Chemical thermodynamics: basic concepts and methods
Gespeichert in:
| Hauptverfasser: | , |
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| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Hoboken, NJ [u.a.]
Wiley
2008
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| Ausgabe: | 7. ed. |
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | XXI, 563 S. graph. Darst. |
| ISBN: | 9780470285237 9780471780151 |
Internformat
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| 100 | 1 | |a Klotz, Irving M. |d 1916-2005 |e Verfasser |0 (DE-588)139387951 |4 aut | |
| 245 | 1 | 0 | |a Chemical thermodynamics |b basic concepts and methods |c Irving M. Klotz ; Robert M. Rosenberg |
| 250 | |a 7. ed. | ||
| 264 | 1 | |a Hoboken, NJ [u.a.] |b Wiley |c 2008 | |
| 300 | |a XXI, 563 S. |b graph. Darst. | ||
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| 337 | |b n |2 rdamedia | ||
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Datensatz im Suchindex
| _version_ | 1804137663133908992 |
|---|---|
| adam_text | CONTENTS
PREFACE xix
1 INTRODUCTION 1
1.1 Origins of Chemical Thermodynamics / 1
1.2 Objectives of Chemical Thermodynamics / 4
1.3 Limitations of Classic Thermodynamics / 4
References / 6
2 MATHEMATICAL PREPARATION FOR THERMODYNAMICS 9
2.1 Variables of Thermodynamics / 10
Extensive and Intensive Quantities / 10
Units and Conversion Factors / 10
2.2 Analytic Methods / 10
Partial Differentiation / 10
Exact Differentials / 15
Homogeneous Functions / 18
Exercises / 21
References / 27
3 THE FIRST LAW OF THERMODYNAMICS 29
3.1 Definitions / 29
Temperature / 31
Work / 33
vii
VÜi CONTENTS
3.2 The First Law of Thermodynamics / 37
Energy / 37
Heat / 38
General Form of the First Law / 38
Exercises / 40
References / 41
4 ENTHALPY, ENTHALPY OF REACTION, AND
HEAT CAPACITY 43
4.1 Enthalpy / 44
Definition / 44
Relationship between Qv and QP / 46
4.2 Enthalpy of Reactions / 47
Definitions and Conventions / 47
4.3 Enthalpy as a State Function / 52
Enthalpy of Formation from Enthalpy of Reaction / 52
Enthalpy of Formation from Enthalpy of Combustion / 53
Enthalpy of Transition from Enthalpy of Combustion / 53
Enthalpy of Conformational Transition of a Protein from
Indirect Calorimetric Measurements / 54
Enthalpy of Solid-State Reaction from Measurements of
Enthalpy of Solution / 56
4.4 Bond Enthalpies / 57
Definition of Bond Enthalpies / 57
Calculation of Bond Enthalpies / 58
Enthalpy of Reaction from Bond Enthalpies / 59
4.5 Heat Capacity / 60
Definition / 61
Some Relationships between CP and Cv / 62
Heat Capacities of Gases / 64
Heat Capacities of Solids / 67
Heat Capacities of Liquids / 68
Other Sources of Heat Capacity Data / 68
4.6 Enthalpy of Reaction as a Function of Temperature / 68
Analytic Method / 69
Arithmetic Method / 71
Graphical or Numerical Methods / 72
Exercises / 72
References / 78
5 APPLICATIONS OF THE FIRST LAW TO GASES 81
5.1 Ideal Gases / 81
Definition / 81
CONTENTS ix
Enthalpy as a Function of Temperature Only / 83
Relationship Between CP and Cv / 84
Calculation of the Thermodynamic Changes in
Expansion Processes / 84
5.2 Real Gases / 94
Equations of State / 94
Joule-Thomson Effect / 98
Calculations of Thermodynamic Quantities in Reversible
Expansions / 102
Exercises / 104
References / 108
6 THE SECOND LAW OF THERMODYNAMICS 111
6.1 The Need for a Second Law / 111
6.2 The Nature of the Second Law / 112
Natural Tendencies Toward Equilibrium / 112
Statement of the Second Law / 112
Mathematical Counterpart of the Verbal Statement / 113
6.3 The Carnot Cycle / 113
The Forward Cycle / 114
The Reverse Cycle / 116
Alternative Statement of the Second Law / 117
Carnot s Theorem / 118
6.4 The Thermodynamic Temperature Scale / 120
6.5 The Definition of S, the Entropy of a System / 125
6.6 The Proof that S is a Thermodynamic Property / 126
Any Substance in a Carnot Cycle / 126
Any Substance in Any Reversible Cycle / 127
Entropy S Depends Only on the State
of the System / 129
6.7 Entropy Changes in Reversible Processes / 130
General Statement / 130
Isothermal Reversible Changes / 130
Adiabatic Reversible Changes / 131
Reversible Phase Transitions / 131
Isobaric Reversible Temperature Changes / 132
