THERMODYNAMICS AND CHEMISTRY

By JAMES MILLER

CONTENTS CHAPTER BASIS AND SCOPE SHORT HISTORIC OVERVIEW THE ENTROPY PRODUCTION IN A HOMOGENEOUS PHASE LINEAR FLUX–FORCE RELATIONS VECTORIAL CONTRIBUTIONS SCALAR CONTRIBUTIONS TENSORIAL CONTRIBUTION DI?ERENTIAL EQUATIONS THE ENTROPY PRODUCTION IN A HETEROGENEOUS SYSTEM THE SURFACE AS AN AUTONOMOUS SYSTEM THE ENTROPY PRODUCTION IN A SURFACE AND A CONTACT LINE SCOPE ACKNOWLEDGEMENTS REFERENCES CHAPTER FLUCTUATING HYDRODYNAMICS AND FLUCTUATION–DISSIPATION THEOREM IN EQUILIBRIUM SYSTEMS INTRODUCTION FLUCTUATING HYDRODYNAMICS FOR A ONE-COMPONENT FLUID FLUCTUATING HYDRODYNAMICS FOR A BINARY MIXTURE SOME EXAMPLES TEMPERATURE FLUCTUATIONS AT CONSTANT PRESSURE CONCENTRATION FLUCTUATIONS AT LARGE LEWIS NUMBER ALTERNATIVE APPROACHES THERMAL FLUCTUATIONS IN NON-EQUILIBRIUM STEADY STATES NON-EQUILIBRIUM ENHANCEMENT OF THERMAL FLUCTUATIONS GRAVITY E?ECTS FINITE-SIZE E?ECTS FLUCTUATION-INDUCED NONEQUILIBRIUM FORCES CONCLUSIONS LOCAL EQUILIBRIUM IN NON-EQUILIBRIUM THERMODYNAMICS VALIDATING THE HYPOTHESIS OF LOCAL EQUILIBRIUM CRITERIA AND TOOLS HOMOGENEOUS PHASES SURFACES MESOSCOPIC SYSTEMS LOCAL VERSUS GLOBAL EQUILIBRIUM: MOLECULAR FLUCTUATIONS LOCAL EQUILIBRIUM AND DENSITY FUNCTIONAL THEORY PREDICTING PROPERTIES FROM THE HYPOTHESIS OF LOCAL EQUILIBRIUM CONCLUSIONS AND PERSPECTIVES DI?USION IN LIQUIDS: EXPERIMENTS, MOLECULAR DYNAMICS, AND ENGINEERING MODELS EXPERIMENTAL METHODS 1D RAMAN SPECTROSCOPY DI?USION MEASUREMENT MICROFLUIDIC DI?USION MEASUREMENT THE USE OF MOLECULAR DYNAMICS TO COMPUTE DI?USIVITIES MOLECULAR DYNAMICS COMPUTING DI?USIVITIES FROM EQUILIBRIUM MOLECULAR DYNAMICS NON-EQUILIBRIUM MOLECULAR DYNAMICS TO COMPUTE MUTUAL DI?USION COE?CIENTS THERMODYNAMIC FACTOR FROM SIMULATIONS ENGINEERING MODELS FOR PREDICTING DI?USIVITIES PREDICTION OF BINARY DI?USION COE?CIENTS AT INFINITE DILUTION PREDICTION OF CONCENTRATION-DEPENDENT BINARY DI?USION COE?CIENTS MULTICOMPONENT EXTENSIONS OF THE DARKEN AND VIGNES EQUATIONS NON-EQUILIBRIUM MOLECULAR DYNAMICS BACKGROUND TRANSPORT COE?CIENTS AND LINEAR RESPONSE NON-EQUILIBRIUM MOLECULAR DYNAMICS SIMULATIONS SYNTHETIC NEMD BOUNDARY-DRIVEN NEMD THERMOPHORETIC FORCES AND SORET COE?CIENT TRANSIENT NON-EQUILIBRIUM MOLECULAR DYNAMICS NEMD APPLICATIONS VERIFICATION OF LOCAL-EQUILIBRIUM AND ONSAGER RECIPROCAL RELATIONS (ORR) NEMD COMPUTATION OF TRANSPORT COE?CIENTS