The prediction of optimal times of separation as a function of the applied electrical field and cation valence have been studied for the case of field flow fractionation [Martin M., Giddings J. C., J. Phys. Chem. 1981, 85, 727] with charged solutes. These predictions can be very useful to a priori design or identify optimal operating conditions for a Couette-based device for field flow fractionation when the orthogonal field is an electrical field. Mathematically friendly relationships are obtained by applying the method of spatial averaging to the solute species continuity equation; this is accomplished after the role of the capillary geometrical dimensions on the applied electrical field equations has been assessed [Oyanader M. A., Arce P., Electrophoresis 2005; 26, 2857]. Moreover, explicit analytical expressions are derived for the effective parameters, i.e. diffusivity and convective velocity as functions of the applied (orthogonal) electrical field. These effective transport parameters are used to study the effect of the cation valence of the solutes and of the magnitude of the applied orthogonal electrical field on the values of the optimal time of separation. These parameters play a significant role in controlling the optimal separation time, leading to a family of minimum values, for particular magnitudes of the applied orthogonal electrical field.