Isochoric Reversible Temperature Changes / 133
6.8 Entropy Changes in Irreversible Processes / 133
Irreversible Isothermal Expansion of an Ideal Gas / 133
Irreversible Adiabatic Expansion of an Ideal Gas / 135
Irreversible Flow of Heat from a Higher Temperature
to a Lower Temperature / 136
X CONTENTS
Irreversible Phase Transitions / 137
Irreversible Chemical Reactions / 138
General Statement / 139
6.9 General Equations for the Entropy of Gases / 142
Entropy of the Ideal Gas / 142
Entropy of a Real Gas / 143
6.10 Temperature- Entropy Diagram / 144
6.11 Entropy as an Index of Exhaustion / 146
Exercises / 150
References / 157
7 EQUILIBRIUM AND SPONTANEITY FOR SYSTEMS AT
CONSTANT TEMPERATURE 159
7.1 Reversibility, Spontaneity, and Equilibrium / 159
Systems at Constant Temperature and Volume / 160
Systems at Constant Temperature and Pressure / 162
Heat of Reaction as an Approximate
Criterion of Spontaneity / 164
7.2 Properties of the Gibbs, Helmholtz, and Planck Functions / 165
The Functions as Thermodynamic Properties / 165
Relationships among G, Y, and A / 165
Changes in the Functions for Isothermal Conditions / 165
Equations for Total Differentials / 166
Pressure and Temperature Derivatives of the
Functions / 167
Equations Derived from the Reciprocity
Relationship / 169
7.3 The Gibbs Function and Chemical Reactions / 170
Standard States / 170
7.4 Pressure and Temperature Dependence of AG / 172
7.5 Useful Work and the Gibbs and Helmholtz Functions / 175
Isothermal Changes / 175
Changes at Constant Temperature and Pressure / 177
Relationship between AHP and QP When Useful Work is
Performed / 178
Application to Electrical Work / 179
Gibbs-Helmholtz Equation / 180
The Gibbs Function and Useful Work in
Biologie Systems / 181
Exercises / 185
References / 191
CONTENTS Xi
8 APPLICATION OF THE GIBBS FUNCTION AND THE
PLANCK FUNCTION TO SOME PHASE CHANGES 193
8.1 Two Phases at Equilibrium as a Function of Pressure
and Temperature / 193
Clapeyron Equation / 194
Clausius-Clapeyron Equation / 196
8.2 The Effect of an Inert Gas on Vapor Pressure / 198
Variable Total Pressure at Constant Temperature / 199
Variable Temperature at Constant Total Pressure / 200
8.3 Temperature Dependence of Enthalpy of Phase Transition / 200
8.4 Calculation of Change in the Gibbs Function for
Spontaneous Phase Change / 202
Arithmetic Method / 202
Analytic Method / 203
Exercises / 205
References / 210
9 THERMODYNAMICS OF SYSTEMS OF
VARIABLE COMPOSITION 211
9.1 State Functions for Systems of Variable Composition / 211
9.2 Criteria of Equilibrium and Spontaneity in Systems of
Variable Composition / 213
9.3 Relationships Among Partial Molar Properties of a
Single Component / 215
9.4 Relationships Between Partial Molar Quantities of Different
Components / 216
Partial Molar Quantities for Pure Phase / 218
9.5 Escaping Tendency / 219
Chemical Potential and Escaping Tendency / 219
9.6 Chemical Equilibrium in Systems of Variable Composition / 221
Exercises / 223
Reference / 226
10 MIXTURES OF GASES AND EQUILIBRIUM IN
GASEOUS MIXTURES 227
10.1 Mixtures of Ideal Gases / 227
The Entropy and Gibbs Function for Mixing
Ideal Gases / 228
The Chemical Potential of a Component of an Ideal
GasMixture / 230
XÜ CONTENTS
Chemical Equilibrium in Ideal Gas Mixtures / 231
Dependence of K on Temperature / 232
Comparison of Temperature Dependence of AG„
and In K / 234
10.2 The Fugacity Function of a Pure Real Gas / 236
Change of Fugacity with Pressure / 237
Change of Fugacity with Temperature / 238
10.3 Calculation of the Fugacity of a Real Gas / 239
Graphical or Numerical Methods / 240
Analytical Methods / 244
10.4 Joule-Thomson Effect for a Van der Waals Gas / 247
Approximate Value of a for a Van der Waals Gas / 247
Fugacity at Low Pressures / 248
Enthalpy of a Van der Waals Gas / 248
Joule-Thomson Coefficient / 249
10.5 Mixtures of Real Gases / 249
Fugacity of a Component of a Gaseous Solution / 250
Approximate Rule for Solutions of Real Gases / 251
Fugacity Coefficients in Gaseous Solutions / 251
Equilibrium Constant and Change in Gibbs Functions and
Planck Functions for Reactions of Real Gases / 252
Exercises / 253
References / 256
