Stripped Charge of Ag Less than Deposited one Owing to Negative Capacitance Caused by Redox Reactions

Anodic stripping voltammetry was made in AgNO₃ solution, here Ag was deposited under long term potentiostatic conditions to evaluate the reduction charge, q_r, and then was stripped by linear sweep voltammetry to determine the oxidation charge, q_o. The charges were unbalanced, satisfying ca. q_o=0.7|q_r|, where other possible reduction charge such as by dioxygen and dichlorosilver were subtracted. The 30 % loss of the anodic charge can be ascribed to the negative capacitance by the potential sweep generation of Ag⁺. The generated Ag⁺ forms a dipole with a counter ion, of which orientation is the same as the direction of the externally applied electric field and opposite to the dipoles of solvent. The redox dipole decreases the conventional double layer capacitance caused by solvent dipoles, and high concentrations of Ag⁺ takes the capacitance to be negative values. The unbalanced charge, however, has no influence on quantitative determination of concentrations Ag⁺ by use of a calibration line.