Electrochemical monitoring of proton transfer across liquid/liquid interfaces on the surface of graphite electrodes

Equilibrium partitioning of HClO4 between aqueous solutions and benzonitrile (BN) or nitrobenzene (NB) was measured and used to evaluate the pK(a) of the acid in the two organic solvents. The potential drop across the BN/H2O interface was evaluated from the known potential drop across the NB/H2O interface and the voltammetrically measured formal potential of a ferrocenium/ferrocene redox couple confined within thin layers of the two organic solvents. The voltammetric reduction of tetrachloro-1, 4-benzoquinone in thin layers of BN was used to monitor changes in the concentration of protons in the layer during proton-consuming faradaic reactions. The rate of proton transfer from the aqueous to the nonaqueous phase across the BN/H2O interface was shown to be adequate to sustain proton-consuming reactions at the electrode/BN interface.