The turbulent diffusion boundary layer in a binary electrolyte was considered at Schmidt numbers of 1, 10 and 100 and exchange current densities between 10(-4) A m(-2) and 10(-2) A m(-2). A numerical scheme was developed for efficient investigation of the dynamics by means of large eddy simulations. The methodology was examined by detailed comparisons with documented data from earlier large eddy and direct numerical simulations and good agreement was found. Application of the methodology to electrochemical mass transfer indicated that the exchange current density seems to have negligible effect on the mean concentration profile but it influences the structure of the fluctuating field in a visible manner.