THERMODYNAMICS
CONTENTS CHAPTER FUNDAMENTALS 1 1 INTRODUCTORY DE?NITIONS REMARKS AND QUERIES 1 2 THE ZEROTH LAW OF THERMODYNAMICS ADDITIONAL INFORMATION 1 3 MATHEMATICAL APPARATUS REMARKS 1 4 THERMODYNAMIC FORCES REFERENCE 1 5 ELEMENTS OF WORK COMMENT AND QUERIES 1 6 THE ELEMENT OF WORK FOR A SYSTEM SUBJECTED TO ELECTROMAGNETIC FIELDS REMARK AND REFERENCE 1 7 THE FIRST LAW OF THERMODYNAMICS NOTES 1 8 THE SECOND LAW OF THERMODYNAMICS FOOTNOTES AND QUERY 1 9 CONSEQUENCES OF THE FIRST AND SECOND LAWS REMARKS AND QUESTIONS 1 10 FUNCTIONS OF STATE; REPRISE APPENDIX A: REMARKS CONCERNING IRREVERSIBLE PROCESSES APPENDIX B: TIME-DEPENDENT IRREVERSIBLE PROCESSES 1 11 STATEMENTS OF THE SECOND LAW; THERMODYNAMIC OPERATION OF HEAT ENGINES; KELVIN AND PLANCK STATEMENTS; TEMPERATURE SCALE EXERCISE 1 12 SYSTEMATIZATION OF RESULTS BASED ON FUNCTIONS OF STATE REVIEW OF ELECTRONIC PROPERTIES OF METALS EXERCISES AND REMARK 1 13 THE THIRD LAW OF THERMODYNAMICS 1 14 THE GIBBS–DUHEM RELATION AND ITS ANALOGS QUERY AND REFERENCE 1 15 HEAT CAPACITIES; FUNDAMENTALS AND APPLICATIONS ACKNOWLEDGMENT EXERCISES AND COMMENTS 1 16 EFFECT OF CHEMICAL CHANGES ON THE ENERGY OF A SYSTEM 1 17 STABILITY OF A SYSTEM; FLUCTUATIONS APPENDICES CHAPTER 2 THERMODYNAMIC PROPERTIES OF IDEAL SYSTEMS 2 1 EQUILIBRIUM IN A SYSTEM OF SEVERAL COMPONENTS AND PHASES EXERCISES 2 2 ACHIEVEMENT OF EQUILIBRIUM COMMENT AND EXERCISE 2 3 SYSTEM OF ONE COMPONENT AND SEVERAL PHASES; THE CLAUSIUS–CLAPEYRON EQUATION REFERENCE AND FOOTNOTE 2 4 PROPERTIES OF IDEAL GASES 2 5 PROPERTIES OF IDEAL SOLUTIONS IN CONDENSED PHASES 2 6 THE DUHEM–MARGULES EQUATION AND ITS CONSEQUENCES 2 7 TEMPERATURE DEPENDENCE OF COMPOSITION OF SOLUTIONS 2 8 LOWERING OF THE FREEZING POINT AND ELEVATION OF THE BOILING POINT OF A SOLUTION 2 9 GENERAL DESCRIPTION OF CHEMICAL REACTIONS AND CHEMICAL EQUILIBRIUM; APPLICATION TO GASES 2 10 CHEMICAL EQUILIBRIUM IN HOMOGENEOUS CONDENSED IDEAL SOLUTIONS COMMENTS 2 11 CHEMICAL EQUILIBRIUM IN IDEAL HETEROGENEOUS SYSTEMS 2 12 EQUILIBRIUM BETWEEN TWO IDEAL PHASES CHAPTER 3 CHARACTERIZATION OF NONIDEAL SOLUTIONS 3 0 INTRODUCTORY REMARKS 3 1 THERMODYNAMIC TREATMENT OF NONIDEAL GAS MIXTURES NOTES AND EXERCISE 3 2 TEMPERATURE AND PRESSURE DEPENDENCE OF THE FUGACITY OF A GAS 3 3 THERMODYNAMIC DESCRIPTION OF REAL SOLUTIONS IN THE CONDENSED STATE 3 4 CHARACTERIZATION OF CHEMICAL EQUILIBRIUM IN NONIDEAL SOLUTIONS 3 5 PRESSURE AND TEMPERATURE DEPENDENCE OF ACTIVITIES AND ACTIVITY COEF?CIENTS 3 6 DETERMINATION OF ACTIVITY COEF?CIENTS AND CALORIMETRIC QUANTITIES IN CHEMICAL PROCESSES REFERENCES AND COMMENTARY 3 7 DETERMINATION OF ACTIVITIES FROM FREEZING POINT LOWERING OF SOLUTIONS 3 8 THERMODYNAMIC PROPERTIES OF NONIDEAL SOLUTIONS 3 9 DEPENDENCE OF HIGHER ORDER PHASE TRANSITIONS ON TEMPERATURE EXERCISES AND REFERENCES 3 10 ELEMENTS OF ORDER–DISORDER THEORY AND APPLICATIONS REFERENCES CHAPTER THERMODYNAMIC PROPERTIES OF ELECTROLYTES AND OF EMF CELLS 4 0 INTRODUCTORY COMMENTS 4 1 ACTIVITIES OF STRONG ELECTROLYTES EXERCISE AND COMMENT 4 2 THEORETICAL DETERMINATION OF ACTIVITIES IN ELECTROLYTE SOLUTIONS; THE