Prediction of Henry's Constant in Polymer Solutions using the Peng-Robinson Equation of State

Authors: Somayeh Tourani, Alireza Behvandi

Abstract:

The peng-Robinson (PR), a cubic equation of state (EoS), is extended to polymers by using a single set of energy (A1, A2, A3) and co-volume (b) parameters per polymer fitted to experimental volume data. Excellent results for the volumetric behavior of the 11 polymer up to 2000 bar pressure are obtained. The EoS is applied to the correlation and prediction of Henry constants in polymer solutions comprising three polymer and many nonpolar and polar solvents, including supercritical gases. The correlation achieved with two adjustable parameter is satisfactory compared with the experimental data. As a result, the present work provides a simple and useful model for the prediction of Henry's constant for polymer containing systems including those containing polar, nonpolar and supercritical fluids.

Keywords: Equation of state, Henry's constant, Peng-Robinson, polymer solution.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1332374

References:

[1] Flory, P. J., Principles of Polymer Chemistry, Ithaca, NY, Cornell University Press (1953).
[2] Oishi, T. and J. M. Prausnitz, "Estimation of solvent activities in polymer solutions using a group-contribution method," Industrial & Engineering Chemistry, Process Design and Development, 17, 333-339 (1978).
[3] Elbro, H. S., A. Fredenslund and P. Rasmussen, "A new simple equation for the prediction of solvent activities in polymer solutions," Macromolecules, 23, 4707- 4714 (1990).
[4] Bondi, A., Physical Properties of Molecular Crystals, Liquids, and Glasses, New York, John Wiley & Sons (1968).
[5] Radfarnia, H. R., G. M. Kontogeorgis, C. Ghotbi and V. Taghikhani, "Classical and recent free-volume models for polymer solutions: A comparative evaluation,"Fluid Phase Equilibria, 257, 63-69 (2007).
[6] Zhong, C., Y. Sato, H. Masuoka and X. Chen, "Improvement of predictive accuracy of the UNIFAC model for vapor-liquid equilibria of polymer solutions," Fluid Phase Equilibria, 123, 97-106 (1996).
[7] Morris, W. O., P. Vimalchand and M. D. Donohue, "Perturbed-soft-chain theory: An equation of state based on the Lennard-Jones potential," Fluid Phase Equilibria, 32, 103-115 (1987).
[8] High, M. S. and R. P. Danner, "Application of the group contribution lattice-fluid equation of state to polymer solutions," AIChE Journal, 36, 1625- 1632 (1990).
[9] Chen, F., A. Fredenslund and P. Rasmussen, "Group-contribution Flory equation of state for vapor-liquid equilibria in mixtures with polymers," Industrial & Engineering Chemistry Research, 29, 875-882 (1990).
[10] Akbarzadeh ,K., M.Moshfeghian, "Application of the polymer chain-ofrotator (PCOR) equation of state and its extension to polymer blends", Fluid Phase Equilibria 187-188 , 347361 (2001) .
[11] Harismiadis, V. I., G. M. Kontogeorgis, A. Fredenslund and D. P. Tassios, "Application of the van der Waals equation of state to polymers II. Prediction" ,Fluid Phase Equilibria, 96, 93-117 (1994).
[12] Peng, D. and D. B. Robinson, "New two-constant equation of state," Industrial & Engineering Chemistry Fundamentals, 15(1), 59-64 (1976).
[13] Androulakis, I.P., N.S. Kalospiros, and D.P. Tassios, Thermophysical properties of pure polar and nonpolar compounds with a modified VdW-711 equation of state, Fluid Phase Equil., 45, 135-163 (1989).
[14] Louli, V. and D. Tassios, "Vapor-liquid equilibrium in polymer-solvent systems with a cubic equation of state," Fluid Phase Equilibria, 168, 165-182 (2000).
[15] Kontogeorgis, G. M., A. Fredenslund and D. P. Tassios, "Simple activity coefficient model for the prediction of solvent activities in polymer solutions," Industrial and Engineering Chemistry Research, 32, 362-372 (1993).
[16] Patrick A. Rodgers,"Pressure-volume-temperature relationships for polymeric liquids: A review of equations of state and their characteristic parameters for 56 polymers", Journal of Applied Polymer Science, 48, 1061- 1079(1993).
[17] Zhong , C. and H. Masuoka," Prediction of Henry's constants for polymer-containing systems using the SRK equation of state coupled with a new modified UNIFAC model ",Fluid Phase Equilibria,126,1-12(1996).
[18] Maloney, D. and J. Prausnitz,"Solubility of ethylene and other organic solutes in liquid, low density polyethylene in the region 124 o to 300 o c", AIChE Journal, 22,74-82(1976).
[19] Leonard , I. and D. Harnish, "Solubility of gases and liquids in molten polystyrene", AIChE journal, 22, 117-121(1976).
[20] Liu, D. M. Prausnits,"Solubilities of volatile solutes in poly vinyl acetate from 125 to 200oC", Journal of polymer science, 15, 145-153(1977).