Perturbation theory of solutions of non-electrolytes. The effect of permanent and induced multipole interactions on excess thermodynamic functions of binary systems

1979 ◽  
Vol 44 (12) ◽  
pp. 3541-3548 ◽  
Author(s):  
Miloš Ševčík ◽  
Tomáš Boublík

Perturbation theory proposed to describe fluids with the multipole interactions was extended to the systems with significant induced interactions. The relations obtained were used to study the effect of the permanent and induced multipole interactions on excess thermodynamic functions of binary solutions formed by a simple fluid (interacting according to the Lennard-Jones pair potential) and a fluid with anisotropic intermolecular forces. Model solutions were studied first; the same procedure was then used to predict behaviour of the real systems cyclopentane-chloroform at 298.15 K and xenon-hydrogen chloride at 195.4 K. A considerable effect of anisotropic interaction on excess quantities of the model- as well as actual solutions was proved.

1974 ◽  
Vol 27 (2) ◽  
pp. 241 ◽  
Author(s):  
CHJ Johnson ◽  
TH Spurling

In this paper we give the results of computing the effect of non-additivity of long range forces on the fourth virial coefficient of a Lennard-Jones 12-6 gas. We have considered only dipolar effects but have included all terms up to the fourth order of perturbation theory. We have also calculated the effect of the fourth-order triple-dipole term on the third virial coefficient. For the fourth virial coefficient we find that the dispersion non-additivity, while being positive at low reduced temperatures, goes through a negative minimum at a reduced temperature of about 1.25 before becoming small and positive at high temperatures. This is in contradistinction to the behaviour of the third virial co-efficient where the dispersion non-additivity is always positive.


1980 ◽  
Vol 45 (9) ◽  
pp. 2375-2383 ◽  
Author(s):  
Miloš Ševčík ◽  
Tomáš Boublík

The second virial coefficient in systems with permanent and induced multipole interactions was studied by using a statistical-thermodynamics correlation based on the perturbation theory of fluids. Several pair potential combinations of the Lennard-Jones function with different, subsequently more complex anisotropic contributions, were considered; the improvement in the description of intermolecular interactions due to these non-central contributions brought about an improvement in the interpretation of experimental data. The characteristic dependence of the parameters ε/k on σ at different temperatures was obtained for all of the three systems studied (Ar, CH4 and CH3F). It was found that if experimental values of the second virial coefficient of methyl fluoride are correlated by a relation derived from the Stockmayer potential, two sets of the ε/k and σ can be employed.


Author(s):  
C. G. Gray ◽  
K. E. Gubbins

Knowledge of the intermolecular potential for simple (i.e. monatomic) molecules has increased greatly in recent years. For polyatomic molecules, on the other hand, such knowledge is still rather meagre, and much more is needed. One needs to know (i) what is the pair potential? (ii) how important are the triplet and other multibody potentials in liquids? These multibody potentials have been studied very little for polyatomic liquids (see refs. 28-35 and §§ 1.2.3, 2.10, and 4.10), and are usually taken into account, if at all, by an effective pair potential. There have been, especially at short range, relatively few theoretical evaluations of the pair potential for diatomic or polyatomic molecules (see, e.g. refs. 21-7 and 40-55a). The most reliable existing knowledge has been obtained from binary collision experiments, or, for the longrange part of the potential, from measurements of properties of single molecules. Examples include molecular beam scattering, induced birefringence, pressure and dielectric virial coefficients, and collision-induced absorption (including gas dimer spectra, which can also be studied by beam resonance spectroscopy) which yield values for the parameters (e.g. Lennard-Jones constants, polarizabilities, dipole moments, quadrupole moments, octopole moments, etc. - see also Appendix D) occurring in the expressions for the intermolecular potentials. The shape of the repulsive core of the potential can be inferred approximately from the molecular structure and charge density as determined experimentally, for example by electron and X-ray diffraction or by quantum calculations. As an example of the last point we show in Fig. 2.1 a contour map for the theoretically calculated charge density of N2 , the prototype molecule for simple nonpolar molecular fluid studies. Over 95 per cent of the total electronic charge is contained within the outermost (0.002 au) contour, and the dimensions of this contour are sometimes used to define a theoretical size of the N2 molecule. The dimensions shown on Fig. 2.1 agree roughly with dimensions obtained experimentally from Lennard- Jones diameters in gases (virial coefficients and viscosity) and so-called van der Waals radii from X-ray diffraction studies of solids.


1990 ◽  
Vol 68 (3) ◽  
pp. 435-439 ◽  
Author(s):  
Maria Asuncion Gallardo ◽  
Maria Del Carmen Lopez ◽  
Jose Santiago Urieta ◽  
Celso Gutierrez Losa

Solubility measurements of He, Ne, Ar, Kr, Xe, H2, D2, N2, CH4, C2H4, C2H6, CF4, SF6, and CO2 in 2,6-dimethylcyclohexanone at temperatures 273.15 to 303.15 K and at a gas partial pressure of 101.33 kPa are reported. Standard changes in Gibbs energy, enthalpy, and entropy for the dissolution process at 298.15 K are also presented. Results for both solubility and thermodynamic functions are compared with those for cyclohexanone and 2-methylcyclohexanone. The scaled particle theory is used to obtain the effective Lennard–Jones (6,12) pair potential parameters for 2,6-dimethylcyclohexanone and, from these, the values it predicts for the solubility of the studied gases in the solvent are obtained. Keywords: gas solubility, Henry coefficient, 2,6-dimethylcyclohexanone, thermodynamic functions of solution, non-polar gases.


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