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Solvent Effect of Oxygen in the Thermolisys Decomposition of the Acetone Diperoxide
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Author(s): M. I. Profeta (Universidad Nacional del Nordeste, Argentina), J. R. Romero (Universidad Nacional del Nordeste, Argentina), L. A. C. Leiva (Universidad Nacional del Nordeste, Argentina), N. L. Jorge (Universidad Nacional del Nordeste, Argentina), M. E. Gomez Vara (Universidad Nacional del Nordeste, Argentina)and E. A. Castro (INIFTA, Argentina)
Copyright: 2013
Pages: 6
Source title:
Methodologies and Applications for Chemoinformatics and Chemical Engineering
Source Author(s)/Editor(s): A. K. Haghi (University of Guilan, Iran)
DOI: 10.4018/978-1-4666-4010-8.ch007
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Abstract
In this paper, the kinetics of the thermal decomposition reaction of 3,3,6,6-tetramethyl-1,2,4,5 tetroxane (ACDP) is investigated in various oxygen solvents at different temperatures. Linear relationships are observed between the enthalpy and entropy of activation of the unimolecular reactions of those diperoxides. The isokinetic temperature calculated by Leffler’s treatment is 527.2K, which is consistent with the proposed Exner correlation between the logarithm of the rate constant values for the same reaction in each solvent at two temperatures, where the corresponding ß value was 523.5K. A true “isokinetic relationship” for the ACDP thermolysis indicates that their reactions constitute a reaction series with similar interaction mechanisms. This can be related to the capacity for hydrogen bonding between the solvent and the diperoxide molecules. The solvanting properties of the media help the peroxidic bond rupture these molecules.
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