Kinetics of tetrachloroethylene‐reductive dechlorination catalyzed by vitamin B12

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Abstract
Reductive dechlorination kinetics of tetrachloroethylene (PCE) to ethylene catalyzed by vitamin B12 using Ti[III] citrate as the bulk reductant was examined in a vapor/water batch system. A kinetic model incorporating substrate–B12 electron‐transfer complex formation and subsequent product release was developed. The model also accounted for the primary reductive dechlorination pathways (hydrogenolysis and reductive β elimination) and vapor/water‐phase partitioning. Reaction rate constants were sequentially determined by fitting the model to experimental kinetic data while moving upward through consecutive reaction pathways. The release of product from the complex was found to be second order with respect to substrate concentration for both PCE and acetylene; all other substrates appeared to release by first order. Reductive β elimination was found to be a significant reaction pathway for trichloroethylene (TCE), and chloroacetylene was observed as a reactive intermediate. Acetylene production appears to be primarily due to the reduction of chloroacetylene derived from TCE. The reduction of cis‐dichloroethylene (cis‐DCE), the primary DCE isomer formed, was extremely slow, leading to a significant buildup of cis‐DCE. The kinetics of acetylene and vinyl chloride reduction appeared to be limited by the formation of relatively stable substrate–B12 complexes. The relatively simple model examined appears to adequately represent the main features of the experimental data.