Prediction of Vapor-Liquid Equilibria in Polymer Solutions Using an Equation Of State/Excess Gibbs Free Energy Model

Kalospiros, Nikolaos S.; Tassios, Dimitrios P.

doi:10.1021/ie00045a021

Cited by 22 publications

(20 citation statements)

References 26 publications

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“…For polymer−solvent and polymer−polymer mixtures, several polymer-specific EoS have been proposed that can be classified into two broad groups: lattice models and continuum models . Applications of cubic EoS to describe VLE in this type of mixture have been undertaken with some success. − …”

Section: Cubic Eos Applied To Polymer Solutionsmentioning

confidence: 99%

The State of the Cubic Equations of State

Valderrama

2003

Ind. Eng. Chem. Res.

493

344

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The development of van der Waals cubic equations of state and their application to the correlation and prediction of phase equilibrium properties is presented and analyzed. The discussion starts with a brief account of the contributions to equation of state development during the years before van der Waals. Then, the original equation proposed in the celebrated thesis of van der Waals in 1873 and its tremendous importance in describing fluid behavior are analyzed. A chronological critical walk through the most important contributions during the first part of the 1900s is made, to arrive at the proposal that I consider to be the most outstanding since van der Waals: the equation proposed by Redlich and Kwong in 1949. The contributions after Redlich and Kwong to the modern development of equations of state and the most recent equations proposed in the literature are analyzed. The application of cubic equations of state to mixtures and the development of mixing rules is put in a proper perspective, and the main applications of cubic equations of state to binary and multicomponent mixtures, to high-pressure phase equilibria, to supercritical fluids, to reservoir fluids, and to polymer mixtures are summarized. Finally, recommendations on which equations of state and which mixing rules to use for given applications are presented.

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Section: Cubic Eos Applied To Polymer Solutionsmentioning

confidence: 99%

The State of the Cubic Equations of State

Valderrama

2003

Ind. Eng. Chem. Res.

493

344

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“…Two binary parameters, the F-H χ and k ij , were fitted to polymer + solvent VLE data. Kalospiros and Tassios (1995) proposed an incorporation method at zero reference pressure using the entropic-FV model (Elbro et al, 1990;Kontogeorgis et al, 1993) with a modified Peng-Robinson EOS (Magoulas and Tassios, 1990). Satisfactory predictions were presented for a few nonpolar and slightly polar solutions.…”

Section: Introductionmentioning

confidence: 99%

Vapor−Liquid Equilibrium of Polymer + Solvent Mixtures by the Chain-of-Rotators Equation of State

Novenario

Caruthers

Chao

1998

Ind. Eng. Chem. Res.

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Vapor−liquid equilibrium (VLE) of polymer + solvent mixtures is described by the chain-of-rotators (COR) equation of state (EOS) using segment parameters that are applicable to polymers of varying molecular weight. Segment parameters a and b are obtained from small molecules of the same chemical structure as the polymer segment. The segment parameter c is then obtained by fitting polymer pressure−volume−temperature (PVT) data. van der Waals and free energy matching mixing rules are investigated to describe mixtures of various types. Excellent correlation of VLE data is obtained for all mixtures studied by using only one constant interaction coefficient for a, k 12, in the van der Waals mixing rule independent of temperature or polymer molecular weight. VLE predictions from the COR EOS by using van der Waals mixing rules with zero k 12 as well as by using UNIFAC free energy matched mixing rules are presented. For the majority of systems studied, both predictive methods gave better or equal results compared to the UNIFAC−FV model (FV = free volume).

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“…Although we have elected, due to its simplicity, to extend the vdW EOS to polymer solutions and-in this work-blend, any other cubic EOS (e.g., SRK) may be used without any complexities. Recently, Kalospiros and Tassios (1995) developed an EOS/GE model for polymer solutions by combining the Peng-Robinson EOS with the Entropic-FV activity coefficient model (Kontogeorgis et al, 1993). These results demonstrate that cubic EOSs retain their flexibility even when applied to polymer solutions.…”

Section: Introductionmentioning

confidence: 84%