11 THE THIRD LAW OF THERMODYNAMICS 259
11.1 Need for the Third Law / 259
11.2 Formulation of the Third Law / 260
Nernst Heat Theorem / 260
Planck s Formulation / 261
Statement of Lewis and Randall / 262
11.3 Thermodynamic Properties at Absolute Zero / 263
Equivalence of G and H / 263
ACP in an Isothermal Chemical Reaction / 263
Limiting Values of CP and Cv / 264
Temperature Derivatives of Pressure and Volume / 264
11.4 Entropies at 298 K / 265
Typical Calculations / 266
Apparent Exceptions to the Third Law / 270
Tabulations of Entropy Values / 274
Exercises / 277
References / 280
CONTENTS XÜi
12 APPLICATION OF THE GIBBS FUNCTION TO
CHEMICAL CHANGES 281
12.1 Determination of AG„ from Equilibrium Measurements / 281
12.2 Determination of AG°m from Measurements of
Cell potentials / 284
12.3 Calculation of AG°m from Calorimetric Measurements / 285
12.4 Calculation of a Gibbs Function of a Reaction from Standard
Gibbs Function of Formation / 286
12.5 Calculation of a Standard Gibbs Function from Standard
Entropies and Standard Enthalpies / 287
Enthalpy Calculations / 287
Entropy Calculations / 290
Change in Standard Gibbs Function / 290
Exercises / 293
References / 301
13 THE PHASE RULE 303
13.1 Derivation of the Phase Rule / 303
Nonreacting Systems / 304
Reacting Systems / 306
13.2 One-Component Systems / 307
13.3 Two-Component Systems / 309
Two Phases at Different Pressures / 312
Phase Rule Criterion of Purity / 315
Exercises / 316
References / 316
14 THE IDEAL SOLUTION 319
14.1 Definition / 319
14.2 Some Consequences of the Definition / 321
Volume Changes / 321
HeatEffects / 322
14.3 Thermodynamics of Transfer of a Component from
One Ideal Solution to Another / 323
14.4 Thermodynamics of Mixing / 325
14.5 Equilibrium between a Pure Solid and an Ideal
Liquid Solution / 327
Change of Solubility with Pressure at a Fixed Temperature / 328
Change of Solubility with Temperature / 329
XIV CONTENTS
14.6 Equilibrium between an Ideal Solid Solution and an Ideal
Liquid Solution / 332
Composition of the Two Phases in Equilibrium / 332
Temperature Dependence of the Equilibrium Compositions / 333
Exercises / 333
References / 335
15 DILUTE SOLUTIONS OF NONELECTROLYTES 337
15.1 Henry sLaw / 337
15.2 Nernst s Distribution Law / 340
15.3 Raoult sLaw / 341
15.4 Van t Hoff s Law ofOsmotic Pressure / 344
Osmotic Work in Biological Systems / 349
15.5 Van t Hoff s Law of Freezing-Point Depression and Boiling-Point
Elevation / 350
Exercises / 353
References / 355
16 ACTIVITIES, EXCESS GIBBS FUNCTIONS, AND STANDARD
STATES FOR NONELECTROLYTES 357
16.1 Definitions of Activities and Activity Coefficients / 358
Activity / 358
Activity Coefficient / 358
16.2 Choice of Standard States / 359
Gases / 359
Liquids and Solids / 360
16.3 Gibbs Function and the Equilibrium Constant in
Terms of Activity / 365
16.4 Dependence of Activity on Pressure / 367
16.5 Dependence of Activity on Temperature / 368
Standard Partial Molar Enthalpies / 368
Equation for Temperature Derivative of the Activity / 369
16.6 Standard Entropy / 370
16.7 Deviations from Ideality in Terms of Excess Thermodynamic
Functions / 373
Representation of G„ as a Function of Composition / 374
16.8 Regulär Solutions and Henry s Law / 376
16.9 Regulär Solutions and Limited Miscibility / 378
Exercises / 381
References / 384
CONTENTS XV
17 DETERMINATION OF NONELECTROLYTE ACTIVITIES AND
EXCESS GIBBS FUNCTIONS FROM EXPERIMENTAL DATA 385
17.1 Activity from Measurements of Vapor Pressure / 385
Solvent / 385
Solute / 386
17.2 Excess Gibbs Function from Measurement of Vapor Pressure / 388
17.3 Activity of a Solute from Distribution between
Two Immiscible Solvents / 391
17.4 Activity from Measurement of Cell Potentials / 393
17.5 Determination of the Activity of One Component from the
Activity of the Other / 397
Calculation of Activity of Solvent from That of Solute / 398
Calculation of Activity of Solute from That of Solvent / 399
17.6 Measurements of Freezing Points / 400
Exercises / 401
References / 406
18 CALCULATION OF PARTIAL MOLAR QUANTITIES
AND EXCESS MOLAR QUANTITIES FROM EXPERIMENTAL
DATA: VOLUME AND ENTHALPY 407
18.1 Partial Molar Quantities by Differentiation of J as a
