Compensation effect as a consequence of vibrational energy transfer in homogeneous and isotropic heat field
By kinetics of decomposition of solids in both isothermal and non-isothermal conditions, the compensation effect (CE) is rather a rule. The topic of this work is to suggest an activation mechanism which leads to the dependences similar with CE. The solid is assimilated to a system of the harmonic os...
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Veröffentlicht in: | Journal of thermal analysis and calorimetry 2008-04, Vol.92 (1), p.313-317 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | By kinetics of decomposition of solids in both isothermal and non-isothermal conditions, the compensation effect (CE) is rather a rule.
The topic of this work is to suggest an activation mechanism which leads to the dependences similar with CE.
The solid is assimilated to a system of the harmonic oscillator with a Bose-Einstein energy distribution.
Considering an activation process due to a vibrational energy transfer from a homogeneous and isotropic field of thermic oscillators to the solid-state oscillator, the thermodynamic functions are in the relationship
where Δ
H
* and Δ
S
* are the activation functions and
T
is
is the isokinetic temperature.
Taking into account the definitions of
H
and
S
by means of the partition function, the isokinetic temperature is assimilated with the characteristic temperature
An important consequence, a correlation between the isokinetic temperature and the spectroscopic wavenumber of the activated bond, is illustrated by a number of decomposition reactions under non-isothermal conditions. |
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ISSN: | 1388-6150 1588-2926 1572-8943 |
DOI: | 10.1007/s10973-007-8723-2 |