Yu. V. Alekseeva, b
a Karpov Research Institute of Physical Chemistry, ul. Vorontsovo pole 10, Moscow, 105064 Russia
b Institute of High Temperatures Scientific Association (IVTAN), Russian Academy of Sciences,
Izhorskaya ul. 13/19, Moscow, 127412 Russia
e-mail: alekseevlevgeorg@rambler.ru
Received January 31, 2008
Abstract—The paper presents examples of the selection of basic statistical objects for modeling certain phys-
icochemical systems largely related to electrochemistry and metal corrosion. Analytic components (sets of mol-
ecules and ions of each electrolyte) were selected as basic elements for a statistical description of the thermo-
dynamic properties of “symmetrical” electrolyte-solvents, where equilibria are maintained by protolysis. The
model provides close agreement with the experimental data on the concentration dependences of saturated
vapor pressures over aqueous solutions of “strong” electrolytes such as solutions of nitric and sulfuric acids. In
the problem of the solution of a passive alloy, the passivating film is treated as a solid solution of constituting
oxides, and just these oxides are selected as the basic elements of the statistical model. The calculated depen-
dence of the rate of alloy solution on alloy composition is in agreement with experiment. The statistical model
of the solution of a crystal formulated in terms of atom positions on the surface provides a correct description
of self-consistency between the topography of the atomic relief and the rate of solution. The model is used to
explain effects observed in the solution (corrosion) of metals and related to changes in topography caused by
nonstationary conditions or the presence of impurities.
DOI: 10.1134/S0036024408100117
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