辐射诱发的五氯乙烷和正四氯乙烷脱氯。1,1,2,2-四氯乙基和1,2,2-三氯乙基自由基的反应

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI:10.1039/TF9716702354

M. Katz, A. Horowitz, L. Rajbenbach

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引用次数: 17

摘要

五氯乙基1,1,2,2-四氯乙基和1,1,2-三氯乙基自由基是由五氯乙烷和正四氯乙烷辐射分解生成的。研究了c-C6H11+ C2Cl5H→c-C6H11Cl + C2Cl4H(2)、c-C6H11+ C2Cl5H→c-C6H12+ C2Cl5(3)、C2Cl4H + c-C6H12→C2Cl4H2+ C2Cl3H2(11)、c-C6H11+ C2Cl4H2→c-C6H11Cl + C2Cl3H2(12)、C2Cl3H2+ c-C6H12→C2Cl3H3+ c-C6H11(13)、C2Cl3H2→C2Cl2H2+ Cl的反应动力学。(14)。得到的速率表达式如下:log10(k2/k3)= 1.40±0.15 -(660±230)/4.576T;log10 (k11 / k12) = 1.07±0.06 - 4.576(3780±120)/ t: log10 (k5 / k4)(摩尔。)= 5.63±0.07 -(8100±100)/ 4.576 t;log10 (k14 / k13)(摩尔。)= 5.91±0.21 - 4.576(6900±400)/ t。取气体常数R为1.9872 cal K-1mol-1，随后的活化能以cal mol-1表示(1 cal = 4.1855 J)。

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Radiation-induced dechlorination of pentachloroethane and sym-tetrachloroethane. Reactions of 1,1,2,2-tetrachloroethyl and 1,2,2-trichloroethyl radicals

Pentachloroethyl 1,1,2,2-tetrachloroethyl and 1,1,2-trichloroethyl radicals were produced by the reactions of radiolytically generated cyclohexyl radicals with pentachloroethane and sym-tetrachloroethane. The kinetics of the following reactions were studied: c-C6H11+ C2Cl5H →c-C6H11Cl + C2Cl4H (2), c-C6H11+ C2Cl5H →c-C6H12+ C2Cl5(3), C2Cl4H + c-C6H12→C2Cl4H2+ c-C6H11(4), C2Cl4H →C2Cl3H + Cl (5), c-C6H11+ C2Cl4H2→c-C6H11Cl + C2Cl3H2(11), c-C6H11+ C2Cl4H2→c-C6H12+ C2Cl4H (12), C2Cl3H2+ c-C6H12→C2Cl3H3+ c-C6H11(13), C2Cl3H2→C2Cl2H2+ Cl. (14). The following rate expressions were obtained: log10(k2/k3)= 1.40±0.15 –(660±230)/4.576T; log10(k11/k12)= 1.07±0.06 –(3780±120)/4.576T: log10(k5/k4)(mol l.–1)= 5.63±0.07 –(8100±100)/4.576T; log10(k14/k13)(mol l.–1)= 5.91±0.21 –(6900±400)/4.576T. R the gas constant was taken to be 1.9872 cal K–1mol–1 and subsequent activation energies expressed in cal mol–1(1 cal = 4.1855 J).

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Transactions of The Faraday Society

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