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The soption-striction phenomenon is a change in the dimensions of a porous body in the course of sorption due to the strain caused by the action of molecular forces. The formulation of the theory of the phenomenon includes the following problems: the statistical-mechanical calculation of the pressure tensor in the pore interior as a function of the pore shape and size; the analysis of the role of surface tension in the mechanical equilibrium condition at the pore wall and producing strain at various mechanisms (physical or chemical) of sorption; the calculation of the body strain within the theory of elasticity. The calculation of the pressure tensor was performed for spherical, cylindrical, and flat (slit-like) pores using asymptotic relations for ordinary dispersion forces (in the context of the nano-scaled pore size) and dispersion forces with electromagnetic retardation (for micropores of larger dimensions), with the pair potential exponents -6 and -7, respectively. The results obtained consider both an initial contraction of a porous body in a vacuum and an additional contraction, if any, or the body expansion on the initial stage of the gas sorption. The exact calculation of strain is given for a cylindrical and spherical pore. The role of surface tension is shown to be reduced, first, to the initial contractive strain of a porous body in a vacuum and, second, to the body dilatation in the course of the gas sorption. A small additional contraction of a porous body on the initial stage of sorption (that, as is shown, cannot be caused by surface tension) is explained by the peculiarities of the sorbate pressure tensor in a pore. The effect is more pronounced the smaller the pore size and the lower the temperature, and is typical for nanoporous bodies. A general consideration based on the Irving-Kirkwood pressure tensor qualitatively confirms the regularities established for any kind of molecular interaction.
Original language | English |
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Pages (from-to) | 371-392 |
Number of pages | 22 |
Journal | Russian Journal of General Chemistry |
Volume | 77 |
Issue number | 3 |
DOIs | |
State | Published - 1 Mar 2007 |
ID: 51304949