Liquids, Solutions, and Interfaces: From Classical Macroscopic..

Cover Page......Page 1
Title Page......Page 4
ISBN 0195094328......Page 5
Preface......Page 8
Contents (with page links)......Page 12
Fundamental Constants......Page 17
1.1 Most Liquid Solutions Are Not Ideal......Page 20
1.2 Concentration Units......Page 21
1.3 Thermodynamic Quantities......Page 23
1.4 Partial Molar Quantities......Page 26
1.5 Ideal Solutions—Raoult's Law......Page 32
1.6 Thermodynamics of Ideal Solutions......Page 33
1.7 Non-Ideal Solutions......Page 35
1.8 Thermodynamics of Non-Ideal Solutions......Page 38
1.9 Regular Solutions......Page 41
1.10 An Empirical Approach to Non-Ideal Solutions......Page 47
1.11 Ideally Dilute Solutions......Page 50
1.12 Thermodynamics of Ideally Dilute Solutions......Page 51
1.13 Experimental Determination of Solution Activities......Page 55
1.14 Concluding Remarks......Page 57
Problems......Page 58
2.1 What Is a Liquid?......Page 62
2.2 The Statistical Thermodynamics of Liquids......Page 64
2.3 Intermolecular Forces......Page 69
2.4 Distribution and Correlation Functions......Page 78
2.5 The Experimental Study of Liquid Structure......Page 82
2.6 The Direct Correlation Function and the Mean Spherical Approximation......Page 87
2.7 Computer Simulations of Simple Liquids......Page 90
2.8 Estimation of Thermodynamic Properties from the Pair Correlation Function......Page 92
2.9 The Properties of a Hard-Sphere Fluid......Page 96
2.10 The Structure of Water......Page 101
2.11 Distribution Functions for Liquid Solutions......Page 105
2.12 Concluding Remarks......Page 107
References......Page 108
Problems......Page 109
3.1 Electrolyte Solutions Are Always Non-Ideal......Page 112
3.2 Ionic Size in Solutions......Page 114
3.3 The Thermodynamics of Ion–Solvent Interactions......Page 117
3.4 Ion–Solvent Interactions According to the Born Model......Page 119
3.5 Ion–Solvent Interactions According to the Mean Spherical Approximation......Page 123
3.6 The Thermodynamics of Electrolyte Solutions......Page 128
3.7 The Experimental Determination of Activity Coefficients for Electrolytes......Page 133
3.8 Ion–Ion Interactions According to the Debye–Hückel Model......Page 138
3.9 Ion–Ion Interactions According to the MSA......Page 147
3.10 The Thermodynamics of Ion Association......Page 152
3.11 Ion Association According to the MSA......Page 157
3.12 Concluding Remarks......Page 160
References......Page 161
Problems......Page 162
4.1 What Constitutes a Polar Liquid?......Page 165
4.2 Some Important Properties of Polar Solvents......Page 166
4.3 The Static Solvent Permittivity on the Basis of Continuum Models......Page 170
4.4 The Static Solvent Permittivity According to the MSA......Page 179
4.5 Dielectric Relaxation Phenomena......Page 186
4.6 The Permittivity of Electrolyte Solutions......Page 193
4.7 The Dielectric Relaxation Parameters......Page 197
4.8 Ion Solvation in Polar Solvents......Page 201
4.9 Polar Solvents as Lewis Acids and Bases......Page 208
4.10 Concluding Remarks......Page 216
References......Page 217
Problems......Page 218
5. Spectroscopic Studies of Liquid Structure and Solvation......Page 221
5.1 What Spectroscopic Techniques Are Available?......Page 222
5.2 X-Ray and Neutron Diffraction Experiments......Page 223
5.3 Nuclear Magnetic Resonance Spectroscopy in Solutions......Page 230
5.4 NMR Studies of Ion Solvation in Water......Page 236
5.5 NMR Studies of Ion Solvation in Non-Aqueous Solvents......Page 240
5.6 Vibrational Spectroscopy in Solutions......Page 243
5.7 Infrared Spectroscopy of Polar Solvents......Page 249
5.8 Infrared Spectroscopy of Non-Electrolyte Solutions......Page 256
5.9 Infrared Spectroscopy of Electrolyte Solutions......Page 259
5.10 Ultraviolet–Visible Spectroscopy and Solvatochromic Effects......Page 262
5.11 Concluding Remarks......Page 267
References......Page 268
Problems......Page 269
6.1 Non-Equilibrium Processes Are Usually Complex......Page 271
6.2 The Thermodynamics of Irreversible Processes......Page 272
