Phase Equilibria and Fluid Properties in the Chemical Industry. Estimation and Correlation

Title Page
......Page 1
Copyright......Page 2
ACS Symposium Series......Page 3
FOREWORD......Page 4
DEDICATION......Page 5
PdftkEmptyString......Page 0
PREFACE......Page 6
Acknowledgments......Page 8
1 Origin of the Acentric Factor......Page 9
Literature Cited......Page 17
2 State-of-the-Art Review of Phase Equilibria......Page 19
Thermodynamics: Not Magic but a Tool......Page 20
Equations of State for Both Fluid Phases......Page 24
Vapor-Phase Fugacity Coefficients......Page 35
Liquid-Phase Activity Coefficients......Page 43
Local Composition to Describe Nonrandomness......Page 47
Group-Contributions for Activity Coefficients......Page 54
Chemical Theory for Activity Coefficients......Page 57
Supercritical Components in the Liquid Phase......Page 58
Aqueous Solutions of Weak Volatile Electrolytes......Page 59
Conclusion......Page 63
Literature Cited......Page 68
3 Industrial View of the State-of-the-Art in Phase Equilibria......Page 70
HOW Are Phase Equilibria Problems Treated?......Page 72
WHAT Models Are Used And WHY?......Page 77
WHERE Should Future Development Work Be Directed?......Page 90
Nomenclature......Page 92
B. Equations of State......Page 93
E. Enthalpy......Page 94
4 Measurement of Vapor-Liquid Equilibrium......Page 95
Thermodynamic Considerations......Page 96
Isothermal vs. Isobaric Data......Page 97
Direct vs. Indirect Determination of Vapor Compositions......Page 98
Extension of Isothermal VLE Data with Temperature......Page 100
Measurement of Low-Pressure VLE Data......Page 101
Conclusions and Remarks......Page 104
Notation......Page 105
Literature Cited......Page 106
5 Equilibria in Aqueous Electrolyte Systems at High Temperatures and Pressures......Page 107
Critical Curves and Miscibility......Page 109
Dielectric Behavior......Page 114
Ionization and Complex Formation......Page 117
Conclusion......Page 121
References......Page 124
General Principles......Page 126
Single Component, Two Phase Systems Solid/Solid Equilibria in Crystalline Polymers......Page 127
The Glass/Rubbery State "Equilibrium"......Page 131
The Rubbery State/Liquid Equilibrium......Page 132
Polymer Melt/Monomer Liquid(s)......Page 134
Adsorption Equilibria......Page 143
Conclusions......Page 145
Literature Cited......Page 147
Discussion......Page 149
Characteristics of Equations of State Required by Industry......Page 158
Equations of State Adopted by Industry......Page 164
Soave Equation......Page 170
Practical Applications......Page 180
Summary......Page 202
Nomenclature......Page 204
References......Page 205
8 Applications of the Peng-Robinson Equation of State......Page 208
The Peng-Robinson Equation......Page 209
Applications......Page 211
Nomenclature......Page 224
Literature Cited......Page 227
9 Application of Equations of State in Exxon's Production Operations......Page 229
Literature Cited......Page 231
Discussion......Page 232
Conclusions......Page 235
Acknowledgment......Page 238
I. Correlation of Fluid Properties with Analytic ES......Page 239
II. Non-Analytic ES......Page 241
Literature Cited......Page 242
Desired Characteristics of an EOS for VLE Calculations......Page 244
Characterization of Heavy Hydrocarbons (NBP>200F)......Page 246
Literature Cited......Page 248
Displacement Mechanisms in CO2--Reservoir Oil Systems......Page 249
Phase and Flow Behavior Characteristics of CO2--Reservoir Oil Systems......Page 252
Calculations......Page 258
Literature Cited......Page 261
14 A Computer Model for Calculating Physical and Thermodynamic Properties of Synthetic Gas Process Streams......Page 264
Possibilities for New Prediction Methods......Page 266
A New Modified Van der Waals Equation for Both Polar and Non-Polar Compounds and Their Mixtures......Page 267
Nomenclature......Page 289
Appendix......Page 292
Literature Cited......Page 296
Scope......Page 297
Design Basis and Process Description......Page 300
Effects of K-Value Predictions......Page 303
Effects of Thermophysical Property Correlations for Enthalpy and Entropy......Page 305
Conclusions......Page 311
Literature Cited......Page 315
Discussion......Page 317
References......Page 321
16 Prediction of Thermodynamic Properties......Page 324
The Virial Expansion......Page 325
Intermolecular Forces......Page 326
Liquid and Dense Gas Mixtures......Page 327
Advantages and Disadvantages of the Principle of Corresponding States as a Method of Prediction......Page 334
Literature Cited......Page 336
Formal Theory......Page 338
Comparison with Experiment for the Dilute Gas......Page 341
Corresponding States......Page 344
Modification of the Transport Expressions......Page 346
Comparisons with Experimental Data Mixtures......Page 348
Literature Cited......Page 351
18 Polar and Quadrupolar Fluid Mixtures......Page 352
Intermolecular Forces......Page 353
Theory......Page 354
Results......Page 357
References......Page 373
Discussion......Page 375
19 Criteria of Criticality......Page 377
Development of the General Criticality Criteria......Page 379
Alternate Criteria in the U-Representation......Page 384
Alternate Criteria in Other Potential Functions......Page 386
Criteria in Gibbs Free Energy......Page 393
Concluding Remarks......Page 395
Literature Cited......Page 396
What are the Synthetic Fuels?......Page 398
How are Synthetic Fuels Made?......Page 401
New Gasification Processes......Page 414
Shale Oil......Page 417
What are the Data Needs?......Page 421
How Good Do the Data Need to Be?......Page 423
When Are the Data Needed?......Page 424
Literature Cited......Page 425
Discussion......Page 426
References......Page 428
21 A Group Contribution Molecular Model for Liquids and Solutions Composed of the Groups CH3, CH2, OH,and CO......Page 429
Abstract......Page 431
Literature Cited......Page 436