Function of Composition / 407
Partial Molar Volume / 409
Partial Molar Enthalpy / 413
Enthalpies of Mixing / 414
Enthalpies of Dilution / 417
18.2 Partial Molar Quantities of One Component from those of
Another Component by Numerical Integration / 420
Partial Molar Volume / 421
Partial Molar Enthalpy / 421
18.3 Analytic Methods for Calculation of Partial Molar Properties / 422
Partial Molar Volume / 422
Partial Molar Enthalpy / 423
18.4 Changes in J for Some Processes in Solutions / 423
Transfer Process / 423
Integral Process / 425
18.5 Excess Properties: Volume and Enthalpy / 426
Excess Volume / 426
Excess Enthalpy / 426
Exercises / 427
References / 436
XVi CONTENTS
19 ACTIVITY, ACTIVITY COEFFICIENTS, AND OSMOTIC
COEFFICIENTS OF STRONG ELECTROLYTES 439
19.1 Definitions and Standard states for Dissolved Electrolytes / 440
Uni-univalent Electrolytes / 440
Multivalent Electrolytes / 443
Mixed Electrolytes / 446
19.2 Determination of Activities of Streng Electrolytes / 448
Measurement of Cell Potentials / 449
Solubility Measurements / 453
Colligative Property Measurement: The Osmotic Coefficient / 455
Extension of Activity Coefficient Data to Additional Temperatures
with Enthalpy of Dilution Data / 460
19.3 Activity Coefficients of Some Streng Electrolytes / 462
Experimental Values / 462
Theoretical Correlation / 462
Exercises / 464
References / 470
20 CHANGES IN GIBBS FUNCTION FOR PROCESSES
IN SOLUTIONS 471
20.1 Activity Coefficients of Weak Electrolytes / 471
20.2 Determination of Equilibrium Constants for Dissociation of
Weak Electrolytes / 472
From Measurements of Cell Potentials / 473
From Conductance Measurements / 475
20.3 Some Typical Calculations for AfGS, / 480
Standard Gibbs Function for Formation of
Aqueous Solute: HC1 / 480
Standard Gibbs Function of Formation of Individual
Ions: HC1 / 482
Standard Gibbs Function for Formation of Solid
Solute in Aqueous Solution / 482
Standard Gibbs Function for Formation of Ion of
Weak Electrolyte / 484
Standard Gibbs Function for Formation of
Moderately Streng Electrolyte / 485
Effect of Salt Concentration on Geological Equilibrium
Involving Water / 486
General Comments / 486
20.4 Entropies of Ions / 487
The Entropy of an Aqueous Solution of a Salt / 488
CONTENTS XVÜ
Entropy of Formation of Individual Ions / 488
Ion Entropies in Thermodynamic Calculations / 491
Exercises / 491
References / 496
21 SYSTEMS SUBJECT TO A GRAVITATIONAL OR A
CENTRIFUGAL FIELD 499
21.1 Dependence of the Gibbs Function on External Field / 499
21.2 System in a Gravitational Field / 502
21.3 System in a Centrifugal Field / 505
Exercises / 509
References / 510
22 ESTIMATION OF THERMODYNAMIC QUANTITIES 511
22.1 Empirical Methods / 511
Group Contribution Method of Andersen, Beyer,
Watson, and Yoneda / 512
Typical Examples of Estimating Entropies / 516
Other Methods / 522
Accuracy of the Approximate Methods / 522
Equilibrium in Complex Systems / 523
Exercises / 523
References / 524
23 CONCLUDING REMARKS 527
References / 529
APPENDIX A PRACTICAL MATHEMATICALTECHNIQUES 531
A.l Analytical Methods / 531
Linear Least Squares / 531
Nonlinear Least Squares / 534
A.2 Numerical and Graphical Methods / 535
Numerical Differentiation / 535
Numerical Integration / 538
Use of the Digital Computer / 540
Graphical Differentiation / 541
Graphical Integration / 542
Exercises / 542
References / 543
INDEX 545
|
| adam_txt |
CONTENTS
PREFACE xix
1 INTRODUCTION 1
1.1 Origins of Chemical Thermodynamics / 1
1.2 Objectives of Chemical Thermodynamics / 4
1.3 Limitations of Classic Thermodynamics / 4
References / 6
2 MATHEMATICAL PREPARATION FOR THERMODYNAMICS 9
2.1 Variables of Thermodynamics / 10
Extensive and Intensive Quantities / 10
Units and Conversion Factors / 10
2.2 Analytic Methods / 10
Partial Differentiation / 10
Exact Differentials / 15
Homogeneous Functions / 18
Exercises / 21
References / 27
3 THE FIRST LAW OF THERMODYNAMICS 29
3.1 Definitions / 29
Temperature / 31
Work / 33
vii
VÜi CONTENTS
3.2 The First Law of Thermodynamics / 37
Energy / 37
Heat / 38
General Form of the First Law / 38
Exercises / 40
References / 41
4 ENTHALPY, ENTHALPY OF REACTION, AND
HEAT CAPACITY 43
4.1 Enthalpy / 44
