The kinetics of the radiation-induced chain dechlorination of hexachloroethane in alcohols.

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概要

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• The kinetics of the radiation-induced dechlorination of hexachloroethane was investigated in deoxygenated alcohol solutions. The major products were hydrogen chloride, pentachloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, and aldehydes or acetone. No 1,1,1,2-tetrachloroethane was observed. The radiationchemical yields of these products and the disappearance of hexachloroethane were quite high; these facts indicate that a chain reaction is involved in these processes. After the hexachloroethane had effectively dechlorinated down to tetrachloro compounds, there were no marked changes in the lower chlorinated compound upon continuous irradiation. Tetrachloroethane was formed <I>via</I> pentachloroethane, but tetrachloroethylene was produced by means of C<SUB>2</SUB>Cl<SUB>5</SUB>→C<SUB>2</SUB>Cl<SUB>4</SUB>+Cl reaction and the yield was paticularly high in methanol compared with the other alcohols. The chain length of the dechlorination from hexachloroethane to pentachloroethane and from pentachloroethane to tetrachloroethane increased in the order of 2-propanol>ethanol>methanol. The <I>G</I>(−C<SUB>2</SUB>Cl<SUB>6</SUB>) and G(products) were proportional to (dose rate)<SUP>−1⁄2</SUP>, and the ratio of <I>G</I>(C<SUB>2</SUB>HCl<SUB>5</SUB>) to <I>G</I>(C<SUB>2</SUB>Cl<SUB>4</SUB>) was a constant in each alcohol solution, regardless of the dose rate. The α-hydroxy alkyl radical is the chain carrier for the dechlorination reaction of hexachloroethane in alcohol solutions. The relative rates of the dechlorination were found to be 1, 3, and 14 for \dotCH<SUB>2</SUB>OH, CH<SUB>3</SUB>\dotCHOH, and (CH<SUB>3</SUB>)<SUB>2</SUB>\dotCOH, respectively. The order in the rate is in agreement with that of the redox potential of these radicals. The effect of the irradiation temperature on the products yields was also examined.

• 公益社団法人 日本化学会の論文

著者

• SHIMOKAWA Toshinari

  Tokyo Metropolitan Industrial Technology Research Institute Radiation laboratory

• Ohara Naoki

  Tokyo Metropolitan Isotope Research Center

• Sawai Takeshi

  Tokyo Metropolitan Isotope Research Center

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