Determination of the surface charge density of a mercury electrode by extrusion : a new method for correction of the faradaic component

Abstract The accurate determination of the surface charge density at the mercury ∣ solution interface by the method of extrusion of mercury drops is impaired by the faradaic current caused by traces of electroactive species. This paper describes a new design of a hanging mercury drop electrode with accurate control of the extruded electrode area, to within 0.1%, together with a new and reliable procedure for correction of the faradaic current. The procedure is based on first obtaining the correction parameters in the presence of increasing amounts of electroactive species and then using these parameters for correction of the faradaic component so as to obtain the surface charge density of the electrode. Implementation of the method with a microcomputer controlled system provides automatic acquisition of corrected electrode charge density values as a function of the electrode potential. The results obtained with this new method are in excellent agreement with those obtained by other methods, as illustrated for aqueous sodium fluoride solution.