Gibbs Energy and Helmholtz Energy : Liquids, Solutions and Vapours / edited by Emmerich Wilhelm and Trevor M. Letcher.

Format:

Book

Contributor:

Wilhelm, Emmerich, editor.

Letcher, T. M. (Trevor M.), editor.

Language:

English

Subjects (All):

Thermodynamics.

Helmholtz equation.

Gibbs' equation.

Physical Description:

1 online resource (505 pages)

Edition:

First edition.

Place of Publication:

London, England : The Royal Society of Chemistry, [2022]

Summary:

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.

Contents:

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

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

Derivation of eqn (3.13)

Acknowledgements

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

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

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

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

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

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

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

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

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

Chapter 13 - The Statistical Associating Fluid Theory

13.1 Introduction

13.2 Statistical Associating Fluid Theory

13.3 SAFT VR Mie

13.4 Conclusion

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.

Notes:

Description based on publisher supplied metadata and other sources.

Description based on print version record.

Includes bibliographical references.

ISBN:

9781839164095

1839164093

9781839164101

1839164107

OCLC:

1273000656