Kinetic parameter estimation for decomposition of organic peroxides by means of DSC measurements

Talouba, Imed Ben; Balland, Laurent; Mouhab, Nordine; Abdelghani-Idrissi, M.A.

doi:10.1016/j.jlp.2011.02.001

Cited by 49 publications

(12 citation statements)

References 10 publications

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“…The relationship between activation energy decrease and catalysts content did not receive, to our knowledge, any theoretical formalism. However, the catalysts effect on the decomposition of hydroperoxides is for example illustrated in the case of: -HOOH where E 1 drops from 180 to 100 for catalyzed decomposition by copper complexes [58], -cumene hydroperoxide where E 1 falls from 100 kJ mol À1 [59,60] to values less than 75 kJ mol À1 in presence of copper [61],…”

Section: On the Stability Of Hydroperoxidesmentioning

confidence: 99%

Kinetic analysis of polydicyclopentadiene oxidation

Defauchy

Gac

Guinault

et al. 2017

Polymer Degradation and Stability

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is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. b s t r a c tThe in situ thermal oxidation of thin unstabilized polydicyclopentadiene was studied by TGA to monitor mass gain, and DSC to characterize hydroperoxides concentration. Results were discussed using kinetic analysis, which allowed the estimation of activation energies for key reactions of the oxidation process. Activation energy for termination was shown to be higher than in hydrocarbon liquids, which was discussed from the theory of diffusion controlled reactions, and a possible link with local motions associated with sub-glassy transition. Activation energy of thermal decomposition of hydroperoxides was found lower than for model hydroperoxides, suggesting an accelerating effect of organometallic catalysts. Despite those two results that indicate a poor thermal stability of thin pDCPD films, measurements of oxygen diffusivity at several temperatures show that oxidation remains confined in a relatively thin surface layer which would allow the pDCPD properties to be preserved.

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Section: On the Stability Of Hydroperoxidesmentioning

confidence: 99%

Kinetic analysis of polydicyclopentadiene oxidation

Defauchy

Gac

Guinault

et al. 2017

Polymer Degradation and Stability

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“…The exothermic decomposition of pure DCPO was carried out under dynamic and isothermal conditions to determine the n-th order kinetics, activation energy, frequency factor, and the heat of decomposition [40]. Combining both the decomposition products in a GC/MS and calorimetry, mechanism on the decomposition of DCPO was proposed explicitly [40].…”

Section: Dcpo (Dicumyl Peroxide)mentioning

confidence: 99%

Thermal decompositions of dialkyl peroxides studied by DSC

Duh

Lee

et al. 2014

J Therm Anal Calorim

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Studies on the thermal decompositions of diamyl peroxide (DAPO), dicumyl peroxide (DCPO), and tert-butyl cumyl peroxide (TBCP) were conducted by DSC. Heat of decomposition, exothermic onset point, and chemical kinetics were determined and compared to those data of ditert-butyl peroxide (DTBP), a model compound for studying thermokinetics of organic peroxide and standardization of a calorimeter. Similarities and differences of decomposition mechanisms between these organic peroxides were proposed and verified. Kinetics on decomposition of uni-molecular reaction via these similar alkoxyl radials accompanying b C-C bond scission were discussed and compared to the results from ab initio calculations. The ranking of thermal stability on dialkyl peroxides is determined to be in the following sequence: DCPO \ TBCP \ DAPO \ DTBP. This ratedetermining step in thermal decomposition of dialkyl peroxides possessed an average eigenvalue of log A at about 13.1 ± 1.2. Activation energy on the thermal decomposition of these peroxides was calculated to be 139.5 ± 14.4 kJ mol -1 .

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“…[22][23][24][25][26] A literature survey shows that the thermal decomposition of pure crystalline DCP is a strong exothermal process that develops with large gas and heat evolution following an apparent reaction order kinetic. [22][23][24][25][26][27][28] Table 1 reports the thermokinetic parameters found in the literature cited for the thermal decomposition of DCP.…”

Section: Resultsmentioning

confidence: 99%

“…The radical chain propagation that follow leads to the formation of different termination products such as acetophenone, dimethyl phenyl carbinol, and cumyl methyl ether in the condensed phase and CH 4 , C 2 H 6 C 2 H 4 in the gas phase. 28 If a semiempirical approach is taken a strong simplifying hypothesis that is considered is represented by the Eq. 2 (single step hypothesis).…”

Section: Resultsmentioning

confidence: 99%

Adiabatic behavior of thermal unstable compounds evaluated by means of dynamic scanning calorimetric (DSC) techniques

Sanchirico

2013

AIChE Journal

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The article investigates the possibility of obtaining reliable information on the adiabatic behavior of thermally unstable substances based on the thermokinetic data collected by differential scanning calorimetric experiments. In particular, it is developed a novel numerical algorithm which allows the estimation of the adiabatic onset temperature. Theoretical results are verified considering the thermal decomposition of dicumyl peroxide carried out under different calorimetric conditions. Encouraging results point out that the procedures developed allow the assessment of adiabatic critical parameters that are very close to the values determined during the experiments.

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Kinetic parameter estimation for decomposition of organic peroxides by means of DSC measurements

Cited by 49 publications

References 10 publications

Kinetic analysis of polydicyclopentadiene oxidation

Kinetic analysis of polydicyclopentadiene oxidation

Thermal decompositions of dialkyl peroxides studied by DSC

Adiabatic behavior of thermal unstable compounds evaluated by means of dynamic scanning calorimetric (DSC) techniques

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