Abstract
Abstract The thermal behavior of the guest molecule trapped in the clathrate compounds, M(diam)M′(CN)4·2C6H6, where M and M′ are bivalent metal atoms and diam is two ammonia molecules or one molecule of diamine, and the structural changes of the host lattice upon heating were studied by means of derivatographic and isothermal measurements. In Cd(NH3)2Ni(CN)4·2C6H6, the elimination of guest benzene molecules was found to proceed in two steps. X-Ray powder diffraction patterns suggest that the skeleton of the host is preserved, at least during the first liberation of 1 mol of benzene, but the skeleton collapses after the complete liberation of benzene and ammonia. The host skeleton of Cd(en)Ni(CN)4·2C6H6 was preserved till the liberation of 75% of benzene. The activation energies were a little larger than the respective enthalpy changes. The replacement of M′=Ni by Pd or of M′=Cd by Hg in the clathrate compounds, if M and diamine are the same, scarcely changes the activation energy for the liberation of the guest molecule, but the replacement of M and diamine by other ones somewhat changes the activation energy.
Published Version
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