ELEMENTARY CHEMISTRY: A TEXT-BOOK
CONTENTS INTRODUCTION ORIGINS OF CHEMICAL THERMODYNAMICS / OBJECTIVES OF CHEMICAL THERMODYNAMICS / LIMITATIONS OF CLASSIC THERMODYNAMICS / REFERENCES / MATHEMATICAL PREPARATION FOR THERMODYNAMICS VARIABLES OF THERMODYNAMICS / EXTENSIVE AND INTENSIVE QUANTITIES / UNITS AND CONVERSION FACTORS / ANALYTIC METHODS / PARTIAL DIFFERENTIATION / EXACT DIFFERENTIALS / HOMOGENEOUS FUNCTIONS / EXERCISES / THE FIRST LAW OF THERMODYNAMICS DE?NITIONS / TEMPERATURE / WORK / THE FIRST LAW OF THERMODYNAMICS / ENERGY / HEAT / GENERAL FORM OF THE FIRST LAW / ENTHALPY, ENTHALPY OF REACTION, AND HEAT CAPACITY ENTHALPY / DE?NITION / RELATIONSHIP BETWEEN QV AND QP / ENTHALPY OF REACTIONS / DE?NITIONS AND CONVENTIONS / ENTHALPY AS A STATE FUNCTION / ENTHALPY OF FORMATION FROM ENTHALPY OF REACTION / ENTHALPY OF FORMATION FROM ENTHALPY OF COMBUSTION / ENTHALPY OF TRANSITION FROM ENTHALPY OF COMBUSTION / ENTHALPY OF CONFORMATIONAL TRANSITION OF A PROTEIN FROM INDIRECT CALORIMETRIC MEASUREMENTS / ENTHALPY OF SOLID-STATE REACTION FROM MEASUREMENTS OF ENTHALPY OF SOLUTION / BOND ENTHALPIES / DE?NITION OF BOND ENTHALPIES / CALCULATION OF BOND ENTHALPIES / ENTHALPY OF REACTION FROM BOND ENTHALPIES / HEAT CAPACITY / SOME RELATIONSHIPS BETWEEN CP AND CV / HEAT CAPACITIES OF GASES / HEAT CAPACITIES OF SOLIDS / HEAT CAPACITIES OF LIQUIDS / OTHER SOURCES OF HEAT CAPACITY DATA / ENTHALPY OF REACTION AS A FUNCTION OF TEMPERATURE / ANALYTIC METHOD / ARITHMETIC METHOD / GRAPHICAL OR NUMERICAL METHODS / APPLICATIONS OF THE FIRST LAW TO GASES IDEAL GASES / CONTENTS ENTHALPY AS A FUNCTION OF TEMPERATURE ONLY / RELATIONSHIP BETWEEN CP AND CV / CALCULATION OF THE THERMODYNAMIC CHANGES IN EXPANSION PROCESSES / REAL GASES / EQUATIONS OF STATE / JOULE–THOMSON EFFECT / CALCULATIONS OF THERMODYNAMIC QUANTITIES IN REVERSIBLE EXPANSIONS / THE SECOND LAW OF THERMODYNAMICS THE NEED FOR A SECOND LAW / THE NATURE OF THE SECOND LAW / NATURAL TENDENCIES TOWARD EQUILIBRIUM / STATEMENT OF THE SECOND LAW / MATHEMATICAL COUNTERPART OF THE VERBAL STATEMENT / THE CARNOT CYCLE / THE FORWARD CYCLE / THE REVERSE CYCLE / ALTERNATIVE STATEMENT OF THE SECOND LAW / CARNOT’S THEOREM / THE THERMODYNAMIC TEMPERATURE SCALE / THE DE?NITION OF S, THE ENTROPY OF A SYSTEM / THE PROOF THAT S IS A THERMODYNAMIC PROPERTY / ANY SUBSTANCE IN A CARNOT CYCLE / ANY SUBSTANCE IN