Chemical Thermodynamics. Basic Concepts and Methods

Cover Page......Page 1
Title Page......Page 0
ISBN 0471780154......Page 3
CONTENTS (with page links)......Page 5
PREFACE......Page 17
1.1 Origins of Chemical Thermodynamics......Page 21
1.3 Limitations of Classic Thermodynamics......Page 24
References......Page 26
2 MATHEMATICAL PREPARATION FOR THERMODYNAMICS......Page 29
Partial Differentiation......Page 30
Exact Differentials......Page 35
Homogeneous Functions......Page 38
Exercises......Page 41
References......Page 47
3.1 Definitions......Page 49
Temperature......Page 51
Work......Page 53
Energy......Page 57
General Form of the First Law......Page 58
Exercises......Page 60
References......Page 61
4 ENTHALPY, ENTHALPY OF REACTION, AND HEAT CAPACITY......Page 63
Definition......Page 64
Relationship between Q(V) and Q(P)......Page 66
Definitions and Conventions......Page 67
Enthalpy of Formation from Enthalpy of Reaction......Page 72
Enthalpy of Transition from Enthalpy of Combustion......Page 73
Enthalpy of Conformational Transition of a Protein from Indirect Calorimetric Measurements......Page 74
Enthalpy of Solid-State Reaction from Measurements of Enthalpy of Solution......Page 76
Definition of Bond Enthalpies......Page 77
Calculation of Bond Enthalpies......Page 78
Enthalpy of Reaction from Bond Enthalpies......Page 79
4.5 Heat Capacity......Page 80
Definition......Page 81
Some Relationships between C(P) and C(V)......Page 82
Heat Capacities of Gases......Page 84
Heat Capacities of Solids......Page 87
4.6 Enthalpy of Reaction as a Function of Temperature......Page 88
Analytic Method......Page 89
Arithmetic Method......Page 91
Exercises......Page 92
References......Page 98
Definition......Page 101
Enthalpy as a Function of Temperature Only......Page 103
Calculation of the Thermodynamic Changes in Expansion Processes......Page 104
Equations of State......Page 114
Joule-Thomson Effect......Page 118
Calculations of Thermodynamic Quantities in Reversible Expansions......Page 122
Exercises......Page 124
References......Page 128
6.1 The Need for a Second Law......Page 131
Statement of the Second Law......Page 132
6.3 The Carnot Cycle......Page 133
The Forward Cycle......Page 134
The Reverse Cycle......Page 136
Alternative Statement of the Second Law......Page 137
Carnot’s Theorem......Page 138
6.4 The Thermodynamic Temperature Scale......Page 140
6.5 The Definition of S, the Entropy of a System......Page 145
Any Substance in a Carnot Cycle......Page 146
Any Substance in Any Reversible Cycle......Page 147
Entropy S Depends Only on the State of the System......Page 149
Isothermal Reversible Changes......Page 150
Reversible Phase Transitions......Page 151
Isobaric Reversible Temperature Changes......Page 152
Irreversible Isothermal Expansion of an Ideal Gas......Page 153
Irreversible Adiabatic Expansion of an Ideal Gas......Page 155
Irreversible Flow of Heat from a Higher Temperature to a Lower Temperature......Page 156
Irreversible Phase Transitions......Page 157
Irreversible Chemical Reactions......Page 158
General Statement......Page 159
Entropy of the Ideal Gas......Page 162
Entropy of a Real Gas......Page 163
6.10 Temperature-Entropy Diagram......Page 164
6.11 Entropy as an Index of Exhaustion......Page 166
Exercises......Page 170
References......Page 177
7.1 Reversibility, Spontaneity, and Equilibrium......Page 179
Systems at Constant Temperature and Volume......Page 180
Systems at Constant Temperature and Pressure......Page 182
Heat of Reaction as an Approximate Criterion of Spontaneity......Page 184
Changes in the Functions for Isothermal Conditions......Page 185
Equations for Total Differentials......Page 186
Pressure and Temperature Derivatives of the Functions......Page 187
Equations Derived from the Reciprocity Relationship......Page 189
Standard States......Page 190
Isothermal Changes......Page 195
Changes at Constant Temperature and Pressure......Page 197
Relationship between ΔH(P) and Q(P) When Useful Work is Performed......Page 198
Application to Electrical Work......Page 199
Gibbs-Helmholtz Equation......Page 200
The Gibbs Function and Useful Work in Biologic Systems......Page 201
Exercises......Page 205
References......Page 211
