Solution Thermodynamics and Its Application to Aqueous Solutions - 2nd Edition - ISBN: 9780444636294, 9780444636300

Solution Thermodynamics and Its Application to Aqueous Solutions

2nd Edition

A Differential Approach

Authors: Yoshikata Koga
eBook ISBN: 9780444636300
Paperback ISBN: 9780444636294
Imprint: Elsevier Science
Published Date: 28th March 2017
Page Count: 444
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Solution Thermodynamics and its Application to Aqueous Solutions: A Differential Approach, Second Edition introduces a differential approach to solution thermodynamics, applying it to the study of aqueous solutions. This valuable approach reveals the molecular processes in solutions in greater depth than that gained by spectroscopic and other methods.

The book clarifies what a hydrophobe, or a hydrophile, and in turn, an amphiphile, does to H2O. By applying the same methodology to ions that have been ranked by the Hofmeister series, the author shows that the kosmotropes are either hydrophobes or hydration centers, and that chaotropes are hydrophiles. This unique approach and important updates make the new edition a must-have reference for those active in solution chemistry.

Key Features

  • Unique differential approach to solution thermodynamics allows for experimental evaluation of the intermolecular interaction
  • Incorporates research findings from over 40 articles published since the previous edition
  • Numerical or graphical evaluation and direct experimental determination of third derivatives, enthalpic and volumetric AL-AL interactions and amphiphiles are new to this edition
  • Features new chapters on spectroscopic study in aqueous solutions as well as environmentally friendly and hostile water aqueous solutions


Researchers studying water and aqueous solutions (senior undergraduate, graduate, and up)

Table of Contents

Chapter 0: Introduction

  • Abstract
  • [0-1] Introduction
  • [0-2] Qualitative Judgments and Sciences
  • [0-3] Outline of This Book

Part A: A Differential Approach in Solution Thermodynamics

Chapter I: Basics of Thermodynamics—Derivatives of Gibbs Energy, G

  • Abstract
  • [I-1] System, State, the First, and Second Laws of Thermodynamics
  • [I-2] Giles' Derivation of Entropy
  • [I-3] Logical (Mathematical) Deduction
  • [I-4] Stability Criteria
  • [I-5] MultiComponent System—Partial Molar Quantities
  • [I-6] Excess Quantities
  • [I-7] Response Functions
  • [I-8] Thermodynamic Quantities—Order of Derivative
  • [I-9] Interaction Functions—Third Derivatives

Chapter II: Solution Thermodynamics—Use of the Second and Third Derivatives of G

  • Abstract
  • [II-1] Mixture
  • [II-2] Gibbs-Duhem Relation
  • [II-3] Vapor Pressures—Phase Equilibrium
  • [II-4] Raoult's Law and Henry's Law
  • [II-5] Process of Mixing—Mixing Entropy
  • [II-6] Conversion From (nB, nW) to (xB, N) Variable Systems
  • [II-7] Interaction Functions Due to the Ideal Mixing Entropy
  • [II-8] Phase Separation—Critical Point (UCST or LCST)
  • [II-9] Azeotrope
  • [II-10] Phase Transitions

Chapter III: Determination of the Second and Third Derivatives of G

  • Abstract
  • [III-1] Introduction
  • [III-2] Calculation of HiE From HmE
  • [III-3] Experimental Determination of Excess Partial Molar Enthalpy
  • [III-4] Experimental Determination of Excess Partial Molar Volume
  • [III-5] Excess Partial Molar Entropy-Excess Chemical Potential
  • [III-6] Boissonnas Analysis-Excess Chemical Potential
  • [III-7] Partial Pressures of 1-Propanol (1P)-H2O: How to Deal With an Azeotrope
  • [III-8] Numerical or Graphical Evaluation of Third Derivatives Using Second Derivative Data
  • [III-9] Direct Experimental Determination of a Third Derivative, SVδB

Chapter IV: Fluctuation and Partial Molar Fluctuation—Understanding H2O

  • Abstract
  • [IV-1] Introduction
  • [IV-2] Fluctuation Functions—Coarse Grain
  • [IV-3] H2O vs n-Hexane
  • [IV-4] Site-Correlated Percolation Model of Liquid H2O
  • [IV-5] Concentration Fluctuations and Kirkwood-Buff Integrals

Part B: Studies of Aqueous Solutions Using the Second, the Third, and the Fourth Derivatives of G

Chapter V: Mixing Schemes in Aqueous Mono-ols

  • Abstract
  • [V-1] Mixing Schemes in 2-Butoxyethanol (BE)-H2O
  • [V-2] Mixing Schemes on Other Mono-ols(AL)-H2O
  • [V-3] Fluctuation Functions—More About Mixing Scheme I
  • [V-4] Concentration Fluctuations—Mixing Scheme II
  • [V-5] Mixing Scheme III—Second and Third Derivative Quantities in the Alcohol-Rich Region
  • [V-6] Mixing Schemes of Aqueous Alcohols (AL) Studied by Other Methods

