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L. B. Crider W. J. Kroenke} j ' 1 J''' * " '* I Avon Lake Technical Center Brecksville Research and Development as -//jp ! 12/17/73 i>: -. ' Determining Exposure of Personnel to Gaseous Vinyl Chloride. This note is a response to our conversation of December 13, 1973. It reports my opinions about the possibility of using inorganic or organometallic detector systems for either detecting or providing a cumulative measure of exposure to VC1. Ideally, such systems would be in the form of a badge, similar to the ones we now wear to detect exposure to x-rays. But with one additional feature. This is the ability to show, probably by means of a color change, immediately when a person has been exposed to some significant quantity of VC1. My conclusions and the discussion which follows are based on searching Chemical Abstracts up to July, 1972, and surveying the review literature pertaining to the formation of metal-vinyl compounds. The scientific literature reports only a limited number of complexes or compounds formed between VCl and metal compounds which lead to the forma tion of stable metal-vinyl compounds. Of these only a few merit consideration in terms of the VC1 detection problem, and they are discussed below: (1) VCl-Organocyanocobaltate (III) Complexes VCl reportedly reacts with an aqueous solution of K3[CO(CN)5H] at room temperature. * The solution turns yellow with the formation of a 1/1 molar complex between VCl and the complex hydride. A yellow solid can be recovered from the solution. Supposedly, the reaction proceeds as shown below: 3- [Co(CN)sH] + CHa = CHC1 -----------------) [Co(CN)s(CHC1CH3)]3-I--------- } [Co{CN)s(CHa = CHa) ]3" + HC1 The K3 [CO(CN)sH] solution is made by bubbling Hg through an aqueous solution of K3[Co(CN)5]. (2) VCl-Stannite Ion Reaction VBr is reported to react under alkaline conditions at 0C with N H* O to PI o BFG09303 2- - 2 hydroxy stannite ions. CHa=CH + Na[Sn(OH)3] Br [CHa =CHSn(OH) O] + NaBr+RjO I do not know if the vinyl stannoic acid is colored or if VCl would react the same way as VBr, but I would expect the same reaction. (3) VC1 - Hg (OAc) Adducts 3 VC1 reportedly forms a stable adduct with Hg(OAc)2 . I do not know the details of this reaction, but the adduct can be isolated from a strongly ammoniacal mixture of alcohols using thin layer chromatography on silica gel. I did find one other interesting report in the literature. It is in the form of a Russian Patent which claims that VC1 reacts with aqueous Ni(OH)a to form acetaldehyde. ^ Since aldehydes can generate colors by reacting with appropriate organic compounds, the VCl-Ni(OH)3 reaction might provide the basis for a VC1 detection system. In summary, the chemical literature only reports a limited chemistry between VC1 and either inorganic or organometallic compounds. Especially as applicable to the development of a VCl detection system. Although I have provided a few promising leads, they need additional researching in the literature and/or in the laboratory before their true potential would be apparent. William J. Kroenke bak cc: R&D Files (4016 R. J. Fawcett D. E. Ley C. H. Lufter R. G. Parker J. B. Pausch Avon Lake A. L. Schultz M. M. O'Mara References 1 J. Kwiatek and J. K. Seyler, J. Organometallic Chem. , 3^, 421-32 (1965). ^A Solerio, Gazz, Chim. ital. , 8_5, 61 (1955). ^D. Braun and G. Vorendohre, Z. Anal. Chem., 199, 37-41 (1963). ^U.S.S.R. Patent, 107, 489, September 25, 1957. 21095002 BFG09304