Solution Thermodynamics and its Application to Aqueous Solutions: A Differential Approach
Koga, Yoshikata
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Table of contents
- Cover
- Table of Contentsvii
- Prefacexi
- Acknowledgementsxiii
- Chapter 0 Introduction1
- [0-1] Introduction1
- [0-2] Qualitative judgments and sciences2
- [0-3] Outline of this book3
- Part A A Differential Approach to Solution Thermodynamics7
- Chapter I Basics of thermodynamics – Derivatives of Gibbs energy, G9
- [I-1] System, state, first and second laws of thermodynamics9
- [I-2] Giles’ derivation of entropy11
- [I-2-1] State, process, and irreversibility of process11
- [I-2-2] Entropy, and potentials – Defining T, and p12
- [I-3] Logical (mathematical) deduction14
- [I-4] Stability criteria16
- [I-5] Multi-component system – Partial molar quantities17
- [I-6] Excess quantities18
- [I-7] Response functions19
- [I-8] Thermodynamic quantities – Order of derivative20
- [I-9] Interaction functions – Third derivatives21
- Chapter II Solution thermodynamics – Use of the second and third derivatives of G23
- [II-1] Mixture23
- [II-2] Gibbs-Duhem relation25
- [II-3] Vapor pressures30
- [II-4] Raoult’s Law and Henry’s Law33
- [II-5] Process of mixing – Mixing entropy35
- [II-6] Conversion from (nB, nW) to (xB, N) variable systems37
- [II-7] Interaction functions due to the ideal mixing entropy40
- [II-8] Phase separation – Critical point (UCST or LCST)41
- [II-9] Azeotrope48
- Chapter III Determination of the partial molar quantities51
- [III-1] Introduction51
- [III-2] Calculation of HEi from HEm51
- [III-3] Experimental determination of excess partial molar enthalpy54
- [III-4] Experimental determination of excess partial molar volume58
- [III-5] Excess partial molar entropy – Excess chemical potential58
- [III-6] Boissonnas analysis – Excess chemical potential60
- [III-7] Partial pressures of 1-propanol (1P)ŠH2O66
- Chapter IV Fluctuation and partial molar fluctuation – Understanding H2O69
- [IV-1] Introduction69
- [IV-2] Fluctuation functions – Coarse grain69
- [IV-3] H2O vs. n-hexane73
- [IV-4] Site-correlated percolation model of H2O78
- [IV-5] Concentration fluctuations and Kirkwood-Buff integrals84
- Part B Studies of Aqueous Solutions using the Second and the Third Derivatives of G87
- Chapter V Mixing schemes in aqueous mono-ols89
- [V-1] Mixing schemes in 2-butoxyethanol (BE)–H2O89
- [V-2] Mixing schemes in other mono-ols (AL)–H2O106
- [V-3] Fluctuation functions – More about Mixing Scheme I117
- [V-4] Concentration fluctuations – Mixing Scheme II130
- [V-5] Mixing Scheme III – Second and third derivative quantities in the alcohol-rich region134
- [V-6] Mixing schemes of aqueous alcohols (AL) studied by other techniques147
- Chapter VI Mixing schemes in aqueous solutions of non-electrolytes151
- [VI-1] Introduction151
- [VI-2] Type (a) – Aqueous solutions of iso-butoxyethanol (iBE) at 20°C and acetonitrile (ACN) at155
- [VI-3] Type (d) – Aqueous solutions of glycerol (Gly), acetone (AC), 1,3-propanediol (13P), and te160
- [VI-4] Type (b) – Aqueous solutions of iso-butyric acid (IBA) and 2-butanone (BUT)166
- [VI-5] Type (c) – Aqueous solutions of dimethylsulfoxide (DMSO) and 1,2-propanediol (12P)168
- [VI-6] Mixing schemes of aqueous non-electrolytes studied by other techniques170
- Chapter VII Effects of non-electrolytes on the molecular organization of H2O: 1-propanol (1P) probin175
- [VII-1] Introduction – 1-propanol (1P) probing methodology175
- [VII-2] Effects of methanol (ME), 2-propanol (2P) and tert-butanol (TBA) on H2O as probed by the HE1179
- [VII-3] Effects of urea (U), tetramethyl urea (TMU) and acetone (AC) on H2O as probed by the HE1PŠ1187
- [VII-4] Effects of ethylene glycol (EG), 1,2- and 1,3-propanediol (12P and 13P), glycerol (Gly) and193
- [VII-5] Concluding remarks – Summary200
- Chapter VIII The effects of salts on the molecular organization of H2O: 1-propanol (1P)-probing meth205
