Solution Thermodynamics and its Application to Aqueous Solutions: A Differential ApproachAs 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.
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Contents
| 1 | |
| 7 | |
Part B Studies of Aqueous Solutions using the Second and the Third Derivatives of G | 87 |
Appendix A Graphical differentiation by means of Bspline | 267 |
Appendix B GibbsKonovalov Correction | 269 |
Appendix C Heat capacity anomalies associated with phase transitions Two level approximation | 271 |
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Solution Thermodynamics and Its Application to Aqueous Solutions: A ... Yoshikata Koga No preview available - 2007 |
Common terms and phrases
1-propanol 1P 2-butoxyethanol AL−AL American Chemical Society amphiphile anomaly aqueous solutions B-spline BE−BE binary bond percolation bulk H2O Calorimetry and Thermal Canadian Journal chemical potential clusters Copyright 2005 Council of Canada cross fluctuation decrease derivative of G DMSO effect enthalpic interaction entropy entropy volume ethanol excess partial molar H1E P−1P pattern H2O molecules H2O-rich region Hence HiE−i hydration hydration center hydration number hydrogen bond network hydrogen bond probability hydrophilic hydrophobic i-th component iceberg increases intensive quantity Journal of Chemistry Journal of Physical kosmotropic LCST Liltorp liquid H2O mixture mole fraction National Research Council network of H2O NRC Research Press partial molar enthalpy partial molar volume partial pressures phase separation Physical Chemistry Reproduced with permission shown in Fig shows Society of Calorimetry Table temperature tert-butanol thermodynamic third derivative quantities Trandum value of H1E vapor pressure x1P Fig
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Page 11 - If we limit our attention to the case where work is done only by volume expansion, (1-4) where p is the pressure of the surroundings and V is the volume of the system.