Charge neutralization process of mobile species at any distance from the electrode/solution interface. 2. Concentration gradients during potential pulse experiments

FERNANDO GARAY AND CESAR A. BARBERO

ANALYTICAL CHEMISTRY

Año: 2006 vol. 78 p. 6740 - 6746

0003-2700

The theoretical model presented in part 1 of this work is employed to simulate and fit experimental probe beam deflection (PBD) data of Fe(CN)6(3-)/Fe(CN)6(4-) and Fe(3+)/ Fe(2+) couples. Current and beam deviation dependency on time at constant potential (chronoamperometry and chronodeflectometry) is analyzed via a new treatment based on the migration and diffusion properties of all the species involved. The diffusion coefficients of electroactive species are obtained by fitting chronoamperometric curves. Those coefficients are then employed to simulate the respective chronodeflectometric profiles. The experimental data and the theoretical function are fitted by the minimum squares Simplex algorithm. The effect of working with systems in which both electroactive species are charged is discussed in detail. Specifically, the possibility of quantitative analysis of nonspecific techniques data is analyzed when a relative high concentration of supporting electrolyte is used. Such analysis widens the scope of techniques as PBD since in many cases the effect of supporting electrolyte species could be negligible as compared to the response of electroactive species. The variation of the refraction index with the concentration gradient of each soluble species is also discussed.