Physical and Chemical Equilibrium for Chemical Engineers

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  • Edition: 2nd
  • Format: Hardcover
  • Copyright: 2012-03-20
  • Publisher: Wiley
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Supplemental Materials

What is included with this book?


Using the simplest mathematics, this resource accurately and rigorously covers physical and chemical equilibrium in depth. The second edition continues to cover topics found in the first edition, with numerous updates including: changes in naming and notation (this edition uses the more popular Gibbs Energy and Partial Molar Properties), changes in symbols (this edition only uses popular notation), as well as adding entirely new problems. Finally, the second edition includes an appendix about the Bridgman table and its use.

Author Biography

NOEL de NEVERS, PhD, followed five years of working for Chevron with thirty-seven years as a Professor in the Chemical Engineering Department of the University of Utah. His textbooks (and research papers) are in fluid mechanics, thermodynamics, and air pollution control engineering. He regularly consults as an expert on explosions, fires, and toxic exposures.
In addition to technical work, he has three "de Nevers's Laws" in a Murphy's Laws compilation and won the title "Poet Laureate of Jell-O Salad" in a Salt Lake City competition, with three limericks and a quatrain. He has climbed the Grand Teton, Mt. Rainier, Mt. Whitney, Kala Pattar, and Mt. Kilimanjaro, and is the official discoverer of Private Arch in Arches National Park.

