Solution Thermodynamics and its Application to Aqueous Solutions

1st Edition

A Differential Approach

Authors: Yoshikata Koga Yoshikata Koga
Paperback ISBN: 9780444530738
eBook ISBN: 9780080551876
Imprint: Elsevier Science
Published Date: 3rd October 2007
Page Count: 310
270.00 + applicable tax
205.00 + applicable tax
250.00 + applicable tax
165.00 + applicable tax
Unavailable
Compatible Not compatible
VitalSource PC, Mac, iPhone & iPad Amazon Kindle eReader
ePub & PDF Apple & PC desktop. Mobile devices (Apple & Android) Amazon Kindle eReader
Mobi Amazon Kindle eReader Anything else

Institutional Access


Description

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.

Key Features

  • 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

Readership

Researchers, students

Table of Contents

Chapter 0 Introduction [0-1] Introduction. [0-2] Qualitative judgments and sciences. [0-3] Outline of this book.

PART A A Differential Approach to Solution Thermodynamics.

Chapter I. Basics of thermodynamics – Derivatives of Gibbs energy, G. [I-1] System, state, first and second laws of thermodynamics. [I-2] Giles’ derivation of entropy. [I-2-1] State, process, and irreversibility of process. [I-2-2] Entropy and potentials – defining p and T.
[I-3] Logical (mathematical) deduction. [I-4] Stability criteria. [I-5] Multi-component 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 the third derivatives of G. [II-1] Mixture. [II-2] Gibbs-Duhem relation. [II-3] Vapor pressures. [II-4] Raoult’s law and Henry’s law. [II-5] Process of mixing – mixing entropy. [II-6] Conversion from ( , ) to ( , 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.

Chapter III. Determination of the partial molar quantities. [III-1] Introduction. [III-2] Calculation of from . [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 potenti

Details

No. of pages:
310
Language:
English
Copyright:
© Elsevier Science 2007
Published:
Imprint:
Elsevier Science
eBook ISBN:
9780080551876
Paperback ISBN:
9780444530738

About the Author

Yoshikata Koga

Affiliations and Expertise

The University of British Columbia, Vancouver, Canada

Yoshikata Koga

Affiliations and Expertise

The University of British Columbia, Vancouver, Canada

Reviews

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.