IN BULK FLUIDS AND INTERFACES COUPLING PHENOMENA NON-EQUILIBRIUM MOLECULAR SELF-ASSEMBLY GENERAL PRINCIPLES EQUILIBRIUM GIBBS ENERGY OF FORMATION GIBBS ENERGY OF REACTION, THE THERMODYNAMIC DRIVING FORCE CONVERSION RATE WORK: AVAILABLE AND LOST FUELLED SELF-ASSEMBLY BI-STABILITY AUTOCATALYSIS ROLE OF NON-EQUILIBRIUM THERMODYNAMICS FOR SELF-ASSEMBLY CONCLUSION NON-EQUILIBRIUM THERMODYNAMICS FOR EVAPORATION AND CONDENSATION NON-EQUILIBRIUM THEORIES FOR PHASE TRANSITIONS HETEROGENEOUS SYSTEMS ENTROPY PRODUCTION AT SURFACES SYMMETRY RULES EVAPORATION OR CONDENSATION IN A PURE FLUID INTERFACIAL TRANSFER RESISTIVITIES INTERFACIAL TRANSFER RESISTIVITIES FROM KINETIC THEORY THE SIGN AND MAGNITUDE OF THE HEATS OF TRANSFER AT THE SURFACE SQUARE GRADIENT THEORY, INTEGRAL RELATIONS FOR INTERFACE TRANSFER COE?CIENTS COE?CIENTS FROM SIMULATIONS, EXPERIMENTS AND SQUARE GRADIENT THEORY EVAPORATION OR CONDENSATION IN TWO-COMPONENT FLUIDS THERMODYNAMIC PROPERTIES OF A CONTACT LINE CONCLUDING REMARKS NON-EQUILIBRIUM THERMODYNAMICS APPLIED TO ADSORPTION INTRODUCTION TO ADSORPTION PHENOMENA STATE-OF-THE-ART ADSORPTION OF N-BUTANE ON SILICALITE-1: THE EQUILIBRIUM STATE ADSORPTION PROCESS: NON-EQUILIBRIUM DESCRIPTION THE GAS AND THE CRYSTAL PHASE THE CRYSTAL–GAS INTERFACE MOLECULAR DYNAMICS SIMULATION OF ADSORPTION MASS AND HEAT FLUX IN THE CRYSTAL IN STATIONARY STATE MASS AND HEAT FLUX ACROSS THE INTERFACE IN A STATIONARY STATE INTERFACE PHENOMENA DURING ADSORPTION UPTAKE CHAPTER 10 NON-EQUILIBRIUM THERMODYNAMICS OF AQUEOUS SOLUTION–CRYSTAL INTERFACES CRYSTALLISATION SYSTEM EXPERIMENTAL EXPERIMENTAL SET-UPS AND PROCEDURES DATA ANALYSIS AND INVESTIGATIONS ON INTERFACE TEMPERATURE JUMPS HEAT AND MASS TRANSPORT, AND THE ENTROPY PRODUCTION EQUATIONS FOR CRYSTALLISATION INTERFACE (I) EQUATIONS OF TRANSPORT FOR CRYSTAL GROWTH DETERMINATION OF TRANSFER RESISTIVITIES CHAPTER 11 MEMBRANE TRANSPORT NON-EQUILIBRIUM THERMODYNAMICS DESCRIPTION OF HEAT AND MASS TRANSPORT ACROSS A MEMBRANE SYSTEM APPLICATIONS SINGLE-COMPONENT PERVAPORATION GAS PERMEATION TWO-COMPONENT PERVAPORATION CHAPTER 12 ELECTROCHEMICAL ENERGY CONVERSION NON-EQUILIBRIUM THERMODYNAMICS IN THE ELECTROCHEMICAL LITERATURE THERMODYNAMIC PROPERTIES OF A TOTAL CELL A FORMATION CELL EXAMPLE ENTROPY PRODUCTION IN THREE- AND TWO-DIMENSIONAL SUBSYSTEMS OPERATIONALLY DEFINED VARIABLES IONIC FLUXES AS