Definition / 44
Relationship between Qv and QP / 46
4.2 Enthalpy of Reactions / 47
Definitions and Conventions / 47
4.3 Enthalpy as a State Function / 52
Enthalpy of Formation from Enthalpy of Reaction / 52
Enthalpy of Formation from Enthalpy of Combustion / 53
Enthalpy of Transition from Enthalpy of Combustion / 53
Enthalpy of Conformational Transition of a Protein from
Indirect Calorimetric Measurements / 54
Enthalpy of Solid-State Reaction from Measurements of
Enthalpy of Solution / 56
4.4 Bond Enthalpies / 57
Definition of Bond Enthalpies / 57
Calculation of Bond Enthalpies / 58
Enthalpy of Reaction from Bond Enthalpies / 59
4.5 Heat Capacity / 60
Definition / 61
Some Relationships between CP and Cv / 62
Heat Capacities of Gases / 64
Heat Capacities of Solids / 67
Heat Capacities of Liquids / 68
Other Sources of Heat Capacity Data / 68
4.6 Enthalpy of Reaction as a Function of Temperature / 68
Analytic Method / 69
Arithmetic Method / 71
Graphical or Numerical Methods / 72
Exercises / 72
References / 78
5 APPLICATIONS OF THE FIRST LAW TO GASES 81
5.1 Ideal Gases / 81
Definition / 81
CONTENTS ix
Enthalpy as a Function of Temperature Only / 83
Relationship Between CP and Cv / 84
Calculation of the Thermodynamic Changes in
Expansion Processes / 84
5.2 Real Gases / 94
Equations of State / 94
Joule-Thomson Effect / 98
Calculations of Thermodynamic Quantities in Reversible
Expansions / 102
Exercises / 104
References / 108
6 THE SECOND LAW OF THERMODYNAMICS 111
6.1 The Need for a Second Law / 111
6.2 The Nature of the Second Law / 112
Natural Tendencies Toward Equilibrium / 112
Statement of the Second Law / 112
Mathematical Counterpart of the Verbal Statement / 113
6.3 The Carnot Cycle / 113
The Forward Cycle / 114
The Reverse Cycle / 116
Alternative Statement of the Second Law / 117
Carnot's Theorem / 118
6.4 The Thermodynamic Temperature Scale / 120
6.5 The Definition of S, the Entropy of a System / 125
6.6 The Proof that S is a Thermodynamic Property / 126
Any Substance in a Carnot Cycle / 126
Any Substance in Any Reversible Cycle / 127
Entropy S Depends Only on the State
of the System / 129
6.7 Entropy Changes in Reversible Processes / 130
General Statement / 130
Isothermal Reversible Changes / 130
Adiabatic Reversible Changes / 131
Reversible Phase Transitions / 131
Isobaric Reversible Temperature Changes / 132
Isochoric Reversible Temperature Changes / 133
6.8 Entropy Changes in Irreversible Processes / 133
Irreversible Isothermal Expansion of an Ideal Gas / 133
Irreversible Adiabatic Expansion of an Ideal Gas / 135
Irreversible Flow of Heat from a Higher Temperature
to a Lower Temperature / 136
X CONTENTS
Irreversible Phase Transitions / 137
Irreversible Chemical Reactions / 138
General Statement / 139
6.9 General Equations for the Entropy of Gases / 142
Entropy of the Ideal Gas / 142
Entropy of a Real Gas / 143
6.10 Temperature- Entropy Diagram / 144
6.11 Entropy as an Index of Exhaustion / 146
Exercises / 150
References / 157
7 EQUILIBRIUM AND SPONTANEITY FOR SYSTEMS AT
CONSTANT TEMPERATURE 159
7.1 Reversibility, Spontaneity, and Equilibrium / 159
Systems at Constant Temperature and Volume / 160
Systems at Constant Temperature and Pressure / 162
Heat of Reaction as an Approximate
Criterion of Spontaneity / 164
7.2 Properties of the Gibbs, Helmholtz, and Planck Functions / 165
The Functions as Thermodynamic Properties / 165
Relationships among G, Y, and A / 165
Changes in the Functions for Isothermal Conditions / 165
Equations for Total Differentials / 166
Pressure and Temperature Derivatives of the
Functions / 167
Equations Derived from the Reciprocity
Relationship / 169
7.3 The Gibbs Function and Chemical Reactions / 170
Standard States / 170
7.4 Pressure and Temperature Dependence of AG / 172
7.5 Useful Work and the Gibbs and Helmholtz Functions / 175
Isothermal Changes / 175
Changes at Constant Temperature and Pressure / 177
Relationship between AHP and QP When Useful Work is
Performed / 178
Application to Electrical Work / 179
Gibbs-Helmholtz Equation / 180
The Gibbs Function and Useful Work in
Biologie Systems / 181
Exercises / 185
References / 191
CONTENTS Xi
