Noel de Nevers

Physical & Chemical Equil, 2e

• Gebundenes Buch

Produktbeschreibung

This book concentrates on the topic of physical and chemical equilibrium. Using the simplest mathematics along with numerous numerical examples it accurately and rigorously covers physical and chemical equilibrium in depth and detail. It continues to cover the topics found in the first edition however numerous updates have been made including: Changes in naming and notation (the first edition used the traditional names for the Gibbs Free Energy and for Partial Molal Properties, this edition uses the more popular Gibbs Energy and Partial Molar Properties,) changes in symbols (the first edition used the Lewis-Randal fugacity rule and the popular symbol for the same quantity, this edition only uses the popular notation,) and new problems have been added to the text. Finally the second edition includes an appendix about the Bridgman table and its use.

Produktdetails

• Verlag: Wiley & Sons
• 2. Aufl.
• Seitenzahl: 384
• Erscheinungstermin: 20. März 2012
• Englisch
• Abmessung: 286mm x 221mm x 25mm
• Gewicht: 1078g
• ISBN-13: 9780470927106
• ISBN-10: 0470927100
• Artikelnr.: 34437822

Autorenporträt

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.

Inhaltsangabe

Preface xiii About the Author xv Nomenclature xvii 1 Introduction to Equilibrium 1 1.1 Why Study Equilibrium?
1 1.2 Stability and Equilibrium
4 1.3 Time Scales and the Approach to Equilibrium
5 1.4 Looking Ahead
Gibbs Energy
5 1.5 Units
Conversion Factors
and Notation
6 1.6 Reality and Equations
8 1.7 Phases and Phase Diagrams
8 1.8 The Plan of this Book
10 1.9 Summary
10 References
11 2 Basic Thermodynamics 13 2.1 Conservation and Accounting
13 2.2 Conservation of Mass
14 2.3 Conservation of Energy; the First Law of Thermodynamics
15 2.4 The Second Law of Thermodynamics
17 2.5 Convenience Properties
19 2.6 Using the First and Second Laws
19 2.7 Datums and Reference States
21 2.8 Measurable and Immeasurable Properties
22 2.9 Work and Heat
22 2.10 The Property Equation
23 2.11 Equations of State (EOS)
24 2.12 Corresponding States
26 2.13 Departure Functions
28 2.14 The Properties of Mixtures
28 2.15 The Combined First and Second Law Statement; Reversible Work
29 2.16 Summary
31 References
33 3 The Simplest Phase Equilibrium Examples and Some Simple Estimating Rules 35 3.1 Some General Statements About Equilibrium
35 3.2 The Simplest Example of Phase Equilibrium
37 3.3 The Next Level of Complexity in Phase Equilibrium
37 3.4 Some Simple Estimating Rules: Raoult's and Henry's "Laws"
39 3.5 The General Two-Phase Equilibrium Calculation
43 3.6 Some Simple Applications of Raoult's and Henry's Laws
43 3.7 The Uses and Limits of Raoult's and Henry's Laws
46 3.8 Summary
46 References
48 4 Minimization of Gibbs Energy 49 4.1 The Fundamental Thermodynamic Criterion of Phase and Chemical Equilibrium
49 4.2 The Criterion of Equilibrium Applied to Two Nonreacting Equilibrium Phases
51 4.3 The Criterion of Equilibrium Applied to Chemical Reactions
53 4.4 Simple Gibbs Energy Diagrams
54 4.5 Le Chatelier's Principle
58 4.6 Summary
58 References
60 5 Vapor Pressure
the Clapeyron Equation
and Single Pure Chemical Species Phase Equilibrium 61 5.1 Measurement of Vapor Pressure
61 5.2 Reporting Vapor-Pressure Data
61 5.3 The Clapeyron Equation
62 5.4 The Clausius-Clapeyron Equation
63 5.5 The Accentric Factor
64 5.6 The Antoine Equation and Other Data-Fitting Equations
66 5.7 Applying the Clapeyron Equation to Other Kinds of Equilibrium
67 5.8 Extrapolating Vapor-Pressure Curves
