THERMODYNAMICS, ABRIDGED

By JOSHUA TAYLOR

CONTENTS INTRODUCTION RELEVANT QUESTIONS FOR THERMODYNAMICS WORK AND ENERGY EXERCISES THE POSTULATES OF THERMODYNAMICS THE POSTULATIONAL APPROACH THE ?RST LAW: ENERGY CONSERVATION DE?NITION OF HEAT EQUILIBRIUM STATES ENTROPY, THE SECOND LAW, AND THE FUNDAMENTAL RELATION DE?NITIONS OF TEMPERATURE, PRESSURE, AND CHEMICAL POTENTIAL TEMPERATURE DIFFERENCES AND HEAT ?OW PRESSURE DIFFERENCES AND VOLUME CHANGES THERMODYNAMICS IN ONE DIMENSION SUMMARY GENERALIZED THERMODYNAMIC POTENTIALS LEGENDRE TRANSFORMS EXTREMUM PRINCIPLES FOR THE POTENTIALS THE MAXWELL RELATIONS THE THERMODYNAMIC SQUARE SECOND-ORDER COEF?CIENTS THERMODYNAMIC MANIPULATIONS ONE- AND TWO-DIMENSIONAL SYSTEMS A NON-IDEAL RUBBER BAND UNZIPPING DNA LANGMUIR ADSORPTION FIRST APPLICATIONS OF THERMODYNAMICS STABILITY CRITERIA ENTROPY INTERNAL ENERGY GENERALIZED POTENTIALS SINGLE-COMPONENT VAPOR–LIQUID EQUILIBRIUM THE SPINODAL CURVE OF A VAN DER WAALS ?UID THE BINODAL (OR COEXISTENCE) CURVE OF A VAN DER WAALS ?UID THE GENERAL FORMULATION APPROXIMATIONS BASED ON THE CLAPEYRON EQUATION CRYSTALLIZATION OF SOLIDS THERMODYNAMIC DIAGRAMS CONSTRUCTION OF FUNDAMENTAL RELATIONS FROM TWO EQUATIONS OF STATE FOR SINGLE-COMPONENT SYSTEMS RESIDUAL PROPERTIES APPLICATION TO PROCESS DESIGN: ?OW SYSTEMS MACROSCOPIC MASS, ENERGY, AND ENTROPY BALANCES THE THROTTLING PROCESS SPECI?CATIONS FOR A TURBINE GENERATOR WORK REQUIREMENTS FOR A PUMP THE RANQUE–HILSCH VORTEX TUBE FUEL CELLS CYCLES THE CARNOT CYCLE THE RANKINE POWER CYCLE THE REFRIGERATION CYCLE STATISTICAL MECHANICS ENSEMBLE AND TIME AVERAGES THE CANONICAL ENSEMBLE IDEAL GASES A SIMPLE IDEAL GAS A GENERAL IDEAL GAS THE GRAND CANONICAL ENSEMBLE AN ELASTIC STRAND FLUCTUATIONS MOLECULAR INTERACTIONS INTERMOLECULAR INTERACTIONS THE SIGNI?CANCE OF “KBT” INTERACTIONS AT LONG DISTANCES INTERACTIONS AT SHORT DISTANCES EMPIRICAL POTENTIAL-ENERGY FUNCTIONS HYDROGEN BONDS MOLECULAR SIMULATIONS THE VIRIAL EXPANSION EQUATIONS OF STATE FOR LIQUIDS EXPERIMENTAL MANIFESTATIONS OF INTERMOLECULAR INTERACTIONS CONCLUSIONS FUGACITY AND VAPOR–LIQUID EQUILIBRIUM GENERAL EQUATIONS OF PHASE EQUILIBRIA MIXTURES OF IDEAL GASES MIXTURES: PARTIAL MOLAR PROPERTIES DE?NITION OF A PARTIAL MOLAR PROPERTY GENERAL PROPERTIES OF PARTIAL MOLAR QUANTITIES RESIDUAL PARTIAL