AN INTRODUCTION TO GENERAL THERMODYNAMICS

By M. JORAU

CONTENTS PART I FORMULATION OF THE THEORY MACROSCOPIC SYSTEMS AND EMPIRICAL TEMPERATURE MACROSCOPIC SYSTEMS MACROSCOPIC OBSERVER THERMODYNAMIC STATE THE CONCEPT OF EMPIRICAL TEMPERATURE THE PERCEPTION OF HOTNESS AND COLDNESS THE EMPIRICAL TEMPERATURE AND THE ZEROTH PRINCIPLE OF THERMODYNAMICS EQUILIBRIUM STATE THE ZEROTH PRINCIPLE THE FIRST PRINCIPLE OF THERMODYNAMICS INTRODUCTION CLOSED SYSTEMS ADIABATIC WALLS AND ADIABATIC TRANSFORMATIONS THE DE?NITION OF ENERGY ENERGY OF FAMILIAR ADIABATIC SYSTEMS DE?NITION OF HEAT (QUANTITY OF) IN?NITESIMAL TRANSFORMATIONS FORMULATION OF THE FIRST PRINCIPLE OF THERMODYNAMICS THE SECOND PRINCIPLE OF THERMODYNAMICS NATURAL AND UNNATURAL PROCESSES QUASI-STATIC PROCESSES REVERSIBLE PROCESSES FORMULATION OF THE SECOND PRINCIPLE: DE?NITION OF S AND T STATE FUNCTIONS EXTENSIVE AND INTENSIVE QUANTITIES MEASURING S THE ABSOLUTE, OR THERMODYNAMIC, TEMPERATURE T DISCONTINUOUS SYSTEMS APPROXIMATION RESUME ON THE PREDICTIVE POWER OF THERMODYNAMICS EF?CIENCY OF THERMAL ENGINES CARNOT CYCLES ON THE DETERMINATION OF THE NEW SCALE OF TEMPERATURE T THE CARNOT ENGINE AND ENDOREVERSIBLE ENGINES COEF?CIENT OF PERFORMANCE (COP) REFRIGERATOR HEAT PUMP AVAILABILITY AND MAXIMUM WORK PROBLEMS THE FUNDAMENTAL RELATION AND THE THERMODYNAMIC POTENTIALS THE EQUILIBRIUM STATE POSTULATE FOR CLOSED SYSTEMS WITH NO CHEMICAL REACTIONS SIMPLE SYSTEMS THE FUNDAMENTAL RELATION THE GENERAL CASE FOR OPEN SYSTEMS WITH VARIABLE COMPOSITION: THE CHEMICAL POTENTIAL OTHER THERMODYNAMIC POTENTIALS THE FREE ENERGY AND ISOTHERMAL PROCESSES IN CLOSED SYSTEMS THE ENTHALPY AND ISOBARIC PROCESSES THE GIBBS POTENTIAL AND ISOTHERMAL AND ISOBARIC PROCESSES THE STABILITY PROBLEM IN A THERMODYNAMICAL SYSTEM ADIABATIC SYSTEMS SYSTEMS AT CONSTANT TEMPERATURE SYSTEMS AT CONSTANT ENTROPY THE ISOTHERMAL COMPRESSIBILITY THE DEPENDENCE OF ENTROPY ON TEMPERATURE OTHER CONSEQUENCES FROM THE STABILITY CONDITIONS MAXWELL RELATIONS SOME PROPERTIES OF MATERIALS THE VOLUME AND PRESSURE DEPENDANCE OF ENTROPY THE HEAT CAPACITIES AND THE TEMPERATURE DEPENDANCE OF ENTROPY THE HEAT CAPACITY AT CONSTANT PRESSURE THE HEAT CAPACITY AT CONSTANT VOLUME THE RELATION BETWEEN CP AND CV THE ADIABATIC COMPRESSIBILITY COEF?CIENT THE EQUATIONS OF THE ADIABATIC TRANSFORMATIONS CONCLUDING REMARKS AND THE ROLE OF CP, A, VT ISOTHERMAL PROCESSES FREE EXPANSION PRESSURE DROP IN FREE EXPANSION TEMPERATURE–PRESSURE VARIATIONS IN ADIABATIC TRANSFORMATIONS TEMPERATURE–VOLUME VARIATIONS IN ADIABATIC TRANSFORMATIONS PART II APPLICATIONS GENERAL PROPERTIES OF GASEOUS SYSTEMS ISOTHERMAL BEHAVIOR OF GASES THE FIRST VIRIAL COEF?CIENT FOR GASES THE JOULE–THOMSON EXPERIMENT SOME THERMODYNAMIC POTENTIALS FOR GASES CALORIMETRIC MEASUREMENTS FOR THE DETERMINATION OF THE FIRST VIRIAL COEF?CIENT DE?NITION OF THE TEMPERATURE SCALE BY MEANS OF GASES