Gibbs Energy and Helmholtz Energy : Liquids, Solutions and Vapours

"This book contains the latest information on all aspects of the most important chemical thermodynamic properties of Gibbs energy and Helmholtz energy, as related to fluids. Both the Gibbs energy and Helmholtz energy are very important in the fields of thermodynamics and material properties as many other properties are obtained from the temperature or pressure dependence. Bringing all the information into one authoritative survey, the book is written by acknowledged world experts in their respective fields. Each of the chapters will cover theory, experimental methods and techniques and results for all types of liquids and vapours. This book is the fourth in the series of Thermodynamic Properties related to liquids, solutions and vapours, edited by Emmerich Wilhelm and Trevor Letcher. The previous books were: Heat Capacities (2010), Volume Properties (2015), and Enthalpy (2017). This book fills the gap in fundamental thermodynamic properties and is the last in the series"-- Page 4 of cover Cover Gibbs Energy and Helmholtz Energy: Liquids, Solutions and Vapours Foreword Preface Contents Chapter 1 - Gibbs Energy and Helmholtz Energy: Introduction, Concepts and Selected Applications 1.1 Introduction 1.2 Thermodynamic Fundamentals 1.3 More Thermodynamics and Selected Applications 1.3.1 Real Fluids: Fundamentals 1.3.2 Residual Properties, Fugacities and Fugacity Coefficients 1.3.3 Empirical (Thermal) Equations of State and More: Selected Comments 1.3.4 Property Changes on Mixing and Excess Properties 1.4 Concluding Remarks, Future Directions and Acknowledgements Appendix References Chapter 2 - Low- pressure Solubility of Gases in Liquids 2.1 Introduction 2.2 Thermodynamics 2.2.1 Fundamentals 2.2.2 Experimental Reality: Subtleties of Approximation 2.3 Selected Results 2.4 Concluding Remarks References Chapter 3 - Assembly of Hard Spheres in Liquid Water 3.1 Introduction and Statement of the Problem 3.2 Model Solvation Free Energies 3.2.1 Small Solutes 3.2.2 Large Solutes 3.3 Detailed Model Free Energy for Assembly 3.4 Driving Forces for Assembly 3.5 Perspective and Implications Appendix Derivation of eqn (3.13) Acknowledgements References Chapter 4 - Excess Molar Gibbs Energies: Related Properties and Formalisms Using DISQUAC 4.1 Introduction 4.2 Some Equations and Models 4.2.1 Vapour–Liquid Equilibria Under Isothermal Conditions 4.2.2 Solid–Liquid Equilibria 4.2.3 Liquid–Liquid Equilibria 4.2.4 The Concentration–Concentration Structure Factor 4.2.5 Kirkwood–Buff Integrals 4.2.6 DISQUAC 4.3 Phase Equilibria Results 4.3.1 Vapour–Liquid Equilibria 4.3.2 Solid–Liquid Equilibria 4.3.3 Liquid–Liquid Equilibria 4.4 Results for SCC(0) and Kirkwood–Buff Integrals 4.4.1 1- Alkanol (1) or Polar Compound (1) + Heptane (2) 4.4.2 1- Alkanol (1) + Polar Compound (2) 4.4.2.1 1- Alkanol (1) + DPE (2) 4.4.2.2 1- Alkanol (1) + DMC (2) or + EtN (2) 4.4.2.3 1- Alkanol (1) + 2- Alkanone (2) 4.4.2.4 1- Alkanol (1) + Tertiary Amide (2) 4.4.2.5 The Gia − Gib Differences 4.5 Situation of Systems in the GEm versus HEm Diagram 4.6 Conclusion Appendix References Chapter 5 - Simultaneous Determination of Equilibrium Constants, Enthalpy Changes and Stoichiometries by Titration Calorimetry 5.1 Introduction 5.2 History 5.3 Data Analysis 5.4 Operating Parameters 5.5 Instrument Calibration 5.6 Statistical Error Analysis of the Inferred Parameters 5.7 Method for Optimizing Operating Conditions 5.8 Typical Applications in Biophysics 5.8.1 Advantages of Isothermal Titration Calorimetry (ITC) 5.8.2 Food Science 5.8.3 Nutritional Science 5.8.4 Pharmaceuticals References Chapter 6 - Solvation Free Energy by 3D- RISM- KH Theory 6.1 Introduction 6.1.1 3D- RISM- KH Theory 6.2 Solvation Free Energies from the 3D- RISM- KH Theory 6.2.1 Hydration Free Energy 6.2.2 Solvation Free Energies in Non- aqueous Solvents 6.2.2.1 SFEs in Cyclohexane 6.2.2.2 SFEs in Chloroform 6.2.2.3 SFEs in Hexadecane 6.2.2.4 SFEs in n- Octanol 6.2.2.5 SFEs in DMSO 6.2.2.6 SFEs in Acetonitrile 6.2.3 Overall Performance of the 3D- RISM- KH Theory in Predicting SFE 6.3 Molar Partition Coefficients Using the 3D- RISM- KH Theory 6.4 Conclusion Acknowledgements