Thermolysis of Organic Peroxides in Solution

Antonovskiĭ, V. L.; Хурсан, С. Л.

doi:10.1002/chin.200419278

Cited by 3 publications

(14 citation statements)

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“…(3), equals to 3.90 Â 10 6 L mol À1 s À1 . Usually, values of rate constants of unsaturated hydrocarbon ozonolysis are of the order 10 2 to 10 7 L mol À1 s À1 [10,22]. So, the rate constant calculated above is comparable with those, but it should be compared with experimental data of the C 60 fullerene ozonolysis.…”

Section: Rate Constant Of Ozone [66]-addition To the C 60 Fullerenementioning

confidence: 82%

“…Using average experimental values for Arrhenius equation, we have found the experimental rate constant, which is $2.05 Â 10 5 L mol À1 s À1 . The experimental and the calculated rate constants differ by one order of magnitude, but it should be noted that there are some difficulties in measurement of the experimental rate constants if a reaction has a low activation barrier (<40 kJ mol À1 ), and estimation of Arrhenius factor can be in the range of 1-3 orders [10,22]. Also the present quantum chemical investigation does not include the solvent effect on the kinetics.…”

Section: Rate Constant Of Ozone [66]-addition To the C 60 Fullerenementioning

confidence: 94%

“…1). 1,4-Addition should lead to a transannular adduct similar to the behavior of polycyclic aromatic hydrocarbons [10]. Moreover, 1,4-adducts have been detected among products of the other reactions of addition to the C 60 fullerene [18].…”

Section: Ways Of Ozone Addition To C 60mentioning

confidence: 99%

“…However, those works have not paid attention to the steps of interaction between the C 60 fullerene and ozone, which forego the PO formation. Moreover, these calculations have been performed with semiempirical AM1 method, which does not allow correct description of polar molecules, such as ozone and products of its addition [10].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ozone addition to C60 and C70 fullerenes: A DFT study

Sabirov

Хурсан

Булгаков

2008

Journal of Molecular Graphics and Modelling

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Section: Rate Constant Of Ozone [66]-addition To the C 60 Fullerenementioning

confidence: 82%

Section: Rate Constant Of Ozone [66]-addition To the C 60 Fullerenementioning

confidence: 94%

Section: Ways Of Ozone Addition To C 60mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ozone addition to C60 and C70 fullerenes: A DFT study

Sabirov

Хурсан

Булгаков

2008

Journal of Molecular Graphics and Modelling

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“…In section 'Data, mathematical model and methods' the thermal decomposition of peroxides is discussed in general and a collection of experimentally measured kinetic and thermochemical data is tabulated, from which the data for the three peroxides investigated in this work are selected. The CSTR paradigm used in this work is discussed, the model equations are presented and the method of computing 5 where radicals from the solvent attack the undissociated peroxide 16 .…”

Section: Introductionmentioning

confidence: 99%

Thermal Oscillations in the Decomposition of Organic Peroxides: Identification of a Hazard, Utilization, and Suppression

Ball

2012

Ind. Eng. Chem. Res.

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The purpose of this research is to identify and characterise oscillatory thermal instability in organic peroxides that are used in vast quantities in industry and misused by terrorists. The explosive thermal decompositions of lauroyl peroxide, methyl ethyl ketone peroxide and triacetone triperoxide are investigated computationally, using a continuous stirred tank reactor model and literature values of the kinetic and thermal parameters. Mathematical stability analysis is used to identify and track the oscillatory instability, which may be violent. In the mild oscillatory regime it is shown that, in principle, the oscillatory thermal signal may be used in microcalorimetry to detect and identify explosives. Stabilization of peroxide thermal decomposition via Endex coupling is investigated. It is usually assumed that initiation of explosive thermal decomposition occurs via classical (Semenov) ignition at a turning point or saddle-node bifurcation, but this work shows that oscillatory ignition is characteristic of thermoreactive liquids and that Semenov theory and purely steady state analyses are inadequate for identifying thermal hazard in such systems. 2

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Density Functional Theory Study on the Decay of Fullerenyl Radicals RC₆₀^•, ROC₆₀^•, and ROOC₆₀^• (R = tert-Butyl and Cumyl) and Polarizability of the Formed Fullerene Dimers

2013

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Currently, there are no comparative studies on the possible routes of decay of fullerenyl radicals. Such information is required for development of new synthetic approaches to the fullerene derivatives, obtained via radical reactions, and understanding mechanisms of oxidative destruction of fullerene-containing materials. In the present work, we have performed a theoretical study on the possible reactions of the selected fullerenyl radicals, generated in the well-known experimental systems. We consider three main routes for the radical decay: formation of fullerene bisadducts via XC60(•) + X(•) reactions, dimerization of XC60(•), and their interaction with molecular oxygen. The calculated heat effects explain the experimental regularities of fullerene radical reactions (e.g., the reversibility of the dimerization and low reactivity of fullerenyls toward molecular oxygen). We have found that the heat effects are maximal for the dimerization of ROOC60(•), so the interaction of C60 with peroxy radicals may provide more effective synthetic routes to the single-bonded C60 dimers compared to the known ones. Moreover, the exothermicity of ROO(•) addition to C60 is increased during the subsequent addition that allows reconsidering the reasons underlying C60 antioxidant activity. Additionally, polarizability and its nonadditivity of fullerene dimers XC60-C60X have been found. Guided by the calculated polarizabilities, we assume a new bistable system "fullerenyl ↔ dimer" for molecular machinery. Depending on the conditions, such a system can exist in two states differing by their response to external electric fields.

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Thermolysis of Organic Peroxides in Solution

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 3 publications

References 1 publication

Ozone addition to C60 and C70 fullerenes: A DFT study

Ozone addition to C60 and C70 fullerenes: A DFT study

Thermal Oscillations in the Decomposition of Organic Peroxides: Identification of a Hazard, Utilization, and Suppression

Density Functional Theory Study on the Decay of Fullerenyl Radicals RC₆₀^•, ROC₆₀^•, and ROOC₆₀^• (R = tert-Butyl and Cumyl) and Polarizability of the Formed Fullerene Dimers

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Thermolysis of Organic Peroxides in Solution

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 3 publications

References 1 publication

Ozone addition to C60 and C70 fullerenes: A DFT study

Ozone addition to C60 and C70 fullerenes: A DFT study

Thermal Oscillations in the Decomposition of Organic Peroxides: Identification of a Hazard, Utilization, and Suppression

Density Functional Theory Study on the Decay of Fullerenyl Radicals RC60•, ROC60•, and ROOC60• (R = tert-Butyl and Cumyl) and Polarizability of the Formed Fullerene Dimers

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Density Functional Theory Study on the Decay of Fullerenyl Radicals RC₆₀^•, ROC₆₀^•, and ROOC₆₀^• (R = tert-Butyl and Cumyl) and Polarizability of the Formed Fullerene Dimers