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Framework for correlating the effect of temperature on nonelectrolyte and ionic liquid activity coefficients
Author(s) -
Frank Timothy C.,
Arturo Steven G.,
Holden Bruce S.
Publication year - 2014
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.14557
Subject(s) - thermodynamics , enthalpy , exponent , chemistry , activity coefficient , ionic liquid , dilution , binary number , ionic bonding , entropy (arrow of time) , solvent , liquid phase , mathematics , organic chemistry , physics , ion , linguistics , philosophy , arithmetic , aqueous solution , catalysis
A power‐law expression is proposed for correlating the temperature dependence of infinite‐dilution activity coefficients ( γ i j ∞) for nonelectrolyte solute–solvent binary pairs and for pairs including an ionic liquid:ln γ i j ∞ ( at T ) / ln γ i j ∞( at T ref ) =(T ref/ T )θ i j, where θ ij = 0 for Lewis–Randall ideal solutions, θ ij = 1 for classic enthalpy‐based Scatchard–Hildebrand regular solution and van Laar models, and −5 < θ ij < 5 for most real binaries. The exponent θ ij is a function of partial molar excess enthalpy (h ¯i j E , ∞) and entropy (s ¯i j E , ∞) such thatθ i j = 1 / [ 1 − ( Ts ¯i j E , ∞ /h ¯i j E , ∞ ) ] . Real binaries are classified into seven types corresponding to distinct domains ofγ i j ∞and θ ij . The new method provides a framework for correlating phase‐equilibrium driven temperature effects for a wide variety of chemical and environmental applications. © 2014 American Institute of Chemical Engineers AIChE J , 60: 3675–3690, 2014