Tafel plots were generated from simulations of fully irreversible CVs (Figure ). This degree of irreversibility has never been demonstrated experimentally due to extremely fast kinetics for ion transfer at the ITIES and a practical limitation on how small nanopipette orifices can be. However, it can be artificially simulated by forcing the exchange current density in the model to be small relative to the cell's mass transfer coefficient. The resulting current-potential plot (Figure ) shows classic kinetically irreversible electrochemical behavior, where the exponential rise in current at low overpotentials is purely controlled by electrochemical kinetics, and at larger overpotentials the current levels off as diffusion of species to the interface becomes rate limiting. To highlight changes in the kinetic regime, the logarithm of the current axis is taken to generate a Tafel plot for the simulated facilitated ion transfer reaction, and the exchange current for the interfacial-direct pathway was forced to be 10 times slower than the interfacial-sequential pathway so that the influence of the partition coefficient could be clearly seen (Figure ). In this representation, increasing the partition coefficient of the proton acceptor creates a shoulder in the currentpotential response, which represents the finite and potential-independent rate of the preceding neutral phase-transfer step. In this scheme, the maximum rate of the partitioning step is proportional to the rate constant for B(org) B(aq) transfer 𝑘𝑘 𝑃𝑃ℎ𝑇𝑇,𝑏𝑏 which can be equivalently expressed in terms of the B(aq) B(org) rate constant and partition coefficient 𝑘𝑘 𝑃𝑃ℎ𝑇𝑇,𝑓𝑓 /𝑃𝑃. When the partition coefficient exceeds 10 8 in this simulation, the Tafel plot for the combined mechanism almost completely overlaps with the Tafel plot of pure interfacial direct transfer, agreeing with the intuition that very hydrophobic molecules will resist aqueous to organic phase transfer, and if an alternative pathway can bypass this energetically uphill intermediate step, it will carry most of the current.