Langmuir, Vol.12, No.25, 6151-6163, 1996
Predictive Models for Interfacial Properties of Associating Systems - A Statistical Thermodynamic Approach
The article presents a simple approach for predicting interfacial properties of multicomponent systems exhibiting acid-base interactions. The strategy involves incorporation of association effects arising due to the presence of strong intermolecular interactions, such as hydrogen bonding, into any existing model that accounts for physical interactions. A system under consideration is treated as a mixture of various hydrogen-bonded complexes of associating molecules and monomers of nonassociating components. These molecular entities are assumed to interact with each other through forces as described by a chosen physical model. For the purpose of illustration of the proposed approach, the theory developed by Prigogine and Marechal has been chosen to represent the physical interactions among the molecular entities. The theory requires surface tensions of (only) the monomeric species present in the liquid phase as input parameters. This information can be extracted using the proposed theory from the physical component of interfacial tension of associating systems, which, in turn, can be obtained using the method proposed by Fowkes. The theory also requires information on the number distribution of various molecular entities, associated and nonassociated, present in the system. For simple mixtures, such as those that contain any number of nonassociating components but contain only one associating component whose molecules possess one proton donor and one proton acceptor site, the distribution of hydrogen-bonded associates is obtained by modeling association by a series of equilibrium chemical reactions in which monomers react with n-mers to form (n + 1)-mers. For more complex : mixtures, such as those containing multiple associating components in multiple phases, each possessing any number of proton donor and proton acceptor sites, the reaction equilibrium approach becomes cumbersome. Hence, an equivalent but a more generalized treatment is provided on the basis of the thermodynamic perturbation theory (TPT), which solves for chemical equilibrium through the application of statistical mechanical cluster diagrams. The basic input parameters for TPT are the enthalpy and entropy of various types of hydrogen bonds present in the system and the number of proton donor/acceptor sites present in the various associating molecules. In this study, these parameters were obtained from available spectroscopic/molecular simulation data. A comparison between experimental data and theoretical predictions of (a) surface tension of aqueous liquid mixtures and (b) contact angle of a few pure liquids and their aqueous mixtures on associating solid surfaces, has been presented to demonstrate the utility of the proposed theoretical approach.
Keywords:DIRECTIONAL ATTRACTIVE FORCES;SURFACE-TENSION COMPONENTS;ACID-BASE APPROACH;CONTACT ANGLES;GENERALIZED EQUATION;LIFSHITZ-VAN;FREE-ENERGY;STATE;FLUIDS;LIQUIDS