Reduction of perchlorate using zero-valent titanium (ZVT) anode: Kinetic models

The kinetics of perchlorate reduction by zero-valent titanium (ZVT) undergoing electrical pitting corrosion was described by interactions of two domains (pit and solution). Two kinetic models were developed based on two possible inhibition mechanisms. A competitive adsorption model was developed based on surface coverage of perchlorate and chloride on bare ZVT, and a Ti(II) consumption model was developed based on Ti(II) oxidation by electrochemically developed chlorine. Both models well predicted perchlorate concentration changes in the solution. The competitive adsorption model showed that chloride has a higher adsorption affinity on both sites where oxidative dissolution of ZVT occurs and where chloride oxidation occurs. Also, the rates of perchlorate removal and chloride oxidation were directly proportional to current applied. For the Ti(II) consumption model, the rate constant of Ti(II) production was dependent on current. The rate of chloride oxidation is also believed to be proportional to current, but this conclusion cannot be made with confidence. Both kinetic models described changes in perchlorate concentration well. However, the Ti(II) consumption model was limited in its ability to predict chloride concentration. This limitation was probably caused by a lack of available information like electrochemical oxidation of chloride on bare ZVT and Ti(II) oxidation by chlorine.

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► Chloride showed a much higher adsorption affinity to chloride oxidation sites.
► Rate of perchlorate reduction and chloride oxidation was proportional to current.
► The rate constant of Ti(II) production was directly proportional to current.