Electrochemical investigation of the rate-limiting mechanisms for trichloroethylene and carbon tetrachloride reduction at iron surfaces.

The mechanisms involved in reductive dechlorination of carbon tetrachloride (CT) and trichloroethylene (TCE) at iron surfaces were studied to determine if their reaction rates were limited by rates of electron transfer. Chronoamperometry and chronopotentiometry analyses were used to determine the kinetics of CT and TCE reduction by a rotating disk electrode in solutions of constant halocarbon concentration. Rate constants for CT and TCE dechlorination were measured as a function of the electrode potential over a temperature range from 2 to 42 degrees C. Changes in dechlorination rate constants with electrode potential were used to determine the apparent electron-transfer coefficients at each temperature. The transfer coefficient for CT dechlorination was 0.22 +/- 0.02 and was independent of temperature. The temperature independence of the CT transfer coefficient is consistent with a rate-limiting mechanism involving an outer-sphere electron-transfer step. Conversely, the transfer coefficient for TCE was temperature dependent and ranged from 0.06 +/- 0.01 at 2 degrees C to 0.21 +/- 0.02 at 42 degrees C. The temperature-dependent TCE transfer coefficient indicated that its reduction rate was limited by chemical dependent factors and not exclusively by the rate of electron transfer. In accord with a rate-limiting mechanism involving an electron-transfer step, the apparent activation energy (Ea) for CT reduction decreased with decreasing electrode potential and ranged from 33.0 +/- 1.6 to 47.8 +/- 2.0 kJ/mol. In contrast, the Ea for TCE reduction did not decline with decreasing electrode potential and ranged from 29.4 +/- 3.4 to 40.3 +/- 3.9. The absence of a potential dependence for the TCE Ea supports the conclusion that its reaction rate was not limited by an electron-transfer step. The small potential dependence of TCE reaction rates can be explained by a reaction mechanism in which TCE reacts with atomic hydrogen produced from reduction of water.