TY - JOUR
T1 - Reductive dechlorination of 1,1,2,2-tetrachloroethane
AU - Arnold, William A.
AU - Winget, Paul
AU - Cramer, Christopher J.
PY - 2002/8/15
Y1 - 2002/8/15
N2 - Products of the transformation of organic pollutants in the environment are often predicted based on the structure of the parent compounds. In some cases, however, multiple products may result from the same reaction pathway. In this study, the reduction of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) is investigated both experimentally and computationally. Experimental results and data available in the literature reveal that the ratio of Z-1,2-dichloroethylene (Z-DCE) to E-1,2-dichloroethylene (E-DCE) produced from the reductive β-elimination of 1,1,2,2-TeCA is approximately 2:1, and this ratio is independent of the reductant used. The exception is iron metal, which results in a ratio of 4.5:1. Computational results reveal that the 1,2,2-trichloroethyl radicals (1,1,2-TCA) formed upon the transfer of the first electron are nearly isoenergetic and are in rapid equilibrium. Thus, the conformer population of the 1,1,2,2-TeCA does not dictate the product distribution. Using Marcus theory, it is demonstrated that the Z:E ratio of 2:1 reflects the relative rates of the two possible electron transfer steps to the two radical conformers. Further analysis of the thermochemistry of the reaction reveals that this ratio of rate constants should be essentially independent of the thermodynamic driving force,which is consistent with the experimental results. The different observed product distribution when iron metal is the reductant is hypothesized to result from an organometallic intermediate. The reduction of the 1,1,2,2-TeCA is an overall two-electron process, butthe fact thatthe radicals equilibrate at a rate more rapid than the transfer of the second electron suggests that reductants employed act as decoupled single electron-transfer agents.
AB - Products of the transformation of organic pollutants in the environment are often predicted based on the structure of the parent compounds. In some cases, however, multiple products may result from the same reaction pathway. In this study, the reduction of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) is investigated both experimentally and computationally. Experimental results and data available in the literature reveal that the ratio of Z-1,2-dichloroethylene (Z-DCE) to E-1,2-dichloroethylene (E-DCE) produced from the reductive β-elimination of 1,1,2,2-TeCA is approximately 2:1, and this ratio is independent of the reductant used. The exception is iron metal, which results in a ratio of 4.5:1. Computational results reveal that the 1,2,2-trichloroethyl radicals (1,1,2-TCA) formed upon the transfer of the first electron are nearly isoenergetic and are in rapid equilibrium. Thus, the conformer population of the 1,1,2,2-TeCA does not dictate the product distribution. Using Marcus theory, it is demonstrated that the Z:E ratio of 2:1 reflects the relative rates of the two possible electron transfer steps to the two radical conformers. Further analysis of the thermochemistry of the reaction reveals that this ratio of rate constants should be essentially independent of the thermodynamic driving force,which is consistent with the experimental results. The different observed product distribution when iron metal is the reductant is hypothesized to result from an organometallic intermediate. The reduction of the 1,1,2,2-TeCA is an overall two-electron process, butthe fact thatthe radicals equilibrate at a rate more rapid than the transfer of the second electron suggests that reductants employed act as decoupled single electron-transfer agents.
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U2 - 10.1021/es025655+
DO - 10.1021/es025655+
M3 - Article
C2 - 12214646
AN - SCOPUS:0037104613
SN - 0013-936X
VL - 36
SP - 3536
EP - 3541
JO - Environmental Science and Technology
JF - Environmental Science and Technology
IS - 16
ER -