Encyclopedia of Physical Science and Technology, 3e, Physical Chemistry

Cover......Page 1
Glossary......Page 2
Mathematical Manipulation of Rate Data......Page 3
Computer Modeling of Reaction Systems......Page 4
Conventional Methods......Page 5
High-Pressure Methods......Page 8
Stopped-Flow Methods......Page 9
Gas-Flow Methods......Page 10
Flash Photolysis......Page 11
Pulse Radiolysis......Page 14
Shock Tubes......Page 15
Relaxation Methods......Page 16
Electrochemical Methods......Page 17
References......Page 19
Glossary......Page 20
Thermodynamic Systems and Properties......Page 21
Composition Variables......Page 22
Second Law......Page 23
Homogeneous Systems......Page 24
Electrochemical Systems......Page 25
Caloric Equation......Page 26
Definitions......Page 27
Molar Quantities of Pure Compounds and Molar Quantities at Infinite Dilution......Page 28
Chemical Potential in Gas Mixtures......Page 29
Chemical Potentials in Condensed Phases......Page 30
Conversion of Reference Potentials and Activity Coefficients......Page 31
Generalized Forces and Internal Variables......Page 32
Equilibria at Phase Boundaries......Page 33
Theory of Phase Diagrams......Page 34
Generalized Forces and Internal Variables in Chemical Reactions......Page 35
Equilibrium of Electrochemical Systems......Page 36
Liquid–Liquid Equilibria......Page 37
Electrochemical System Equilibria......Page 38
References......Page 39
Glossary......Page 40
Methods Used in Computational Chemistry......Page 41
Energy Terms......Page 42
Torsion energy.......Page 43
Parametrization......Page 44
Wave Function Quantum-Mechanical Methods......Page 45
Hartree-Fock Method......Page 46
Neglect of diatomic differential overlap.......Page 48
Electron-Correlated Methods......Page 49
Multiconfiguration self-consistent field.......Page 50
Many-body perturbation theory.......Page 51
Coupled cluster methods.......Page 52
Basis Sets......Page 53
Density Functional Theory......Page 54
Applications of Computational Chemistry......Page 55
Wave Function Analysis in Terms of Basis Functions......Page 56
Computing Properties......Page 57
Outlook for Computational Chemistry......Page 58
References......Page 59
Glossary......Page 60
Kinetics and Collision Theory......Page 61
Activated Complex Theory......Page 67
Statistical Theories of Unimolecular Decomposition......Page 68
Reactions in Solution......Page 69
Cross Section Measurements......Page 70
Angular and Velocity Resolved Studies......Page 71
Product Detection Using Spectroscopic Methods......Page 75
Spectroscopy of the Transition State......Page 77
References......Page 78
Glossary......Page 79
lonogenes......Page 80
Fundamentals......Page 81
Activity Coefficients......Page 82
Ionic Equilibria......Page 83
Partial and Apparent Molar Quantities......Page 84
Ion Solvation......Page 86
Distribution Functions and Mean Force Potential......Page 87
Fundamentals......Page 89
Ion-Pair Concept......Page 90
Debye-H¨uckel Theory and Extensions......Page 91
Mean Spherical Approximation......Page 92
Hypernetted Chain and Percus-Yevick Approximations......Page 93
Semiempirical Equations......Page 94
Generalities......Page 95
Vapor Pressure Measurements......Page 96
Molar Volumes......Page 97
Heats of Solution and Dilution......Page 98
Electromotive Force......Page 99
References......Page 100
Glossary......Page 102
Definitions......Page 103
Electrolyte Solutions in Irreversible Thermodynamic Processes......Page 104
Chemical Diffusion......Page 105
Reaction–Diffusion Coupling......Page 106
Hamiltonian Models of Transport Processes......Page 107
Single-Ion and Electrolyte Conductivity......Page 109
Dispersion of Conductance......Page 110
Conductivity Equations of Dilute Electrolyte Solutions......Page 111
Theory of Transference Numbers of Dilute Solutions......Page 113
Triple-Ion and Higher-Ion Aggregate Formation......Page 114
Empirical Equations......Page 115
Conductivity Equations......Page 117
References......Page 118
Glossary......Page 119
Introduction......Page 120
