Chemistry Reference
In-Depth Information
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Fluctuation Solution
Theory
A Primer
Paul E. Smith, Enrico Matteoli,
and John P. O'Connell
CONTENTS
1.1 Background and Theory ................................................................................... 2
1.1.1 Basic Thermodynamics ........................................................................ 3
1.1.2 Solution Thermodynamics .................................................................... 5
1.1.3 More on Chemical Potentials ............................................................... 6
1.1.4 Statistical Thermodynamics ................................................................. 9
1.1.5 Distribution Functions and Kirkwood-Buff Integrals ....................... 11
1.2 Fluctuation Theory of Solutions ..................................................................... 14
1.2.1 General Expressions ........................................................................... 14
1.2.2 Fluctuation Theory of Binary Solutions ............................................. 17
1.2.3 General Matrix Formulation of Fluctuation Theory .......................... 18
1.2.4 Inversion of Fluctuation Theory ......................................................... 19
1.2.5 Summary of Fundamental Relations .................................................. 20
1.3 Applications of Fluctuation Theory ................................................................ 21
1.3.1 Pure Liquids ........................................................................................ 21
1.3.2 Closed Binary Systems ....................................................................... 22
1.3.3 Closed Ternary Systems ..................................................................... 24
1.3.4 Preferential Solvation in Binary and Ternary Systems ....................... 26
1.3.5 Open Systems ..................................................................................... 27
1.3.6 Electrolyte Solutions ........................................................................... 28
1.3.7 Ideal Solutions .................................................................................... 30
1.3.8 Chemical and Association Equilibria ................................................. 31
1.3.9 Technical Issues Surrounding the Application of Fluctuation
Solution Theory .................................................................................. 32
1.4 Conclusions ..................................................................................................... 34
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