Solution Thermodynamics and Its Application to Aqueous Solutions

A Differential Approach

2nd Edition - March 28, 2017
Imprint: Elsevier Science
Author: Yoshikata Koga
Language: English
Paperback ISBN:
9 7 8 - 0 - 4 4 4 - 6 3 6 2 9 - 4
eBook ISBN:
9 7 8 - 0 - 4 4 4 - 6 3 6 3 0 - 0

Solution Thermodynamics and its Application to Aqueous Solutions: A Differential Approach, Second Edition introduces a differential approach to solution thermodynamics, applying… Read more

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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.

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 (n_B, n_W) to (x_B, 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 H_i^E From H_m^E
[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, ^SVδ_B

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 H_1P-1P^E Pattern Change—Hydration Centers
[VIII-3] Effects of NaBr and NaI to H₂O as Probed by the H_1P-1P^E Pattern Change—Hydrophilic Ions
[VIII-4] Effects of Normal Cations and Anions on H₂O as Probed by the H_1P-1P^E 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, ɛ^E, and Excess Partial Molar Absorptivity of Solute S, ɛ_S^E, in Aqueous Solutions
[X-3] Spectra of Excess Molar Absorptivity, ɛ^E, and Excess Partial Molar Absorptivity of Solute, ɛ_S^E, for Aqueous Solutions of Acetonitrile (AN) and Acetone (AC)
[X-4] Spectra of Excess Molar Absorptivity, ɛ^E, and Excess Partial Molar Absorptivity of Salt, ɛ_S^E, in Aqueous Solutions of Na-Halides
[X-5] Spectra of Excess Molar Absorptivity, ɛ^E, 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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