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

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

J. of Supercritical Fluids 55 (2010) 472–478 Contents lists available at ScienceDirect The Journal of Supercritical Fluids journal homepage: /locate/supflu Near-critical and supercritical dilute solutions viewed from macroscopic and molecular-scale perspectives R. Fernández-Prini a,b,?, M. Laura Japas b,c, Ernesto Marceca a a INQUIMAE/DQIAQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires, Argentina b Gerencia Química, Comisión Nacional de Energía Atómica, Av. Libertador 8250, 1429 Buenos Aires, Argentina c Escuela de Ciencia y Tecnología, Universidad Nacional de San Martín, Martín de Irigoyen 3100, 1650 San Martín, Prov. Buenos Aires, Argentina article info Article history: Received 18 June 2010 Received in revised form 6 October 2010 Accepted 7 October 2010 Keywords: Near-critical solvents Krichevskii’s function Solvation Intermolecular interactions Critical behaviour abstract 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 in?nity, 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) ?uctuations in the presence of intermolecular interacti