Parsons-Zobel plots: an independent way to determine surface complexation parameters?

Parsons-Zobel plots can in principle be used to estimate inner Helmholtz-layer capacitance values and electrochemical surface areas for mineral particles. Their application to aqueous suspensions of various minerals has been documented in the literature. For the experimental data used so far, the expected linear relationship between the overall and the diffuse-layer capacitances has been reported. The extracted values either have not been used at all subsequently in a surface complexation model to describe the mineral surface charge versus pH curves, or were found not to be suitable entirely for such purposes. In the latter case, the reported failure was not explained. In one part of the present paper, the Parsons-Zobel plot concept is tested with data generated from a surface complexation model, for which the interfacial structure closely corresponds to that assumed in the application of the Parsons-Zobel plot. From the analysis of the results it turns out that electrolyte binding and non-Nernstian surface potential-pH curves more or less strongly affect the outcome of Parsons-Zobel plots. Despite the fact that the analysis in this paper is restricted to iron(III) minerals only, it is concluded, in general, that the use of Parsons-Zobel plots with aqueous mineral suspensions to determine inner Helmholtz-layer capacitances for subsequent application to surface complexation models cannot be recommended, since the reasons for failure can be traced very nicely with applications to model-generated data. Such application requires the determination of further parameters, and it was found that low electrolyte binding and Nernstian slopes should be imposed. Of these two issues, the more important is electrolyte binding. For the surface complexation models, an inner Helmholtz-layer capacitance and weak electrolyte binding were required for a good fit to experimental data. The values of the electrolyte binding constants required to achieve this end are in conflict with the assumptions of the Parsons-Zobel plot (absence of specific adsorption). However, these parameters would not necessarily cause specific adsorption in terms of a classical colloid chemistry definition (i.e., would not shift isoelectric points). The electrochemical surface areas were found to be in good agreement with the value used to generate the data. Based on this, there is a potential for using the approach to determine surface areas in situ from titration curves. Consequently, in a second part of the paper, Parsons-Zobel plots are applied to experimental data with the objective of determining electrochemical surface areas in situ. Application to various sets of published experimental titration data for hydrous ferric oxide yielded consistently very large electrochemical surface areas for fresh samples. This can be explained by very small particles and/or inclusion of substantial amounts of water in the suspended particles. As would be expected, the electrochemical surface area for aged ferrihydrite was found to be substantially lower.