Solution Thermodynamics and its Application to Aqueous Solutions (eBook)

A Differential Approach

Yoshikata Koga (Autor)

eBook Download: EPUB

2007 | 1. Auflage
310 Seiten
Elsevier Science (Verlag)
978-0-08-055187-6 (ISBN)

Infos

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

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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 "e;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 "e;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

Inhalt

Front Cover 1
Solution Thermodynamics and its Application to Aqueous Solutions A Differential Approach 4
Copyright Page 5
Table of Contents 8
Preface 12
Acknowledgements 14
Chapter 0 Introduction 16
[0-1] Introduction 16
[0-2] Qualitative judgments and sciences 17
[0-3] Outline of this book 18
Part A A Differential Approach to Solution Thermodynamics 22
Chapter I Basics of thermodynamics – Derivatives of Gibbs energy, G 24
[I-1] System, state, first and second laws of thermodynamics 24
[I-2] Giles’ derivation of entropy 26
[I-2-1] State, process, and irreversibility of process 26
[I-2-2] Entropy, and potentials – Defining T, and p 27
[I-3] Logical (mathematical) deduction 29
[I-4] Stability criteria 31
[I-5] Multi-component system – Partial molar quantities 32
[I-6] Excess quantities 33
[I-7] Response functions 34
[I-8] Thermodynamic quantities – Order of derivative 35
[I-9] Interaction functions – Third derivatives 36
Chapter II Solution thermodynamics – Use of the second and third derivatives of G 38
[II-1] Mixture 38
[II-2] Gibbs-Duhem relation 40
[II-3] Vapor pressures 45
[II-4] Raoult’s Law and Henry’s Law 48
[II-5] Process of mixing – Mixing entropy 50
[II-6] Conversion from (nB, nW) to (xB, N) variable systems 52
[II-7] Interaction functions due to the ideal mixing entropy 55
[II-8] Phase separation – Critical point (UCST or LCST) 56
[II-9] Azeotrope 63
Chapter III Determination of the partial molar quantities 66
[III-1] Introduction 66
[III-2] Calculation of HEi from HEm 66
[III-3] Experimental determination of excess partial molar enthalpy 69
[III-4] Experimental determination of excess partial molar volume 73
[III-5] Excess partial molar entropy – Excess chemical potential 73
[III-6] Boissonnas analysis – Excess chemical potential 75
[III-7] Partial pressures of 1-propanol (1P) H2O 81
Chapter IV Fluctuation and partial molar fluctuation – Understanding H2O 84
[IV-1] Introduction 84
[IV-2] Fluctuation functions – Coarse grain 84
[IV-3] H2O vs. n-hexane 88
[IV-4] Site-correlated percolation model of H2O 93
[IV-5] Concentration fluctuations and Kirkwood-Buff integrals 99
Part B Studies of Aqueous Solutions using the Second and the Third Derivatives of G 102
Chapter V Mixing schemes in aqueous mono-ols 104
[V-1] Mixing schemes in 2-butoxyethanol (BE)–H2O 104
[V-2] Mixing schemes in other mono-ols (AL)–H2O 121
[V-3] Fluctuation functions – More about Mixing Scheme I 132
[V-4] Concentration fluctuations – Mixing Scheme II 145
[V-5] Mixing Scheme III – Second and third derivative quantities in the alcohol-rich region 149
[V-6] Mixing schemes of aqueous alcohols (AL) studied by other techniques 162
Chapter VI Mixing schemes in aqueous solutions of non-electrolytes 166
[VI-1] Introduction 166
[VI-2] Type (a) – Aqueous solutions of iso-butoxyethanol (iBE) at 20°C and acetonitrile (ACN) at 6 to 45°C 170
[VI-3] Type (d) – Aqueous solutions of glycerol (Gly), acetone (AC), 1,3-propanediol (13P), and tetramethyl urea (TMU) 175
[VI-4] Type (b) – Aqueous solutions of iso-butyric acid (IBA) and 2-butanone (BUT) 181
[VI-5] Type (c) – Aqueous solutions of dimethylsulfoxide (DMSO) and 1,2-propanediol (12P) 183
[VI-6] Mixing schemes of aqueous non-electrolytes studied by other techniques 185
Chapter VII Effects of non-electrolytes on the molecular organization of H2O: 1-propanol (1P) probing methodology 190
[VII-1] Introduction – 1-propanol (1P) probing methodology 190
[VII-2] Effects of methanol (ME), 2-propanol (2P) and tert-butanol (TBA) on H2O as probed by the HE1P 1P pattern change 194
[VII-3] Effects of urea (U), tetramethyl urea (TMU) and acetone (AC) on H2O as probed by the HE1P 1P pattern change 202
[VII-4] Effects of ethylene glycol (EG), 1,2- and 1,3-propanediol (12P and 13P), glycerol (Gly) and poly (ethylene glycol) (PEG) on H2O as probed by the 208
[VII-5] Concluding remarks – Summary 215
Chapter VIII The effects of salts on the molecular organization of H2O: 1-propanol (1P)-probing methodology 220
[VIII-1] Introduction – Hofmeister series 220
[VIII-2] Effects of NaF and NaCl on H2O as probed by the HE1P 1P pattern change 222
[VIII-3] Effects of NaBr and NaI on H2O as probed by the HE1P 1P pattern change 226
[VIII-4] Effects of Na2SO4, NaOOCCH3 (NaOAc), NaClO4, and NaSCN on H2O as probed by the HE1P 1P pattern change 233
[VIII-5] Effects of CaCl2, NH4Cl and tetramethyl ammonium chloride (TMACl) on H2O as probed by the HE1P 1P pattern change 240
[VIII-6] Hydration number of glycine and its salts as probed by the HE1P 1P pattern change 244
[VIII-7] Concluding remarks in relation to other studies on aqueous electrolytes in the literature 249
[VIII-7-1] Ion pairing 249
[VIII-7-2] Hydration number, nH 250
[VIII-7-3] Hofmeister series 252
Chapter IX Interactions in ternary aqueous solutions – General treatment 256
[IX-1] Introduction 256
[IX-2] Solute–solute interactions in tert-butanol (TBA) – Dimethylsulfoxide (DMSO)–H2O 257
[IX-3] Solute–solute interactions in 2-butoxyethanol (BE)–dimethyl sulfoxide (DMSO)–H2O 271
Chapter X In closing – Executive summary on the effect of solute on H2O 280
Appendix A Graphical differentiation by means of B-spline 282
Appendix B Gibbs-Konovalov Correction 284
Appendix C Heat capacity anomalies associated with phase transitions – Two level approximation 286
Appendix D Freezing point depression 296
Appendix E Titration calorimetry with dilute titrant 300
References 302
Index 310

Produkt-Details

• Erscheint lt. Verlag: 12.11.2007
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Technische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Festkörperphysik
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Thermodynamik
• Themenwelt: Technik ► Umwelttechnik / Biotechnologie
• ISBN-10: 0-08-055187-4 / 0080551874
• ISBN-13: 978-0-08-055187-6 / 9780080551876