- [VIII-1] Introduction – Hofmeister series205
- [VIII-2] Effects of NaF and NaCl on H2O as probed by the HE1PŠ1P pattern change207
- [VIII-3] Effects of NaBr and NaI on H2O as probed by the HE1PŠ1P pattern change211
- [VIII-4] Effects of Na2SO4, NaOOCCH3 (NaOAc), NaClO4, and NaSCN on H2O as probed by the HE1PŠ1P pat218
- [VIII-5] Effects of CaCl2, NH4Cl and tetramethyl ammonium chloride (TMACl) on H2O as probed by the H225
- [VIII-6] Hydration number of glycine and its salts as probed by the HE1PŠ1P pattern change229
- [VIII-7] Concluding remarks in relation to other studies on aqueous electrolytes in the literature234
- [VIII-7-1] Ion pairing234
- [VIII-7-2] Hydration number, nH235
- [VIII-7-3] Hofmeister series237
- Chapter IX Interactions in ternary aqueous solutions – General treatment241
- [IX-1] Introduction241
- [IX-2] Solute–solute interactions in tert-butanol (TBA) – Dimethylsulfoxide (DMSO)–H2O242
- [IX-3] Solute–solute interactions in 2-butoxyethanol (BE)–dimethyl sulfoxide (DMSO)–H2O256
- Chapter X In closing – Executive summary on the effect of solute on H2O265
- Appendix A Graphical differentiation by means of B-spline267
- Appendix B Gibbs-Konovalov Correction269
- Appendix C Heat capacity anomalies associated with phase transitions – Two level approximation271
- Appendix D Freezing point depression281
- Appendix E Titration calorimetry with dilute titrant285
- References287
- Index295
Book details
- Vendor Elsevier S & T
- SKU 9780444530738
- ISBN-13 9780080551876
- Author Koga, Yoshikata
- Category Science
- Subject Physical & Theoretical
Do you have questions about this book?
As the title suggests, we introduce a novel differential approach to solution thermodynamics and use it for the study of aqueous solutions. We evaluate the quantities of higher order derivative than the normal thermodynamic functions. We allow these higher derivative data speak for themselves without resorting to any model system. We thus elucidate the molecular processes in solution, (referred to in this book “mixing scheme), to the depth equal to, if not deeper, than that gained by spectroscopic and other methods. We show that there are three composition regions in aqueous solutions of non-electrolytes, each of which has a qualitatively distinct mixing scheme. The boundary between the adjacent regions is associated with an anomaly in the third derivatives of G. The loci of the anomalies in the temperature-composition field form the line sometimes referred as “Koga line. We then take advantage of the anomaly of a third derivative quantity of 1-propanol in the ternary aqueous solution, 1-propanol – sample species – H2O. We use its induced change as a probe of the effect of a sample species on H2O. In this way, we clarified what a hydrophobe, or a hydrophile, and in turn, an amphiphile, does to H2O. We also apply the same methodology to ions that have been ranked by the Hofmeister series. We show that the kosmotropes (salting out, or stabilizing agents) are either hydrophobes or hydration centres, and that chaotropes (salting in, or destablizing agents) are hydrophiles.
- A new differential approach to solution thermodynamics
- A particularly clear elucidation of the mixing schemes in aqueous solutions
- A clear understandings on the effects of hydrophobes, hydrophiles, and amphiphiles to H2O
- A clear understandings on the effects of ions on H2O in relation to the Hofmeister effect
- A new differential approach to studies in muti-component aqueous solutions
- A new differential approach to solution thermodynamics
- A particularly clear elucidation of the mixing schemes in aqueous solutions
- A clear understandings on the effects of hydrophobes, hydrophiles, and amphiphiles to H2O
- A clear understandings on the effects of ions on H2O in relation to the Hofmeister effect
- A new differential approach to studies in muti-component aqueous solutions
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