Table of Contents

Prefacep. xiii
About the Authorp. xv
Nomenclaturep. xvii
Introduction to Equilibriump. 1
Why Study Equilibrium?p. 1
Stability and Equilibriump. 4
Time Scales and the Approach to Equilibriump. 5
Looking Ahead, Gibbs Energyp. 5
Units, Conversion Factors, and Notationp. 6
Reality and Equationsp. 8
Phases and Phase Diagramsp. 8
The Plan of this Bookp. 10
Summaryp. 10
Referencesp. 11
Basic Thermodynamicsp. 13
Conservation and Accountingp. 13
Conservation of Massp. 14
Conservation of Energy; the First Law of Thermodynamicsp. 15
The Second Law of Thermodynamicsp. 17
Reversibilityp. 17
Entropyp. 18
Convenience Propertiesp. 19
Using the First and Second Lawsp. 19
Datums and Reference Statesp. 21
Measurable and Immeasurable Propertiesp. 22
Work and Heatp. 22
The Property Equationp. 23
Equations of State (EOS)p. 24
EOSs Based on Theoryp. 25
EOSs Based on Pure Data Fittingp. 25
Corresponding Statesp. 26
Departure Functionsp. 28
The Properties of Mixturesp. 28
The Combined First and Second Law Statement; Reversible Workp. 29
Summaryp. 31
Referencesp. 33
The Simplest Phase Equilibrium Examples and Some Simple Estimating Rulesp. 35
Some General Statements About Equilibriump. 35
The Simplest Example of Phase Equilibriump. 37
A Digression, the Distinction between Vapor and Gasp. 37
Back to the Simplest Equilibriump. 37
The Next Level of Complexity in Phase Equilibriump. 37
Some Simple Estimating Rules: RaoultâÇÖs and HenryâÇÖs âÇ£LawsâÇ p. 39
The General Two-Phase Equilibrium Calculationp. 43
Some Simple Applications of RaoultâÇÖs and HenryâÇÖs Lawsp. 43
The Uses and Limits of RaoultâÇÖs and HenryâÇÖs Lawsp. 46
Summaryp. 46
Referencesp. 48
Minimization of Gibbs Energyp. 49
The Fundamental Thermodynamic Criterion of Phase and Chemical Equilibriump. 49
The Criterion of Equilibrium Applied to Two Nonreacting Equilibrium Phasesp. 51
The Criterion of Equilibrium Applied to Chemical Reactionsp. 53
Simple Gibbs Energy Diagramsp. 54
Comparison with Enthalpy and Entropyp. 55
Gibbs Energy Diagrams for Pressure-Driven Phase Changesp. 55
Gibbs Energy Diagrams for Chemical Reactionsp. 57
Le ChatelierâÇÖs Principlep. 58
Summaryp. 58
Referencesp. 60
Vapor Pressure, the Clapeyron Equation, and Single Pure Chemical Species Phase Equilibriump. 61
Measurement of Vapor Pressurep. 61
Reporting Vapor-Pressure Datap. 61
Normal Boiling Point (NBP)p. 61
The Clapeyron Equationp. 62
The ClausiusâÇôClapeyron Equationp. 63
The Accentric Factorp. 64
The Antoine Equation and Other Data-Fitting Equationsp. 66
Choosing a Vapor-Pressure Equationp. 67
Applying the Clapeyron Equation to Other Kinds of Equilibriump. 67
Extrapolating Vapor-Pressure Curvesp. 68
Vapor Pressure of Solidsp. 69
Vapor Pressures of Mixturesp. 69
Summaryp. 69
Referencesp. 72
Partial Molar Propertiesp. 73
Partial Molar Propertiesp. 73
The Partial Molar Equationp. 74
Tangent Slopesp. 74
Tangent Interceptsp. 77
The Two Equations for Partial Molar Propertiesp. 78
Using the Idea of Tangent Interceptsp. 79
Partial Mass Propertiesp. 80
Heats of Mixing and Partial Molar Enthalpiesp. 80
Differential Heat of Mixingp. 80
Integral Heat of Mixingp. 81
The GibbsâÇôDuhem Equation and the Counterintuitive Behavior of the Chemical Potentialp. 82
Summaryp. 84
Referencesp. 87
Fugacity, Ideal Solutions, Activity, Activity Coefficientp. 89
Why Fugacity?p. 89
Fugacity Definedp. 89
The Use of the Fugacityp. 90
Pure Substance Fugacitiesp. 90
The Fugacity of Pure Gasesp. 91
The Fugacity of Pure Liquids and Solidsp. 94
Fugacities of Species in Mixturesp. 95
Mixtures of Ideal Gasesp. 95
Why Ideal Solutions?p. 95
Ideal Solutions Definedp. 96
The Consequences of the Ideal Solution Definitionp. 96
Why Activity and Activity Coefficients?p. 98
Activity and Activity Coefficients Definedp. 98
Fugacity Coefficient for Pure Gases and Gas Mixturesp. 100
Estimating Fugacities of Individual Species in Gas Mixturesp. 100
Fugacities from Gas PvT Datap. 100
Fugacities from an EOS for Gas Mixturesp. 102
The Lewis and Randall (L-R) Fugacity Rulep. 102
Other Mixing Rulesp. 103
Liquid Fugacities from Vapor-Liquid Equilibriump. 104
Summaryp. 104
Referencesp. 105
VaporâÇôLiquid Equilibrium (VLE) at Low Pressuresp. 107
