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American Chemical Society, Environmental Science and Technology, 20(32), p. 3149-3154, 1998

DOI: 10.1021/es980125s

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Comparison of 1-pKand 2-pKVersions of Surface Complexation Theory by the Goodness of Fit in Describing Surface Charge Data of (Hydr)oxides

Journal article published in 1998 by Johannes Lützenkirchen ORCID
This paper is available in a repository.
This paper is available in a repository.

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Abstract

1-pK and 2-pK formulations exist in surface complexation theory with respect to the description of basic charging behavior of (hydr)oxide electrolyte interfaces. The 2-pK approach has been commonly used with at least four different electrostatic models, whereas the 1-pK model has been primarily used with only one of those electrostatic models. In this paper the 1-pK approach is combined with three more electrostatic models. The eight resulting possible combinations have been tested on several sets of data. Applying the 2-pK basic Stern model (BSM) and the triple-layer model (TLM) was not satisfactory: due to the high number of adjustable parameters involved in these model variations the optimization procedure of the applied computer codes did not converge. This was taken as an a priori justification to exclude even more complicated (four-layer) models. For the remaining six models which could be successfully applied in the present paper, the goodness of fit parameter given by a computer code was used to compare the quality of the description of the chosen experimental data by the respective models. A purely diffuse layer model (DLM) generally gave the poorest fit to experimental data when combined with the 1-pK approach and was only sligthly better when combined with the 2-pK formalism. Either the 1-pK BSM or the 2-pK constant capacitance model (CCM) gave the best fit to the data in all the examples. However, it was found in two cases that some arbitrary constraint was necessary to define a unique (and thus meaningful) parameter set for the 2-pK CCM. The 1-pK TLM version allowed in more than half of the examples to determine a unique parameter set, which is impossible with the 2-pK TLM. It is concluded that the 1-pK BSM should be considered as the first choice model with respect to the goodness of fit and the uniqueness of the estimated parameters. The 2-pK CCM is still a good choice for a constant ionic strength case when the experimental data allow a determination of unique parameters and if only goodness of fit is used as a criterion.