Advances in Colloid and Interface Science (v.95, #2-3)
Calorimetric effects accompanying ion adsorption at the charged metal oxide/electrolyte interfaces: effects of the correlations between the binding-to-surface energies of various surface complexes by W. Rudziński; W. Piasecki; R. Charmas; G. Panas (95-143).
As has been shown in our earlier publications, a theoretical description of ion adsorption at the real, energetically heterogeneous oxide/electrolyte interfaces, involves necessary assumption about the correlations between the adsorption energies of the various surface complexes formed at this interface. So far, only two extreme models have been considered in such theoretical descriptions: one model assuming that high correlations exist, and the other assuming that practically no correlations exist. The purpose of this paper is to develop yet another description based on a model assuming that some partial correlations exist between the adsorption energies of the various surface complexes. The other purpose of this publication is to test these three models by analysing some experimental data reported so far in literature. Such data sets must include necessary information about the enthalpic effects accompanying ion adsorption. This is because enthalpic effects are known to be more sensitive to the mechanistic models underlying a theoretical description of adsorption systems. With such requirements in mind, we have selected three adsorption systems: Al2O3/NaCl, TiO2/NaCl and silica/NaCl, for our analysis. Our theoretical–numerical analysis of the behaviour of these adsorption systems suggests that either none or partial correlations exist between the adsorption energies of the various surface complexes. However, that analysis also shows, that the present accuracy of the experimental data does not allow us to draw more elaborate conclusions.
Keywords: Adsorption; Metal oxide/electrolyte interfaces; Calorymetry; Heat of adsorption;
Wetting film stability and flotation kinetics by J. Ralston; S.S. Dukhin; N.A. Mishchuk (145-236).
Single bubble experiments performed with different size fractions of quartz particles and different, but known, contact angles revealed two modes of flotation dynamics in superclean water. (1.) A monotonic increase of collection efficiency E coll with increasing particle size was observed at high particle hydrophobicity and, correspondingly, a low wetting film stability (WFS). (2.) At low particle hydrophobicity and, correspondingly, high WFS, an extreme dependence of E coll on particle size was observed. The use of superclean water in our experiments prevented the retardation of bubble surface movement caused by surfactants or other impurities that is usual for other investigations and where particle–bubble inertial hydrodynamic interactions are suppressed. In the present study the free movement of the bubble surface enhances particle–bubble inertial interaction, creating conditions for different flotation modes, dependent on WFS. At the instant of inertial impact, a particle deforms the bubble surface, which may cause its rebound. Where the stability of the thin water film, formed between opposing surfaces of a bubble and a particle, is low, its rupture is accompanied with three phase contact line extension and contact angle formation before rebound. This prevents rebound, i.e. the first collision is accompanied by attachment. A high WFS prevents rupture during an impact. As a result, a contact angle does not arise and rebound is not prevented. However, rebound is accompanied by a second collision, the kinetic energy of which is smaller and can cause attachment at repetitive collision. These qualitative considerations are confirmed by the model quantification and comparison with measured E coll. For the first time the Sutherland equation (SE) for E coll is confirmed by experiment for smaller particle sizes and, correspondingly, very small Stokes numbers. The larger the particle size, the larger is the measured deviation from the SE. The SE is generalized, accounting for the centrifugal force, pressing hydrodynamic force and drainage in the low WFS case and, correspondingly, attachment occurs at first collision or during sliding. The derived generalized Sutherland equation (GSE) describes experimental data at low WFS. However, its application without account for possible rebound does not explain the measured extreme dependence in the case of high WFS. The theory for drainage during particle impact and the beginning of rebound enables conditions for either attachment or rebound in terms of the normal component of the impact velocity and the critical film thickness to be derived. Combining this condition with the GSE allowed the equation for E coll to be derived, accounting for attachment area shrinkage and attachment during a repetitive collision. This equation predicts the extreme dependence. Thus the WFS determines the modes of flotation dynamics and, in turn, probably affects the mechanisms, which control the flotation domain. At low WFS its upper boundary is controlled by the stability of the particle–bubble aggregate. At high WFS the upper boundary can be controlled by rebound because the latter reduces the attachment efficiency by a factor of 30 or more even with repetitive collision.
Keywords: Flotation kinetics; Single bubble; Superclean water; Rebound; Wetting film stability;
Kinetics of adsorption from micellar solutions by B.A Noskov (237-293).
Previous studies on surfactant adsorption mostly deal with dilute systems without aggregation in the bulk phase. At the same time, micellar solutions can be more important from the point of view of applications. If one attempts to estimate the equilibrium adsorption, neglecting the influence of micelles can lead to reasonable results. The situation differs for non-equilibrium systems when the adsorption rate can increase by an order of magnitude at the increase of the surfactant concentration beyond the CMC. A critical survey of various models describing the influence of micelles on adsorption kinetics at the liquid–gas interface is given and the theoretical results are compared with existing experimental data. The theories proposed for the case of large deviations from the equilibrium are usually based on some unjustifiable assumptions and can describe the kinetic dependencies of adsorption in only a limited number of situations. Consequently, only rough estimates of the kinetic coefficients of micellization can be obtained from experimental data on dynamic surface tension. More rigorous equations can be derived if the system only deviates slightly from equilibrium. In the latter case, the agreement between theoretical and experimental results is essentially better and measurements of the dynamic surface elasticity of micellar solutions allow us to study the micellization kinetics.
Keywords: Surfactants; Liquid–gas interface; Micellization kinetics; Adsorption kinetics; Dynamic surface properties;
Interaction potentials, structural ordering and effective charges in dispersions of charged colloidal particles by M Quesada-Pérez; J Callejas-Fernández; R Hidalgo-Álvarez (295-315).
As colloidal dispersions of charged particles exhibit a wide variety of commercial, technological and scientific applications, a considerable theoretical effort has been devoted to finding an effective interaction potential from primitive models. The forces derived from this potential should justify the spatial ordering experimentally observed under certain conditions. This paper reviews the advances in these theoretical studies as well as some experiments (based on the mentioned order) that try to corroborate them. Special attention has been paid to the Derjaguin–Landau–Verwey–Overbeek (DLVO) potential. Nowadays, many of these theoretical investigations suggest that it could be applied if some of its parameters are renormalized. Nevertheless, to achieve a renormalization procedure in a strict way (from a primitive model) is a difficult task as a result of the size and charge asymmetries between small ions and macroions. Thus, several procedures for computing renormalized charges in a simple way have been developed. However, the notion of effective charge has also been widely used (as a adjustable parameter) in order to justify results found for several kinds of colloids (like solid particle dispersions or micellar systems) by means of quite different experimental techniques. Renormalization (as well as ion condensation) approaches, experiments and the controversial relationship between theoretical and phenomenological effective charges are also reviewed in this work.
Keywords: Structural ordering; Interaction potential; Effective charges; Colloidal dispersions; Primitive models;