OTHER DETERMINATIONS OF THE TEMPERATURE SCALE THE UNIVERSAL CONSTANT OF GASES THE JOULE–THOMSON COEF?CIENT THE INVERSION CURVE LIQUEFACTION OF GASES AND THE ATTAINABILITY OF LOW TEMPERATURES A SIMPLE APPROXIMATION OF THE ISOTHERMAL BEHAVIOR OF GASES THE CHEMICAL POTENTIAL IN DILUTED GASES MOLAR HEAT AT CONSTANT VOLUME FOR DILUTE GASES MICROSCOPIC DEGREES OF FREEDOM ENERGY EQUIPARTITION ON THE TEMPERATURE DEPENDENCE OF MOLAR HEATS PHASE TRANSITIONS PHASES EQUILIBRIUM LATENT HEAT LIQUID–VAPOR EQUILIBRIUM EQUILIBRIUM BETWEEN CONDENSED PHASES: SOLID–LIQUID SOLID–VAPOR EQUILIBRIUM TRIPLE POINT PHASE DIAGRAMS (P; V) DIAGRAMS MOLAR HEAT AT EQUILIBRIUM TEMPERATURE DEPENDENCE OF THE LATENT HEATS CONTINUITY OF STATES CONTINUOUS-PHASE TRANSITIONS DIFFERENCES BETWEEN CONTINUOUS- AND DISCONTINUOUS-PHASE TRANSITIONS EXERCISES VAN DER WAALS EQUATION A SIMPLE MODI?CATION TO THE EQUATION OF STATE FOR IDEAL GASES SUCCESSES AND FAILURES OF THE VAN DER WAALS EQUATION VAN DER WAALS EQUATION AND THE BOYLE TEMPERATURE THE CRITICAL POINT THE DEPENDENCE OF THE ENERGY OF A VAN DER WAALS GAS ON VOLUME THE COEF?CIENT OF THERMAL EXPANSION FOR A VAN DER WAALS GAS THE MOLAR HEATS AT CONSTANT VOLUME AND AT CONSTANT PRESSURE IN A VAN DER WAALS GAS THE JOULE–THOMSON COEF?CIENT AND THE INVERSION CURVE FOR A VAN DER WAALS GAS DETERMINATION OF VAPOR PRESSURE FROM THE VAN DER WAALS EQUATION FREE ENERGY IN A VAN DER WAALS GAS THE LAW OF CORRESPONDING STATES CORRESPONDING STATES FOR THE SECOND VIRIAL COEF?CIENT THE COMPRESSIBILITY FACTOR AND THE GENERALIZED COMPRESSIBILITY CHART VAPOR PRESSURE AND LATENT HEAT OF VAPORIZATION TRIPLE POINT AND THE LAW OF CORRESPONDING STATES THE INVERSION CURVE AND THE LAW OF CORRESPONDING STATES THE LAW OF CORRESPONDING STATES AND THE VAN DER WAALS’S EQUATION POWER LAWS AT THE CRITICAL POINT IN A VAN DER WAALS GAS SURFACE SYSTEMS SURFACE TENSION PROPERTIES OF SURFACE LAYERS STABILITY OF EQUILIBRIUM STATES INTERFACES AT THE CONTACT BETWEEN TWO PHASES IN EQUILIBRIUM CURVATURE EFFECT ON VAPOR PRESSURE: KELVIN’S RELATION NUCLEATION PROCESSES AND METASTABILITY IN SUPERSATURATED VAPOR SPINODAL DECOMPOSITION TEMPERATURE DEPENDENCE SURFACE TENSION AND THE LAW OF CORRESPONDING STATES INTERFACES AT CONTACT BETWEEN THREE PHASES IN EQUILIBRIUM ELECTROSTATIC FIELD THE RESPONSE OF MATTER THE DIELECTRIC CONSTANT THERMODYNAMIC POTENTIALS FOR LINEAR DIELECTRICS THERMODYNAMIC POTENTIALS FOR LINEAR DIELECTRICS WITHOUT ELECTROSTRICTION DIELECTRIC CONSTANT FOR IDEAL GASES MAGNETIC FIELD ELECTRIC WORK, MAGNETIC WORK, AND RADIATION CONSTITUTIVE RELATIONS UNIFORM MEDIUM DIAMAGNETIC MATERIALS PARAMAGNETIC MATERIALS LONG, RECTILINEAR, AND HOMOGENEOUS SOLENOID THERMODYNAMIC POTENTIALS IN THE PRESENCE OF MAGNETOSTATIC FIELDS EXPRESSION OF THE THERMODYNAMIC POTENTIALS LINEAR MEDIA ADIABATIC DEMAGNETIZATION FERROMAGNETIC MATERIALS THERMODYNAMICS OF RADIATION KIRCHHOFF’S