Solution Thermodynamics and Its Application to Aqueous Solutions

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