VARIABLES RELATIONS BETWEEN VARIABLES THE SURFACE POTENTIAL JUMP IN THE REVERSIBLE LIMIT THE OVERPOTENTIAL AT ISOTHERMAL CONDITIONS TRANSPORT PROCESSES IN THE ELECTROLYTE TRANSPORT NUMBERS AND TRANSFERENCE COE?CIENTS THE ELECTROLYTE CONTRIBUTION TO THE MEASURED CELL POTENTIAL THE PLANCK POTENTIAL THE MEASURED CELL POTENTIAL A FORMATION CELL WITH A CONCENTRATION GRADIENT A NON-ISOTHERMAL FORMATION CELL CONCLUSION AND PERSPECTIVE CHAPTER 13 ENTROPY PRODUCTION MINIMIZATION WITH OPTIMAL CONTROL THEORY MINIMUM ENTROPY PRODUCTION AND ENERGY E?CIENCY THE ENTROPY PRODUCTION IN A SIMPLE EXPANSION PROCESS IDENTIFICATION OF THE STATE OF MINIMUM ENTROPY PRODUCTION STEP 1: CONSERVATION EQUATIONS OF THE PROCESS UNIT STEP 2: DERIVING THE LOCAL ENTROPY PRODUCTION STEP 3: THE OPTIMAL CONTROL THEORY FORMULATION STEP 4: NUMERICAL SOLUTION OF THE PROBLEM KEY RESULTS FROM THE LITERATURE EQUIPARTITION OF THE ENTROPY PRODUCTION AND FORCES HIGHWAYS IN STATE SPACE RULES OF THUMB FOR ENERGY-E?CIENT PROCESS DESIGN CONCLUSIONS AND FUTURE CHALLENGES CHAPTER 14 MESOSCOPIC NON-EQUILIBRIUM THERMODYNAMICS STATISTICAL NON-EQUILIBRIUM THERMODYNAMICS OF MESOSCOPIC SYSTEMS MESOSCOPIC NON-EQUILIBRIUM THERMODYNAMICS FOR ACTIVATED PROCESSES OTHER INTERNAL VARIABLES FLUCTUATING MESOSCOPIC NON-EQUILIBRIUM THERMODYNAMICS CHAPTER 15 NON-EQUILIBRIUM THERMODYNAMICS FOR NUCLEATION KINETICS KINETICS AND THERMODYNAMICS OF NUCLEATION: CLASSICAL NUCLEATION THEORY NUCLEATION KINETICS USING MNET NOVEL SIMULATION TECHNIQUES TO STUDY NUCLEATION NON-ISOTHERMAL NUCLEATION THE INFLUENCE OF CARRIER GAS PRESSURE ON NUCLEATION NUCLEATION IN THE PRESENCE OF GRADIENTS CHAPTER 16 MESOSCOPIC NON-EQUILIBRIUM THERMODYNAMICS IN BIOLOGY THE MESOSCOPIC APPROACH TO CHEMICAL REACTIONS BIOCHEMICAL REACTIONS MICHAELIS–MENTEN KINETICS ENERGY CONVERSION IN BIOCHEMICAL SYSTEMS ENERGY CONVERSION AND COUPLING OF ION CONCENTRATION GRADIENTS ENERGY CONVERSION IN BIOMOLECULAR PUMPS SINGLE-MOLECULE STRETCHING DISCUSSION CHAPTER 17 DYNAMICS OF COMPLEX FLUID–FLUID INTERFACES COMPLEX FLUID–FLUID INTERFACES SURFACE EXCESS VARIABLES SURFACE VARIABLES FOR SIMPLE INTERFACES SURFACE VARIABLES FOR COMPLEX INTERFACES CONSERVATION PRINCIPLES FOR SURFACE MASS, MOMENTUM, AND ENERGY CONSTITUTIVE EQUATIONS FOR SURFACE FLUXES CLASSICAL IRREVERSIBLE THERMODYNAMICS EXTENDED IRREVERSIBLE THERMODYNAMICS GENERIC CONCLUSIONS AND OUTLOOK