Near-critical and supercritical dilute solutions viewed from macroscopic and molecular-scale perspectives

Partial molar properties of dilute solutes in near-critical solvents exhibit a strong dependence on temperature and density which hinders the description of their behaviour under those conditions. We used the well-behaved Krichevskii function, J = ( dp/ dx) V,T supra infinity, to describe that regio...

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Bibliographic Details
Published in:The Journal of supercritical fluids 2010-12, Vol.55 (2), p.472-478
Main Authors: Fernández-Prini, R., Laura Japas, M., Marceca, Ernesto
Format: Article
Language:English
Subjects:
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Critical behaviour
Density
Dilution
Exploration
Fluctuation
Infinity
Intermolecular interactions
Krichevskii's function
Near-critical solvents
Solvation
Solvents
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Summary:Partial molar properties of dilute solutes in near-critical solvents exhibit a strong dependence on temperature and density which hinders the description of their behaviour under those conditions. We used the well-behaved Krichevskii function, J = ( dp/ dx) V,T supra infinity, to describe that region of the thermodynamic space, and have extended its use to ternary solutions (two solutes + one near-critical solvent) successfully. The use of supercritical solvents permits a controlled and continuous exploration of the density dependence of solutes’ properties without undergoing phase transitions, hence the availability of a non-diverging property like J to describe the systems is greatly important. We show its application for binary and ternary systems that have been studied and also give some information about the molecular structure of near-critical solutions. This knowledge provides a better understanding about solvation and its dependence on long-range (critical) fluctuations in the presence of intermolecular interactions.
ISSN:0896-8446
1872-8162
DOI:10.1016/j.supflu.2010.10.009