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The Virial Coefficients of Pure Gases and Mixtures. A Simply Additivity Scheme of Group Interactions

This document proposes a simple additivity scheme to estimate second virial coefficients (B) of pure gases and mixtures based on group interactions. It suggests that B increases linearly with molecular surface area. The proposed equation calculates B12 values based on the surface areas and number of interactions between groups on each molecule, with adjustable parameters (aij) representing interaction strengths. Preliminary aij values were obtained and fit 350 B values for alkanes and mixtures with standard deviation of 30 cm3/mole using a temperature-dependent form of aij. The scheme allows accurate prediction of second virial coefficients and PVT properties up to half the critical density.

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134 views

The Virial Coefficients of Pure Gases and Mixtures. A Simply Additivity Scheme of Group Interactions

This document proposes a simple additivity scheme to estimate second virial coefficients (B) of pure gases and mixtures based on group interactions. It suggests that B increases linearly with molecular surface area. The proposed equation calculates B12 values based on the surface areas and number of interactions between groups on each molecule, with adjustable parameters (aij) representing interaction strengths. Preliminary aij values were obtained and fit 350 B values for alkanes and mixtures with standard deviation of 30 cm3/mole using a temperature-dependent form of aij. The scheme allows accurate prediction of second virial coefficients and PVT properties up to half the critical density.

Uploaded by

Ludwin Salazar Valdivia
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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The Virial Coefficients of Pure Gases and Mixtures.

a Simply Additivity Scheme of Group


Interactions

L. LeporiC,S, E. Matteoli, A. Spanedda and G. C. Bussolino


Istituto Processi Chimico-Fisici, Pisa, Italy
[email protected]

Many predicting methods have been proposed to evaluate virial coefficients B. Most of them are limited because
they depend on the knowledge of molecular properties or on fitted parameters, which are often not available [1].
A few group parameterisation methods have been developed. The best known one [2] requires the critical
temperature and is restricted to pure components. In the present work, a simple scheme based on additivity of
group interactions is proposed with the aim of i) estimating second virial coefficients of both pure gases (B11)
and mixtures (B12); ii) obtaining information on the interactions between molecules responsible of the deviations
of gases from ideal behaviour.

It has been observed that the magnitude of B11 for both alkanes and perfluoroalkanes increases almost linearly
with increasing cubic molecular surface area (as well as with volume and number of carbon atoms). On the basis
of this finding, the following equation has been suggested to reproduce B12 values at a given temperature T for
the general case of molecules 1 and 2. Calculations for pure gases are made by setting molecule 1 identical to
molecule 2.
B12 (T) = ∑ n ija ij (T)s i s j S1S 2

S1 and S2 are total surface areas of molecules, si and sj are the surface areas of i and j groups (in units of CH2
surface), respectively, nij is the number of i-j interactions, and aij is an adjustable parameter, that is, a measure of
the interaction strength between i and j per unit interaction surface. B data were taken from Dymond and Smith
[3], the surface areas S and s were computed from Bondi increments [4]. From preliminary calculations the
following aij values (cm3 mol-1 nCH2-3) at 298.15 K have been obtained for the pair interactions: CH2-CH2 (-5.2),
CF2-CF2 (-1.4), CH2-CF2 (-2.2), CH2-OH (-12), OH-OH (-433), CH2-O (+4), O-O (-297), CH2-CO (-8.5),
CO-CO (-214), CHar-CHar (-17). As function describing the temperature dependence of aij (and B) either an
empirical equation or a semiempirical one based on the chemical theory has been employed. This latter was
found more appropriate, requiring in most cases a lesser number of coefficients. A set of 350 selected B values
for alkanes C1 to C8 and their mixtures in the temperature range 180-700 K were reproduced with a standard
deviation of 30 cm3/mole using three adjustable coefficients for the temperature dependence of only one
interaction parameter aij(T). The second virial coefficients BM of multicomponents mixtures can be easily
calculated from Bij estimated with the above equation. The virial equation for such mixtures even when
terminated at the second coefficient BM, can furnish accurate PVT predictions up to a density of about one half
of the critical.

[1] E.B. Poling, J.M. Prausnitz and J.P. O'Connell, The properties of gases and liquids, McGraw-Hill,
New York (2001).
[2] D.W. McCann and P.D. Danner, Ind. Eng. Chem. Process Des. Dev., 23, 529-533 (1984).
[3] J.H. Dymond and E.B. Smith, The virial coefficients of pure gases and mixtures, Clarendon Press, Oxford
(1980).
[4] A. Bondi, J. Phys. Chem., 68, 441 (1964).

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