Collect. Czech. Chem. Commun. 2009, 74, 363-391
Published online 2009-02-23 10:15:15

A new combining rule for fluid mixtures

José Alfredo González-Calderón and Fernando del Río*

Laboratorio de Termodinámica, Departamento de Física, Universidad Autónoma Metropolitana, Iztapalapa, San Rafael Atlixco 186, México, DF, 0934, Mexico


We present evidence for the regular behaviour of the Boyle temperature TB in gaseous binary mixtures of small molecules with negligible multipolar moments. We use this regularity to construct a new combining rule for the prediction of the cross interaction u12(r) in those mixtures. The combining rule gives TB of the cross interaction as the harmonic mean of the Boyle temperatures of the pure components. The validity of this harmonic rule is based on experimental data of 28 binary mixtures, whose TB have been obtained from experimental data of the cross virial coefficient B12(T). In determining TB we make use of non-conformal potentials that have been proven to represent very accurately the effective interactions of the molecules investigated. The new combining rule is used to give interaction parameters of several dozens of binary mixtures involving noble gases (Ne, Ar, Kr and Xe), diatomic molecules (N2, O2 and CO) and n-alkanes (from methane to n-octane). These interaction parameters lead to a prediction of cross virial coefficients B12(T) within experimental error. Electrostatic interactions, originating in permanent dipolar, quadrupolar, octupolar and hexadecapolar moments and exemplified by molecules of HCl, CO2, CF4 and SF6, depart from the regular non-polar behaviour.

Keywords: Combining rules; Virial coefficients; Binary mixtures; Interactions; Polar and non-polar molecules; Boyle temperature; ANC potentials.

References: 40 live references.