Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

We present evidence for the regular behaviour of the Boyle temperature T_B 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 T_B 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 T_B have been obtained from experimental data of the cross virial coefficient B₁₂(T). In determining T_B 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.