Two Model Calculations......Page 121
Fundamental Issues: Qualitative Overview......Page 125
The Hamiltonian......Page 127
Classical Mechanics......Page 128
Integrable Systems......Page 129
Mixing......Page 130
Typical Molecular Systems......Page 131
Anharmonicity of H0.......Page 132
Overlapping resonances.......Page 133
Quantum Dynamics......Page 134
Statistical Approximations and Dynamics......Page 140
Experimental Studies......Page 141
See also the Following Articles......Page 142
References......Page 143
Glossary......Page 144
Interaction Energy......Page 148
Induction Interaction......Page 150
Exchange Interaction......Page 151
Multipole Expansion......Page 152
Many-Body Effects......Page 153
Analytic Representations of Potential Surfaces......Page 155
Nature of Hydrogen Bond......Page 156
Properties of Hydrogen Bonds......Page 161
Types of Hydrogen Bonds......Page 162
Dimers......Page 163
Trimers and Larger Clusters......Page 164
Hydrogen Bonds in Solids......Page 167
Hydrogen Bonds in Liquids......Page 169
Proton Transfer......Page 172
Hydrogen Bonds in Biological Structures......Page 173
References......Page 176
Glossary......Page 178
Ion Energetics......Page 179
Ion Kinetics......Page 180
Threshold Determination......Page 181
Ion Enthalpies of Formation from Threshold Energies......Page 184
Proton and Electron Transfer Equilibria......Page 186
Molecular Recognition......Page 187
The Kinetic Method......Page 188
Sources of Evaluated Data......Page 189
Ion-Neutral Collision Cross Sections and Rates......Page 190
Low-Temperature Dynamics......Page 192
Vibrational-State Resolution in Ion–Molecule Reactions......Page 193
Mode-Selective Chemistry......Page 194
References......Page 195
Glossary......Page 196
Basic Kinetic Principles......Page 197
Molecularity......Page 199
Temperature And Reaction Rates......Page 200
Statistical Theories Of Rates......Page 202
Reaction Dynamics......Page 204
Reactions In The Gas Phase......Page 206
Reactions In Solution......Page 207
Reactions On Surfaces......Page 209
Composite Reaction Mechanisms......Page 210
Photochemical And Radiation-Chemical Reactions......Page 213
Homogeneous Catalysis......Page 214
References......Page 217
Glossary......Page 218
Monolayer Membranes......Page 219
Chemical Etching......Page 220
Liquid Membranes......Page 221
Membrane Modifiers......Page 222
Channel Molecules......Page 223
Electron Microscopy......Page 224
The Donnan Equilibrium......Page 225
See also the Following Articles......Page 226
References......Page 227
Glossary......Page 228
Micelle Formation......Page 229
The Hydrophobic Effect......Page 230
Electrostatic Interactions......Page 231
The Hydrocarbon Core......Page 232
Hydration in the Micelle......Page 233
Surfactant Organization in Micelles......Page 234
Micellar Kinetics......Page 235
Solubilization......Page 236
Micellar Catalysis......Page 237
Surfactant Aggregates at Solid-Liquid Interfaces......Page 239
Aggregates at Hydrophilic Surfaces......Page 241
See also the Following Articles......Page 243
References......Page 244
Glossary......Page 245
Duality of Matter and Energy; Uncertainty Principle......Page 246
Hydrogen-Like Atom; Electronic Transitions......Page 247
Molecular Systems: Chemical Bond......Page 248
Spectroscopy......Page 249
Free Energy; Experimental Measurements......Page 250
Statistical Mechanics; Partition Function......Page 251
Liquids; van der Waals Theory; Critical Point; Renormalization Group......Page 252
Mixtures......Page 253
Solids......Page 254
Kinetic Theory of Gases......Page 255
Transport Properties......Page 256
Chemical Kinetics; Activated Complex Theory......Page 257
Reaction Dynamics; Inelastic Collisions......Page 258
Reactions in Solution......Page 259
Reactions at Surfaces; Heterogeneous Catalysis; Corrosion......Page 260
References......Page 262
Glossary......Page 263
Quantum Mechanical Basis for Adiabatic Potential Energy Surfaces......Page 264
Topology of Adiabatic Potential Energy Surfaces......Page 266