DEBYE–HU¨CKEL EQUATION COMMENT AND EXERCISES EXPERIMENTAL DETERMINATION OF ACTIVITIES AND ACTIVITY COEF?CIENTS OF STRONG ELECTROLYTES EQUILIBRIUM PROPERTIES OF WEAK ELECTROLYTES 4 3 GALVANIC CELLS 4 4 OPERATION OF GALVANIC CELLS 4 5 GALVANIC CELLS; OPERATIONAL ANALYSIS 4 6 LIQUID JUNCTION POTENTIALS 4 7 EMF DEPENDENCE ON ACTIVITIES EXAMPLES OF OPERATING CELLS TYPES OF OPERATING CELLS QUERIES 4 8 THERMODYNAMIC INFORMATION FROM GALVANIC CELLS ASSIGNMENT THERMODYNAMIC PROPERTIES OF MATERIALS IN EXTERNALLY APPLIED FIELDS 5 0 INTRODUCTORY COMMENTS 5 1 THERMODYNAMICS OF GRAVITATIONAL AND CENTRIFUGAL FIELDS 5 2 THERMODYNAMICS OF ADSORPTION PROCESSES REFERENCES AND EXERCISES 5 3 HEATS OF ADSORPTION REFERENCE AND EXERCISES 5 4 SURFACE VS BULK EFFECTS: THERMODYNAMICS OF SELF-ASSEMBLY 5 5 PRESSURE OF ELECTROMAGNETIC RADIATION 5 6 THERMODYNAMIC CHARACTERIZATION OF ELECTRODYNAMIC RADIATION 5 7 EFFECTS OF ELECTRIC FIELDS ON THERMODYNAMIC PROPERTIES OF MATTER 5 8 SYSTEMATIZATION OF ELECTROMAGNETIC FIELD EFFECTS IN THERMODYNAMICS COMMENTS AND ASSIGNMENTS 5 9 ADIABATIC DIAMAGNETIZATION AND TRANSITIONS TO SUPERCONDUCTIVITY 5 10 THERMODYNAMIC CHARACTERIZATION OF ANISOTROPIC MEDIA 5 11 THERMODYNAMIC PROPERTIES OF ANISOTROPIC MEDIA REFERENCE AND EXERCISE 5 12 THERMODYNAMICS OF INTERACTING ELECTRON ASSEMBLIES REMARKS AND REFERENCES CHAPTER 6 IRREVERSIBLE THERMODYNAMICS 6 0 INTRODUCTORY COMMENTS 6 1 GENERALITIES NOTES AND QUERIES 6 2 SHOCK PHENOMENA 6 3 LINEAR PHENOMENOLOGICAL EQUATIONS 6 4 STEADY-STATE CONDITIONS AND PRIGOGINE’S THEOREM COMMENTS AND QUESTIONS 6 5 ONSAGER RECIPROCITY CONDITIONS 6 6 THERMOMOLECULAR MECHANICAL EFFECTS 6 7 ELECTROKINETIC PHENOMENA 6 8 THE SORET EFFECT 6 9 THERMOELECTRIC EFFECTS COMMENTS AND EXERCISES 6 10 IRREVERSIBLE THERMOMAGNETIC PHENOMENA IN TWO DIMENSIONS CRITICAL PHENOMENA 7 0 INTRODUCTORY REMARKS 7 1 PROPERTIES OF MATERIALS NEAR THEIR CRITICAL POINT NOTES AND REFERENCES 7 2 HOMOGENEITY REQUIREMENTS, CORRELATION LENGTHS, AND SCALING PROPERTIES FOOTNOTES 7 3 DERIVATION OF GRIF?TH’S AND RUSHBROOKE’S INEQUALITY 7 4 SCALED EQUATION OF STATE 7 5 LANDAU THEORY OF CRITICAL PHENOMENA AND PHASE TRANSITIONS TOPICS RELATED TO CRITICAL PHENOMENA 8 1 HOMOGENEOUS FUNCTIONS 8 2 FIXED POINTS 8 3 REMARKS CONCERNING CHAOS THEORY APPENDIX: THE ROLE OF FISHER INFORMATION THEORY IN THE DEVELOPMENT OF PHYSICAL LAWS REPRISE TO THE SECOND LAW MATHEMATICAL PROOF OF THE CARATHE´ODORY THEOREM AND RESULTING INTERPRETATIONS 9 1 FUNDAMENTALS 9 2 PROOF OF HOLONOMICITY 9 3 NECESSARY CONDITION FOR ESTABLISHING THE CARATHE´ODORY’S THEOREM 9 4 RELEVANCE TO THERMODYNAMICS 9 5 DERIVATION OF THE LIMITING FORM FOR THE DEBYE–H}UCKEL EQUATION REFERENCES AND QUERY CHAPTER 10 ELEMENTS OF STATISTICAL THERMODYNAMICS 10 1 DISTRIBUTIONS AND STATISTICS 10 2 THE BOLTZMANN RELATION FOR THE ENTROPY 10 3 DISTRIBUTION FUNCTIONS 10 4 DIGRESSION ON THE CONCEPTS OF WORK AND HEAT 10 5 STATISTICAL REPRESENTATION OF FUNCTIONS OF STATE 10 6 SUMMARY 10 7 ALTERNATIVE STATISTICAL INTERPRETATION FOR ENTROPY IN TERMS OF PROPERTIES OF A SYSTEM 10 8 DERIVATION OF CURIE’S LAW AND OHM’S LAW