Chapter VI: Mixing Schemes in Aqueous Solutions of Nonelectrolytes

  • Abstract
  • [VI-1] Introduction
  • [VI-2] Type (a)—Aqueous Solutions of iso-Butoxyethanol (iBE) at 20°C, Acetonitrile (ACN) at 6–45°C, and Trifluoroethanol (TFE) at 25°C
  • [VI-3] Type (d)—Aqueous Solutions of Glycerol (Gly), Urea (UR), Acetone (AC), 1,3-Propanediol (13P), and Tetramethyl Urea (TMU)
  • [VI-4] Type (b)—Aqueous Solutions of iso-Butyric Acid (IBA) and 2-Butanone (BUT)
  • [VI-5] Type (c)—Aqueous Solutions of Dimethylsulfoxide (DMSO) and 1,2-Propanediol (12P)
  • [VI-6] Amphiphiles—Aqueous Solutions of Methanol (ME) and Tetrahydrofuran (THF)
  • [VI-7] Fourth Derivative of G—Acceleration of the Effect of Solute on S-V Cross Fluctuations
  • [VI-8] The Koga Line—Temperature Dependence of Boundary Between Mixing Scheme I and II
  • [VI-9] Anomalies in the Third Derivative of G in Pure Stable Liquid H2O—Liquid H2O Revisited
  • [VI-10] Mixing Schemes of Aqueous Nonelectrolytes Studied by Other Techniques

Chapter VII: Effects of Nonelectrolytes on the Molecular Organization of H2O—1-Propanol (1P) Probing Methodology

  • Abstract
  • [VII-1] Introduction—1-Propanol (1P) Probing Methodology
  • [VII-2] Effects of Hydrophobes on the Molecular Organization of H2O as Probed by the Pattern Shifts
  • [VII-3] Effects of Hydrophiles on the Molecular Organization of H2O as Probed by the Pattern Shifts
  • [VII-4] Effects of Amphiphiles on the Molecular Organization of H2O as Probed by the Pattern Shifts
  • [VII-5] Concluding Remarks—Summary

Chapter VIII: Effects of Ions on the Molecular Organization of H2O—1-Propanol (1P)-Probing Methodology

  • Abstract
  • [VIII-1] Introduction: Hofmeister Series
  • [VIII-2] Effects of NaF and NaCl on H2O as Probed by the H1P-1PE Pattern Change—Hydration Centers
  • [VIII-3] Effects of NaBr and NaI to H2O as Probed by the H1P-1PE Pattern Change—Hydrophilic Ions
  • [VIII-4] Effects of Normal Cations and Anions on H2O as Probed by the H1P-1PE Pattern Change
  • [VIII-5] Constituent Ions of Room Temperature Ionic Liquids (RTIL)
  • [VIII-6] Physical Meanings of the Axes of the Hydrophobicity/Hydrophilicity Maps
  • [VIII-7] Concluding Remarks in Relation to Other Studies on Aqueous Electrolytes in the Literature

Chapter IX: Interactions in Ternary Aqueous Solutions—General Treatment

  • Abstract
  • [IX-1] Introduction
  • [IX-2] Solute-Solute Interactions in tert-Butanol (TBA)-Dimethyl Sulfoxide (DMSO)-H2O
  • [IX-3] Solute-Solute Interactions in 2-Butoxyethanol (BE)-Dimethyl Sulfoxide (DMSO)-H2O

Chapter X: Differential Approach Applied to Spectroscopic Studies on Aqueous Solutions

  • Abstract
  • [X-1] Spectroscopic Versus Thermodynamic Studies: Introduction
  • [X-2] Excess Molar Absorptivity, ɛE, and Excess Partial Molar Absorptivity of Solute S, ɛSE, in Aqueous Solutions
  • [X-3] Spectra of Excess Molar Absorptivity, ɛE, and Excess Partial Molar Absorptivity of Solute, ɛSE, for Aqueous Solutions of Acetonitrile (AN) and Acetone (AC)
  • [X-4] Spectra of Excess Molar Absorptivity, ɛE, and Excess Partial Molar Absorptivity of Salt, ɛSE, in Aqueous Solutions of Na-Halides
  • [X-5] Spectra of Excess Molar Absorptivity, ɛE, in Aqueous Solutions of Some Other Salts

Chapter XI: The Koga Line—Boundary Between Environmentally Friendly and Hostile Water and Aqueous Solutions

  • Abstract
  • [XI-1] Introduction
  • [XI-2] The Nature of Aqueous Solution in Mixing Scheme I
  • [XI-3] Observations of the Survival of Life Forms
  • [XI-4] How to Identify a Body of Aqueous Solution That is Friendly to Life Forms

Chapter XII: In Closing—Executive Summary of the Effect of Solute on H2O

  • Abstract


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About the Author

Yoshikata Koga

Yoshikata Koga

Dr. Koga's group introduced a new approach to the thermodynamic studies of aqueous solutions. They devised methods of measuring various thermodynamic quantities differentially. These methods allow them to experimentally evaluate the intermolecular interaction, the key quantity in the so-called "many-body problem.” The group has started applying this new methodology to aqueous solutions of biopolymers. As a recognition of his contribution to solution thermodynamics, he was awarded the Society Award by The Japan Society of Calorimetry and Thermal Analysis in 2006. In 2011, he obtained for the first time in the world a fourth derivative of Gibbs energy and named it "Acceleration of the effect of solute on entropy-volume cross fluctuation density."

Affiliations and Expertise

The University of British Columbia, Vancouver, Canada

Ratings and Reviews