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Acknowledgement
About the Authors
Preface
Abbreviations and Symbols
Introduction
1 Thermodynamics for Process and Product Design
References
Appendix 1 A
Appendix 1B
2 Intermolecular Forces and Thermodynamic Models
2.1 General
2.2 Coulombic and van der Waals forces
2.3 Quasi-chemical forces with emphasis on hydrogen bonding
2.4 Some applications of intermolecular forces in model development
2.5 Concluding remarks
References
Part A: The Classical Models
3 Cubic Equations of state – The classical mixing rules
3.1 General
3.2 On the parameter estimation
3.3 Analysis of the advantages and shortcomings of cubic EoS
3.4 Some recent developments with cubic EoS
3.5 Concluding remarks
References
Appendix 3A
Appendix 3B
4. Activity coefficient models. Part 1. Random-mixing based models 4.1 Introduction to the random-mixing models
4.2 Experimental activity coefficients
4.3 The Margules equation
4.4 From the van der Waals to van Laar and to the Regular Solution Theory
4.5 Applications of the Regular Solution Theory
4.6 Solid-Liquid Equilibria with emphasis on Wax formation
4.7 Asphaltene precipitation
4.8 Concluding Remarks about the random-based models – In two words
References
Appendix 4A
Appendix 4B
Appendix 4C
5. Activity Coefficient Models. Part 2. Local-composition models: From Wilson and NRTL to UNIQUAC and UNIFAC
5.1 General
5.2 Overview of the local composition models
5.3 The theoretical limitations
5.4 Range of applicability of the LC models
5.5 On the theoretical significance of the interaction parameters
5.6 Local-composition models – some unifying concepts
5.7 The group-contribution principle and UNIFAC
5.8 Local composition – Free Volume models for polymers
5.9 Conclusions. Is UNIQUAC the best local composition model available today?
References
Appendix 5A
Appendix 5B
Appendix 5C
6. The EoS/GE mixing rules for cubic equations of state
6.1 General
6.2 The infinite pressure limit (the Huron-Vidal mixing rule)
6.3 The zero-reference pressure limit (The Michelsen approach)
6.4 Successes and limitations of zero reference pressure models
6.5 The Wong-Sandler (WS) mixing rule
6.6 EoS/GE approaches suitable for asymmetric mixtures
6.7 Applications of the LCVM, MHV2, PSRK and WS mixing rules
6.8 Cubic Equations of State for polymers
6.9 Conclusions.Achievements and Limitations of the EoS/GE models
6.10 Recommended models – so far
References
Appendix 6A
Part B: Advanced Models and their Applications
7. Association theories and models – and the role of spectroscopy
7.1 Introduction
7.2 Three different association theories
7.3 The Chemical and Perturbation Theories
7.4 Spectroscopy and Association theories
7.5 Concluding remarks
References
Appendix 7A
Appendix 7B
8. The Statistical Associating Fluid Theory (SAFT)
8.1 The SAFT EoS – history and major developments, a fast look
8.2 The SAFT equations
8.3 Parameterization of SAFT
8.4 Applications of SAFT to non-polar molecules
8.5 Group-contribution (GC) SAFT approaches
8.6 Concluding remarks
References
Appendix 8A
Appendix 8B
9. The Cubic-Plus-Association (CPA) equation of state
9.1 Introduction
9.2 The CPA Equation of State
9.3 Parameter estimation – Pure compounds
9.4 The first applications
9.5 Conclusions
References
Appendix 9A
Appendix 9B
Appendix 9C
Appendix 9D
10. Applications of CPA to the oil and gas industry
10.1 General
10.2 Glycol – water – hydrocarbon phase equilibria
10.3 Gas hydrates
10.4 Gas phase water content calculations
10.5 Mixtures with acid gases CO2 and H2S
10.6 Reservoir fluids
10.7 Conclusions
References
11. Applications of CPA to chemical industries
11.1 Introduction
11.2 Aqueous mixtures with heavy alcohols
11.3 Amines and Ketones
11.4 Mixtures with organic acids
11.5 Mixtures with ethers and esters
11.6 Multifunctional chemicals – glycolethers and alkanolamines
11.7 Complex aqueous mixtures
11.8 Concluding remarks
References
Appendix 11A
12. Extension of CPA and SAFT to new systems: Worked out examples
and guidelines
12.1 Introduction
12.2 The case of sulfolane – CPA application
12.3 Application of sPC-SAFT to sulfolane related systems
12.4 Applicability of association theories and cubic EoS with advanced mixing rules (EoS/GEmodels) to polar chemicals
12.5 Phenols
12.6 Conclusions
References
13. Applications of SAFT to polar and associating mixtures
13.1 Introduction
13.2 Water-hydrocarbons
13.3 Alcohols, amines and alkanolamines
13.4 Glycols
13.5 Organic Acids
13.6 Polar non-associating compounds
13.7 Flow assurance (asphaltenes and gas hydrate inhibitors)
13.8 Concluding Remarks
References
14. Applications of SAFT to polymers
14.1 Overview
14.2 Estimation of parameters for polymers for SAFT-type equations of state
14.3 Low pressure phase equilibria (VLE and LLE) using simplified
PC-SAFT
14.4 High pressure phase equilibria
14.5 Co-polymers
14.6 Concluding remarks
References
Appendix 14A
Appendix 14B
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