ANY REVERSIBLE CYCLE / ENTROPY S DEPENDS ONLY ON THE STATE OF THE SYSTEM / ENTROPY CHANGES IN REVERSIBLE PROCESSES / GENERAL STATEMENT / ISOTHERMAL REVERSIBLE CHANGES / ADIABATIC REVERSIBLE CHANGES / REVERSIBLE PHASE TRANSITIONS / ISOBARIC REVERSIBLE TEMPERATURE CHANGES / ISOCHORIC REVERSIBLE TEMPERATURE CHANGES / ENTROPY CHANGES IN IRREVERSIBLE PROCESSES / IRREVERSIBLE ISOTHERMAL EXPANSION OF AN IDEAL GAS / IRREVERSIBLE ADIABATIC EXPANSION OF AN IDEAL GAS / IRREVERSIBLE FLOW OF HEAT FROM A HIGHER TEMPERATURE TO A LOWER TEMPERATURE / CONTENTS IRREVERSIBLE PHASE TRANSITIONS / IRREVERSIBLE CHEMICAL REACTIONS / GENERAL EQUATIONS FOR THE ENTROPY OF GASES / ENTROPY OF THE IDEAL GAS / ENTROPY OF A REAL GAS / 6 10 TEMPERATURE–ENTROPY DIAGRAM / 6 11 ENTROPY AS AN INDEX OF EXHAUSTION / EQUILIBRIUM AND SPONTANEITY FOR SYSTEMS AT CONSTANT TEMPERATURE REVERSIBILITY, SPONTANEITY, AND EQUILIBRIUM / SYSTEMS AT CONSTANT TEMPERATURE AND VOLUME / SYSTEMS AT CONSTANT TEMPERATURE AND PRESSURE / HEAT OF REACTION AS AN APPROXIMATE CRITERION OF SPONTANEITY / PROPERTIES OF THE GIBBS, HELMHOLTZ, AND PLANCK FUNCTIONS / THE FUNCTIONS AS THERMODYNAMIC PROPERTIES / RELATIONSHIPS AMONG G, Y, AND A / CHANGES IN THE FUNCTIONS FOR ISOTHERMAL CONDITIONS / EQUATIONS FOR TOTAL DIFFERENTIALS / PRESSURE AND TEMPERATURE DERIVATIVES OF THE FUNCTIONS / EQUATIONS DERIVED FROM THE RECIPROCITY RELATIONSHIP / THE GIBBS FUNCTION AND CHEMICAL REACTIONS / STANDARD STATES / PRESSURE AND TEMPERATURE DEPENDENCE OF DG / USEFUL WORK AND THE GIBBS AND HELMHOLTZ FUNCTIONS / ISOTHERMAL CHANGES / CHANGES AT CONSTANT TEMPERATURE AND PRESSURE / RELATIONSHIP BETWEEN DHP AND QP WHEN USEFUL WORK IS PERFORMED / APPLICATION TO ELECTRICAL WORK / GIBBS–HELMHOLTZ EQUATION / THE GIBBS FUNCTION AND USEFUL WORK IN BIOLOGIC SYSTEMS / APPLICATION OF THE GIBBS FUNCTION AND THE PLANCK FUNCTION TO SOME PHASE CHANGES TWO PHASES AT EQUILIBRIUM AS A FUNCTION OF PRESSURE AND TEMPERATURE / CLAPEYRON EQUATION / CLAUSIUS–CLAPEYRON EQUATION / THE EFFECT OF AN INERT GAS ON VAPOR PRESSURE / VARIABLE TOTAL PRESSURE AT CONSTANT TEMPERATURE / VARIABLE TEMPERATURE AT CONSTANT TOTAL PRESSURE / TEMPERATURE DEPENDENCE OF ENTHALPY OF PHASE TRANSITION / CALCULATION OF CHANGE IN THE GIBBS FUNCTION FOR SPONTANEOUS PHASE CHANGE / THERMODYNAMICS OF SYSTEMS OF VARIABLE COMPOSITION STATE FUNCTIONS FOR SYSTEMS OF VARIABLE