Measurement of VLEp. 107
Presenting Experimental VLE Datap. 110
The Mathematical Treatment of Low-Pressure VLE Datap. 110
RaoultâÇÖs Law Againp. 111
The Four Most Common Types of Low-Pressure VLEp. 112
Ideal Solution Behavior (Type I)p. 114
Positive Deviations from Ideal Solution Behavior (Type II)p. 114
Negative Deviations from Ideal Solution Behavior (Type III)p. 115
Azeotropesp. 117
Two-Liquid Phase or Heteroazeotropes (Type IV)p. 118
Zero Solubility and Steam Distillationp. 120
Distillation of the Four Types of Behaviorp. 121
GasâÇôLiquid Equilibrium, HenryâÇÖs Law Againp. 122
The Effect of Modest Pressures on VLEp. 122
Liquidsp. 123
Gases, the L-R Rulep. 123
Standard States Againp. 124
Low-Pressure VLE Calculationsp. 125
Bubble-Point Calculationsp. 127
Temperature-Specified Bubble Pointp. 127
Pressure-Specified Bubble Pointp. 128
Dew-Point Calculationsp. 129
Temperature-Specified Dew Pointp. 129
Pressure-Specified Dew Pointp. 129
Isothermal Flashes (T- and P-Specified Flashes)p. 130
Adiabatic Flashesp. 131
Traditional K-Factor Methodsp. 132
More Uses for RaoultâÇÖs Lawp. 132
Nonvolatile Solutes, Boiling-Point Elevationp. 132
Freezing-Point Depressionp. 135
Colligative Properties of Solutionsp. 136
Summaryp. 136
Referencesp. 143
Correlating and Predicting Nonideal VLEp. 145
The Most Common Observations of Liquid-Phase Activity Coefficientsp. 145
Why Nonideal Behavior?p. 145
The Shapes of ln, gx Curvesp. 146
Limits on Activity Coefficient Correlations, the GibbsâÇôDuhem Equationp. 147
Excess Gibbs Energy and Activity Coefficient Equationsp. 148
Activity Coefficients at Infinite Dilutionp. 150
Effects of Pressure and Temperature on Liquid-Phase Activity Coefficientsp. 151
Effect of Pressure Changes on Liquid-Phase Activity Coefficientsp. 151
Effect of Temperature Changes on Liquid-Phase Activity Coefficientsp. 152
Ternary and Multispecies VLEp. 153
Liquid-Phase Activity Coefficients for Ternary Mixturesp. 154
Vapor-Phase Nonidealityp. 155
VLE from EOSp. 158
Solubility Parameterp. 158
The Solubility of Gases in Liquids, HenryâÇÖs Law Againp. 160
Summaryp. 163
Referencesp. 167
VaporâÇôLiquid Equilibrium (VLE) at High Pressuresp. 169
Critical Phenomena of Pure Speciesp. 169
Critical Phenomena of Mixturesp. 170
Estimating High-Pressure VLEp. 174
Empirical K-Value Correlationsp. 175
Estimation Methods for Each Phase Separately, Not Based on RaoultâÇÖs Lawp. 175
Estimation Methods Based on Cubic EOSsp. 176
Computer Solutionsp. 178
Summaryp. 178
Referencesp. 179
LiquidâÇôLiquid, LiquidâÇôSolid, and GasâÇôSolid Equilibriump. 181
LiquidâÇôLiquid Equilibrium (LLE)p. 181
The Experimental Determination of LLEp. 181
Reporting and Presenting LLE Datap. 182
Practically Insoluble Liquid Pairs at 25Cp. 183
Partially Soluble Liquid Pairs at 25Cp. 183
Miscible Liquid Pairs at 25Cp. 183
Ternary LLE at 25Cp. 184
LLE at Temperatures Other Than 25Cp. 186
The Elementary Theory of LLEp. 187
The Effect of Pressure on LLEp. 190
Effect of Temperature on LLEp. 191
Distribution Coefficientsp. 194
LiquidâÇôSolid Equilibrium (LSE)p. 195
One-Species LSEp. 195
The Experimental Determination of LSEp. 195
Presenting LSE Datap. 195
Eutecticsp. 197
Gas Hydrates (Clathrates)p. 199
The Elementary Thermodynamics of LSEp. 200
GasâÇôSolid Equilibrium (GSE) at Low Pressuresp. 202
GSE at High Pressuresp. 203
GasâÇôSolid Adsorption, VaporâÇôSolid Adsorptionp. 204
LangmuirâÇÖs Adsorption Theoryp. 205
Vapor-solid Adsorption, BET Theoryp. 207
Adsorption from Mixturesp. 208
Heat of Adsorptionp. 209
Hysteresisp. 210
Summaryp. 211
Referencesp. 215
Chemical Equilibriump. 217
Introduction to Chemical Reactions and Chemical Equilibriump. 217
Formal Description of Chemical Reactionsp. 217
Minimizing Gibbs Energyp. 218
Reaction Rates, Energy Barriers, Catalysis, and Equilibriump. 219
The Basic Thermodynamics of Chemical Reactions and Its Convenient Formulationsp. 220
The Law of Mass Action and Equilibrium Constantsp. 222
Calculating Equilibrium Constants from Gibbs Energy Tables and then Using Equilibrium Constants to Calculate Equilibrium Concentrationsp. 223
Change of Reactant Concentration, Reaction Coordinatep. 224
