Introduction to Non-equilibrium Physical Chemistry
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Table of contents
- Cover
- Table of Contentsvii
- PREFACExiii
- ACKNOWLEDGEMENTSxv
- COLOUR PLATE SECTIONxvii
- CHAPTER 1 INTRODUCTION1
- 1.1. Real systems1
- 1.2. Equilibrium and non-equilibrium states1
- 1.3. Open systems2
- 1.4. Approach to equilibrium2
- 1.5. Non-equilibrium states3
- 1.6. Complex non-equilibrium phenomena4
- 1.7. Scope4
- References7
- PART ONE NON-EQUILIBRIUM STEADY STATES CLOSE TO EQUILIBRIUM9
- CHAPTER 2 BASIC PRINCIPLES OF NON-EQUILIBRIUM THERMODYNAMICS11
- 2.1. Introduction11
- 2.2. Second law of thermodynamics for open systems13
- 2.3. Law of conservation of mass, charge and energy15
- 2.4. Gibbs equation16
- 2.5. Phenomenological equations for single flows17
- 2.6. Phenomenological equations for coupled flows17
- 2.7. Onsager reciprocity relation19
- 2.8. Entropy production in multi-variable systems21
- 2.9. Basic postulates of non-equilibrium thermodynamics close to equilibrium22
- 2.10. Experimental test of LNT22
- 2.11. Application to other disciplines: sociology, economics and finance23
- 2.12. Concluding remarks23
- References24
- CHAPTER 3 APPLICATIONS TO TYPICAL STEADY-STATES PHENOMENA27
- 3.1. Introduction27
- 3.2. Thermodynamic theory of thermo-osmosis27
- 3.3. Thermodynamic theory of thermo-osmosis of gaseous non-reacting mixtures35
- 3.4. Experimental studies44
- 3.5. Thermo-osmosis of gases and gaseous mixtures51
- 3.6. Thermo-osmosis in biological systems55
- References56
- CHAPTER 4 ELECTRO-OSMOTIC PHENOMENA59
- 4.1. Introduction59
- 4.2. Non-equilibrium thermodynamics of electro-osmotic phenomena59
- 4.3. Theories based on models of membranes64
- 4.4. Experimental test of thermodynamic theory71
- 4.5. Concluding remarks76
- References77
- CHAPTER 5 NON-EQUILIBRIUM PHENOMENA IN CONTINUOUS SYSTEMS81
- 5.1. Introduction81
- 5.2. Theory: thermodynamic considerations81
- 5.3. Experimental studies in gaseous systems85
- 5.4. Dufour effect in liquid mixtures86
- 5.5. Thermal diffusion potential87
- 5.6. Electric potentials generated at crystal interface89
- References91
- CHAPTER 6 ELECTROPHORESIS AND SEDIMENTATION POTENTIAL93
- 6.1. Introduction93
- 6.2. Thermodynamic theory93
- 6.3. Comparison with Helmholtz double layer theory95
- 6.4. Test of theory: experimental studies96
- References98
- PART TWO NON-LINEAR STEADY STATES – DISSIPATIVE STRUCTURE (TIME ORDER AND SPACE ORDER)99
- CHAPTER 7 NON-LINEAR STEADY STATES101
- 7.1. Introduction101
- 7.2. Non-linear flux equations in electro-kinetic phenomena101
- 7.3. Non-linear steady states104
- 7.4. Interpretation of second-order coefficients in the light of double layer theory105
- 7.5. Non-linear transport equations in gaseous medium109
- 7.6. Non–linear flux equations and non-linear steady states in chemical reactions111
- 7.7. General remarks115
- References116
- CHAPTER 8 BIFURCATION PHENOMENON AND MULTI-STABILITY119
- 8.1. Introduction119
- 8.2. Dynamical non-linear systems119
- 8.3. Typical types of bifurcation121
- 8.4. Bifurcation from steady state to bistability125
- 8.5. Bifurcation from steady state to oscillatory state125
- 8.6. Multi-stability126
- 8.7. A simple mathematical model of bistability126
- 8.8. A simple model for reacting systems127
- 8.9. Bistability in reacting systems128
- 8.10. Spatial bistability132
- 8.11. Bistability in magnetic resonance132
- 8.12. Bistability in electro-kinetic phenomena133
- 8.13. Bistability in biological systems136
- References137
- CHAPTER 9 TIME ORDER – CHEMICAL OSCILLATIONS139
- 9.1. Introduction139
- 9.2. Isothermal chemical dissipative structures139
- 9.3. Chemical oscillators140
- 9.4. Modelling of oscillatory reactions148
- 9.5. Mechanism of B–Z reaction; positive and negative feedback149
- 9.6. Alternate control mechanism153
- 9.7. Dual control mechanism154
- 9.8. Coupled oscillators160
- 9.9. Logic function162
- References162
- CHAPTER 10 CHEMICAL WAVES AND STATIONARY PATTERNS165
- 10.1. Introduction165
- 10.2. Chemical waves and stationary patterns165
- 10.3. One-dimensional chemical waves166
- 10.4. Mechanism of wave propagation167
- 10.5. Wave formation on membranes169
- 10.6. Wave structures170
- 10.7. Turing instability171
- 10.8. Logic functions175
- 10.9. Precipitation patterns176
- References184
- PART THREE COMPLEX NON-EQUILIBRIUM PHENOMENA FAR FROM EQUILIBRIUM187
- CHAPTER 11 DYNAMIC INSTABILITY AT INTERFACES189
- 11.1. Introduction189
- 11.2. Dynamic instability at solid–liquid interface190
- 11.3. Dynamic instability at liquid–liquid interface along with solid–liquid interface199
- 11.4. Dynamic instability at liquid–vapour interface209
- 11.5. Dynamic instability at solid–gas interface [60–68]213
- References215
- CHAPTER 12 COMPLEX OSCILLATIONS AND CHAOS217
- 12.1. Introduction217
- 12.2. Complex oscillations217
- 12.3. Deterministic chaos223
- 12.4. Routes to chaos226
- 12.5. Characterization of chaos226
- 12.6. Modelling and test of reliability229
- 12.7. Control of chaos231
- 12.8. Noise232
- 12.9. Turbulence233
- 12.10. Future perspectives233
- References234
- CHAPTER 13 COMPLEX PATTERN FORMATION235
- 13.1. Introduction235
- 13.2. Experimental studies of complex patterns247