8 APPLICATION OF THE GIBBS FUNCTION AND THE
PLANCK FUNCTION TO SOME PHASE CHANGES 193
8.1 Two Phases at Equilibrium as a Function of Pressure
and Temperature / 193
Clapeyron Equation / 194
Clausius-Clapeyron Equation / 196
8.2 The Effect of an Inert Gas on Vapor Pressure / 198
Variable Total Pressure at Constant Temperature / 199
Variable Temperature at Constant Total Pressure / 200
8.3 Temperature Dependence of Enthalpy of Phase Transition / 200
8.4 Calculation of Change in the Gibbs Function for
Spontaneous Phase Change / 202
Arithmetic Method / 202
Analytic Method / 203
Exercises / 205
References / 210
9 THERMODYNAMICS OF SYSTEMS OF
VARIABLE COMPOSITION 211
9.1 State Functions for Systems of Variable Composition / 211
9.2 Criteria of Equilibrium and Spontaneity in Systems of
Variable Composition / 213
9.3 Relationships Among Partial Molar Properties of a
Single Component / 215
9.4 Relationships Between Partial Molar Quantities of Different
Components / 216
Partial Molar Quantities for Pure Phase / 218
9.5 Escaping Tendency / 219
Chemical Potential and Escaping Tendency / 219
9.6 Chemical Equilibrium in Systems of Variable Composition / 221
Exercises / 223
Reference / 226
10 MIXTURES OF GASES AND EQUILIBRIUM IN
GASEOUS MIXTURES 227
10.1 Mixtures of Ideal Gases / 227
The Entropy and Gibbs Function for Mixing
Ideal Gases / 228
The Chemical Potential of a Component of an Ideal
GasMixture / 230
XÜ CONTENTS
Chemical Equilibrium in Ideal Gas Mixtures / 231
Dependence of K on Temperature / 232
Comparison of Temperature Dependence of AG„
and In K / 234
10.2 The Fugacity Function of a Pure Real Gas / 236
Change of Fugacity with Pressure / 237
Change of Fugacity with Temperature / 238
10.3 Calculation of the Fugacity of a Real Gas / 239
Graphical or Numerical Methods / 240
Analytical Methods / 244
10.4 Joule-Thomson Effect for a Van der Waals Gas / 247
Approximate Value of a for a Van der Waals Gas / 247
Fugacity at Low Pressures / 248
Enthalpy of a Van der Waals Gas / 248
Joule-Thomson Coefficient / 249
10.5 Mixtures of Real Gases / 249
Fugacity of a Component of a Gaseous Solution / 250
Approximate Rule for Solutions of Real Gases / 251
Fugacity Coefficients in Gaseous Solutions / 251
Equilibrium Constant and Change in Gibbs Functions and
Planck Functions for Reactions of Real Gases / 252
Exercises / 253
References / 256
11 THE THIRD LAW OF THERMODYNAMICS 259
11.1 Need for the Third Law / 259
11.2 Formulation of the Third Law / 260
Nernst Heat Theorem / 260
Planck's Formulation / 261
Statement of Lewis and Randall / 262
11.3 Thermodynamic Properties at Absolute Zero / 263
Equivalence of G and H / 263
ACP in an Isothermal Chemical Reaction / 263
Limiting Values of CP and Cv / 264
Temperature Derivatives of Pressure and Volume / 264
11.4 Entropies at 298 K / 265
Typical Calculations / 266
Apparent Exceptions to the Third Law / 270
Tabulations of Entropy Values / 274
Exercises / 277
References / 280
CONTENTS XÜi
12 APPLICATION OF THE GIBBS FUNCTION TO
CHEMICAL CHANGES 281
12.1 Determination of AG„ from Equilibrium Measurements / 281
12.2 Determination of AG°m from Measurements of
Cell potentials / 284
12.3 Calculation of AG°m from Calorimetric Measurements / 285
12.4 Calculation of a Gibbs Function of a Reaction from Standard
Gibbs Function of Formation / 286
12.5 Calculation of a Standard Gibbs Function from Standard
Entropies and Standard Enthalpies / 287
Enthalpy Calculations / 287
Entropy Calculations / 290
Change in Standard Gibbs Function / 290
Exercises / 293
References / 301
13 THE PHASE RULE 303
13.1 Derivation of the Phase Rule / 303
Nonreacting Systems / 304
Reacting Systems / 306
13.2 One-Component Systems / 307
13.3 Two-Component Systems / 309
Two Phases at Different Pressures / 312
Phase Rule Criterion of Purity / 315
Exercises / 316
References / 316
14 THE IDEAL SOLUTION 319
14.1 Definition / 319
14.2 Some Consequences of the Definition / 321
Volume Changes / 321
HeatEffects / 322
14.3 Thermodynamics of Transfer of a Component from
One Ideal Solution to Another / 323
14.4 Thermodynamics of Mixing / 325
14.5 Equilibrium between a Pure Solid and an Ideal
Liquid Solution / 327