References Chapter 7 - Calculation Itinerary to Check the Quality of Vapour–Liquid Equilibrium Data 7.1 Introduction 7.2 Thermodynamic Consistency of VLE Data 7.3 Some Methods to Analyse Thermodynamic Consistency 7.3.1 Area Test (Herington/Redlich and Kister) (Global) 7.3.2 Composition Resolution and Infinite Dilution Tests (Global) 7.3.3 Van Ness Test and the Fredenslund Modification (Global and Point- to- point) 7.3.4 Wisniak Test (Global and Point- to- point) 7.3.5 Van Ness Direct Test (Global and Point- to- point) 7.3.6 Differential–Integral Method for Thermodynamic Consistency (Global and Point- to- point) 7.3.6.1 Integral Form of the Test 7.3.6.2 Differential Form of the Test 7.3.6.3 A Practical Application of the Integral–Differential Method 7.4 Practical Application of the Calculation Methodology to Verify the Quality of Experimental Data for an Iso- p VLE System 7.5 Conclusion Symbols and Abbreviations General Symbols Greek Letters Superscripts and Subscripts Abbreviation References Chapter 8 - Correlative and Predictive Models for GE 8.1 Introduction 8.2 Activity Coefficients 8.3 Activity Coefficient Models 8.3.1 GE Functions for Multicomponent Systems 8.4 Pressure and Temperature Dependence of GE and Activity Coefficients 8.5 Prediction Methods for Activity Coefficients 8.5.1 Group Contribution Models 8.5.2 Quantum Mechanical Methods 8.5.2.1 Direct Molecular Simulation of Phase Behaviour 8.5.2.2 Prediction of Activity Coefficient Model Parameters from QM 8.5.2.2.1 Direct Calculation of Model Parameters from QM.QM calculations for minimum energy configurations can be used to determine interm... 8.5.2.2.2 Quantitative Structure–Property Relations (QSPR).Quantitative structure–property relations (QSPR) involve the description of mol... 8.5.2.3 Continuum Solvation Models 8.5.3 Empirical and Extrapolative Models 8.5.3.1 Non- random Two- liquid Segment Activity Coefficient Model (NRTL- SAC) 8.5.3.2 UNISAC and Extended UNISAC 8.5.4 Application of Predictive Activity Models to High- pressure and Non- ideal Vapour Phases 8.5.5 General Application of Predictive Models to Phase Equilibria Predictions Abbreviations Acknowledgements References Chapter 9 - Gibbs Energies in Biomolecular Solutions 9.1 Introduction 9.2 Thermodynamics: the Macroscopic Perspective 9.3 Statistical Mechanics: the Microscopic Perspective 9.4 Connecting the Microscopic and Macroscopic Perspectives 9.5 A Biopolymer Toy Model as a Simple Quantitative Example References Chapter 10 - Solvation Gibbs Energy: The Equation of State Approach 10.1 Introduction 10.2 Two Alternative Equation of State Approaches to Solvation 10.2.1 The UMR– PRU Equation of State Model 10.2.2 The LFHB Equation of State Model 10.3 Applications 10.3.1 Prediction of Solvation Gibbs Energies with the UMR– PRU EOS 10.3.2 LFHB Calculations of Solvation Gibbs Energy and Its Components 10.3.2.1 Hydration of Homologous Series of Solutes 10.3.2.2 Calculation of Self- solvation of Common Solutes and Their Solvation Quantities in 1- octanol 10.3.2.3 Calculation of Hydration Quantities of Key Metabolites 10.4 Discussion and Conclusion References Chapter 11 - Limiting Activity Coefficients: New Procedures, Computations and Measurements 11.1 Differential Ebulliometry 11.1.1 Finding the Liquid Equilibrium Composition 11.1.2 The Evaporation Ratio Φ 11.1.3 Finding the Value of the Exponent n 11.1.4 Calculation of Entropy Generation 11.1.5 Calculation of Molar Flow Rate F 11.2 Very Dilute Gas or Gas–Liquid Systems 11.2.1 Equipment Description 11.2.2 Preparing Gas Mixtures 11.2.3 Calculation of the Prepared Mixture Concentration 11.2.4 Measurement of Gas or Gas Mixture Non- ideality 11.2.5 Very Dilute Gas or Gas–Liquid Mixtures 11.2.6 Mixing Impure “Pure” Gases 11.2.7 Impure Gas–Impure Liquid Mixtures 11.3 Automation References Chapter 12 - Free Energy in Thermal and Chemical Protein Unfolding 12.1 Introduction 12.2 Standard Two- state Model. Thermal Unfolding 12.3 Two- state Model. Chemical Denaturation 12.4 System Two- state Partition Function. Thermal Unfolding 12.5 System Two- state Partition Function. Chemical Unfolding 12.6 Molecular Multi- state Partition Function. Thermal Unfolding 12.7 Molecular Multi- state