THERMODYNAMICS OF NATURAL SYSTEMS
CONTENTS WHAT IS THERMODYNAMICS? INTRODUCTION WHAT IS THE PROBLEM? A MECHANICAL ANALOGY LIMITATIONS OF THE THERMODYNAMIC MODEL SUMMARY DEFINING OUR TERMS SOMETHING IS MISSING SYSTEMS EQUILIBRIUM STATE VARIABLES PHASES AND COMPONENTS PROCESSES THE FIRST LAW OF THERMODYNAMICS TEMPERATURE AND PRESSURE SCALES INTERNAL ENERGY ENERGY TRANSFERS ENTHALPY, THE HEAT OF REACTION HOW FAR HAVE WE GOT? THE MODEL AGAIN THE SECOND LAW OF THERMODYNAMICS THE PROBLEM RESTATED THERMODYNAMIC POTENTIALS ENTROPY THE FUNDAMENTAL EQUATION THE USV SURFACE THOSE OTHER FORMS OF WORK APPLICABILITY OF THE FUNDAMENTAL EQUATION CONSTRAINTS AND METASTABLE STATES THE ENERGY INEQUALITY EXPRESSION ENTROPY AND HEAT CAPACITY A MORE USEFUL THERMODYNAMIC POTENTIAL GIBBS AND HELMHOLTZ FUNCTIONS AS WORK OPEN SYSTEMS THE MEANING OF ENTROPY A WORD ABOUT CARNOT THE END OF THE ROAD GETTING DATA WHAT TO MEASURE? SOLUTION CALORIMETRY THE THIRD LAW THE PROBLEM RESOLVED DATA AT HIGHER TEMPERATURES DATA AT HIGHER PRESSURES OTHER METHODS SOME SIMPLE APPLICATIONS SOME PROPERTIES OF WATER SIMPLE PHASE DIAGRAMS THE SLOPE OF PHASE BOUNDARIES ANOTHER EXAMPLE IDEAL SOLUTIONS MEASURES OF CONCENTRATION PROPERTIES OF IDEAL SOLUTIONS IDEAL SOLUTION LAWS IDEAL SOLUTION EQUATIONS NEXT STEP – THE ACTIVITY FUGACITY AND ACTIVITY FUGACITY ACTIVITY STANDARD STATES AND ACTIVITY COEFFICIENTS EFFECT OF TEMPERATURE AND PRESSURE ON ACTIVITIES ACTIVITIES AND STANDARD STATES: AN OVERALL VIEW THE EQUILIBRIUM CONSTANT REACTIONS IN SOLUTION REACTIONS AT EQUILIBRIUM THE MOST USEFUL EQUATION IN THERMODYNAMICS SPECIAL MEANINGS FOR K K IN SOLID–SOLID REACTIONS CHANGE OF K WITH TEMPERATURE I CHANGE OF K WITH TEMPERATURE II CHANGE OF K WITH PRESSURE THE AMINO ACID EXAMPLE AGAIN SOME CONVENTIONS REGARDING COMPONENTS 10 REAL SOLUTIONS SOLUTION VOLUMES THE INFINITE DILUTION STANDARD STATE EXCESS PROPERTIES ENTHALPY AND HEAT CAPACITY GIBBS ENERGIES MARGULES EQUATIONS BEYOND MARGULES THE GIBBS–DUHEM EQUATION 10 10 SUMMARY 11 THE PHASE RULE DERIVATION OF THE PHASE RULE COMPONENTS AND SPECIES DUHEM’S THEOREM BUFFERED SYSTEMS 12 REDOX REACTIONS ELECTRON TRANSFER REACTIONS THE ROLE OF OXYGEN A SIMPLE ELECTROLYTIC CELL THE NERNST EQUATION SOME NECESSARY CONVENTIONS MEASURING ACTIVITIES MEASURING REDOX CONDITIONS EH–PH DIAGRAMS 12 10 OXYGEN FUGACITY 12 11 REDOX REACTIONS IN ORGANIC CHEMISTRY 12 12 SUMMARY 13 EQUATIONS OF STATE THE IDEAL GAS TWO KINDS OF EOS CUBIC EQUATIONS OF STATE THE VIRIAL EQUATION THERMAL EQUATIONS OF STATE OTHER EQUATIONS OF STATE 14 SOLID SOLUTIONS SOLID SOLUTIONS ACTIVITY COEFFICIENTS IN SOLID SOLUTIONS 15 ELECTROLYTE SOLUTIONS ACTIVITIES OF ELECTROLYTE COMPONENTS NUMERICAL VALUES FOR SINGLE-ION PROPERTIES THE DEBYE–HÜCKEL THEORY ACTIVITY COEFFICIENTS OF NEUTRAL MOLECULES ION ASSOCIATION, ION PAIRS, AND COMPLEXES THE PITZER EQUATIONS THE HKF MODEL FOR AQUEOUS ELECTROLYTES COMPARISON OF PITZER AND HKF MODELS 16 ROCK–WATER SYSTEMS REAL PROBLEMS IS THE SEA SATURATED WITH CALCIUM CARBONATE? DETERMINING THE IAP – SPECIATION COMBINING THE IAP AND THE KSP MINERAL STABILITY DIAGRAMS 17 PHASE DIAGRAMS WHAT IS A PHASE DIAGRAM? UNARY SYSTEMS BINARY SYSTEMS TERNARY SYSTEMS 18 PROCESS MODELING KINETICS USING THE PROGRESS VARIABLE AFFINITY AND THE PROGRESS VARIABLE FINAL COMMENT REFERENCES