1,1,2,2-tetrachloroethane reactions with OH-, Cr(II), granular iron, and a copper-iron bimetal: insights from product formation and associated carbon isotope fractionation.
Despite widespread implementation of zero-valent iron remediation schemes, the manner and order of chemical bond cleavage in iron-mediated organohalide transformations remains imperfectly understood. We present insights from carbon isotope fractionation for the dehalogenation of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) and 1,1,1-trichloroethane (1,1,1-TCA) by various reactants. Elimination of HCl by OH- gave isotope fractionation in 1,1,2,2-TeCA of Euro = -25.6 per thousand, KIE(c) = 1.02 to 1.03 per carbon center, consistentwith a concerted (E2) mechanism. In contrast, 1,1,1-TCA reduction by Cr(II), Fe(0), and Cu-plated iron (Cu/Fe) resulted in Euro = -13.6 per thousand to -15.8 per thousand indicating the initial involvement of a single C-Cl bond (KIE(c) approximately 1.03). 1,1,2,2-TeCA reduction by Cr(II), Fe(0), and Cu/Fe yielded Euro = -18.7 per thousand, -19.3 per thousand, and -17.0 per thousand, respectively. In the two latter cases, depletion of the minor product TCE by 26 per thousand indicated its formation via nonreductive dehydrohalogenation. The major 1,1,2,2-TeCA reduction products, cis- and trans-DCE, differed by 2.3 per thousand +/- 1.0 per thousand in Cr(II) systems, but were equivalent in Fe(0) and Cu/Fe systems. In contrast, the ratio of cis-DCE to trans-DCE concentration was 2.5 for reduction with Cr(II) and Fe(0), but -3.8 with Cu/Fe. Complementary isotope and concentration data therefore suggest differences in the transition state geometry and/ or reaction intermediates in each reductant system.
Elsner
Martin
M
Stable Isotope Laboratory, University of Toronto, 22 Russell Street, Toronto, Ontario M5S 3B1, Canada. martin.elsner@gsf.de
Cwiertny
David M
DM
Roberts
A Lynn
AL
Lollar
Barbara Sherwood
BS
D002247:Carbon Isotopes; D005591:Chemical Fractionation; D002857:Chromium / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004980:Ethane / Q000031:analogs & derivatives* / Q000737:chemistry; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry*
D002247:Carbon Isotopes; D006843:Hydrocarbons, Chlorinated; D006878:Hydroxides; D014874:Water Pollutants, Chemical; D002857:Chromium; C015530:1,1,2,2-tetrachloroethane; D003300:Copper; D007501:Iron; D004980:Ethane