8.1 Two Phases at Equilibrium as a Function of Pressure and Temperature......Page 213
Clapeyron Equation......Page 214
Clausius-Clapeyron Equation......Page 216
8.2 The Effect of an Inert Gas on Vapor Pressure......Page 218
Variable Total Pressure at Constant Temperature......Page 219
8.3 Temperature Dependence of Enthalpy of Phase Transition......Page 220
Arithmetic Method......Page 222
Analytic Method......Page 223
Exercises......Page 225
References......Page 230
9.1 State Functions for Systems of Variable Composition......Page 231
9.2 Criteria of Equilibrium and Spontaneity in Systems of Variable Composition......Page 233
9.3 Relationships Among Partial Molar Properties of a Single Component......Page 235
9.4 Relationships Between Partial Molar Quantities of Different Components......Page 236
Partial Molar Quantities for Pure Phase......Page 238
Chemical Potential and Escaping Tendency......Page 239
9.6 Chemical Equilibrium in Systems of Variable Composition......Page 241
Exercises......Page 243
Reference......Page 246
10.1 Mixtures of Ideal Gases......Page 247
The Entropy and Gibbs Function for Mixing Ideal Gases......Page 248
The Chemical Potential of a Component of an Ideal Gas Mixture......Page 250
Chemical Equilibrium in Ideal Gas Mixtures......Page 251
Dependence of K on Temperature......Page 252
10.2 The Fugacity Function of a Pure Real Gas......Page 256
Change of Fugacity with Pressure......Page 257
Change of Fugacity with Temperature......Page 258
10.3 Calculation of the Fugacity of a Real Gas......Page 259
Graphical or Numerical Methods......Page 260
Analytical Methods......Page 264
Approximate Value of α for a Van der Waals Gas......Page 267
Enthalpy of a Van der Waals Gas......Page 268
10.5 Mixtures of Real Gases......Page 269
Fugacity of a Component of a Gaseous Solution......Page 270
Fugacity Coefficients in Gaseous Solutions......Page 271
Equilibrium Constant and Change in Gibbs Functions and Planck Functions for Reactions of Real Gases......Page 272
Exercises......Page 273
References......Page 276
11.1 Need for the Third Law......Page 279
Nernst Heat Theorem......Page 280
Planck’s Formulation......Page 281
Statement of Lewis and Randall......Page 282
ΔC(P) in an Isothermal Chemical Reaction......Page 283
Temperature Derivatives of Pressure and Volume......Page 284
11.4 Entropies at 298 K......Page 285
Typical Calculations......Page 286
Apparent Exceptions to the Third Law......Page 290
Tabulations of Entropy Values......Page 294
Exercises......Page 297
References......Page 300
12.1 Determination of ΔG°(m) from Equilibrium Measurements......Page 301
12.2 Determination of ΔG°(m) from Measurements of Cell potentials......Page 304
12.3 Calculation of ΔG°(m) from Calorimetric Measurements......Page 305
12.4 Calculation of a Gibbs Function of a Reaction from Standard Gibbs Function of Formation......Page 306
Enthalpy Calculations......Page 307
Change in Standard Gibbs Function......Page 310
Exercises......Page 313
References......Page 321
13.1 Derivation of the Phase Rule......Page 323
Nonreacting Systems......Page 324
Reacting Systems......Page 326
13.2 One-Component Systems......Page 327
13.3 Two-Component Systems......Page 329
Two Phases at Different Pressures......Page 332
Phase Rule Criterion of Purity......Page 335
References......Page 336
14.1 Definition......Page 339
Volume Changes......Page 341
Heat Effects......Page 342
14.3 Thermodynamics of Transfer of a Component from One Ideal Solution to Another......Page 343
14.4 Thermodynamics of Mixing......Page 345
14.5 Equilibrium between a Pure Solid and an Ideal Liquid Solution......Page 347
Change of Solubility with Pressure at a Fixed Temperature......Page 348
Change of Solubility with Temperature......Page 349
Composition of the Two Phases in Equilibrium......Page 352
Exercises......Page 353
References......Page 355
15.1 Henry’s Law......Page 357
15.2 Nernst’s Distribution Law......Page 360
15.3 Raoult’s Law......Page 361
15.4 Van’t Hoff’s Law of Osmotic Pressure......Page 364
Osmotic Work in Biological Systems......Page 369
15.5 Van’t Hoff’s Law of Freezing-Point Depression and Boiling-Point Elevation......Page 370
Exercises......Page 373
References......Page 375