Change of Solubility with Pressure at a Fixed Temperature / 328
Change of Solubility with Temperature / 329
XIV CONTENTS
14.6 Equilibrium between an Ideal Solid Solution and an Ideal
Liquid Solution / 332
Composition of the Two Phases in Equilibrium / 332
Temperature Dependence of the Equilibrium Compositions / 333
Exercises / 333
References / 335
15 DILUTE SOLUTIONS OF NONELECTROLYTES 337
15.1 Henry'sLaw / 337
15.2 Nernst's Distribution Law / 340
15.3 Raoult'sLaw / 341
15.4 Van't Hoff s Law ofOsmotic Pressure / 344
Osmotic Work in Biological Systems / 349
15.5 Van't Hoff s Law of Freezing-Point Depression and Boiling-Point
Elevation / 350
Exercises / 353
References / 355
16 ACTIVITIES, EXCESS GIBBS FUNCTIONS, AND STANDARD
STATES FOR NONELECTROLYTES 357
16.1 Definitions of Activities and Activity Coefficients / 358
Activity / 358
Activity Coefficient / 358
16.2 Choice of Standard States / 359
Gases / 359
Liquids and Solids / 360
16.3 Gibbs Function and the Equilibrium Constant in
Terms of Activity / 365
16.4 Dependence of Activity on Pressure / 367
16.5 Dependence of Activity on Temperature / 368
Standard Partial Molar Enthalpies / 368
Equation for Temperature Derivative of the Activity / 369
16.6 Standard Entropy / 370
16.7 Deviations from Ideality in Terms of Excess Thermodynamic
Functions / 373
Representation of G„ as a Function of Composition / 374
16.8 Regulär Solutions and Henry's Law / 376
16.9 Regulär Solutions and Limited Miscibility / 378
Exercises / 381
References / 384
CONTENTS XV
17 DETERMINATION OF NONELECTROLYTE ACTIVITIES AND
EXCESS GIBBS FUNCTIONS FROM EXPERIMENTAL DATA 385
17.1 Activity from Measurements of Vapor Pressure / 385
Solvent / 385
Solute / 386
17.2 Excess Gibbs Function from Measurement of Vapor Pressure / 388
17.3 Activity of a Solute from Distribution between
Two Immiscible Solvents / 391
17.4 Activity from Measurement of Cell Potentials / 393
17.5 Determination of the Activity of One Component from the
Activity of the Other / 397
Calculation of Activity of Solvent from That of Solute / 398
Calculation of Activity of Solute from That of Solvent / 399
17.6 Measurements of Freezing Points / 400
Exercises / 401
References / 406
18 CALCULATION OF PARTIAL MOLAR QUANTITIES
AND EXCESS MOLAR QUANTITIES FROM EXPERIMENTAL
DATA: VOLUME AND ENTHALPY 407
18.1 Partial Molar Quantities by Differentiation of J as a
Function of Composition / 407
Partial Molar Volume / 409
Partial Molar Enthalpy / 413
Enthalpies of Mixing / 414
Enthalpies of Dilution / 417
18.2 Partial Molar Quantities of One Component from those of
Another Component by Numerical Integration / 420
Partial Molar Volume / 421
Partial Molar Enthalpy / 421
18.3 Analytic Methods for Calculation of Partial Molar Properties / 422
Partial Molar Volume / 422
Partial Molar Enthalpy / 423
18.4 Changes in J for Some Processes in Solutions / 423
Transfer Process / 423
Integral Process / 425
18.5 Excess Properties: Volume and Enthalpy / 426
Excess Volume / 426
Excess Enthalpy / 426
Exercises / 427
References / 436
XVi CONTENTS
19 ACTIVITY, ACTIVITY COEFFICIENTS, AND OSMOTIC
COEFFICIENTS OF STRONG ELECTROLYTES 439
19.1 Definitions and Standard states for Dissolved Electrolytes / 440
Uni-univalent Electrolytes / 440
Multivalent Electrolytes / 443
Mixed Electrolytes / 446
19.2 Determination of Activities of Streng Electrolytes / 448
Measurement of Cell Potentials / 449
Solubility Measurements / 453
Colligative Property Measurement: The Osmotic Coefficient / 455
Extension of Activity Coefficient Data to Additional Temperatures
with Enthalpy of Dilution Data / 460
19.3 Activity Coefficients of Some Streng Electrolytes / 462
Experimental Values / 462
Theoretical Correlation / 462
Exercises / 464
References / 470
20 CHANGES IN GIBBS FUNCTION FOR PROCESSES
IN SOLUTIONS 471
20.1 Activity Coefficients of Weak Electrolytes / 471
20.2 Determination of Equilibrium Constants for Dissociation of
Weak Electrolytes / 472
From Measurements of Cell Potentials / 473
From Conductance Measurements / 475
20.3 Some Typical Calculations for AfGS, / 480
Standard Gibbs Function for Formation of
Aqueous Solute: HC1 / 480
Standard Gibbs Function of Formation of Individual
