Generalized van der Waals Theory of Interfaces in Simple Fluid Mixtures

Corrected Debye–Hückel Analysis of Surface Complexation

“…In particular, it shares with modern methods of quantum chemistry the great computational advantage of the variational principle and the direct access to the most fundamental property, i.e., in quantum chemistry the energy or in our case the free energy. Many applications to adsorption and surface tension phenomena in simple fluids (39)(40)(41)(42)(43)(44) have clearly illustrated the ability of the GvdW theory to resolve the structure and properties of inhomogeneous fluids.…”

Classical density functional theory for the prediction of the surface tension and interfacial properties of fluids mixtures of chain molecules based on the statistical associating fluid theory for potentials of variable range

“…A quantitative assessment of the theory is made by comparison with the interfacial data for mixtures of halocarbons. Nordholm and collaborators [80][81][82] have also developed a generalized van der Waals theory of interfaces, based on a perturbative DFT treated with a local density approximation (LDA), and have applied it to mixtures of alkanes and light gases. In an interesting and recent study, Bryk et al 83 have employed DFT to study the phase behaviour and the interfacial structure of two coexisting (liquid-vapour and liquid-liquid) phases and adsorption in slit-like pores for binary mixtures of chain and spherical particles.…”

Corrected Debye–Hückel analysis of surface complexation

“…The determination of Z can now proceed by first minimizing F sc (κ) to obtain the optimal κ-value and then minimizing the total free energy with respect to Z. Alternatively, we can start from the equivalent equality of chemical potentials, where we note that the chemical potential of a bound proton has now acquired a new contribution from the screening mechanism, i.e., (12) …”

“…The CDH analysis [7] is based on the generalized van der Waals (GvdW) theory of fluids [8], where some basic ideas of cell theory and a density functional approach are used to derive an equation of state for a fluid as well as nonuniform fuid properties such as adsorption excess and surface tension. The GvdW theory is unconventional in that it is based on a density functional expressing the free energy in terms of the ion densities, but it is a well-established theory that has produced new insights and valuable predictions of many fluid properties [9][10][11][12]. A linear electrostatic response is assumed in the CDH theory but compared with the traditional Debye-Hückel theory [13,14] two new mechanisms related to ion size are introduced, namely the excluded volume effect and the hole correction of electrostatic interactions.…”