Compensation effect as a consequence of vibrational energy transfer in homogeneous and isotropic heat field

• Published in: Journal of thermal analysis and calorimetry 2008-04, Vol.92 (1), p.313-317
• Main Authors: Pop, Nicolina, Vlase, Gabriela, Vlase, T., Doca, N., Mogoş, A., Ioiţescu, A.
• Format: Article
• Language: English
• Subjects: Analytical Chemistry; Chemistry; Chemistry and Materials Science; Exact sciences and technology; General and physical chemistry; Inorganic Chemistry; Measurement Science and Instrumentation; Physical Chemistry; Polymer Sciences; Theory of reactions, general kinetics; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 1388-6150; 1588-2926; 1572-8943
• DOI: 10.1007/s10973-007-8723-2

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.