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Chemical Thermodynamics for Process Simulation


Chemical Thermodynamics for Process Simulation


2nd Completely Revised and Enlarged Edition

von: Jürgen Gmehling, Michael Kleiber, Bärbel Kolbe, Jürgen Rarey

102,99 €

Verlag: Wiley-VCH
Format: EPUB
Veröffentl.: 09.04.2019
ISBN/EAN: 9783527809448
Sprache: englisch
Anzahl Seiten: 808

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Beschreibungen

The only textbook that applies thermodynamics to real-world process engineering problems <br> <br> This must-read for advanced students and professionals alike is the first book to demonstrate how chemical thermodynamics work in the real world by applying them to actual engineering examples. It also discusses the advantages and disadvantages of the particular models and procedures, and explains the most important models that are applied in process industry. All the topics are illustrated with examples that are closely related to practical process simulation problems. At the end of each chapter, additional calculation examples are given to enable readers to extend their comprehension. <br> <br> Chemical Thermodynamics for Process Simulation instructs on the behavior of fluids for pure fluids, describing the main types of equations of state and their abilities. It discusses the various quantities of interest in process simulation, their correlation, and prediction in detail. Chapters look at the important terms for the description of the thermodynamics of mixtures; the most important models and routes for phase equilibrium calculation; models which are applicable to a wide variety of non-electrolyte systems; membrane processes; polymer thermodynamics; enthalpy of reaction; chemical equilibria, and more. <br> <br> -Explains thermodynamic fundamentals used in process simulation with solved examples <br> -Includes new chapters about modern measurement techniques, retrograde condensation, and simultaneous description of chemical equilibrium <br> -Comprises numerous solved examples, which simplify the understanding of the often complex calculation procedures, and discusses advantages and disadvantages of models and procedures <br> -Includes estimation methods for thermophysical properties and phase equilibria thermodynamics of alternative separation processes <br> -Supplemented with MathCAD-sheets and DDBST programs for readers to reproduce the examples <br> <br> Chemical Thermodynamics for Process Simulation is an ideal resource for those working in the fields of process development, process synthesis, or process optimization, and an excellent book for students in the engineering sciences. <br>
<p>Preface xiii</p> <p>Preface to the Second Edition xvii</p> <p>List of Symbols xix</p> <p>About the Authors xxix</p> <p><b>1 Introduction </b><b>1</b></p> <p><b>2 <i>PvT</i> Behavior of Pure Components </b><b>5</b></p> <p>2.1 General Description 5</p> <p>2.2 Caloric Properties 10</p> <p>2.3 Ideal Gases 14</p> <p>2.4 Real Fluids 16</p> <p>2.4.1 Auxiliary Functions 16</p> <p>2.4.2 Residual Functions 17</p> <p>2.4.3 Fugacity and Fugacity Coefficient 19</p> <p>2.4.4 Phase Equilibria 22</p> <p>2.5 Equations of State 25</p> <p>2.5.1 Virial Equation 26</p> <p>2.5.2 High-Precision Equations