6.3 The Viscosity of Liquids......Page 276
6.4 Isothermal Diffusion in Solutions......Page 281
6.5 Linear Diffusion from a Wall......Page 283
6.6 The Electrochemical Potential......Page 288
6.7 The Conductivity of Electrolyte Solutions......Page 291
6.8 Experimental Studies of Conductivity......Page 300
6.9 The Debye–Onsager Model for Conductivity......Page 305
6.10 Transport Phenomena in Non-Aqueous Solutions......Page 311
6.11 Proton Transport Phenomena......Page 315
6.12 Concluding Remarks......Page 317
Problems......Page 318
7.1 What Time Scales Are Involved for Chemical Reactions in Solution?......Page 321
7.2 Fundamental Concepts......Page 322
7.3 General Types of Solution Reactions......Page 329
7.4 Temperature Effects and Transition State Theory......Page 340
7.5 Diffusion-Controlled Rapid Reactions......Page 346
7.6 Relaxation Techniques for Rapid Reactions......Page 349
7.7 Laser Spectroscopy and Femtochemistry in Solutions......Page 355
7.8 The Theory of Homogeneous Electron Transfer......Page 363
7.9 NMR Spectroscopy and Chemical Exchange Reactions......Page 375
7.10 Medium Effects in Solution Reactions......Page 383
7.11 Linear Gibbs Energy Relationships......Page 392
7.12 Concluding Remarks......Page 394
References......Page 396
Problems......Page 397
8.1 The Molecular Environment at the Interface Is Different than in the Bulk......Page 400
8.2 The Interfacial Tension of Liquids......Page 402
8.3 The Thermodynamics of Fluid Interfaces......Page 407
8.4 The Electrical Aspects of Interfaces......Page 412
8.5 The Work Function for Electrons in Metals......Page 415
8.6 The Liquid | Gas Interface and the Adsorption Isotherm......Page 418
8.7 Experimental Measurement of the Volta Potential Difference at Interfaces......Page 425
8.8 The Metal | Solution Interface......Page 439
8.9 The Liquid | Liquid Interface......Page 443
8.10 Surface Films on Liquids......Page 450
8.11 Spectroscopy at Liquid Interfaces......Page 454
8.12 Concluding Remarks......Page 459
References......Page 460
Problems......Page 461
9.1 Electrochemical Equilibria Occur at a Wide Variety of Interfaces......Page 464
9.2 Electrochemical Cells......Page 465
9.3 The Thermodynamic Basis of the Nernst Equation......Page 473
9.4 The Absolute Electrode Potential......Page 478
9.5 Experimental Studies of Electrochemical Cells......Page 481
9.6 Electrochemical Cells for Electroanalysis......Page 491
9.7 The Liquid Junction Potential......Page 494
9.8 Membrane Potentials and the Donnan Effect......Page 501
9.9 Ion-Selective Electrodes......Page 511
9.10 p-Functions and the Definition of pH......Page 519
9.11 Concluding Remarks......Page 521
Problems......Page 522
10.1 The Electrical Double Layer Is an Example of Electrostatic Equilibrium......Page 525
10.2 The Thermodynamics of the Ideally Polarizable Interface......Page 527
10.3 The Experimental Study of the Double Layer......Page 533
10.4 The Structure of the Double Layer......Page 547
10.5 The Potential of Zero Charge and the Role of the Metal......Page 552
10.6 The Gouy–Chapman Model of the Diffuse Double Layer......Page 559
10.7 The Structure of the Inner Layer in the Absence of Adsorption......Page 569
10.8 The Specific Adsorption of Ions......Page 575
10.9 The Adsorption of Molecules at Electrodes......Page 586
10.10 Concluding Remarks......Page 593
References......Page 594
Problems......Page 596
A.1 Laplace Transforms......Page 599
A.2 Fourier Transforms......Page 601
A.3 Complex Numbers and Functions......Page 602
A.4 Power Series......Page 603
Appendix B. The Laws of Electricity and Magnetism......Page 606
C.1 The Principle of Least Squares......Page 612
C.2 Linear Regression......Page 616
C.3 Multiple Linear Regression......Page 622
C.4 Numerical Methods......Page 625
C.5 Numerical Interpolation......Page 627
C.6 Numerical Integration......Page 629
C.7 Numerical Differentiation......Page 631
D......Page 634
F......Page 635
K......Page 636
R......Page 637
Y......Page 638
Back Page......Page 639