Associating fluids

As discussed in Chapter 3, the virial equation is suitable for describing vapor-phase nonidealities of nonassociating (or weakly associating) fluids at moderate densities. Equation (1) gives the second virial coefficient which is used directly in Equation (3-lOb) to calculate the fugacity coefficients. 

Various equations of state have been developed to treat association ia supercritical fluids. Two of the most often used are the statistical association fluid theory (SAET) (60,61) and the lattice fluid hydrogen bonding model (LEHB) (62). These models iaclude parameters that describe the enthalpy and entropy of association. The most detailed description of association ia supercritical water has been obtained usiag molecular dynamics and Monte Carlo computer simulations (63), but this requires much larger amounts of computer time (64—66). 

A variety of equations-of-state have been applied to supercritical fluids, ranging from simple cubic equations like the Peng-Robinson equation-of-state to the Statistical Associating Fluid Theoiy. All are able to model nonpolar systems fairly successfully, but most are increasingly chaUenged as the polarity of the components increases. The key is to calculate the solute-fluid molecular interaction parameter from the pure-component properties. Often the standard approach (i.e. corresponding states based on critical properties) is of limited accuracy due to the vastly different critical temperatures of the solutes (if known) and the solvents other properties of the solute... 

III. Nonuniform Associating Fluids with Directional Forces 192... 

A. A Monte Carlo study of wetting of associating fluids 229... 

The theory of inhomogeneous associating fluids evidently has benefited from the developments available for bulk associating models. The theory of... 

The present chapter is organized as follows. We focus first on a simple model of a nonuniform associating fluid with spherically symmetric associative forces between species. This model serves us to demonstrate the application of so-called first-order (singlet) and second-order (pair) integral equations for the density profile. Some examples of the solution of these equations for associating fluids in contact with structureless and crystalline solid surfaces are presented. Then we discuss one version of the density functional theory for a model of associating hard spheres. All aforementioned issues are discussed in Sec. II. 

Sec. Ill is concerned with the description of models with directional associative forces, introduced by Wertheim. Singlet and pair theories for these models are presented. However, the main part of this section describes the density functional methodology and shows its application in the studies of adsorption of associating fluids on partially permeable walls. In addition, the application of the density functional method in investigations of wettability of associating fluids on solid surfaces and of capillary condensation in slit-like pores is presented. 

Finally, in Sec. IV, two examples of the application of the Monte Carlo simulation to investigate the structure and thermodynamic properties of adlayers of an associating fluid are given. The results of simulations are compared with those from theoretical approaches. In conclusion, we discuss some methodological perspectives in the discussed area of research. 

The structure of the bulk associating fluid in the framework of the model in question can be determined by solving the common Ornstein-Zernike (OZ) equation... 

The inaccuracy seems not to prohibit study of the structural properties of associating fluids, at least at low values of the association energy. However, what is most important is that this difficulty results in the violation of the mass action law, see Refs. 62-64 for detailed discussion. To overcome the problem, one can apply thermodynamical correspondence between a dimerizing fluid and a mixture of free monomers of density p o = P/30 = Po/2 and dimer species [12]. The equation of state of the corresponding mixture... 

The EMSA requires the degree of dimerization A as an input parameter. This is quite disappointing. However, it ehminates the deficiency of the Percus-Yevick approximation, Eq. (38). The EMSA represents a simpHfied version, to obtain an analytic solution, of a more sophisticated site-site extended mean spherical approximation (SSEMSA) [67-69]. The results of the aforementioned closures can be used as an input for subsequent calculations of the structure of nonuniform associating fluids. 

FIG. 1 Total local density p(z) for bulk density p = 0.821 and e /k T = 4.25. The solid line is for PYl theory, the dashed line is for HNCl approximation and the points denote the Monte Carlo simulation results. (Reprinted from S. Sokolowski, D. Henderson, A. Trokhymchuk, O. Pizio. Density profiles of associating fluid near a hard wall PY/EMSA and HNC/EMSA singlet theory, Physica A, 220, 22-32. (1995), with permission from Elsevier Science.)... 

The singlet-level theories have also been applied to more sophisticated models of the fluid-solid interactions. In particular, the structure of associating fluids near partially permeable surfaces has been studied in Ref. 70. On the other hand, extensive studies of adsorption of associating fluids in a slit-like [71-74] and in spherical pores [75], as well as on the surface of spherical colloidal particles [29], have been undertaken. We proceed with the application of the theory to more sophisticated impermeable surfaces, such as those of crystalline solids. 

Associating Fluid in Contact with a Crystalline Solid... 

The singlet-level theory has also been used to describe the structure of associating fluids near crystalline surfaces [30,31,76,77]. The surface consists explicitly of atoms which are arranged on a lattice of a given symmetry. The fluid atom-surface atom potential can also involve an associative term, i.e., the chemical-type bonding of the adsorbate particles with the surface may be included into the model. However, we restrict ourselves to the case of a nonassociative crystalline surface first. 

Second-Order Integral Equations for Associating Fluids As mentioned above in Sec. II A, the second-order theory consists of simultaneous evaluation of the one-particle (density profile) and two-particle distribution functions. Consequently, the theory yields a much more detailed description of the interfacial phenomena. In the case of confined simple fluids, the PY2 and HNC2 approaches are able to describe surface phase transitions, such as wetting and layering transitions, in particular see, e.g.. Ref. 84. 

Again, we consider the model of an associating fluid by Cummings and Stell [25-27]. The fluid is studied in contact with a hard wall Uq,(z) is given by Eq. (41). In this case Eq. (16) becomes [85,86]... 

III. NONUNIFORM ASSOCIATING FLUIDS WITH DIRECTIONAL FORCES... 

In the case of an associating fluid with the repulsive-attractive reference system potential, the attractive van der Waals forces between molecules may also be considered in a perturbational manner [114]. The Helmholtz free energy can be written as a sum of three terms... 

---