HANDBOOK OF POLYMER SOLUTION THERMODYNAMICS
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1 HANDBOOK OF POLYMER SOLUTION THERMODYNAMICS Ronald P. Danner Martin S. High Department of Chemical Engineering The Pennsylvania State University University Park, PA Design Institute for Physical Property Data American Institute of Chemical Engineers American Institute of Chemical Engineers
2 TABLE OF CONTENTS HANDBOOK OF POLYMER SOLUTION THERMODYNAMICS PREFACE i Chapter 1: INTRODUCTION 1 A. OBJECTIVES OF THE HANDBOOK OF POLYMER SOLUTION THERMODYNAMICS 1 Chapter 2: FUNDAMENTALS OF POLYMER SOLUTION THERMODYNAMICS... 3 A. PURE POLYMER PVT BEHAVIOR 3 B. PHASE EQUILIBRIA THERMODYNAMICS 4 С MODELING APPROACHES TO POLYMER SOLUTION THERMODYNAMICS 6 D. LATTICE MODELS 8 1. Flory-Huggins Model 8 2. Solubility Parameters and the Flory-Huggins Model 9 3. Modifications of the Flory-Huggins Model Sanchez-Lacombe Equation of State Panayiotou-Vera Equation of State Kumar Equation of State High-Danner Equation of State Oishi-Prausnitz Activity Coefficient Model 15 E. VAN DER WAALS MODELS Flory Equation of State Chen, Fredenslund, and Rasmussen Equation of State 18 F. LIQUID-LIQUID EQUILIBRIA OF POLYMER SOLUTIONS Thermodynamics of Liquid-Liquid Equilibria Types of Liquid-Liquid Equilibria Models for Liquid-Liquid Equilibria Computation of Liquid-Liquid Equilibria Compositions Parameter Estimation from Liquid-Liquid Equilibria Data Sample Correlations of Liquid-Liquid Equilibria Data 27 G. EFFECT OF POLYDISPERSION 29 Handbook of Polymer Solution Thermodynamics
3 TABLE OF CONTENTS (Continued) Chapter 3: RECOMMENDED PROCEDURES 31 A. SELECTION OF MODELS Correlation of Pure Polymer PVT Behavior Prediction of Vapor-Liquid Equilibria 32 B. PROCEDURE: METHOD FOR ESTIMATING THE SPECIFIC VOLUME OF A PURE POLYMER LIQUID Method Procedure Limitations and Reliability Comments Literature Sources Example 39 С PROCEDURE: OISHI-PRAUSNITZ METHOD FOR ESTIMATING THE ACTIVITY COEFFICIENTS OF SOLVENTS IN POLYMER SOLUTIONS Method Procedure Limitations and Reliability Comments Literature Sources Example 48 D. PROCEDURE: CHEN-FREDENSLUND-RASMUSSEN EQUATION OF STATE FOR ESTIMATING THE ACTIVITY COEFFICIENTS OF SOLVENTS IN POLYMER SOLUTIONS Method Procedure Limitations and Reliability Literature Source Example 69 E. PROCEDURE: HIGH-DANNER EQUATION OF STATE FOR ESTIMATING THE ACTIVITY COEFFICIENT OF A SOLVENT IN A POLYMER SOLUTION Method Procedure Limitations and Reliability Literature Sources Example 79
4 TABLE OF CONTENTS (Continued) F. PROCEDURE: FLORY-HUGGINS CORRELATION FOR VAPOR-LIQUID EQUILIBRIA OF POLYMER SOLVENT SYSTEMS Method Procedure Limitiations and Reliability Literature Source Example 83 Chapter 4: POLYMER DATA BASE 85 A. INTRODUCTION 85 B. EXPERIMENTAL METHODS Inverse Gas Chromatography (IGC) Piezoelectric Sorption (PZS) Differential Vapor Pressure (DVP) Gravimetric Sorption (GS) Light Scattering (LS) Ultracentrifuge (UC) Turbidimetry (ТВ) and Light Scattering Turbidimetry (LST) Microanalytical (MA) Ultraviolet Spectrometry (UVS) and Infrared Spectrometry (IRS) Size Exclusion Chromatography (SEC) 92 С DATA REDUCTION PROCEDURES Pure Polymer PVT Data Finite Dilution Flory Chi Parameter Infinite Dilution Flory Chi Parameter Differential Vapor Pressure, Gravimetric Sorption, and Piezoelectric Sorption Methods Gas Chromatograph Data at Infinite Dilution Henry's Law Constant Osmotic Pressure Data 102 D. LISTING OF SYSTEMS INCLUDED IN DATA BASES Pure Polymer PVT Data Finite Concentration VLE Data Infinite Dilution VLE Data Binary Liquid-Liquid Equilibria Data Ternary Liquid-Liquid Equilibria Data 118
5 TABLE OF CONTENTS (Concluded) Chapter 5: COMPUTER PROGRAMS 121 A. PHASE EQUILIBRIA CALCULATIONS - POLYPROG Installation Features Tutorial Session 124 B. DATA RETRIEVAL - POLYDATA Installation Features Tutorial Session 132 C. FILE FORMATS USED BY POLYDATA Pure Polymers Infinitely Dilute Solvent Weight Fraction Activity Coefficients (WFAC) Finite Concentration Solvent Weight Fraction Activity Coefficients (WFAC) Binary LLE Ternary LLE Bibliographic Sources Polymer Synonyms 140 Chapter 6: APPENDICES 141 A. GLOSSARY OF TERMS 141 B. STANDARD POLYMER ABBREVIATIONS 142 С NOMENCLATURE 147 D. UNITS AND CONVERSION FACTORS Units and Symbols Prefixes Usage Format Conversion 156 E. TEXT REFERENCES 161 F. DATA REFERENCES 166
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