Initiation of eq 1 via eqs 4 or 5 can therefore be ruled out on kinetic grounds. (Details of how kf and kf were estimated are presented in the Supporting Information.) Initiation of autocatalysis is also possible via the one-electron transfer from C2O4 2-to S2O8 2-(eq 6, labeled as ET in Scheme 1). However, this reaction has a positive free energy change of 83 kJ/mol, and is non-spontaneous based on thermodynamic considerations. To confirm that the autocatalytic reaction between S2O8 2-and C2O4 does not rapidly occur at room temperature without a catalyst, the cyclic voltammetric (CV) response of a solution containing 10 mM S2O8 and 10 mM C2O4 was recorded before and after allowing the solution to sit for 24 hours, Figure . No significant decrease in the voltammetric currents associated with S2O8 2-reduction or C2O4 oxidation was observed, demonstrating that both species are stable and that eq 6 does not occur to an appreciable extent over the course of a day.