Understanding electrochemical inactivation of contaminants in water
Committee ChairFarrell, James
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PublisherThe University of Arizona.
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AbstractThis research investigated the mechanism, kinetics, and feasibility of chlorinated aliphatic compounds inactivation by electrochemical reduction using nickel and iron electrodes. Reactions of trichloroethylene (TCE) and tetrachloroethylene (PCE) with zerovalent iron were investigated to determine the role of atomic hydrogen in their reductive dechlorination using Tafel analysis and electrochemical impedance spectroscopy (EIS). Comparison of iron corrosion rates with those for TCE reaction showed that TCE reduction occurred almost exclusively via atomic hydrogen at low pH values and via atomic hydrogen and direct electron transfer at neutral pH values. In contrast, reduction of PCE occurred primarily via direct electron transfer at both low and neutral pH values. The EIS data showed that all the rate limitations for TCE and PCE dechlorination occurred during the transfer of the first two electrons. Carbon tetrachloride (CT) reductive dechlorination was studied at a nickel rotating disk electrode using chronoampermetry (CA) and EIS. Only trace levels of methylene chloride and chloromethane were produced, indicating that sequential hydrogenolysis was not the predominant pathway for methane production. EIS showed that the ratelimiting step for CT reduction was the transfer of the first electron to a physically adsorbed CT molecule. The feasibility of an electrochemical reductive dechlorination method for removing CT from potable water was carried out in a flow-through reactor using bare and polymer coated porous nickel electrodes. Destruction of half-life values for CT with the bare nickel electrode ranged from 3.5 to 5.8 minutes for electrode potentials ranging from -652 to -852 mV with respect to the standard hydrogen electrode (SHE). Faradic current efficiencies could be increased by 100 to 360% by coating the electrode with a silicone polymer. This research also investigated electrochemical oxidation of triclosan, a biocidal agent, using Ebonex® and boron-doped diamond (BDD) film anodes. Product analysis showed that breaking the ether linkage was easier than opening the aromatic ring. Microtox® testing indicated that residual triclosan accounted for nearly all the toxicity in the treated water, despite the fact that chlorinated byproduct concentrations were significantly higher than those of triclosan itself.
Degree ProgramChemical and Environmental Engineering