Ions: HC1 / 482
Standard Gibbs Function for Formation of Solid
Solute in Aqueous Solution / 482
Standard Gibbs Function for Formation of Ion of
Weak Electrolyte / 484
Standard Gibbs Function for Formation of
Moderately Streng Electrolyte / 485
Effect of Salt Concentration on Geological Equilibrium
Involving Water / 486
General Comments / 486
20.4 Entropies of Ions / 487
The Entropy of an Aqueous Solution of a Salt / 488
CONTENTS XVÜ
Entropy of Formation of Individual Ions / 488
Ion Entropies in Thermodynamic Calculations / 491
Exercises / 491
References / 496
21 SYSTEMS SUBJECT TO A GRAVITATIONAL OR A
CENTRIFUGAL FIELD 499
21.1 Dependence of the Gibbs Function on External Field / 499
21.2 System in a Gravitational Field / 502
21.3 System in a Centrifugal Field / 505
Exercises / 509
References / 510
22 ESTIMATION OF THERMODYNAMIC QUANTITIES 511
22.1 Empirical Methods / 511
Group Contribution Method of Andersen, Beyer,
Watson, and Yoneda / 512
Typical Examples of Estimating Entropies / 516
Other Methods / 522
Accuracy of the Approximate Methods / 522
Equilibrium in Complex Systems / 523
Exercises / 523
References / 524
23 CONCLUDING REMARKS 527
References / 529
APPENDIX A PRACTICAL MATHEMATICALTECHNIQUES 531
A.l Analytical Methods / 531
Linear Least Squares / 531
Nonlinear Least Squares / 534
A.2 Numerical and Graphical Methods / 535
Numerical Differentiation / 535
Numerical Integration / 538
Use of the Digital Computer / 540
Graphical Differentiation / 541
Graphical Integration / 542
Exercises / 542
References / 543
INDEX 545 |
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| discipline | Chemie / Pharmazie Physik Chemie |
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| id | DE-604.BV023323356 |
| illustrated | Illustrated |
| index_date | 2024-07-02T20:54:33Z |
| indexdate | 2024-07-09T21:15:52Z |
| institution | BVB |
| isbn | 9780470285237 9780471780151 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-016507412 |
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| physical | XXI, 563 S. graph. Darst. |
| publishDate | 2008 |
| publishDateSearch | 2008 |
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| publisher | Wiley |
| record_format | marc |
| spelling | Klotz, Irving M. 1916-2005 Verfasser (DE-588)139387951 aut Chemical thermodynamics basic concepts and methods Irving M. Klotz ; Robert M. Rosenberg 7. ed. Hoboken, NJ [u.a.] Wiley 2008 XXI, 563 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Thermodynamics Thermochemie (DE-588)4078260-8 gnd rswk-swf Thermodynamik (DE-588)4059827-5 gnd rswk-swf Thermochemie (DE-588)4078260-8 s DE-604 Thermodynamik (DE-588)4059827-5 s Rosenberg, Robert M. 1926- Verfasser (DE-588)139387986 aut HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016507412&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Klotz, Irving M. 1916-2005 Rosenberg, Robert M. 1926- Chemical thermodynamics basic concepts and methods Thermodynamics Thermochemie (DE-588)4078260-8 gnd Thermodynamik (DE-588)4059827-5 gnd |
| subject_GND | (DE-588)4078260-8 (DE-588)4059827-5 |
| title | Chemical thermodynamics basic concepts and methods |
| title_auth | Chemical thermodynamics basic concepts and methods |
| title_exact_search | Chemical thermodynamics basic concepts and methods |
| title_exact_search_txtP | Chemical thermodynamics basic concepts and methods |
| title_full | Chemical thermodynamics basic concepts and methods Irving M. Klotz ; Robert M. Rosenberg |
| title_fullStr | Chemical thermodynamics basic concepts and methods Irving M. Klotz ; Robert M. Rosenberg |
| title_full_unstemmed | Chemical thermodynamics basic concepts and methods Irving M. Klotz ; Robert M. Rosenberg |
| title_short | Chemical thermodynamics |
| title_sort | chemical thermodynamics basic concepts and methods |
| title_sub | basic concepts and methods |
| topic | Thermodynamics Thermochemie (DE-588)4078260-8 gnd Thermodynamik (DE-588)4059827-5 gnd |
| topic_facet | Thermodynamics Thermochemie Thermodynamik |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016507412&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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