A series of chlorinated low-molecular-weight alkanes and alkenes was transformed electrolytically at metal cathodes at potentials from -0.3 to -1.4V (vs. SHE). Products included nonchlorinated hydrocarbons and less chlorinated intermediates. Product distributions are highly dependent on cathode material and applied cathode potential. Kinetics was first-order in the concentration of the halogenated targets. The specific first-order rate constants are function of cathode potential, cathode material, solution characteristics, and reactant identify. When transformation kinetics was governed by polarization resistance, rate constants were correlated with degree of halogenation and standard reduction potential for the predominant transformation reaction (as indicated by product analysis). Log-transformed reaction rate constants for reduction of chlorinated alkanes, derived via experiments at the same cathode potential (E(c) = -1.0 or -1.2V vs. SHE), were linearly related to carbon-halogen bond dissociation energies. A physical model for the observed correlation was developed from transition-state theory. The chlorinated ethenes reacted much faster than predicted from bond enthalpy calculations, suggesting that alkenes are not transformed via the same mechanism as the chlorinated alkanes. Polarographic study demonstrated that the shift of E₁/₂ of CCl₄ reduction was correlated with water concentration in solvent-predominated mixtures. Successful interpretation of these findings with a physical model suggested that solvents involved the rate-determining step of CCl₄ electrolysis both kinetically and mechanistically. The capture of trichloromethyl radicals with a spin trap (PBN) in an electrochemical system provided direct evidence supporting the free radical mechanism in electrolytic reduction of CCl₄. Gas-phase reductions of chlorinated alkanes and alkenes were studied in a modified fuel cell. Reactor performance was a function of the metal catalyst amended to the reactor cathode, the reactor potential, cathode temperature, the target compound identity, the partial pressure of O₂(g) in the cathode chamber and the condition (time in service) of the cathode. Single-pass CCl₄ conversions could achieve 90 percent with a mean residence time for gases in the porous cathode much less than a second. Reactor performance deteriorated with the presence of oxygen and time in service. Conversion efficiency was restored, however, by temporarily eliminating the halogenated target(s) from the influent stream or by briefly reversing reactor polarity.
展开▼