COMPOSITION / CRITERIA OF EQUILIBRIUM AND SPONTANEITY IN SYSTEMS OF VARIABLE COMPOSITION / RELATIONSHIPS AMONG PARTIAL MOLAR PROPERTIES OF A SINGLE COMPONENT / RELATIONSHIPS BETWEEN PARTIAL MOLAR QUANTITIES OF DIFFERENT COMPONENTS / PARTIAL MOLAR QUANTITIES FOR PURE PHASE / ESCAPING TENDENCY / CHEMICAL POTENTIAL AND ESCAPING TENDENCY / CHEMICAL EQUILIBRIUM IN SYSTEMS OF VARIABLE COMPOSITION / REFERENCE / MIXTURES OF GASES AND EQUILIBRIUM IN GASEOUS MIXTURES MIXTURES OF IDEAL GASES / THE ENTROPY AND GIBBS FUNCTION FOR MIXING IDEAL GASES / THE CHEMICAL POTENTIAL OF A COMPONENT OF AN IDEAL GAS MIXTURE / CONTENTS CHEMICAL EQUILIBRIUM IN IDEAL GAS MIXTURES / DEPENDENCE OF K ON TEMPERATURE / COMPARISON OF TEMPERATURE DEPENDENCE OF DG8M AND LN K / THE FUGACITY FUNCTION OF A PURE REAL GAS / CHANGE OF FUGACITY WITH PRESSURE / CHANGE OF FUGACITY WITH TEMPERATURE / CALCULATION OF THE FUGACITY OF A REAL GAS / ANALYTICAL METHODS / JOULE–THOMSON EFFECT FOR A VAN DER WAALS GAS / APPROXIMATE VALUE OF A FOR A VAN DER WAALS GAS / FUGACITY AT LOW PRESSURES / ENTHALPY OF A VAN DER WAALS GAS / JOULE–THOMSON COEF?CIENT / MIXTURES OF REAL GASES / FUGACITY OF A COMPONENT OF A GASEOUS SOLUTION / APPROXIMATE RULE FOR SOLUTIONS OF REAL GASES / FUGACITY COEF?CIENTS IN GASEOUS SOLUTIONS / EQUILIBRIUM CONSTANT AND CHANGE IN GIBBS FUNCTIONS AND PLANCK FUNCTIONS FOR REACTIONS OF REAL GASES / THE THIRD LAW OF THERMODYNAMICS NEED FOR THE THIRD LAW / FORMULATION OF THE THIRD LAW / NERNST HEAT THEOREM / PLANCK’S FORMULATION / STATEMENT OF LEWIS AND RANDALL / THERMODYNAMIC PROPERTIES AT ABSOLUTE ZERO / EQUIVALENCE OF G AND H / DCP IN AN ISOTHERMAL CHEMICAL REACTION / LIMITING VALUES OF CP AND CV / TEMPERATURE DERIVATIVES OF PRESSURE AND VOLUME / ENTROPIES AT 298 K / TYPICAL CALCULATIONS / APPARENT EXCEPTIONS TO THE THIRD LAW / TABULATIONS OF ENTROPY VALUES / APPLICATION OF THE GIBBS FUNCTION TO CHEMICAL CHANGES DETERMINATION OF DG8M FROM EQUILIBRIUM MEASUREMENTS / DETERMINATION OF DG8M FROM MEASUREMENTS OF CELL POTENTIALS / CALCULATION OF DG8M FROM CALORIMETRIC MEASUREMENTS / CALCULATION OF A GIBBS FUNCTION OF A REACTION FROM STANDARD GIBBS FUNCTION OF FORMATION / CALCULATION OF A STANDARD GIBBS FUNCTION FROM STANDARD ENTROPIES AND STANDARD ENTHALPIES / ENTHALPY CALCULATIONS / ENTROPY CALCULATIONS / CHANGE IN STANDARD GIBBS FUNCTION / THE PHASE RULE DERIVATION