Fig. 2: Automated exhaustive CV experiments that illustrate the scarcity of useful data for electrokinetic analysis.

a Representative sets of six voltammograms, tested with automatic iR compensation. [Co^IITPP] = 1 mM in DMF solvent using 0.1 M NBu₄PF₆ supporting electrolyte; RX = 1-bromobutane (n-BuBr) and [RX] ∈ [0, 20] mM; six logarithmically-sampled scan rates (ν) with the maximal and minimal ν differing by a factor of 10 (ν_min/ν_max = 1/10) and ν_min ∈ [0.01, 0.2] V/s. b The DL-generated propensity of an EC mechanism (denoted as EC%) obtained from 420 combinations, representing 2520 voltammograms, of [n-BuBr] and ν_min ([n-BuBr] ∈ [0, 20] mM and ν_min ∈ [0.01, 0.2] V/s). c The observed pseudo-first-order kinetic rate constant of the C step (k_obs) derived from and plotted versus i_pa/i_pc (defined in Supplementary Note 5) of the Co^II/I redox in the selected voltammograms with non-zero [n-BuBr] values, with the colors of the data points scaling with increases in [n-BuBr]. The shaded area in (c) suggests that such kinetic analysis should only be performed when i_pa/i_pc ∈ [0.65, 0.75], as the derived k_obs values show little variation under a given [n-BuBr] value and appear to grow proportionally with increases in [n-BuBr]. d The mapping of i_pa/i_pc of the Co^II/I redox in each of the 2520 voltammograms as a function of ν and [n-BuBr] (ν ∈ [0.01, 2] V/s and [n-BuBr] ∈ [0, 20] mM). The shaded area in (d) highlights that the experimental conditions for i_pa/i_pc ∈ [0.65, 0.75] correspond to only 4.2% of the sampling space. e A linear regression of log₁₀(k_obs) versus log₁₀[n-BuBr] among those valid k_obs values derived from i_pa/i_pc ∈ [0.65, 0.75] in (c), yielding the reaction order (n) and k₀ for n-BuBr. The colors of the data points scale with increases in [n-BuBr], and the vertical error bars represent the standard deviations of log₁₀(k_obs) among all the valid k_obs values at each [n-BuBr] value. Data distributions underlying the error bars in (e) are presented in Source Data file.