Abstract
The electrochemical reduction of peroxycitric acid (PCA) coexisting with citric acid and hydrogen peroxide (H 2O 2) in the equilibrium mixture was extensively studied at a gold electrode in acetate buffer solutions containing 0.1 M Na 2SO 4 (pH 2.0–6.0) using cyclic and hydrodynamic voltammetric, and hydrodynamic chronocoulometric measurements. The reduction of PCA was characterized to be an irreversible, diffusion-controlled process, and the cyclic voltammetric reduction peak potential ( E p c ) was found to be more positive by ca. 1.0 V than that of the coexisting H 2O 2, e.g., the E p c values obtained at 0.1 V s −1 for PCA and H 2O 2 were 0.35 and −0.35 V, respectively, vs. Ag|AgCl|KCl (sat.) at pH 3.3. The E p c of PCA was found to depend on pH, i.e., at pH > 4.5, the plot of E p c vs. pH gave the slope (−64 mV decade −1) which is close to the theoretical value (−59 mV decade −1) for an electrode process involving the equal number of electron and proton in the rate-determining step, while at pH < 4.5, the E p c was almost independent of pH. The relevant electrochemical parameters, Tafel slope, number of electrons, formal potential ( E 0′), cathodic transfer coefficient and standard heterogeneous rate constant ( k 0′) for the reduction of PCA and the diffusion coefficient of PCA were determined to be ca. 100 mV decade −1, 2, 1.53 V (at pH 2.6), 0.29, 1.2 × 10 −12 cm s −1 and 0.29 × 10 −5 cm 2 s −1, respectively, and except for E 0′, the obtained values were almost independent of the solution pH. The overall mechanism of the reduction of PCA was discussed.
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