16 ACTIVITIES, EXCESS GIBBS FUNCTIONS, AND STANDARD STATES FOR NONELECTROLYTES......Page 377
Activity Coefficient......Page 378
Gases......Page 379
Liquids and Solids......Page 380
16.3 Gibbs Function and the Equilibrium Constant in Terms of Activity......Page 385
16.4 Dependence of Activity on Pressure......Page 387
Standard Partial Molar Enthalpies......Page 388
Equation for Temperature Derivative of the Activity......Page 389
16.6 Standard Entropy......Page 390
16.7 Deviations from Ideality in Terms of Excess Thermodynamic Functions......Page 393
Representation of G(E)(m) as a Function of Composition......Page 394
16.8 Regular Solutions and Henry’s Law......Page 396
16.9 Regular Solutions and Limited Miscibility......Page 398
Exercises......Page 401
References......Page 404
Solvent......Page 405
Solute......Page 406
17.2 Excess Gibbs Function from Measurement of Vapor Pressure......Page 408
17.3 Activity of a Solute from Distribution between Two Immiscible Solvents......Page 411
17.4 Activity from Measurement of Cell Potentials......Page 413
17.5 Determination of the Activity of One Component from the Activity of the Other......Page 417
Calculation of Activity of Solvent from That of Solute......Page 418
Calculation of Activity of Solute from That of Solvent......Page 419
17.6 Measurements of Freezing Points......Page 420
Exercises......Page 421
References......Page 426
18.1 Partial Molar Quantities by Differentiation of J as a Function of Composition......Page 427
Partial Molar Volume......Page 429
Partial Molar Enthalpy......Page 433
Enthalpies of Mixing......Page 434
Enthalpies of Dilution......Page 437
18.2 Partial Molar Quantities of One Component from those of Another Component by Numerical Integration......Page 440
Partial Molar Enthalpy......Page 441
Partial Molar Volume......Page 442
Transfer Process......Page 443
Integral Process......Page 445
Excess Enthalpy......Page 446
Exercises......Page 447
References......Page 456
19 ACTIVITY, ACTIVITY COEFFICIENTS, AND OSMOTIC COEFFICIENTS OF STRONG ELECTROLYTES......Page 459
Uni-univalent Electrolytes......Page 460
Multivalent Electrolytes......Page 463
Mixed Electrolytes......Page 466
19.2 Determination of Activities of Strong Electrolytes......Page 468
Measurement of Cell Potentials......Page 469
Solubility Measurements......Page 473
Colligative Property Measurement: The Osmotic Coefficient......Page 475
Extension of Activity Coefficient Data to Additional Temperatures with Enthalpy of Dilution Data......Page 480
Theoretical Correlation......Page 482
Exercises......Page 484
References......Page 490
20.1 Activity Coefficients of Weak Electrolytes......Page 491
20.2 Determination of Equilibrium Constants for Dissociation of Weak Electrolytes......Page 492
From Measurements of Cell Potentials......Page 493
From Conductance Measurements......Page 495
Standard Gibbs Function for Formation of Aqueous Solute: HCl......Page 500
Standard Gibbs Function for Formation of Solid Solute in Aqueous Solution......Page 502
Standard Gibbs Function for Formation of Ion of Weak Electrolyte......Page 504
Standard Gibbs Function for Formation of Moderately Strong Electrolyte......Page 505
General Comments......Page 506
20.4 Entropies of Ions......Page 507
Entropy of Formation of Individual Ions......Page 508
Exercises......Page 511
References......Page 516
21.1 Dependence of the Gibbs Function on External Field......Page 519
21.2 System in a Gravitational Field......Page 522
21.3 System in a Centrifugal Field......Page 525
Exercises......Page 529
References......Page 530
22.1 Empirical Methods......Page 531
Group Contribution Method of Andersen, Beyer, Watson, and Yoneda......Page 532
Typical Examples of Estimating Entropies......Page 536
Accuracy of the Approximate Methods......Page 542
Exercises......Page 543
References......Page 544
23 CONCLUDING REMARKS......Page 547
References......Page 549
Linear Least Squares......Page 551
Nonlinear Least Squares......Page 554
Numerical Differentiation......Page 555
Numerical Integration......Page 558
Use of the Digital Computer......Page 560
Graphical Differentiation......Page 561
Exercises......Page 562
References......Page 563
INDEX (with page links)......Page 565