OF THE PHASE RULE / NONREACTING SYSTEMS / REACTING SYSTEMS / ONE-COMPONENT SYSTEMS / TWO-COMPONENT SYSTEMS / TWO PHASES AT DIFFERENT PRESSURES / PHASE RULE CRITERION OF PURITY / THE IDEAL SOLUTION SOME CONSEQUENCES OF THE DE?NITION / VOLUME CHANGES / HEAT EFFECTS / THERMODYNAMICS OF TRANSFER OF A COMPONENT FROM ONE IDEAL SOLUTION TO ANOTHER / THERMODYNAMICS OF MIXING / EQUILIBRIUM BETWEEN A PURE SOLID AND AN IDEAL LIQUID SOLUTION / CHANGE OF SOLUBILITY WITH PRESSURE AT A FIXED TEMPERATURE / CHANGE OF SOLUBILITY WITH TEMPERATURE / EQUILIBRIUM BETWEEN AN IDEAL SOLID SOLUTION AND AN IDEAL LIQUID SOLUTION / COMPOSITION OF THE TWO PHASES IN EQUILIBRIUM / TEMPERATURE DEPENDENCE OF THE EQUILIBRIUM COMPOSITIONS / DILUTE SOLUTIONS OF NONELECTROLYTES HENRY’S LAW / NERNST’S DISTRIBUTION LAW / RAOULT’S LAW / VAN’T HOFF’S LAW OF OSMOTIC PRESSURE / OSMOTIC WORK IN BIOLOGICAL SYSTEMS / VAN’T HOFF’S LAW OF FREEZING-POINT DEPRESSION AND BOILING-POINT ELEVATION / ACTIVITIES, EXCESS GIBBS FUNCTIONS, AND STANDARD STATES FOR NONELECTROLYTES DE?NITIONS OF ACTIVITIES AND ACTIVITY COEF?CIENTS / ACTIVITY / ACTIVITY COEF?CIENT / CHOICE OF STANDARD STATES / GASES / LIQUIDS AND SOLIDS / GIBBS FUNCTION AND THE EQUILIBRIUM CONSTANT IN TERMS OF ACTIVITY / DEPENDENCE OF ACTIVITY ON PRESSURE / DEPENDENCE OF ACTIVITY ON TEMPERATURE / STANDARD PARTIAL MOLAR ENTHALPIES / EQUATION FOR TEMPERATURE DERIVATIVE OF THE ACTIVITY / STANDARD ENTROPY / DEVIATIONS FROM IDEALITY IN TERMS OF EXCESS THERMODYNAMIC FUNCTIONS / REPRESENTATION OF GM E AS A FUNCTION OF COMPOSITION / REGULAR SOLUTIONS AND HENRY’S LAW / REGULAR SOLUTIONS AND LIMITED MISCIBILITY / DETERMINATION OF NONELECTROLYTE ACTIVITIES AND EXCESS GIBBS FUNCTIONS FROM EXPERIMENTAL DATA ACTIVITY FROM MEASUREMENTS OF VAPOR PRESSURE / SOLVENT / SOLUTE / EXCESS GIBBS FUNCTION FROM MEASUREMENT OF VAPOR PRESSURE / ACTIVITY OF A SOLUTE FROM DISTRIBUTION BETWEEN TWO IMMISCIBLE SOLVENTS / ACTIVITY FROM MEASUREMENT OF CELL POTENTIALS / DETERMINATION OF THE ACTIVITY OF ONE COMPONENT FROM THE ACTIVITY OF THE OTHER / CALCULATION OF ACTIVITY OF SOLVENT FROM THAT OF SOLUTE / CALCULATION OF ACTIVITY OF SOLUTE FROM THAT OF SOLVENT / MEASUREMENTS OF FREEZING POINTS / CALCULATION OF PARTIAL MOLAR QUANTITIES AND EXCESS MOLAR QUANTITIES FROM EXPERIMENTAL DATA: VOLUME AND ENTHALPY PARTIAL MOLAR QUANTITIES BY DIFFERENTIATION OF J AS A