Abstract
The electrochemical reduction of carbon tetrachloride (CCl4) in aqueous micellar solutions of imidazolium based surface active ionic liquid (SAIL), dodecyl-3-methylimidazolium chloride (DDMIMCl) was investigated. Detailed analysis of the transient current-potential records suggests that the electroreductive dehalogenation of DDMIMCl micelle solubilized CCl4 proceeds through sticky dissociative pathway. Quantification of the associated thermodynamic and kinetic parameters reveals that some strong modifications are required to extend the validity of the conventional sticky dissociative electron transfer model otherwise suited for isotropic/continuum solvents, to electrochemical reactions in micro-heterogeneous micellar systems. The characteristic voltammetric features and the estimated kinetic/thermodynamic parameters suggest that the significant interaction between the electrogenerated Cl− and CCl3. fragments in the very complex water/micellar interface significantly facilitates the electroreduction of CCl4. Present work is first of its kind to highlight the technical/mechanistic advantages associated with the use of SAIL based micelles for the electrochemical detoxification of halocarbons. The presented results strongly support the use of SAIL aqueous based micellar systems for safe, economical, eco-friendly and efficient dehalogenation of halocarbons.
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