of State 30</p> <p>2.5.3 Cubic Equations of State 37</p> <p>2.5.4 Generalized Equations of State and Corresponding-States Principle 42</p> <p>2.5.5 Advanced Cubic Equations of State 49</p> <p>Problems 57</p> <p>References 60</p> <p><b>3 Correlation and Estimation of Pure Component Properties </b><b>63</b></p> <p>3.1 Introduction 63</p> <p>3.2 Characteristic Physical Property Constants 63</p> <p>3.2.1 Critical Data 64</p> <p>3.2.2 Acentric Factor 69</p> <p>3.2.3 Normal Boiling Point 69</p> <p>3.2.4 Melting Point and Enthalpy of Fusion 72</p> <p>3.2.5 Standard Enthalpy and Standard Gibbs Energy of Formation 74</p> <p>3.3 Temperature-Dependent Properties 77</p> <p>3.3.1 Vapor Pressure 78</p> <p>3.3.2 Liquid Density 90</p> <p>3.3.3 Enthalpy of Vaporization 94</p> <p>3.3.4 Ideal Gas Heat Capacity 98</p> <p>3.3.5 Liquid Heat Capacity 105</p> <p>3.3.6 Speed of Sound 109</p> <p>3.4 Correlation and Estimation of Transport Properties 110</p> <p>3.4.1 Liquid Viscosity 110</p> <p>3.4.2 Vapor Viscosity 115</p> <p>3.4.3 Liquid Thermal Conductivity 120</p> <p>3.4.4 Vapor Thermal Conductivity 125</p> <p>3.4.5 Surface Tension 128</p> <p>3.4.6 Diffusion Coefficients 131</p> <p>Problems 135</p> <p>References 138</p> <p><b>4 Properties of Mixtures </b><b>143</b></p> <p>4.1 Introduction 143</p> <p>4.2 Property Changes of Mixing 144</p> <p>4.3 Partial Molar Properties 145</p> <p>4.4 Gibbs–Duhem Equation 148</p> <p>4.5 Ideal Mixture of Ideal Gases 150</p> <p>4.6 Ideal Mixture of Real Fluids 152</p> <p>4.7 Excess Properties 153</p> <p>4.8 Fugacity in Mixtures 154</p> <p>4.8.1 Fugacity of an Ideal Mixture 155</p> <p>4.8.2 Phase Equilibrium 155</p> <p>4.9 Activity and Activity Coefficient 156</p> <p>4.10 Application of Equations of State to Mixtures 157</p> <p>4.10.1 Virial Equation 158</p> <p>4.10.2 Cubic Equations of State 159</p> <p>Problems 169</p> <p>References 170</p> <p><b>5 Phase Equilibria in Fluid Systems </b><b>173</b></p> <p>5.1 Introduction 173</p> <p>5.2 Thermodynamic Fundamentals 185</p> <p>5.3 Application of Activity Coefficients 192</p> <p>5.4 Calculation of Vapor–Liquid Equilibria Using <i>g</i><sup>E </sup>Models 195</p> <p>5.5 Fitting of <i>g</i><sup>E</sup> Model Parameters 212</p> <p>5.5.1 Check of VLE Data for Thermodynamic Consistency 218</p> <p>5.5.2 Recommended <i>g</i><sup>E </sup>Model Parameters 227</p> <p>5.6 Calculation of Vapor–Liquid Equilibria Using Equations of State 229</p> <p>5.6.1 Fitting of Binary Parameters of Cubic Equations of State 235</p> <p>5.7 Conditions for the Occurrence of Azeotropic Behavior 243</p> <p>5.8 Solubility of Gases in Liquids 252</p> <p>5.8.1 Calculation of Gas Solubilities Using Henry Constants 254</p> <p>5.8.2 Calculation of Gas Solubilities Using Equations of State 262</p> <p>5.8.3 Prediction of Gas Solubilities 263</p> <p>5.9 Liquid–Liquid Equilibria 266</p> <p>5.9.1 Temperature Dependence of Ternary LLE 277</p> <p>5.9.2 Pressure Dependence of LLE 279</p> <p>5.10 Predictive Models 280</p> <p>5.10.1 Regular Solution Theory 281</p> <p>5.10.2 Group Contribution Methods 282</p> <p>5.10.3 UNIFAC Method 284</p> <p>5.10.3.1 Modified UNIFAC (Dortmund) 291</p> <p>5.10.3.2 Weaknesses of the Group Contribution Methods UNIFAC and Modified UNIFAC 295</p> <p>5.10.4 Predictive Soave–Redlich–Kwong (PSRK) Equation of State 302</p> <p>5.10.5 VTPR Group Contribution Equation of State 306</p> <p>Problems 315</p> <p>References 319</p> <p><b>6 Caloric Properties </b><b>323</b></p> <p>6.1 Caloric Equations of State 323</p> <p>6.1.1 Internal Energy and Enthalpy 323</p> <p>6.1.2 Entropy 326</p> <p>6.1.3 Helmholtz Energy and Gibbs Energy 327</p> <p>6.2 Enthalpy Description in Process Simulation Programs 329</p> <p>6.2.1 Route A: Vapor as Starting Phase 330</p> <p>6.2.2 Route B: Liquid as Starting Phase 334</p> <p>6.2.3 Route C: Equation of State 335</p> <p>6.3 Caloric Properties in Chemical Reactions 343</p> <p>Problems 349</p> <p>References 350</p> <p><b>7 Electrolyte Solutions </b><b>351</b></p> <p>7.1 Introduction 351</p> <p>7.2 Thermodynamics of Electrolyte Solutions 355</p> <p>7.3 Activity Coefficient Models for Electrolyte Solutions 360</p> <p>7.3.1 Debye–Hückel Limiting Law 360</p> <p>7.3.2 Bromley Extension 361</p> <p>7.3.3 Pitzer Model 361</p> <p>7.3.4 NRTL Electrolyte Model by Chen 364</p> <p>7.3.5 LIQUAC Model 372</p> <p>7.3.6 MSA Model 380</p> <p>7.4 Dissociation Equilibria 381</p> <p>7.5 Influence of Salts on the Vapor–Liquid Equilibrium Behavior 383</p> <p>7.6 Complex Electrolyte Systems 385</p> <p>Problems 386</p> <p>References 386</p> <p><b>8 Solid–Liquid Equilibria </b><b>389</b></p> <p>8.1 Introduction 389</p> <p>8.2 Thermodynamic Relations for the Calculation of Solid–Liquid Equilibria 392</p> <p>8.2.1 Solid–Liquid Equilibria of Simple Eutectic Systems 394</p> <p>8.2.1.1 Freezing Point Depression 401</p> <p>8.2.2 Solid–Liquid Equilibria of Systems with Solid Solutions 402</p> <p>8.2.2.1 Ideal Systems 402</p> <p>8.2.2.2 Solid–Liquid Equilibria for Nonideal Systems 403</p> <p>8.2.3 Solid–Liquid Equilibria with Intermolecular Compound Formation in the Solid State 406</p> <p>8.2.4 Pressure Dependence of Solid–Liquid Equilibria 409</p> <p>8.3 Salt Solubility 409</p> <p>8.4 Solubility of Solids in Supercritical Fluids 414</p> <p>Problems 416</p> <p>References 419</p> <p><b>9 Membrane Processes </b><b>421</b></p> <p>9.1 Osmosis 421</p> <p>9.2 Pervaporation 424</p> <p>Problems 425</p> <p>References 426</p> <p><b>10 Polymer Thermodynamics </b><b>427</b></p> <p>10.1 Introduction 427</p> <p>10.2 <i>g</i><sup>E</sup> Models 433</p> <p>10.3 Equations of State 444</p> <p>10.4 Influence of Polydispersity 460</p> <p>10.5 Influence of Polymer Structure 464</p> <p>Problems 465</p> <p>References 467</p> <p><b>11 Applications of Thermodynamics in Separation Technology </b><b>469</b></p> <p>11.1 Introduction 469</p> <p>11.2 Verification of Model Parameters Prior to Process Simulation 474</p> <p>11.2.1 Verification of Pure Component Parameters 474</p> <p>11.2.2 Verification of <i>g</i><sup>E </sup>Model Parameters 475</p> <p>11.3 Investigation of Azeotropic Points in Multicomponent Systems 483</p> <p>11.4 Residue Curves, Distillation Boundaries, and Distillation Regions 484</p> <p>11.5 Selection of Entrainers for Azeotropic and Extractive Distillation 491</p> <p>11.6 Selection of Solvents for Other Separation Processes 499</p> <p>11.7 Selection of Solvent-Based Separation Processes 499</p> <p>Problems 503</p> <p>References 504</p> <p><b>12 Enthalpy of Reaction and Chemical Equilibria </b><b>505</b></p> <p>12.1 Introduction 