68 5.9 Vapor Pressure of Solids
69 5.10 Vapor Pressures of Mixtures
69 5.11 Summary
69 References
72 6 Partial Molar Properties 73 6.1 Partial Molar Properties
73 6.2 The Partial Molar Equation
74 6.3 Tangent Slopes
74 6.4 Tangent Intercepts
77 6.5 The Two Equations for Partial Molar Properties
78 6.6 Using the Idea of Tangent Intercepts
79 6.7 Partial Mass Properties
80 6.8 Heats of Mixing and Partial Molar Enthalpies
80 6.9 The Gibbs-Duhem Equation and the Counterintuitive Behavior of the Chemical Potential
82 6.10 Summary
84 References
87 7 Fugacity
Ideal Solutions
Activity
Activity Coefficient 89 7.1 Why Fugacity?
89 7.2 Fugacity Defined
89 7.3 The Use of the Fugacity
90 7.4 Pure Substance Fugacities
90 7.5 Fugacities of Species in Mixtures
95 7.6 Mixtures of Ideal Gases
95 7.7 Why Ideal Solutions?
95 7.8 Ideal Solutions Defined
96 7.9 Why Activity and Activity Coefficients?
98 7.10 Activity and Activity Coefficients Defined
98 7.11 Fugacity Coefficient for Pure Gases and Gas Mixtures
100 7.12 Estimating Fugacities of Individual Species in Gas Mixtures
100 7.13 Liquid Fugacities from Vapor-Liquid Equilibrium
104 7.14 Summary
104 References
105 8 Vapor-Liquid Equilibrium (VLE) at Low Pressures 107 8.1 Measurement of VLE
107 8.2 Presenting Experimental VLE Data
110 8.3 The Mathematical Treatment of Low-Pressure VLE Data
110 8.4 The Four Most Common Types of Low-Pressure VLE
112 8.5 Gas-Liquid Equilibrium
Henry's Law Again
122 8.6 The Effect of Modest Pressures on VLE
122 8.7 Standard States Again
124 8.8 Low-Pressure VLE Calculations
125 8.9 Traditional K-Factor Methods
132 8.10 More Uses for Raoult's Law
132 8.11 Summary
136 References
143 9 Correlating and Predicting Nonideal VLE 145 9.1 The Most Common Observations of Liquid-Phase Activity Coefficients
145 9.2 Limits on Activity Coefficient Correlations
the Gibbs-Duhem Equation
147 9.3 Excess Gibbs Energy and Activity Coefficient Equations
148 9.4 Activity Coefficients at Infinite Dilution
150 9.5 Effects of Pressure and Temperature on Liquid-Phase Activity Coefficients
151 9.6 Ternary and Multispecies VLE
153 9.7 Vapor-Phase Nonideality
155 9.8 VLE from EOS
158 9.9 Solubility Parameter
158 9.10 The Solubility of Gases in Liquids
Henry's Law Again
160 9.11 Summary
163 References
167 10 Vapor-Liquid Equilibrium (VLE) at High Pressures 169 10.1 Critical Phenomena of Pure Species
169 10.2 Critical Phenomena of Mixtures
170 10.3 Estimating High-Pressure VLE
174 10.4 Computer Solutions
178 10.5 Summary
178 References
179 11 Liquid-Liquid
Liquid-Solid
and Gas-Solid Equilibrium 181 11.1 Liquid-Liquid Equilibrium (LLE)
181 11.2 The Experimental Determination of LLE
181 11.3 The Elementary Theory of LLE
187 11.4 The Effect of Pressure on LLE
190 11.5 Effect of Temperature on LLE
191 11.6 Distribution Coefficients
194 11.7 Liquid-Solid Equilibrium (LSE)
195 11.8 The Elementary Thermodynamics of LSE
200 11.9 Gas-Solid Equilibrium (GSE) at Low Pressures
202 11.10 GSE at High Pressures
203 11.11 Gas-Solid Adsorption
Vapor-Solid Adsorption
204 11.12 Summary
211 References
215 12 Chemical Equilibrium 217 12.1 Introduction to Chemical Reactions and Chemical Equilibrium
217 12.2 Formal Description of Chemical Reactions
217 12.3 Minimizing Gibbs Energy
218 12.4 Reaction Rates
Energy Barriers
Catalysis
and Equilibrium
219 12.5 The Basic Thermodynamics of Chemical Reactions and Its Convenient Formulations
220 12.6 Calculating Equilibrium Constants from Gibbs Energy Tables and then Using Equilibrium Constants to Calculate Equilibrium Concentrations
223 12.7 More on Standard States