Partition Function. Chemical Unfolding 12.8 Enthalpy, Entropy and Free Energy References Chapter 13 - The Statistical Associating Fluid Theory 13.1 Introduction 13.2 Statistical Associating Fluid Theory 13.3 SAFT VR Mie 13.4 Conclusion Acknowledgements References Chapter 14 - Gibbs–Helmholtz Equation: Practical Applications in Thermochemistry 14.1 Introduction: Thermodynamic Background 14.2 Gibbs–Helmholtz Equation: Experimental and Theoretical Thermochemical Tools 14.2.1 The First Law Method: Reaction Enthalpy Measurements 14.2.2 The Second Law Method: Equilibrium Constant Measurements 14.2.3 Quantum Chemical Calculations: Standard Molar Enthalpy of Formation 14.2.4 Quantum Chemical Calculations: Gas- phase Standard Molar Entropy 14.2.5 Statistical Thermodynamics: Gas- phase Standard Molar Entropy 14.2.6 Standard Molar Entropy in the Liquid/Crystal Phase 14.2.7 Standard Molar Gibbs Energy of Vaporization/Sublimation 14.2.8 Standard Molar Gibbs Energy of Fusion: Walden's Rule 14.2.9 Standard Molar Gibbs Energy of Formation 14.3 Gibbs Energy: Practical Applications in Thermochemistry 14.3.1 Relative Thermodynamic Stability of Diamond and Graphite30 14.3.2 Chemical Equilibria in Non- associated Reaction Mixtures33 14.3.3 Chemical Equilibria in “Ideal” Associated Reaction Mixtures34 14.3.4 Chemical Equilibria in “Real” Associated Reaction Mixtures7 14.3.5 How Do We Obtain the Yield in the Liquid Phase from the Quantum Chemistry- based Gibbs–Helmholtz Equation 14.3.6 In Silico Gibbs–Helmholtz Equation for Hydrogen Storage 14.3.7 In Silico Gibbs–Helmholtz Equation for the Synthesis of Ionic Liquids41 14.4 Conclusion and Outlook Acknowledgements References Chapter 15 - Experimental Determination of Vapor Pressures 15.1 Introduction 15.2 Temperature Dependence of Vapor Pressure 15.3 Experimental Methods for Vapor Pressure Determination 15.3.1 Static Method 15.3.1.1 Manometric Setups 15.3.1.2 Static Technique with Determination of the Gas- phase Concentration 15.3.2 Boiling Point Techniques 15.3.2.1 Ebulliometry 15.3.2.2 Quasi- static Methods 15.3.3 Dynamic Methods 15.3.3.1 Transpiration Technique 15.3.3.2 Thermogravimetric Analysis (TGA) 15.3.3.3 Fast Scanning Calorimetry (FSC) 15.3.4 Kinetic Methods 15.4 Conclusion References Chapter 16 - Stability of Real Liquid Crystals 16.1 Introduction 16.2 Thermodynamic Background 16.3 Liquid Crystals Formed by Hard Anisotropic Particles 16.4 Standard Molecular Theory of the Nematic Phase 16.5 Successive Melting of Molecular Crystals 16.6 Chain Melting in Liquid Crystalline Systems 16.7 Stabilization of Liquid Crystals by Chain Entropy 16.8 Concluding Remarks Acknowledgements References Chapter 17 - Thermodynamics of the Folding and Interconversion of G- quadruplex DNA Structures 17.1 Introduction 17.2 Gibbs Free Energy of Structural Transitions 17.3 Apparent Standard Gibbs Free Energy Is Related to Species Population 17.4 Species Population Is Related to Experimental Signals 17.5 Model Analysis of Experimental Data 17.6 Phase Diagrams 17.7 Thermodynamic Driving Forces of Folding and Interconversion 17.8 Structure- based Calculations of Heat Capacity Changes 17.9 Kinetically Limited G4 (Un)folding Acknowledgements References Subject Index

This book contains the latest information on all aspects of the most important chemical thermodynamic properties of Gibbs energy and Helmholtz energy, as related to fluids. Both the Gibbs energy and Helmholtz energy are very important in the fields of thermodynamics and material properties as many other properties are obtained from the temperature or pressure dependence. Bringing all the information into one authoritative survey, the book is written by acknowledged world experts in their respective fields. Each of the chapters will cover theory, experimental methods and techniques and results for all types of liquids and vapours.

This book is the fourth in the series of Thermodynamic Properties related to liquids, solutions and vapours, edited by Emmerich Wilhelm and Trevor Letcher. The previous books were: Heat Capacities (2010), Volume Properties (2015), and Enthalpy (2017). This book fills the gap in fundamental thermodynamic properties and is the last in the series.