FUNCTION OF COMPOSITION / PARTIAL MOLAR VOLUME / PARTIAL MOLAR ENTHALPY / ENTHALPIES OF MIXING / ENTHALPIES OF DILUTION / PARTIAL MOLAR QUANTITIES OF ONE COMPONENT FROM THOSE OF ANOTHER COMPONENT BY NUMERICAL INTEGRATION / ANALYTIC METHODS FOR CALCULATION OF PARTIAL MOLAR PROPERTIES / CHANGES IN J FOR SOME PROCESSES IN SOLUTIONS / TRANSFER PROCESS / INTEGRAL PROCESS / EXCESS PROPERTIES: VOLUME AND ENTHALPY / EXCESS VOLUME / EXCESS ENTHALPY / ACTIVITY, ACTIVITY COEFFICIENTS, AND OSMOTIC COEFFICIENTS OF STRONG ELECTROLYTES DE?NITIONS AND STANDARD STATES FOR DISSOLVED ELECTROLYTES / UNI-UNIVALENT ELECTROLYTES / MULTIVALENT ELECTROLYTES / MIXED ELECTROLYTES / DETERMINATION OF ACTIVITIES OF STRONG ELECTROLYTES / MEASUREMENT OF CELL POTENTIALS / SOLUBILITY MEASUREMENTS / COLLIGATIVE PROPERTY MEASUREMENT: THE OSMOTIC COEF?CIENT / EXTENSION OF ACTIVITY COEF?CIENT DATA TO ADDITIONAL TEMPERATURES WITH ENTHALPY OF DILUTION DATA / ACTIVITY COEF?CIENTS OF SOME STRONG ELECTROLYTES / EXPERIMENTAL VALUES / THEORETICAL CORRELATION / CHANGES IN GIBBS FUNCTION FOR PROCESSES IN SOLUTIONS ACTIVITY COEF?CIENTS OF WEAK ELECTROLYTES / DETERMINATION OF EQUILIBRIUM CONSTANTS FOR DISSOCIATION OF WEAK ELECTROLYTES / FROM MEASUREMENTS OF CELL POTENTIALS / FROM CONDUCTANCE MEASUREMENTS / SOME TYPICAL CALCULATIONS FOR DFG8M / STANDARD GIBBS FUNCTION FOR FORMATION OF AQUEOUS SOLUTE: HCL / STANDARD GIBBS FUNCTION OF FORMATION OF INDIVIDUAL IONS: HCL / STANDARD GIBBS FUNCTION FOR FORMATION OF SOLID SOLUTE IN AQUEOUS SOLUTION / STANDARD GIBBS FUNCTION FOR FORMATION OF ION OF WEAK ELECTROLYTE / STANDARD GIBBS FUNCTION FOR FORMATION OF MODERATELY STRONG ELECTROLYTE / EFFECT OF SALT CONCENTRATION ON GEOLOGICAL EQUILIBRIUM INVOLVING WATER / GENERAL COMMENTS / ENTROPIES OF IONS / THE ENTROPY OF AN AQUEOUS SOLUTION OF A SALT / CONTENTS ENTROPY OF FORMATION OF INDIVIDUAL IONS / ION ENTROPIES IN THERMODYNAMIC CALCULATIONS / SYSTEMS SUBJECT TO A GRAVITATIONAL OR A CENTRIFUGAL FIELD DEPENDENCE OF THE GIBBS FUNCTION ON EXTERNAL FIELD / SYSTEM IN A GRAVITATIONAL FIELD / SYSTEM IN A CENTRIFUGAL FIELD / ESTIMATION OF THERMODYNAMIC QUANTITIES EMPIRICAL METHODS / GROUP CONTRIBUTION METHOD OF ANDERSEN, BEYER, WATSON, AND YONEDA / TYPICAL EXAMPLES OF ESTIMATING ENTROPIES / OTHER METHODS / ACCURACY OF THE APPROXIMATE METHODS / EQUILIBRIUM IN COMPLEX SYSTEMS / CONCLUDING REMARKS