227 12.8 The Effect of Temperature on Chemical Reaction Equilibrium
229 12.9 The Effect of Pressure on Chemical Reaction Equilibrium
234 12.10 The Effect of Nonideal Solution Behavior
238 12.11 Other Forms of K
238 12.12 Summary
239 References
242 13 Equilibrium in Complex Chemical Reactions 243 13.1 Reactions Involving Ions
243 13.2 Multiple Reactions
244 13.3 Reactions with More Than One Phase
249 13.4 Electrochemical Reactions
252 13.5 Chemical and Physical Equilibrium in Two Phases
255 13.6 Summary
257 References
262 14 Equilibrium with Gravity or Centrifugal Force
Osmotic Equilibrium
Equilibrium with Surface Tension 265 14.1 Equilibrium with Other Forms of Energy
265 14.2 Equilibrium in the Presence of Gravity
266 14.3 Semipermeable Membranes
269 14.4 Small is Interesting! Equilibrium with Surface Tension
271 14.5 Summary
275 References
278 15 The Phase Rule 279 15.1 How Many Phases Can Coexist in a Given Equilibrium Situation?
279 15.2 What Does the Phase Rule Tell Us? What Does It Not Tell Us?
280 15.3 What is a Phase?
280 15.4 The Phase Rule is Simply Counting Variables
281 15.5 More On Components
282 15.6 The Phase Rule for One- and Two-Component Systems
285 15.7 Harder Phase Rule Problems
288 15.8 Summary
288 References
291 16 Equilibrium in Biochemical Reactions 293 16.1 An Example
the Production of Ethanol from Sugar
293 16.2 Organic and Biochemical Reactions
293 16.3 Two More Sweet Examples
294 16.4 Thermochemical Data for Biochemical Reactions
295 16.5 Thermodynamic Equilibrium in Large Scale Biochemistry
296 16.6 Translating between Biochemical and Chemical Engineering Equilibrium Expressions
296 16.7 Equilibrium in Biochemical Separations
298 16.8 Summary
299 References
300 Appendix A Useful Tables and Charts 303 A.1 Useful Property Data for Corresponding States Estimates
303 A.2 Vapor-Pressure Equation Constants
305 A.3 Henry's Law Constants
306 A.4 Compressibility Factor Chart (z Chart)
307 A.5 Fugacity Coefficient Charts
307 A.6 Azeotropes
308 A.7 Van Laar Equation Constants
312 A.8 Enthalpies and Gibbs Energies of Formation from the Elements in the Standard States
at T 1/4 298.15 K 1/4 25C
and P 1/4 1.00 bar
313 A.9 Heat Capacities of Gases in the Ideal Gas State
317 Appendix B Equilibrium with other Restraints
Other Approaches to Equilibrium 319 Appendix C The Mathematics of Fugacity
Ideal Solutions
Activity and Activity Coefficients 323 C.1 The Fugacity of Pure Substances
323 C.2 Fugacities of Components of Mixtures
324 C.3 The Consequences of the Ideal Solution Definition
326 C.4 The Mathematics of Activity Coefficients
326 Appendix D Equations of State for Liquids and Solids Well Below their Critical Temperatures 329 D.1 The Taylor Series EOS and Its Short Form
329 D.2 Effect of Temperature on Density
330 D.3 Effect of Pressure on Density
331 D.4 Summary
332 References
333 Appendix E Gibbs Energy of Formation Values 335 E.1 Values "From the Elements"
335 E.2 Changes in Enthalpy
Entropy
and Gibbs Energy
335 E.3 Ions
337 E.4 Presenting these Data
337 References
337 Appendix F Calculation of Fugacities from Pressure-Explicit EOSs 339 F.1 Pressure-Explicit and Volume-Explicit EOSs
339 F.2 f /P of Pure Species Based on Pressure-Explicit EOSs
339 F.3 Cubic Equations of State
340 F.4 fi /Pyi for Individual Species in Mixtures
Based on Pressure-Explicit EOSs
342 F.5 Mixing Rules for Cubic EOSs
343 F.6 VLE Calculations with a Cubic EOS
344 F.7 Summary
345 References
346 Appendix G Thermodynamic Property Derivatives and the Bridgman Table 347 References
350 Appendix H Answers to Selected Problems 351 Index 353