- 13.3. Concluding remarks266
- References267
- PART FOUR NON-EQUILIBRIUM PHENOMENA IN NATURE AND SOCIETY271
- CHAPTER 14 SOCIAL DYNAMICS, ECONOMICS AND FINANCE273
- 14.1. Complexity in real systems273
- 14.2. Methodology and strategy for study of complex systems273
- 14.3. Analytical studies of real systems277
- 14.4. Quantification of relationship between cause and effect279
- 14.5. Sociology (social sciences)283
- 14.6. Economics289
- References294
- CHAPTER 15 LIVING SYSTEMS297
- 15.1. Introduction297
- 15.2. Transport through biomembranes301
- 15.3. Biological rhythm305
- 15.4. Concluding remarks312
- References313
- EPILOGUE315
- 1. Introduction315
- 2. Beyond linear region316
- 3. Bifurcation phenomena316
- 4. Temporal oscillations317
- 5. Spatio-temporal oscillations (oscillations in time as well as space)317
- 6. Fractal growth318
- 7. Real systems318
- 8. Conclusion318
- APPENDIX I DOMAIN OF VALIDITY OF GIBBS EQUATION321
- 1. Introduction321
- 2. Justification of assumption of local equilibrium321
- 3. Results of experimental studies322
- 4. Recent developments322
- References323
- APPENDIX II EXTENDED IRREVERSIBLE THERMODYNAMICS325
- References327
- APPENDIX III NON-EQUILIBRIUM MOLECULAR DYNAMICS329
- 1. Introduction329
- 2. Molecular scale simulation329
- 3. Limitations of molecular dynamics330
- 4. Equilibrium molecular dynamics330
- 5. Non-equilibrium molecular dynamics330
- 6. Non-equilibrium molecular dynamics simulation (NEMD)331
- 7. Applications331
- References332
- INDEX333
The book presents a critical and comprehensive account of Non-equilibrium Physical Chemistry from theoretical and experimental angle. It covers a wide spectrum of non-equilibrium phenomena from steady state close to equilibrium to non-linear region involving transition to bistability, temporal oscillations, spatio-temporal oscillations and finally to far from equilibrium phenomena such as complex pattern formation, dynamic instability at interfaces, Chaos and complex growth phenomena (fractals) in Physico-chemical systems.
Part I of the book deals with theory and experimental studies concerning transport phenomena in membranes (Thermo-osmosis,Electroosmotic ) and in continuous systems (Thermal diffusion,Soret effect) close to equilibrium Experimental tests provide insight into the domain of validity of Non-equilibrium Thermodynamics ,which is the major theoretical tool for this region. Later developments in Extended Irreversible Thermodynamics and Non-equilibrium Molecular dynamics have been discussed in the Appendix.
Part II deals with non-linear steady states and bifurcation to multistability, temporal and spatio- temporal oscillations (Chemical waves). Similarly Part II deals with more complex phenomena such as Chaos and fractal growth occurring in very far from equilibrium region. Newer mathematical techniques for investigating such phenomena along with available experimental studies.
Part IV deals with analogous non-equilibrium phenomena occurring in the real systems (Socio-political, Finance and Living systems etc.) for which physico-chemical systems discussed in earlier chapters provide a useful model for development of theories based on non-linear science and science of complexity.
Key Features:
- The book provides a critical account of theoretical studies on non-equilibrium phenomenon from region close to equilibrium to far equilibrium.
- Experimental studies have been reported which provide test of the theories and their limitations.
- Impacts of the concepts developed in non-equilibrium Physical Chemistry in sociology, economics and other social science and living systems has been discussed.
Part I of the book deals with theory and experimental studies concerning transport phenomena in membranes (Thermo-osmosis,Electroosmotic ) and in continuous systems (Thermal diffusion,Soret effect) close to equilibrium Experimental tests provide insight into the domain of validity of Non-equilibrium Thermodynamics ,which is the major theoretical tool for this region. Later developments in Extended Irreversible Thermodynamics and Non-equilibrium Molecular dynamics have been discussed in the Appendix.
Part II deals with non-linear steady states and bifurcation to multistability, temporal and spatio- temporal oscillations (Chemical waves). Similarly Part II deals with more complex phenomena such as Chaos and fractal growth occurring in very far from equilibrium region. Newer mathematical techniques for investigating such phenomena along with available experimental studies.
Part IV deals with analogous non-equilibrium phenomena occurring in the real systems (Socio-political, Finance and Living systems etc.) for which physico-chemical systems discussed in earlier chapters provide a useful model for development of theories based on non-linear science and science of complexity.
Key Features:
- The book provides a critical account of theoretical studies on non-equilibrium phenomenon from region close to equilibrium to far equilibrium.
- Experimental studies have been reported which provide test of the theories and their limitations.
- Impacts of the concepts developed in non-equilibrium Physical Chemistry in sociology, economics and other social science and living systems has been discussed.