Solution Thermodynamics and its Application to Aqueous Solutions (eBook)

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