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Structural isotopic effect of the α/β phase transition in vanadium hydride and its influence on the equilibrium coefficient of separation of hydrogen isotopes in the gas-solid systemстатья
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Дата последнего поиска статьи во внешних источниках: 4 июня 2021 г.
- Авторы: Magomedbekov E.P., Bochkarev A.V.
- Журнал: Russian Journal of Physical Chemistry A
- Том: 73
- Номер: 11
- Год издания: 1999
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 1732
- Последняя страница: 1736
- Аннотация: The equilibrium separation coefficient for hydrogen isotopes (αH-D) in the vanadium dihydride VHn(s, n ≈ 0.7)-H2(g) system was measured by equilibration in a circulation unit and laser desorption at 298, 373, and 473 K. The αH-D distribution coefficients determined by the two methods were in close agreement with each other. The literature neutron diffraction data were used to calculate the isotopic ratios of the reduced partition functions and αH-D for the α′ and β′ phases of the V2H and V2D hydrides by direct summation over vibrational energy levels. The calculated isotopic effects (both structural isotopic effects in phase diagrams and the separation coefficient for hydrogen isotopes) were fairly close to the experimental values. This result substantiates the suggestion that the reason for the unusual behavior of the separation coefficient for hydrogen isotopes and for the difference in the crystal structures of vanadium hydride and its deuterated analogue is a combination of a strongly anharmonic potential in octahedral lattice sites and a small difference in the energies of coordination of hydrogen atoms in tetrahedral and octahedral sites.
- Добавил в систему: Магомедбеков Эльдар Парпачевич