LAW ABSORPTIVITY OF MATERIAL BODIES EMISSIVITY OF MATERIAL BODIES BLACK BODY KIRCHHOFF’S LAW FOR THE EMISSIVITY OF A BLACK BODY ONE FUNDAMENTAL CONSEQUENCE OF KIRCHHOFF’S LAW EXTENDED FORM OF THE KIRCHHOFF’S LAW EMITTANCE RADIATION ENERGY DENSITY AND EMISSIVITY WIEN’S LAW WIEN’S LAW ACCORDING TO WIEN WIEN’S LAW AND RELATIVITY SOME CONSEQUENCES OF THE WIEN’S LAW THERMODYNAMIC POTENTIALS FOR RADIATION THERMODYNAMICAL PROCESSES FOR RADIATION ADIABATIC PROCESSES ISOCHORIC TRANSFORMATIONS (CONSTANT VOLUME) PLANCK AND THE PROBLEM OF BLACK-BODY RADIATION THE SITUATION AT THE END OF THE NINETEENTH CENTURY AND THE BLACK-BODY RADIATION PLANCK AND THE PROBLEM OF MATTER–RADIATION INTERACTION THE PLANCK SOLUTION (THROUGH THERMODYNAMICS) THE DAWN OF QUANTUM PHYSICS THIRD LAW OF THERMODYNAMICS THE THIRD LAW OF THERMODYNAMICS FORMULATION ACCORDING TO NERNST AND PLANCK SOME OBSERVATIONAL CONSEQUENCES PART III IRREVERSIBLE PROCESSES IRREVERSIBLE PROCESSES: FUNDAMENTALS REPHRASING THE FIRST PRINCIPLE HEAT EXCHANGE CHEMICAL REACTIONS THE RATE OF REACTION ENTROPY PRODUCTION AND THE CHEMICAL AF?NITY OPEN SYSTEMS ELECTROCHEMICAL REACTIONS GENERALIZED FLUXES AND FORCES DETERMINATION OF GENERALIZED FLUXES AND FORCES ONSAGER RELATIONS THE CURIE SYMMETRY PRINCIPLE THE APPROXIMATION OF LINEARITY CHEMICAL AF?NITY REACTION RATE LINEAR RELATIONS BETWEEN RATES AND AF?NITIES RELAXATION TIME FOR A CHEMICAL REACTION IRREVERSIBLE PROCESSES: APPLICATIONS THERMOMECHANICAL EFFECTS KNUDSEN GASES ELECTROKINETIC EFFECTS STATIONARY STATES CON?GURATIONS OF MINIMAL ENTROPY PRODUCTION DETERMINATION OF THE STATIONARY STATE STABILITY OF STATIONARY STATES AND THE PRINCIPLES OF LE CHATELIER AND OF LE CHATELIER–BRAUN FLUCTUATIONS THEORY OF FLUCTUATIONS IN A ISOLATED SYSTEM FLUCTUATIONS DISTRIBUTION FUNCTION MEAN VALUES AND CORRELATIONS ONSAGER RELATIONS AND THE DECAY OF FLUCTUATIONS IN ISOLATED SYSTEMS THERMODYNAMICS OF CONTINUA DE?NITION OF SYSTEM MASS CONSERVATION EQUATION OF MOTION THE EQUATION FOR ENERGY THE EQUATION FOR ENTROPY ENTROPY BALANCE IN CONTINUOUS SYSTEMS THE ENTROPY PRODUCTION MECHANICAL EQUILIBRIUM THE EINSTEIN RELATION BETWEEN MOBILITY AND DIFFUSION COEF?CIENT THERMOELECTRIC PHENOMENA SEEBECK EFFECT—THERMOELECTRIC POWER PELTIER COEF?CIENT—PHENOMENOLOGY THOMSON EFFECT—PHENOMENOLOGY PELTIER EFFECT—EXPLANATION THOMSON EFFECT GALVANOMAGNETIC AND THERMOMAGNETIC EFFECTS THERMODIFFUSION PROCESSES BINARY SYSTEMS THERMODIFFUSION DUFOUR EFFECT APPENDIX—THE GIBBS–DUHEM RELATION PART IV THERMODYNAMICS AND INFORMATION INTRODUCTION TO THE ROLE OF INFORMATION IN PHYSICS THE MAXWELL’S PARADOX THE LEO SZILARD’S ARTICLE IN 1929 THE OBSERVER CREATES INFORMATION THE SOLUTION OF MAXWELL–SZILARD PARADOX LANDAUER PRINCIPLE ON THE SEPARATION OBSERVER–OBSERVED INFORMATION AS A PHYSICAL QUANTITY WHICH ACQUIRES A PHYSICAL REALITY NEW PERSPECTIVES: THE PHYSICAL ENTROPY ACCORDING TO ZUREK