The present invention directly measures localized electrochemical processes on a planar electrode using differential interferometry. The ionic charge accumulation at the electrode-electrolyte interface may be directly measured by using differential interferometry as a function of magnitude and frequency (for example, 2-50 kHz) of an external potential applied on an electrode. Methods in accordance with the present invention probe the ion dynamics confined to the electrical double layer. An electric field is applied using a pure AC potential and a superposition of AC and DC-ramp potential to measure ion concentration and detect redox processes.