MOLAR QUANTITIES FUGACITY DE?NITION OF FUGACITY PROPERTIES OF FUGACITY ESTIMATING THE FUGACITY OF A PURE VAPOR OR LIQUID CALCULATION OF FUGACITY COEF?CIENTS OF MIXTURES FROM PVT EQUATIONS OF STATE FUGACITY IN IDEAL OR LEWIS MIXTURES LEWIS MIXING PROPERTIES OF LEWIS (IDEAL) MIXTURES A SIMPLE APPLICATION OF LEWIS (IDEAL) MIXING: RAOULT’S LAW SOLUBILITY OF SOLIDS AND LIQUIDS IN COMPRESSED GASES PHASE EQUILIBRIA BETWEEN A SOLID AND A COMPRESSED GAS PHASE EQUILIBRIA BETWEEN A LIQUID AND A COMPRESSED GAS ACTIVITY AND EQUILIBRIUM EXCESS PROPERTIES AND ACTIVITIES A SUMMARY OF FUGACITY AND ACTIVITY CORRELATIONS FOR PARTIAL MOLAR EXCESS GIBBS FREE ENERGY SIMPLE BINARY SYSTEMS THERMODYNAMIC CONSISTENCY SEMI-THEORETICAL EXPRESSIONS FOR ACTIVITY COEF?CIENTS THE VAN LAAR EQUATION WILSON’S EQUATION THE NRTL EQUATION THE UNIQUAC MODEL DILUTE MIXTURES: HENRY’S CONSTANTS MEASUREMENT OF ACTIVITY COEF?CIENTS THE BLOOD–BRAIN BARRIER PARTIAL MISCIBILITY THERMODYNAMIC STABILITY LIQUID–LIQUID EQUILIBRIA IN TERNARY MIXTURES CRITICAL POINTS SIMPLE FREE-ENERGY MODELS FROM STATISTICAL MECHANICS THE MARGULES MODEL EXACT SOLUTION OF THE LATTICE MODEL 10 REACTION EQUILIBRIUM A SIMPLE PICTURE: THE REACTION COORDINATE EXTENT OF REACTION THE EQUILIBRIUM CRITERION THE REACTION EQUILIBRIUM CONSTANT STANDARD PROPERTY CHANGES ESTIMATING THE EQUILIBRIUM CONSTANT DETERMINATION OF EQUILIBRIUM COMPOSITIONS ENZYMATIC CATALYSIS: THE MICHAELIS–MENTEN MODEL DENATURATION OF DNA AND POLYMERASE CHAIN REACTIONS 1091 DENATURATION 1092 POLYMERASE CHAIN REACTION 1010 STATISTICAL MECHANICS OF REACTIONS AND DENATURATION STOCHASTIC ?UCTUATIONS IN REACTIONS DNA DENATURATION 11 THERMODYNAMICS OF POLYMERS SOLUBILITY AND MISCIBILITY OF POLYMER SOLUTIONS GENERALIZATIONS OF THE FLORY–HUGGINS THEORY 1121 THE GENERALIZATION OF QIAN ET AL 1122 THE SANCHEZ–LACOMBE EQUATION OF STATE 1123 THE BGY MODEL BLOCK COPOLYMERS DERIVATION OF THE FLORY–HUGGINS THEORY 12 THERMODYNAMICS OF SURFACES THE INTERFACIAL TENSION OF A PLANAR INTERFACE THE GIBBS FREE ENERGY OF A SURFACE PHASE AND THE GIBBS–DUHEM RELATION CURVED INTERFACES SOLID–LIQUID INTERFACES: WETTING CAPILLARY FORCES SOLID–GAS INTERFACES: ADSORPTION THE TEMPERATURE DEPENDENCE OF SURFACE TENSION INTERFACES IN MIXTURES 1281 VAPOR–LIQUID INTERFACES 1282 MONOLAYER FORMATION ON LIQUID SURFACES