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Molecular association at the microscopic level

2005/03/12 by R. Neumann, Richard M. Neumann, Neumann, Richard M.
Earth and Planetary Sciences · Engineering · Materials Science · Physics and Astronomy · #Material Dynamics and Properties #Phase Equilibria and Thermodynamics #cond-mat.soft #cond-mat.stat-mech #nanoparticles nucleation surface interactions

paper · pdf · doi:10.48550/arxiv.cond-mat/0503310

11 pages, 1 figure

arxiv created 2005/03/12 · arxiv updated 2009/12/01

Abstract

The Helmholtz free-energy W is calculated as a function of separation distance for two molecules in a fluid, A and B, whose mutual interaction is described by a spherically symmetric potential. For the equilibrium A + B = AB occurring in a dilute solution or gas, W is used to evaluate the association constant K, which for ionic A and B is identical to the Bjerrum result. The criterion defining the bound species is not arbitrary; i.e., the cutoff separation distance in the configuration integral used to calculate K arises directly from the definition of W. For a one-component dense fluid, W permits the derivation of the phase-condensation temperature, which for a gas is the critical temperature and for a liquid the freezing temperature. For ionic A and B (e.g., Sodium and Chloride ions in molten NaCl), an expression for the freezing temperature is obtained, which is similar to the expression for the melting temperature derived by Kosterlitz and Thouless for two-dimensional systems.

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