Alkane thiol monolayers that self assemble into well ordered, ultra thin, homogeneous films on polycrystalline gold substrates provide an ideal platform to investigate the process of charge transfer between solid-liquid interfaces because they can modify the surface properties of the solid substrate in a controllable manner. Theoretically, the process of charge transfer is understood to be due to the non adiabatic interaction between the electronic and vibronic orbitals of the metal and electroactive species in the electrolyte respectively as mediated by the long alkane backbone of the monolayer phase. The effect of the organic monolayer phase and the functional group is contained in a quantum mechanical “transfer integral” factor that appears in the rate expression and the explicit formulation of the transfer integral requires a detailed numerical computation of the electronic structure of the alkane backbone and the terminal functional group. The complexity of these computations obscures the effect that applied potential has on the kinetics of the charge transfer process and also, makes it difficult to compare the theoretical results with experimental data. Thus, most detailed experimental work on charge transfer relies on the use of tunneling-modified adiabatic charge transfer theory to explain observed kinetic data and is at odds with theory that describes the electron transfer event as non adiabatic. The use of electroactive species in the electrolyte that act as electron donors or acceptors also obfuscates the effect that background electrolyte properties like pH and ionic concentration have on the electron transfer event since the transfer kinetics are determined by the vibrational energy states of the redox species only. Here, we present a methodology to measure and characterize reaction kinetics at the solid-liquid interface of a monolayer-modified polycrystalline gold electrode in contact with an aqueous electrolyte that contains no redox active species. Impedance data is used to demonstrate the existence of two potential dependent regimes for the electrical response of a gold-monolayer-electrolyte system where the rate limiting process in each regime is either the charge transport through the monolayer phase or charge transfer at the monolayer electrolyte interface. For the case when the rate limiting current potential behavior is due to charge transfer at the monolayer-electrolyte interface, the impedance characteristics of the gold-monolayer-electrolyte system are attributed to the non adiabatic thermal hopping of the transferring electron over an electrostatic potential energy barrier at the monolayer-electrolyte interface. The effect of applied potential on the barrier height is also used to extract parameters that can characterize the properties of the monolayer-electrolyte interface and the influence of electrolyte properties on the electron transfer event is also examined.