This work provides coverage of experimental and theoretical procedures for vapour-liquid equilibria (VLE). A survey of the different models and approaches in recent literature enables the reader to choose the appropriate action.
Author(s): J. David Raal, Andreas L. Mühlbauer
Series: Series in Chemical and Mechanical Engineering
Publisher: CRC Press
Year: 1998
Language: English
Pages: 485
City: Boca Raton
Cover
Half Title
Series
Title
Copyright
Dedication
CONTENTS
Preface
Introduction
Nomenclature
Part 1 Low-Pressure Phase Equilibrium Measurements
1 THERMODYNAMIC FUNDAMENTALS
1.1 Introduction
1.2 Fundamental Laws
1.3 Property Changes in Open Systems and the Criteria for Equilibrium
1.4 Partial Molar Properties
1.5 The Gibbs-Duhem Equation
1.6 Fugacity and Activity Coefficient
1.7 Gibbs-Duhem Equation in Terms of Activity Coefficients
1.8 Determination of Activity Coefficients from Experimental Data
1.9 The Evaluation of Fugacities
1.10 Composition, Temperature, and Pressure Dependence of Activity Coefficients
1.11 Calculation of Partial Molar Properties from Experimental Data
1.12 Liquid-Liquid Equilibria
References
Appendix 1A: Mathematics of Property Changes and the Maxwell Equations
Appendix 1B: Criteria for Equilibrium in a Closed System
2 LOW-PRESSURE VAPOR-LIQUID EQUILIBRIUM MEASUREMENTS
2.1 Introduction
2.2 Low-Pressure VLE Measurement
2.3 Semimicro Techniques
2.4 Measurement of Infinitely Dilute Activity Coefficients
2.5 Dew-Point and Bubble-Point Methods
References
Appendix 2A: Ebulliometric Limiting Activity Coefficients
3 LIQUID-LIQUID EQUILIBRIUM MEASUREMENTS
3.1 Introduction
3.2 Direct Analytical Method
3.3 Turbidimetry
3.4 Rifai and Durandet Method
References
4 GAS-LIQUID CHROMATOGRAPH DETECTOR CALIBRATION AND CHEMICAL PURITY DETERMINATION
4.1 Introduction
4.2 Response Factors
4.3 Determination of Chemical Purity
4.4 More Than Two Impurities, Multicomponent Mixtures
4.5 Detector Calibration for Gas Mixtures and Gas-Liquid Mixtures
References
Part II High-Pressure Phase Equilibrium Measurements
5 BACKGROUND TO HIGH-PRESSURE PHASE EQUILIBRIUM MEASUREMENTS
5.1 Introduction
5.2 Presentation of HPVLE Data in Phase Diagrams
5.3 Classification of Experimental HPVLE Equipment
5.4 Principal Features of HPVLE Experimental Apparatus
5.5 Challenges Encountered During HPVLE Experimentation
5.6 Conclusion
References
6 THE DYNAMIC METHOD FOR HPVLE EXPERIMENTATION
6.1 Introduction
6.2 The Single Vapor Pass Method
6.3 Phase Recirculation Methods
6.4 The Single Vapor and Liquid Pass Method
References
7 THE STATIC METHOD FOR HPVLE EXPERIMENTATION
7.1 Introduction
7.2 The Static Analytical Method
7.3 The Static Nonanalytical Method
7.4 The Static Combined Method
References
8 DEVELOPMENT AND OPERATION OF A HPVLE EXPERIMENTAL APPARATUS
8.1 Introduction
8.2 Development of a Static Experimental Apparatus
8.3 Experimental Procedure
References
9 NEW, VARIABLE-VOLUME, MULTIPHASE HPVLE CELLS WITH DYNAMIC FLOW-THROUGH SAMPLING
9.1 Introduction
9.2 Equilibrium Cell 1
9.3 Equilibrium Cell 2
References
Part III Low-Pressure Phase Equilibrium Calculations
10 COMPUTATION OF LOW-PRESSURE VAPOR-LIQUID EQUILIBRIA
10.1 Introduction
10.2Phase Equilibrium Diagrams
10.3 Vapor-Liquid Equilibria Calculations
References
Appendix 10A: Derivation of UNIQUAC Equation
11 DEW-POINT, BUBBLE-POINT, AND FLASH CALCULATIONS
11.1 Introduction
11.2 Bubble-Point and Dew-Point Calculations
11.3 Flash Calculations
References
12 PREDICTION OF LOW-PRESSURE VAPOR-LIQUID EQUILIBRIUM
12.1 Introduction
12.2 Regular Solutions and the Solubility Parameter
12.3 UNIFAC Method
12.4 Prediction of Vapor-Liquid Equilibria from Heats of Mixing
12.5 Use of Azeotropic Data
References
Appendix 12A: Values of amn for UNIFAC Method
Appendix 12B: Sample Calculation Using UNIFAC
Appendix 12C: Calculation of Vapor-Liquid Equilibriu from Heat of Mixing Data
13 LIQUID-LIQUID EQUILIBRIUM CALCULATIONS
13.1 Introduction
13.2 Calculation of γαi and γβi from Measured Eqilibrium Compositions
13.3 Calculation of Immiscibility if γi, Are Known
13.4 Estimation of Upper and Lower Consolute Temperatures
References
Part IV Computation and Thermodynamic Interpretation of High-Pressure Vapor-Liquid Equilibrium
14 TECHNIQUES FOR HPVLE DATA INTERPRETATION
14.1 Introduction
14.2 Criterion for Equilibrium
14.3 Techniques for HPVLE Data Interpretation
14.4 Critical Region Studies
14.5 Conclusion
References
15 THE DIRECT METHOD AND EQUATIONS OF STATE FOR HPVLE COMPUTATION
15.1 Introduction
15.2 Equations of State and Mixing Rules
15.3 The Statistical Mechanical n-Parameter Virial Equations of State
15.4 Complex Equations of State
15.5 Cubic Equations of State
15.6 Perturbation Theory Equations of State
References
16 THE COMBINED METHOD FOR HPVLE COMPUTATION
16.1 Introduction
16.2 The Theoretical Basis of the Combined Method
16.3 Description of the Liquid Phase in the Combined Method
16.4 Description of the Vapor Phase in the Combined Method
16.5 Challenges in Application of the Combined Method
16.6 Developments in the Combined Method
16.7 Mühlbauer and Raal Combined Method
References
17 THE MODERN DIRECT METHOD AND NOVEL EOS MIXING RULES FOR HPVLE COMPUTATION
17.1 Introduction
17.2 Proposed Classification for Mixing Rules
17.3 Extension of the van der Waals Classical Mixing Rule
17.4 Local Composition Mixing Rules
17.5 Density-Dependent Mixing Rules
17.6 Density-Dependent Local Composition Mixing Rules
17.7 Composition-Dependent Mixing Rules
17.8 Composition-Dependent Local Composition Mixing Rules
17.9 Density- and Composition-Dependent Mixing Rules
17.10 Density-Independent Mixing Rules
References
18 THERMODYNAMIC CONSISTENCY TESTING
18.1 Introduction
18.2 Low-Pressure Vapor-Liquid Equilibrium Tests
18.3 High-Pressure Vapor-Liquid Equilibrium Testing
References
Appendix 18A: Thermodynamic Consistency Test Based on Vapor-Phase Properties
INDEX
