Simulations carried out under the same solution conditions at scan rates of 50 and 250 mV/s also provide excellent agreement between experiment and simulation, Figure . To determine if either path A or path B in Scheme 4 is dominant in the autocatalytic cycle, the goodness of fit of the digital simulations to experimental CVs was examined as a function of the initial steps of paths A and B, kf and kf , respectively. Figure shows a comparison of the experimental voltammetric peak currents in solutions containing 0.54 mM Ru(NH3)6 2+ , 1.0 mM S2O8 2-, and six different concentrations of C2O4 2-, ranging from 0 to 220 mM C2O4 2-, to the FD simulations with either path A or Path B removed from the mechanism (Scheme 1). To simulate path B alone, the rate of the direct reduction of S2O8 2-by CO2 •-in path A was set to zero, i.e., kf = 0 M -1 s -1 . We found that eliminating path A had no effect the simulated peak currents (red dashed line). Conversely, eliminating path B by setting the rate constant for the reduction of Ru(NH3)6 3+ by CO2 • -to zero, i.e., kf = 0 M -1 s -1 , resulted in an ~50% decrease in the simulated currents.