A W/WO3 pH electrode was prepared by a method of sol-gel. In order to study the H+ response dynamic mecha- nism, the electrochemical impedance spectroscopy (EIS) experiment was conducted. It was found that the H+ response course is controlled by the H+ diffusion from the solution to the WO3 film, based on the analysis of EIS spectra. The EIS and potential step method were used to determinate the H+ diffusion coefficient (D) in the course of H+ response of this W/WO3 electrode, and the values of D calculated by these two method correspond very well, which all are about 10?10 cm2/s. The imposed different potential steps make little effect on the calculation of H+ diffusion coefficient, and it was found that the limiting Cottrell equation of short elapsed time fits well to the current transient caused by a potential step, based on the analysis of the time constant.
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