505</p> <p>12.2 Enthalpy of Reaction 506</p> <p>12.2.1 Temperature Dependence 507</p> <p>12.2.2 Consideration of the Real Gas Behavior on the Enthalpy of Reaction 509</p> <p>12.3 Chemical Equilibrium 511</p> <p>12.4 Multiple Chemical Reaction Equilibria 530</p> <p>12.4.1 Relaxation Method 531</p> <p>12.4.2 Gibbs Energy Minimization 535</p> <p>Problems 544</p> <p>References 547</p> <p><b>13 Examples for Complex Systems </b><b>549</b></p> <p>13.1 Introduction 549</p> <p>13.2 Formaldehyde Solutions 549</p> <p>13.3 Vapor Phase Association 555</p> <p>Problems 568</p> <p>References 570</p> <p><b>14 Practical Applications </b><b>573</b></p> <p>14.1 Introduction 573</p> <p>14.2 Flash 573</p> <p>14.3 Joule–Thomson Effect 575</p> <p>14.4 Adiabatic Compression and Expansion 577</p> <p>14.5 Pressure Relief 581</p> <p>14.6 Limitations of Equilibrium Thermodynamics 586</p> <p>Problems 589</p> <p>References 591</p> <p><b>15 Experimental Determination of Pure Component and Mixture Properties </b><b>593</b></p> <p>15.1 Introduction 593</p> <p>15.2 Pure Component Vapor Pressure and Boiling Temperature 594</p> <p>15.3 Enthalpy of Vaporization 598</p> <p>15.4 Critical Data 599</p> <p>15.5 Vapor–Liquid Equilibria 599</p> <p>15.5.1 Dynamic VLE Stills 601</p> <p>15.5.2 Static Techniques 604</p> <p>15.5.3 Degassing 611</p> <p>15.5.4 Headspace Gas Chromatography (HSGC) 613</p> <p>15.5.5 High-Pressure VLE 614</p> <p>15.5.6 Inline True Component Analysis in Reactive Mixtures 616</p> <p>15.6 Activity Coefficients at Infinite Dilution 617</p> <p>15.6.1 Gas Chromatographic Retention Time Measurement 618</p> <p>15.6.2 Inert Gas Stripping (Dilutor) 620</p> <p>15.6.3 Limiting Activity Coefficients of High Boilers in Low Boilers 622</p> <p>15.7 Liquid–Liquid Equilibria (LLE) 622</p> <p>15.8 Gas Solubility 623</p> <p>15.9 Excess Enthalpy 624</p> <p>Problems 626</p> <p>References 626</p> <p><b>16 Introduction to the Collection of Example Problems </b><b>631</b></p> <p>16.1 Introduction 631</p> <p>16.2 Mathcad Examples 631</p> <p>16.3 Examples Using the Dortmund Data Bank (DDB) and the Integrated Software Package DDBSP 633</p> <p>16.4 Examples Using Microsoft Excel and Microsoft Office VBA 634</p> <p><b>Appendix A Pure Component Parameters </b><b>635</b></p> <p><b>Appendix B Coefficients for High-Precision Equations of State </b><b>663</b></p> <p>References 668</p> <p><b>Appendix C Useful Derivations </b><b>669</b></p> <p>A1 Relationship Between (𝜕s/𝜕T)<sub>P </sub>and (𝜕s/𝜕T)<sub>v</sub> 670</p> <p>A2 Expressions for (𝜕u/𝜕v)<sub>T</sub> and (𝜕s/𝜕v)<sub>T</sub> 670</p> <p>A3 c<sub>P</sub> and c<sub>v</sub> as Derivatives of the Specific Entropy 671</p> <p>A4 Relationship Between c<sub>P</sub> and c<sub>v</sub> 672</p> <p>A5 Expression for (𝜕h/𝜕P)<sub>T</sub> 673</p> <p>A6 Expression for (𝜕s/𝜕P)<sub>T</sub> 674</p> <p>A7 Expression for [𝜕(g/RT)/𝜕T]<sub>P </sub>and van’t Hoff Equation 674</p> <p>A8 General Expression for c<sub>v</sub> 675</p> <p>A9 Expression for (𝜕P/𝜕v)<sub>T</sub> 676</p> <p>A10 Cardano’s Formula 676</p> <p>B1 Derivation of the Kelvin Equation 677</p> <p>B2 Equivalence of Chemical Potential μ and Gibbs Energy g for a Pure Substance 678</p> <p>B3 Phase Equilibrium Condition for a Pure Substance 679</p> <p>B4 Relationship Between