Kinetics of the thermal dehydration of trans-fluoroaquobis(ethylenediamine)chromium(III) tetracyanometallate(II) [metal(II) = Ni(II), Pd(II) and Pt(II)] |
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Authors: | J. Ribas M. Serra A. Escuer M.D. Baró |
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Affiliation: | Departament de Química Inorgànica, Facultat de Química, Universitat de Barcelona, Diagonal, 647, Barcelona (28) Spain;Departament de Termologia, Facultat de Ciències, Universitat Autònoma de Barcelona, Bellaterra, Barcelona Spain |
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Abstract: | The solid phase thermal deaquation—anation of trans-[CrF(H2O)(en)2][M(CN)4] (M = Ni, Pd, Pt; en = ethylenediamine) has been investigated by means of non-isothermal DSC and isothermal and non-isothermal TG measurements. The physical model for these reactions (nucleation, growth, diffusion or intermediates) has been found by comparison of the isothermal and non-isothermal TG data for all the principal g(α) expressions (0.2?α?0.8) and by the shape of the isothermal curves. The values found for activation energy are low (~ 130 kJ mol?1 for the Ni compound, ~ 140 kJ mol?1 for the Pd compound, and ~ 100 kJ mol?1 for the Pt compound). These data permit the assignment of the deaquation—anation mechanism of the SN1 type involving a square-base pyramid activated complex and elimination of water as Frenkel defects. |
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Keywords: | To whom correspondence should be addressed. |
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