New PDF release: Fluctuation theory of solutions: applications in chemistry,

By Paul E Smith

ISBN-10: 1439899223

ISBN-13: 9781439899229

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Additional info for Fluctuation theory of solutions: applications in chemistry, chemical engineering, and biophysics

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These are different from the bulk fluctuations characteristic of isothermal isobaric systems. 63) where FST provides the link, in either direction, between local fluctuating quantities and global thermodynamic properties. 3 APPLICATIONS OF FLUCTUATION THEORY In the previous section we outlined the basic equations of FST or KB theory. A general matrix formulation was provided for several thermodynamic properties of solutions in terms of either particle number fluctuations and/­or integrals over pair radial distribution functions.

This is the key aspect to the large number of applications of FST. 5 Distribution Functions and Kirkwood –Buff Integrals The previous expressions involve particle number (and energy) fluctuations. It is more common, and totally equivalent, to use correlation/­distribution functions to replace the number fluctuations. In many cases this can help to clarify the significance of the number fluctuations (correlations) as we indicate in this section. However, in doing so one has to remember that these distributions correspond to a system volume that is open to all species.

We consider this to represent a primary solvent (1), a solute of interest (2), and a series of additional cosolutes or cosolvents (3, 4,…) which may also be present in the solution. However, other notations such as A/­B or u/­v is also used in the various chapters. All summations appearing here refer to the set of thermodynamically independent components (nc) in the mixture unless stated otherwise. Derivatives of the chemical potentials with respect to composition form a central component of the theory.

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Fluctuation theory of solutions: applications in chemistry, chemical engineering, and biophysics by Paul E Smith


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