Partial Molar Property and State Variable (Euler Theorem) 681</p> <p>B5 Chemical Potential in Mixtures 681</p> <p>B6 Relationship Between Second Virial Coefficients of Leiden and Berlin Form 682</p> <p>B7 Derivation of Expressions for the Speed of Sound for Ideal and Real Gases 683</p> <p>B8 Activity of the Solvent in an Electrolyte Solution 685</p> <p>B9 Temperature Dependence of the Azeotropic Composition 686</p> <p>B10 Konovalov Equations 688</p> <p>C1 (s–s<sup>id</sup>)<sub>T,P</sub> 691</p> <p>C2 (h–h<sup>id</sup>)<sub>T,P</sub> 692</p> <p>C3 (g–g<sup>id</sup>)<sub>T,P</sub> 692</p> <p>C4 Relationship Between Excess Enthalpy and Activity Coefficient 692</p> <p>D1 Fugacity Coefficient for a Pressure-Explicit Equation of State 692</p> <p>D2 Fugacity Coefficient of the Virial Equation (Leiden Form) 694</p> <p>D3 Fugacity Coefficient of the Virial Equation (Berlin Form) 695</p> <p>D4 Fugacity Coefficient of the Soave–Redlich–Kwong Equation of State 696</p> <p>D5 Fugacity Coefficient of the PSRK Equation of State 698</p> <p>D6 Fugacity Coefficient of the VTPR Equation of State 702</p> <p>E1 Derivation of the Wilson Equation 707</p> <p>E2 Notation of the Wilson, NRTL, and UNIQUAC Equations in Process Simulation Programs 710</p> <p>E3 Inability of the Wilson Equation to Describe a Miscibility Gap 711</p> <p>F1 (h–h<sup>id</sup>) for Soave–Redlich–Kwong Equation of State 713</p> <p>F2 (s–s<sup>id</sup>) for Soave–Redlich–Kwong Equation of State 715</p> <p>F3 (g–g<sup>id</sup>) for Soave–Redlich–Kwong Equation of State 715</p> <p>F4 Antiderivatives of c<sup>id</sup><sub> P</sub> Correlations 715</p> <p>G1 Speed of Sound as Maximum Velocity in an Adiabatic Pipe with Constant Cross-Flow Area 717</p> <p>G2 Maximum Mass Flux of an Ideal Gas 717</p> <p>References 719</p> <p><b>Appendix D Standard Thermodynamic Properties for Selected Electrolyte Compounds </b><b>721</b></p> <p>Reference 722</p> <p><b>Appendix E Regression Technique for Pure Component Data </b><b>723</b></p> <p><b>Appendix F Regression Techniques for Binary Parameters </b><b>727</b></p> <p>References 741</p> <p><b>Appendix G Ideal Gas Heat Capacity Polynomial Coefficients for Selected Compounds </b><b>743</b></p> <p>Reference 744</p> <p><b>Appendix H UNIFAC Parameters </b><b>745</b></p> <p>Further Reading 746</p> <p><b>Appendix I Modified UNIFAC Parameters </b><b>747</b></p> <p>Further Reading 751</p> <p><b>Appendix J PSRK Parameters </b><b>753</b></p> <p>Further Reading 755</p> <p><b>Appendix K VTPR Parameters </b><b>757</b></p> <p>References 759</p> <p>Further Readings 760</p> <p>Index 761</p>
Jurgen Gmehling, PhD, is Professor of Chemical Engineering at the University of Oldenburg, Germany. He is also president and CEO of DDBST GmbH, Oldenburg, as well as cofounder of LTP GmbH, part of the Carl von Ossietzky University of Oldenburg. <br> <br> Michael Kleiber, PhD, works as a Chief Development Engineer for ThyssenKrupp Uhde, Germany. <br> <br> Barbel Kolbe, PhD, is a senior process engineer for ThyssenKrupp Uhde, Germany. <br> <br> <br> Jurgen Rarey, PhD, is a professor at the University of Oldenburg, Germany, and cofounded DDBST GmbH, Oldenburg. He is also an honorary professor in Durban, South Africa. <br>

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