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Bretherick's Handbook of Reactive Chemical Hazards, 7th Edition (Peter G. Urben, ed., assisted by Malcolm J. Pitt). Jay A. Young. Chemical Safety Cons...
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Chemical Education Today

Book & Media Reviews Bretherick’s Handbook of Reactive Chemical Hazards, 7th Edition edited by Peter G. Urben, assisted by Malcolm J. Pitt Academic Press (an imprint of Elsevier) Burlington, MA. 2006. Volume 1, xxvi + 2182 pages, Volume 2, xix + 446 pages. Volume 1 ISBN-13: 978-0123739452. Volume 2 ISBN-13: 978-0123739469. Set ISBN-13: 9780123725639. $395 (2 volume set) reviewed by Jay A. Young

The publisher describes these two volumes as “an indexed guide to published data”. I hope this review will persuade you that this work is a masterpiece that cannot be adequately described by a few words from the publisher. If you are a chemist working with chemicals, then you know that one way or another all chemicals are hazardous. Every competent chemist, for example, knows that diprotium monoxide is “[a]n extremely reactive liquid, solid, or vapor with a dangerously high thermal capacity in both liquid and vapor state.” It is “[A]lmost level with nitric acid as a cause of memorable mishap [and] the initiator of the single chemical accident with the highest death toll.”1 But who would suspect that argon could explode? For the details, refer to serial number 0091 in Volume 1. Do you know that reducing sugars can be oxidized producing fatal concentrations of carbon monoxide? See the discussion under the topic titled Sugars in Volume 2. Mixtures of sodium hydroxide with ethylene glycol can react exothermically and rapidly to produce hydrogen and burst a closed reaction vessel; check serial number 4439 in Volume 1. Did you know that containers of tetrahydrofuran, sitting undisturbed on a shelf, are subject to spontaneous explosion? For details, see the discussion on caustic alkalies in serial number 1607, Volume 1. Of the approximately 16,000 different reactive chemical hazards described in Volume 1, which one (or two or three) will you encounter next on your own laboratory bench? I suggest we all become Boy Scouts: Be Prepared! Every practicing chemist should have, and use, his or her2 very own personal copy; it just might save their eyesight, or even their life. The first edition of the Handbook of Reactive Chemical Hazards (back then it really was a handbook of a hundred pages or so) was published in 1974 (1). A few years earlier Leslie Bretherick had “resolved to meet … [the] obvious need for a single source of information” describing each hazardous chemical reaction reported in the chemical literature. The British Petroleum Company, Ltd., his employer, generously supported the effort. But by 1977 it became obvious that a new edition was needed; among many others I was asked to help by granting permission to publish information in that new edition about the hazardous reactions that had been compiled over the years by the Manufacturing Chemists Association,3 for whom I was working at the time.

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Today, Volume 1 of the 7th edition, now with Leslie Bretherick’s surname deservedly as part of the title,4 is available, thoroughly revised and with links to incidents not reported in prior editions. Some reactive chemical hazards reported in the currently available chemical literature are not included. A newly reported azide, for example, is included only if it is exceptionally sensitive, or described as a reagent. But except for these justifiable omissions, the editor has attempted to include every reactive chemical hazard reported in the responsible published literature, even those noted on the Internet—if they are responsibly characterized. This allinclusive goal of course cannot be achieved, but as one who knows and respects the editor, I aver that no other editor could come closer to achieving that objective. In Volume 1 each compound is identified by IUPACbased name, CAS registry number, empirical formula, structure, and serial number. In Volume 2 the compounds from Volume 1 are grouped into classes according to similarities in structure or reactivity. Both volumes are completely indexed, the compounds in Volume 1 by chemical name, synonym, serial number, and CAS registry number, 37 pages; the topics in Volume 2 by class, group, title, and type, 16 pages—in fine print. The entries in Volume 1 are ordered according to the Hill system (also used by Chemical Abstracts): C and H if present, then all others by element symbol in alphabetical order. So if you know the empirical formula, you ought to be able to find any listed compound without knowing the chemical name or CAS registry number. And you can do so, but it is a hassle. Instead of printing the pertinent empirical formulas on the upper right corner of each page, the publisher has chosen to print the empirical formulas only on occasional pages, sort of every now and then in what is apparently a random manner. The same criticism applies to serial numbers; in the index each compound is of course listed alphabetically with its serial number (instead of a page number) as a locator. That is a suitable way to set up the index, but alas, there are no serial numbers on the upper corners of any page. Consequently, to find the page or pages that discuss the compound of interest, it is necessary to fiddle through several pages where that empirical formula or serial numbered entry is probably to be found, more or less by a sort of randomized approximation, until finally, the desired information appears—almost as if by magic! Volume 2 is useful as a reference compendium in combination with Volume 1, and I recommend its use as such. But Volume 2 is more than a companion to Volume 1; it stands on its own as a marvelous, understandably written, decidedly useful, textbook. The introduction, which alone is worth the price of both volumes, discusses the basics of reactive chemical hazards: kinetic factors, adiabatic systems, composition and structure, mixtures, and protective measures. But there is more. Summaries of the numerous ways chemicals can be hazardous follow. I’ll abstract one example to give you the flavor: Aldehydes “are very easily oxidized,” “many … liquid aldehydes will eventually inflame if . . . exposed to air,”

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Chemical Education Today edited by

Jeffrey Kovac University of Tennessee Knoxville, TN 37996-1600

“[t]he [probable] mechanism is … initial formation of a peroxy-acid which catalyses the further oxidation.”

Other summaries are concise discussions on azides, boron compounds, disposal, ethers, hypohalites, metal nitrates, phosphorus compounds, tetrazoles, vapor explosions, and vinyl sulfoxides, to list a few of the more than 400 total. Among the readers of this review, those who know me will tell you that Young is stingy with his praise and generous with his constructive (?) criticisms. (I’ll even myself admit to this characteristic.) In this review I have attempted to do both. I strongly recommend that you buy, read, and use your own personal copies of Volumes 1 and 2 and tell every chemist you know to do the same. In my consulting work I know of more than 150 incidents involving chemicals in which, had the persons responsible known of the pertinent hazard(s) described in Bretherick, the resulting fatality, loss of eyesight, disfigurement, pain, and/or loss of property would not have occurred. Neither you nor I want any such thing to happen to you or to those for whom you are responsible.

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Notes 1. This quote, from p 1691 of the book being reviewed, refers to the accident in December 1984, at the Union Carbide plant in Bhopal, India, which caused more than 7,000 reported fatalities when 23 tons of methyl isocyanate were released in the air space where the victims were living. 2. Yes, and Girl Scouts too! 3. Needless to say, I enthusiastically granted permission. 4. Leslie Bretherick died in 2003, having personally nominated Peter Urben to continue the endeavor he had begun.

Literature Cited 1. Bretherick, L. Handbook of Reactive Chemical Hazards; Butterworth: London, 1974.

Jay A. Young is a Chemical Safety Consultant; 12916 Allerton Lane; Silver Spring, MD 20904; [email protected]

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