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Thermodynamic consistency near the liquid-liquid critical point

par Losada Perez, Patricia ;Perez Sanchez, German;Cerdeirina, CA;Troncoso, Jacobo;Romani, Luis
Référence The Journal of Chemical Physics, 130, page (044506)
Publication Publié, 2009-01-28

Article révisé par les pairs

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Résumé :

The thermodynamic consistency of the isobaric heat capacity per unit volume at constant composition Cp,x Cp,x and the density ρ ρ near the liquid-liquid critical point is studied in detail. To this end, Cp,x(T) Cp,x(T) , ρ(T) ρ(T) , and the slope of the critical line (dT/dp)c (dT/dp)c for five binary mixtures composed by 1-nitropropane and an alkane were analyzed. Both Cp,x(T) Cp,x(T) and ρ(T) ρ(T) data were measured along various quasicritical isopleths with a view to evaluate the effect of the uncertainty in the critical composition value on the corresponding critical amplitudes. By adopting the traditionally employed strategies for data treatment, consistency within 0.01 K MPa−1 0.01 K MPa−1 (or 8%) is attained, thereby largely improving the majority of previous results. From temperature range shrinking fits and fits in which higher-order terms in the theoretical expressions for Cp,x(T) Cp,x(T) and ρ(T) ρ(T) are included, we conclude that discrepancies come mainly from inherent difficulties in determining the critical anomaly of ρ ρ accurately: specifically, to get full consistency, higher-order terms in ρ(T) ρ(T) are needed; however, the various contributions at play cannot be separated unambiguously. As a consequence, the use of Cp,x(T) Cp,x(T) and (dT/dp)c (dT/dp)c for predicting the behavior of ρ(T) ρ(T) at near criticality appears to be the best choice at the actual experimental resolution levels. Furthermore, the reasonably good thermodynamic consistency being encountered confirms that previous arguments appealing to the inadequacy of the theoretical expression relating Cp,x Cp,x and ρ ρ for describing data in the experimentally accessible region must be fairly rejected.