The search for kinetic reference materials for adiabatic and differential scanning calorimetry

Blaine, Roger L.

doi:10.1007/s10973-010-1078-0

Cited by 15 publications

(11 citation statements)

References 51 publications

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“…More recently, Iwata [39] studied the thermal decomposition behavior of DTBP10-30 % in toluene mixtures measured with differential adiabatic calorimeter (DAC) and found the activation energy is 155.3 kJ mol -1 . The activation energies for both DTBP and 20 % DTBP in toluene measured by DSC in this study are with excellent precision and accuracy in comparison to the data in the literature [18].…”

Section: Dtbp (Di-tert-butyl Peroxide)supporting

confidence: 70%

“…Activation energy is 124.6 kJ mol -1 for pure DTBP and is 161 kJ mol -1 for DTBP 20 mass% in toluene. Blaine [18] had reviewed the search for the reference materials for obtaining the Arrhenius kinetics by differential and adiabatic calorimetry. The calorimetric data on thermal decomposition were studied and compared in a table of various parameters.…”

Section: Dtbp (Di-tert-butyl Peroxide)mentioning

confidence: 99%

“…The calorimetric data on thermal decomposition were studied and compared in a table of various parameters. Order is from 0.925 to 1.05, the heat of decomposition is from -1190 to -1335 J g -1 , log A is from 11.51 to 16.63, and E a is from 138.4 to 164.5 kJ mol -1 [18]. A set of comparable activation energy from 138 to 167 kJ mol -1 T a the exothermic onset temperature (the point with an exothermic power of 0.2 W g -1 ), T o the extrapolated onset temperature, T p peak temperature with several different decomposition pathways was reported by Oxley et al, [35].…”

Section: Dtbp (Di-tert-butyl Peroxide)mentioning

confidence: 99%

“…For deeply investigating the dynamic behavior, thermal decomposition paid the most attentions to the chemical kinetics and unimolecular elementary reaction, which can be dissected by RRKM (Rice-Ramsperger-Kassel-Marcus) theory or ab initio calculation microscopically [7,17]. Blaine [18] proposed six compounds in an attempt to establish the standard reference materials for studying the kinetics of thermal decomposition by calorimetry. Dialkyl peroxides (or di-tertiary alkyl) are among the most stable of all the commercially available organic peroxides.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Dtbp (Di-tert-butyl Peroxide)supporting

confidence: 70%

Section: Dtbp (Di-tert-butyl Peroxide)mentioning

confidence: 99%

Section: Dtbp (Di-tert-butyl Peroxide)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermal decompositions of dialkyl peroxides studied by DSC

Duh

Lee

et al. 2014

J Therm Anal Calorim

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“…The Ozawa method [16] is adopted to reduce the pyrolysis activation energy, and the Šatava method is used to deduce the mechanism function form. Through calculation and analysis, the pyrolysis kinetic equation can be obtained:…”

Section: Pyrolysis Modelmentioning

confidence: 99%

A volumetric ablation model of EPDM considering complex physicochemical process in porous structure of char layer

Liu

Xiao-Jing

et al. 2017

Open Physics

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A volumetric ablation model for EPDM (ethylenepropylene-diene monomer) is established in this paper. This model considers the complex physicochemical process in the porous structure of a char layer. An ablation physics model based on a porous structure of a char layer and another model of heterogeneous volumetric ablation char layer physics are then built. In the model, porosity is used to describe the porous structure of a char layer. Gas diffusion and chemical reactions are introduced to the entire porous structure. Through detailed formation analysis, the causes of the compact or loose structure in the char layer and chemical vapor deposition (CVD) reaction between pyrolysis gas and char layer skeleton are introduced. The Arrhenius formula is adopted to determine the methods for calculating carbon deposition rate C which is the consumption rate caused by thermochemical reactions in the char layer, and porosity evolution. The critical porosity value is used as a criterion for char layer porous structure failure under gas flow and particle erosion. This critical porosity value is obtained by fitting experimental parameters and surface porosity of the char layer. Linear ablation and mass ablation rates are confirmed with the critical porosity value. Results of linear ablation and mass ablation rate calculations generally coincide with experimental results, suggesting that the ablation analysis proposed in this paper can accurately reflect practical situations and that the physics and mathematics models built are accurate and reasonable.

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Adiabatic time to maximum rate evaluation using an analytical approach

Sanchirico

2017

AIChE Journal

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This article presents an analytical method for the calculation of the adiabatic time to maximum rate. The procedure is developed considering a thermal decomposition process described by a simple n-order kinetic and is based on the introduction of a special function that is possible by integrating analytically. The application of the method requires the knowledge of the thermokinetic parameters of the process under study and allows the calculation of the adiabatic time to maximum rate without the numerical integration of the heat and mass balance equations or the use of relationships based on particular simplifying hypotheses. Its validity has been demonstrated considering numerical and real experiments (thermal decomposition of trityl azide) providing in both cases times to maximum rate values which are very close to the real ones.

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The search for kinetic reference materials for adiabatic and differential scanning calorimetry

Cited by 15 publications

References 51 publications

Thermal decompositions of dialkyl peroxides studied by DSC

Thermal decompositions of dialkyl peroxides studied by DSC

A volumetric ablation model of EPDM considering complex physicochemical process in porous structure of char layer

Adiabatic time to maximum rate evaluation using an analytical approach

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