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