Breakdown of the Adiabatic Approximation......Page 267
Diatomics......Page 268
Larger Molecules......Page 269
References......Page 271
The Structure–Property Relationship......Page 272
Solid-State Structure and Structural Characterization......Page 273
Preparation Techniques and Property Variation......Page 274
References......Page 275
Glossary......Page 277
Disorder in Solids......Page 278
Transport by Diffusion......Page 281
Atomistic Interpretation of the Transport of Ions in Solids......Page 282
Silver Ion Conductors......Page 283
Proton Conductors......Page 284
Galvanic Cells with Solid Electrolytes......Page 285
Measurements under Steady-State Conditions......Page 286
Measurements of Chemical Diffusion Coefficients......Page 287
Electrochemical Investigations of Formation of Surface Layers on Metals......Page 288
Investigations on the Forces of Inertia of the Mobile Ions in Solid Ionic Conductors......Page 289
Sensors......Page 290
Solid Electrolyte Batteries: The Sodium–Sulfur Cell......Page 291
References......Page 292
Glossary......Page 293
Acid Strength and Acidity Scale......Page 294
Bronsted Superacids......Page 295
Fluorosulfuric Acid (HSO3F)......Page 296
Antimony Pentafluoride (SbF5)......Page 297
Boron tris(Trifluoromethanesulfonate) B(OSO2CF3)3]......Page 298
Fluorosulfuric Acid–Antimony Pentafluoride (Magic Acid)......Page 299
HSO3F–Nb(SO3F)5 and HSO3H–Ta(SO3F)5......Page 300
Immobilized Superacids Bound to Inert Supports)......Page 301
Aromatic and Homoaromatic Cations and Carbodications......Page 302
Isomerization......Page 303
Superacids in Organic Syntheses and Superelectrophilic Activation......Page 304
Superelectrophilic Activation......Page 305
References......Page 306
Glossary......Page 307
Field-Ion Microscopy......Page 308
Atomic -Beam Diffraction......Page 309
Ion Scattering......Page 311
Surface Relaxation......Page 313
Stepped and Kinked Surfaces......Page 314
Introduction......Page 315
The Ordering of Adsorbed Monolayers......Page 316
The Effect Surface Irregularities on Ordering......Page 317
Ordered Atomic Monolayers......Page 318
Ordered Organic Monolayers......Page 320
Vibrational Spectroscopy......Page 321
Introduction......Page 322
Surface Tension in a One-Component System......Page 323
Surface Tension of Multicomponent System......Page 324
Equilibrium Shape of a Crystal or a Liquid Droplet......Page 326
Nucleation......Page 327
Physical and Chemical Adsorption......Page 328
Adsorption Isotherms......Page 329
Heat of Adsorption......Page 331
The Energy Level Diagram......Page 333
Surface Dipole and Surface Space Charge......Page 334
Work Function and Contact Potential......Page 335
Electron Emission from Surfaces......Page 337
Photoelectron Specstroscopy......Page 339
Surface Diffusion......Page 341
Surface Reactions......Page 343
Molecular-Beam Scattering......Page 345
Molecular-Beam Reactive Scattering......Page 346
Stoichiometric Surface Reactions......Page 347
Catalytic Surface Reactions......Page 348
Photochemical Surface Reactions......Page 353
References......Page 355
Glossary......Page 356
Basic Experimental Findings......Page 357
Model and Theory......Page 358
Electronic States of a Free Ion......Page 359
Term Splitting Under Oh Symmetry......Page 360
Term-Splitting Under D4h Symmetry......Page 361
Weak- and Strong-Field Methods, Term Diagrams......Page 362
Dq Values and Spectrochemical Series......Page 364
Ligand-Field theory......Page 365
Optical Properties of Complexes......Page 367
Magnetic Properties of Complexes......Page 368
Stabilization of Complexes......Page 369
Heats of Hydration......Page 370
References......Page 371
Introduction......Page 372
Description Based Upon Linear Combination of Atomic Orbitals......Page 373
Contragradience and the Origin of Chemical Bonding......Page 374
The Molecular Orbital Description of H2......Page 375
Comparison of Vb And MO Wave Functions......Page 377
Low-Lying States of Chn......Page 378
Ethylene......Page 379
References......Page 380