred megaton counterforce attack on our North Dakota bases are all part of his own thinking of which he would recommend as a course of action. His touching naivete is revealed in his allusion to Hiroshima-Nagasaki as his idea of a limited nuclear war. This time, Grey, there will be two teams on the field, in case you'd forgotten. And 15 megatons is after all 1000 X 15 kilotons; and it will be Salt Lake City and Chicago and Pittsburgh. W. H. Ferry, formerly a vice president of the Center for the Study of Democratic Institutions, wrote recently: "We Americans are good people. Yet we are preparing to commit the most hideous crime in the annals of mankind. Where Hitler murdered millions, we are ready to annihilate hundreds of millions. Where he despoiled thousands of acres of precious earth, we shall render sterile and useless vast areas of continents. Where he bombed out dozens of cathedrals, libraries, schools, and hospitals, we shall at a stroke do away with entire civilizations, including our own. "There is one significant difference between Germany in the 30's and 40's and the United States in 1980. To this day the "ordinary Germans" alive in the Hitler years protest that they did not know about the gas ovens, the slavery, the starvation that were essential components of the Final Solution. They were not, they assert, coconspirators in such infamy, because Hitler 32
C&EN Sept. 1, 1980
SIR: A recent letter disparaging the efforts of the medical profession in alerting America to the dangers of a nuclear misadventure prompts a comment. The world has not "survived a limited nuclear war in 1945." Such a statement stems from utter naivite, and bears the same credence as saying that World War II was fought with BB guns. A nuclear holocaust is beyond one's imagination of horror. There is no "civil defense" against a catastrophe. Organized society as we know it would cease to exist. The worldwide calamity of nations depending upon our food, our exports, and our moral and monetary assistance cannot be described. Oh, there would be survivors, indeed. The military could come crawling out from under their mountain tops, and the few civilians that managed to burrow deeply could all come out and breathe freely of the contaminated air and fight like animals among themselves foraging for survival. The scenario is so long and endless it is senseless to repeat. Observable history has shown no Soviet use of mass destruction. History has shown our use of the atom bomb, and the massive unloading of explosives upon tiny Vietnam that surpassed all the tonnage loosed upon Nazi Germany in World War II. We must conclude that the Soviets are sincere in wanting to limit weapons of mass destruction. If there is no trust among nations, what is the alternative? Yes, what is the alternative? Let us as a nation not succumb to our fears and phobias, and become a snarling cornered beast, spewing nuclear destruction upon all who dare oppose us. Surely mankind has a more hopeful destiny. A nuclear war is not like the shoot-out at the old corral, where all the bad guys are killed and the good guys ride out into the sunset, as in a John Wayne western. Carl R. Blumenstein Greenville, S.C. SIR: I wish to take issue with a statement in a letter by Don Grey of Salt Lake City in C&EN, July 14, page 4, " . . . the world survived a limited nuclear war in 1945." This statement is outrageously misleading. In 1945 only one side had (rather small) atomic bombs, and the other side promptly surrendered when it became the recipient of two of them. Grey implies that we will not surrender if we are hit with today's much bigger bombs. Does he think the U.S.S.R. will surrender if we retaliate or if we strike first? And if neither side surrenders, when does the war stop? The fact is, the article of May 5 was correct. A "limited" nuclear war, even if there could be such a thing between the U.S. and the U.S.S.R.,
would totally devastate large sections of both countries and cause tens of millions of casualties. Grey may feel that he will be spared, as Salt Lake City would not be a prime target, but even if this is so, it provides small comfort to those who live in or near such cities as New York, Washington, D.C., Chicago, Houston, Los Angeles, Detroit, and others. A nuclear attack on the U.S., whether "limited" or not, would probably not wipe out all human life, but would certainly destroy our modern civilization. Even if Salt Lake City survives, its inhabitants would find their way of life reverting to that of before the industrial revolution. The question is, is there any conceivable gain worth this kind of price? Jerry March Professor of Chemistry, Aldelphi University, Long Island, N. Y.
Assessment of Ph.D.'s SIR: It was refreshing to see an honest assessment of Ph.D. education and the Ph.D. job situation (C&EN, June 16, page 2) from a chemistry faculty member. I concur with Porter that more coursework, not less, should be given in the first two years. Most of the advances in chemistry in the last 15 years, which students need to master before advancing that science, cannot be stuffed into already overfilled undergraduate curricula. Presenting "special topics" courses in the second or third year disrupts concerted research. Furthermore, formal training needs to be given in research skills per se, as opposed to textbook chemistry. Far too often students are left to find out on their own, often in a haphazard way, how to design and build experiments, how to pick up engineering, machinist, and drafting skills. Formal training needs to be given in research strategies—how to get the experiment to produce the right data to test decisively a correctly formulated hypothesis, how to use statistics properly, treat noise, and evaluate the reliability of data, and especially how to avoid false economies of time or money (a skill which too many research advisers lack as well). And industrial employers have expressed in this magazine their disappointment in finding too few Ph.D.s who can work without close supervision. Present Ph.D. education does not systematically provide training in the skills needed to get into or survive in the world of big government or industrial group research. The time for making a science out of doing research, and teaching it at the graduate level, is long overdue. Ph.D. education needs to be more of a team effort by faculty, not only to share diverse skills, but also to avoid situations where a shortcoming of an individual faculty supervisor sometimes seriously damages a student's career. It is a sad commentary on the state of Ph.D. education that there are too many times when the most difficult challenge a student faces is not the chemistry itself. Furthermore, somewhere along the line Ph.D. education has lost or submerged its proper purpose of providing its graduates with all the professional skills necessary to pursue a career in science successfully. Career counseling in any organized and effective fashion, beyond how to fill out a job resume and maybe how to act at a job interview, is virtually nonexistent. And, by
