Introduction to Non-equilibrium Physical Chemistry

Front Cover......Page 1
Introduction to Non-equilibrium Physical Chemistry......Page 4
Copyright Page......Page 5
Table of Contents......Page 8
PREFACE......Page 14
ACKNOWLEDGEMENTS......Page 16
COLOUR PLATE SECTION......Page 18
1.2. Equilibrium and non-equilibrium states......Page 22
1.4. Approach to equilibrium......Page 23
1.5. Non-equilibrium states......Page 24
1.7. Scope......Page 25
References......Page 28
PART ONE NON-EQUILIBRIUM STEADY STATES CLOSE TO EQUILIBRIUM......Page 30
2.1. Introduction......Page 32
2.2. Second law of thermodynamics for open systems......Page 34
2.3. Law of conservation of mass, charge and energy......Page 36
2.4. Gibbs equation......Page 37
2.6. Phenomenological equations for coupled flows......Page 38
2.7. Onsager reciprocity relation......Page 40
2.8. Entropy production in multi-variable systems......Page 42
2.10. Experimental test of LNT......Page 43
2.12. Concluding remarks......Page 44
References......Page 45
3.2. Thermodynamic theory of thermo-osmosis......Page 48
3.3. Thermodynamic theory of thermo-osmosis of gaseous non-reacting mixtures......Page 56
3.4. Experimental studies......Page 65
3.5. Thermo-osmosis of gases and gaseous mixtures......Page 72
3.6. Thermo-osmosis in biological systems......Page 76
References......Page 77
4.2. Non-equilibrium thermodynamics of electro-osmotic phenomena......Page 80
4.3. Theories based on models of membranes......Page 85
4.4. Experimental test of thermodynamic theory......Page 92
4.5. Concluding remarks......Page 97
References......Page 98
5.2. Theory: thermodynamic considerations......Page 102
5.3. Experimental studies in gaseous systems......Page 106
5.4. Dufour effect in liquid mixtures......Page 107
5.5. Thermal diffusion potential......Page 108
5.6. Electric potentials generated at crystal interface......Page 110
References......Page 112
6.2. Thermodynamic theory......Page 114
6.3. Comparison with Helmholtz double layer theory......Page 116
6.4. Test of theory: experimental studies......Page 117
References......Page 119
PART TWO NON-LINEAR STEADY STATES – DISSIPATIVE STRUCTURE (TIME ORDER AND SPACE ORDER)......Page 120
7.2. Non-linear flux equations in electro-kinetic phenomena......Page 122
7.3. Non-linear steady states......Page 125
7.4. Interpretation of second-order coefficients in the light of double layer theory......Page 126
7.5. Non-linear transport equations in gaseous medium......Page 130
7.6. Non–linear flux equations and non-linear steady states in chemical reactions......Page 132
7.7. General remarks......Page 136
References......Page 137
8.2. Dynamical non-linear systems......Page 140
8.3. Typical types of bifurcation......Page 142
8.5. Bifurcation from steady state to oscillatory state......Page 146
8.7. A simple mathematical model of bistability......Page 147
8.8. A simple model for reacting systems......Page 148
8.9. Bistability in reacting systems......Page 149
8.11. Bistability in magnetic resonance......Page 153
8.12. Bistability in electro-kinetic phenomena......Page 154
8.13. Bistability in biological systems......Page 157
References......Page 158
9.2. Isothermal chemical dissipative structures......Page 160
9.3. Chemical oscillators......Page 161
9.4. Modelling of oscillatory reactions......Page 169
9.5. Mechanism of B–Z reaction; positive and negative feedback......Page 170
9.6. Alternate control mechanism......Page 174
9.7. Dual control mechanism......Page 175
9.8. Coupled oscillators......Page 181
References......Page 183
10.2. Chemical waves and stationary patterns......Page 186
10.3. One-dimensional chemical waves......Page 187
10.4. Mechanism of wave propagation......Page 188
10.5. Wave formation on membranes......Page 190
10.6. Wave structures......Page 191
10.7. Turing instability......Page 192
10.8. Logic functions......Page 196
10.9. Precipitation patterns......Page 197
References......Page 205
PART THREE COMPLEX NON-EQUILIBRIUM PHENOMENA FAR FROM EQUILIBRIUM......Page 208
11.1. Introduction......Page 210
11.2. Dynamic instability at solid–liquid interface......Page 211
11.3. Dynamic instability at liquid–liquid interface along with solid–liquid interface......Page 220
11.4. Dynamic instability at liquid–vapour interface......Page 230
11.5. Dynamic instability at solid–gas interface [60–68]......Page 234
References......Page 236
12.2. Complex oscillations......Page 238
12.3. Deterministic chaos......Page 244
12.5. Characterization of chaos......Page 247
12.6. Modelling and test of reliability......Page 250
12.7. Control of chaos......Page 252
12.8. Noise......Page 253
12.10. Future perspectives......Page 254
References......Page 255
13.1. Introduction......Page 256
13.2. Experimental studies of complex patterns......Page 268
13.3. Concluding remarks......Page 287
References......Page 288
PART FOUR NON-EQUILIBRIUM PHENOMENA IN NATURE AND SOCIETY......Page 292
14.2. Methodology and strategy for study of complex systems......Page 294
14.3. Analytical studies of real systems......Page 298
14.4. Quantification of relationship between cause and effect......Page 300
14.5. Sociology (social sciences)......Page 304
14.6. Economics......Page 310
References......Page 315
15.1. Introduction......Page 318
15.2. Transport through biomembranes......Page 322
15.3. Biological rhythm......Page 326
15.4. Concluding remarks......Page 333
References......Page 334
1. Introduction......Page 336
3. Bifurcation phenomena......Page 337
5. Spatio-temporal oscillations (oscillations in time as well as space)......Page 338
8. Conclusion......Page 339
2. Justification of assumption of local equilibrium......Page 342
4. Recent developments......Page 343
References......Page 344
APPENDIX II EXTENDED IRREVERSIBLE THERMODYNAMICS......Page 346
References......Page 348
2. Molecular scale simulation......Page 350
5. Non-equilibrium molecular dynamics......Page 351
7. Applications......Page 352
References......Page 353
INDEX......Page 354