Reversible and Irreversible Reactionsp. 227
More on Standard Statesp. 227
The Effect of Temperature on Chemical Reaction Equilibriump. 229
The Effect of Pressure on Chemical Reaction Equilibriump. 234
Ideal Solution of Ideal Gasesp. 235
Nonideal Solution, Nonideal Gasesp. 236
Liquids and Solidsp. 237
The Effect of Nonideal Solution Behaviorp. 238
Liquid-Phase Nonidealityp. 238
Other Forms of Kp. 238
Summaryp. 239
Referencesp. 242
Equilibrium in Complex Chemical Reactionsp. 243
Reactions Involving Ionsp. 243
Multiple Reactionsp. 244
Sequential Reactionsp. 244
Simultaneous Reactionsp. 245
The Charge Balance Calculation Method and Buffersp. 246
Reactions with More Than One Phasep. 249
Solubility Productp. 249
Gas-Liquid Reactionsp. 249
Electrochemical Reactionsp. 252
Chemical and Physical Equilibrium in Two Phasesp. 255
Dimerization (Association)p. 255
Summaryp. 257
Referencesp. 262
Equilibrium with Gravity or Centrifugal Force, Osmotic Equilibrium, Equilibrium with Surface Tensionp. 265
Equilibrium with Other Forms of Energyp. 265
Equilibrium in the Presence of Gravityp. 266
Centrifugesp. 268
Semipermeable Membranesp. 269
Osmotic Pressurep. 270
Small is Interesting! Equilibrium with Surface Tensionp. 271
Bubbles, Drops and Nucleationp. 271
Capillary Condensationp. 275
Summaryp. 275
Referencesp. 278
The Phase Rulep. 279
How Many Phases Can Coexist in a Given Equilibrium Situation?p. 279
What Does the Phase Rule Tell Us? What Does It Not Tell Us?p. 280
What is a Phase?p. 280
The Phase Rule is Simply Counting Variablesp. 281
More On Componentsp. 282
A Formal Way to Find the Number of Independent Equationsp. 285
The Phase Rule for One- and Two-Component Systemsp. 285
Harder Phase Rule Problemsp. 288
Summaryp. 288
Referencesp. 291
Equilibrium in Biochemical Reactionsp. 293
An Example, the Production of Ethanol from Sugarp. 293
Organic and Biochemical Reactionsp. 293
Two More Sweet Examplesp. 294
Thermochemical Data for Biochemical Reactionsp. 295
Thermodynamic Equilibrium in Large Scale Biochemistryp. 296
Translating between Biochemical and Chemical Engineering Equilibrium Expressionsp. 296
Chemical and Biochemical Equationsp. 297
Equilibrium Constantsp. 297
pH and Buffersp. 298
Ionic Strengthp. 298
Equilibrium in Biochemical Separationsp. 298
Summaryp. 299
Referencesp. 300
Useful Tables and Chartsp. 303
Useful Property Data for Corresponding States Estimatesp. 303
Vapor-Pressure Equation Constantsp. 305
HenryâÇÖs Law Constantsp. 306
Compressibility Factor Chart (z Chart)p. 307
Fugacity Coefficient Chartsp. 307
Azeotropesp. 308
Van Laar Equation Constantsp. 312
Enthalpies and Gibbs Energies of Formation from the Elements in the Standard States, at T ¼ 298.15 K ¼ 25C, and P ¼ 1.00 barp. 313
Heat Capacities of Gases in the Ideal Gas Statep. 317
Equilibrium with other Restraints, Other Approaches to Equilibriump. 319
The Mathematics of Fugacity, Ideal Solutions, Activity and Activity Coefficientsp. 323
The Fugacity of Pure Substancesp. 323
Fugacities of Components of Mixturesp. 324
The Consequences of the Ideal Solution Definitionp. 326
The Mathematics of Activity Coefficientsp. 326
Equations of State for Liquids and Solids Well Below their Critical Temperaturesp. 329
The Taylor Series EOS and Its Short Formp. 329
Effect of Temperature on Densityp. 330
Effect of Pressure on Densityp. 331
Summaryp. 332
Referencesp. 333
Gibbs Energy of Formation Valuesp. 335
Values âÇ£From the ElementsâÇ p. 335
Changes in Enthalpy, Entropy, and Gibbs Energyp. 335
Enthalpy Changesp. 335
Entropy Changesp. 336
Ionsp. 337
Presenting these Datap. 337
Referencesp. 337
Calculation of Fugacities from Pressure-Explicit EOSsp. 339
Pressure-Explicit and Volume-Explicit EOSsp. 339
f /P of Pure Species Based on Pressure-Explicit EOSsp. 339
Cubic Equations of Statep. 340
fi /Pyi for Individual Species in Mixtures, Based on Pressure-Explicit EOSsp. 342
Mixing Rules for Cubic EOSsp. 343
VLE Calculations with a Cubic EOSp. 344
Summaryp. 345
Referencesp. 346
Thermodynamic Property Derivatives and the Bridgman Tablep. 347
Referencesp. 350
Answers to Selected Problemsp. 351
Indexp. 353
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