Electrical Conductivity of Aqueous Salt-Free Concentrated Suspensions. Effects of Water Dissociation and CO2 Contamination

Abstract

In this paper we explore the effects of water dissociation and CO2 contamination on the electrical conductivity of salt-free concentrated suspensions in static electric fields. The conductivity model here presented is based on a new description of the equilibrium double layer for particles in "realistic" salt-free suspensions recently developed by the authors to account for the latter effects (Ruiz-Reina, E.; Carrique, F. J. Phys. Chem. B 2008, 112, 11960). It was shown that in most of the cases the neglecting of those effects would lead to a very poor description of common salt-free suspensions, especially, but not only, if the suspensions have been in contact with air. As shown in this paper, the presence of only water dissociation ions suffices to provoke very important changes in the standard salt-free predictions. A realistic aqueous salt-free suspension consists of an aqueous suspension without any electrolyte added during the preparation but including the following ionic species: (i) the "added counterions" stemming from the particle charging process that counterbalance their surface charge (with just this ionic species, the suspension can be considered as an ideal or pure salt-free one), (ii) the H+ and OH- ions from water dissociation, and (iii) the ions produced by the atmospheric CO2 contamination. The model is based on the classical Poisson-Boltzmann theory, the appropriate local chemical reactions, the standard electrokinetic equations, and the cell model approximation to account for electro-hydrodynamic particle-particle interactions. Thus, we have studied the electrical conductivity of such realistic salt-free suspensions for different particle volume fraction phi and surface charge density sigma, and compared it with results of pure salt-free conductivity predictions. The numerical results have shown that water dissociation ions and/or CO2 contamination has an extreme influence on the suspension conductivity values at low-moderate particle volume fractions. In these situations the role of the added counterions is screened by the other ionic species. Even if the suspensions have not been exposed to the atmosphere, the quantitative changes in conductivity at low volume fractions associated with the presence of water dissociation ions over the added counterions are enormous. It is concluded that it is necessary to take into account the water dissociation influence for phi lower than approximately 10(-2)-10(-3), whereas the atmospheric CO2 contamination is not negligible if phi<10(-1)-10(-2), depending on the particle charge. The present work sets the basis for further theoretical models concerning, particularly, the dynamic electrophoresis and dielectric response of such systems.