Phase equilibria of associating fluids

As a continuation of our work on spherical associating molecules, we have derived expressions for changes in the thermodynamic properties due to association in mixtures of molecules with multiple bonding sites. The equations are written in terms of a hard-core reference whose pair distribution function is known. In practise, the hard-sphere reference mixture is the easiest to use. A reference system of homonuclear chains is examined in order to account for asymmetries in molecular shape; chains are constructed by bonding equal-sized spheres together. An equation of state for hard-sphere chains is obtained which is in good agreement with recent simulation data. Expressions for mixtures of homonuclear chains of different sizes are also presented. The approach is extended to examine associating chain molecules with multiple bonding sites. The phase equilibria of non-associating chains, and of associating chains with one or two bonding sites are determined. In this study, the separate effects of molecular ass...

[1]  J. S. Rowlinson,et al.  Molecular Thermodynamics of Fluid-Phase Equilibria , 1969 .

[2]  David Chandler,et al.  Statistical mechanics of chemical equilibria and intramolecular structures of nonrigid molecules in condensed phases , 1976 .

[3]  M. Wertheim,et al.  Fluids with highly directional attractive forces. I. Statistical thermodynamics , 1984 .

[4]  K. Gubbins,et al.  Phase equilibria of associating fluids : spherical molecules with multiple bonding sites , 1988 .

[5]  H. C. Andersen.  Cluster expansions for hydrogen bonded fluids. II. Dense liquids , 1974 .

[6]  M. Wertheim,et al.  Fluids with highly directional attractive forces. III. Multiple attraction sites , 1986 .

[7]  P. Flory.  Principles of polymer chemistry , 1953 .

[8]  K. E. Starling,et al.  Equilibrium Thermodynamic Properties of the Mixture of Hard Spheres , 1971 .

[9]  John S. Rowlinson,et al.  Liquids and liquid mixtures , 1959 .

[10]  H. C. Andersen.  Cluster expansions for hydrogen‐bonded fluids. I. Molecular association in dilute gases , 1973 .

[11]  M. Wertheim,et al.  Thermodynamic perturbation theory of polymerization , 1987 .

[12]  E. A. Guggenheim.  Applications of Statistical Mechanics , 1966 .

[13]  L. Verlet,et al.  Equilibrium Theory of Simple Liquids , 1972 .

[14]  R. Dickman,et al.  High density Monte Carlo simulations of chain molecules: Bulk equation of state and density profile near walls , 1988 .

[15]  M. Wertheim,et al.  Fluids with highly directional attractive forces. IV. Equilibrium polymerization , 1986 .

[16]  K. E. Starling,et al.  Equation of State for Nonattracting Rigid Spheres , 1969 .

[17]  M. Wertheim.  Fluids of dimerizing hard spheres, and fluid mixtures of hard spheres and dispheres , 1986 .

[18]  R. J. Baxter,et al.  Ornstein–Zernike Relation and Percus–Yevick Approximation for Fluid Mixtures , 1970 .

[19]  M. Wertheim,et al.  Fluids with highly directional attractive forces. II. Thermodynamic perturbation theory and integral equations , 1984 .

[20]  D. Tildesley,et al.  An equation of state for hard dumbell fluids , 1980 .

[21]  K. Olaussen,et al.  Statistical mechanical model with chemical reaction , 1980 .

[22]  M. Wertheim.  Integral equation for the Smith–Nezbeda model of associated fluids , 1988 .

[23]  I. R. Mcdonald,et al.  Theory of simple liquids , 1998 .

[24]  J. Perram.  Hard sphere correlation functions in the Percus-Yevick approximation , 1975 .

[25]  Gustavo Chapela Castañares,et al.  Molecular dynamics of discontinuous potentials , 1984 .

[26]  Tomáš Boublı́k,et al.  Hard‐Sphere Equation of State , 1970 .

[27]  K. Gubbins,et al.  Theory and simulation of associating liquid mixtures. II , 1987 .