Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

Jorge, Nelly L.; Romero, Jorge Marcelo; Grand, André; Laguna, Abilio

doi:10.1016/j.chemphys.2011.11.019

Cited by 7 publications

(3 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The results of density functional calculations with full geometry optimization also supported the stepwise mechanism of formaldehyde diperoxide and the methyl diperoxide decomposition through intermediate diradical species. [9,10] The values of the activation parameters (ΔH # =102.9 ± 1 kJ mol -1 and ΔS # = -49.8 ± 1.1 J mol -1 K -1 ) were determined using the Eyring equation, whose graphical representation is linear (r 2 = 0.9990) in the temperature range ( 36ºC). the negative value of ΔS # observed (Table 2) reflects the decrease that occurs in the degrees of freedom of the molecules of the DFT reagent when passing to a rather rigid «transition state».…”

Section: Resultsmentioning

confidence: 99%

“…[5] Tetroxanes are thermally decomposed through a mechanism of reactions in stages, in which the speed determining stage is assigned to the unimolecular homology of the peroxide bond. The dissociation energy determined for the OO rupture of different peroxy compounds is close to 45 kcal / mol [6], however, the value of this energy can be affected by steric effects caused by the different ring substituents [7] or by the change in physicochemical properties of the solvent used to carry out the kinetic studies [8,9].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Thermal decomposition of 3,6-diphenyl-1,2,4,5-tetroxane in nitromethane solution

Jorge

Bordón

Pila

et al. 2018

JAC

Self Cite

View full text Add to dashboard Cite

The thermal decomposition reaction of benzaldehyde diperoxide (DFT; 0.001 mol L-1) in nitromethane solution studied in the temperature range of 130.0-166.0 °C, follows a first-order kinetic law up to at least 60% DFT conversion. The organic products observed were benzaldheyde and benzoic acid. A stepwise mechanism of decomposition was proposed where the first step is the homolytic unimolecular rupture of the O-O bond. The activation enthalpy and activation entropy for DFT in nitromethane were calculated (DH# = 106.3 ± 1.0 kJ mol-1 and DS# = -58.6 ± 1.1 J mol-1K-1) and compared with those obtained in other solvents to evaluate the solvent effect.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermal decomposition of 3,6-diphenyl-1,2,4,5-tetroxane in nitromethane solution

Jorge

Bordón

Pila

et al. 2018

JAC

Self Cite

View full text Add to dashboard Cite

show abstract

“…In previous theoretical studies, it was determined that in the gas phase the mechanism of the thermal decomposition reaction for 1,2,4,5-tetroxane is a mechanism in stages and not concerted [10].…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition of Diphenyl Tetroxane in Chlorobenzene Solution

Bordón¹,

Pila²,

Profeta³

et al. 2019

IJOC

View full text Add to dashboard Cite

The thermal decomposition of Cyclic Diperoxide of Benzaldehyde 3,6-diphenyl-1,2,4,5-tetroxane, (DFT) in chlorobenzene solution in the studied temperature range (130˚C-166˚C) satisfactorily satisfies a first order law up to 60% conversions of diperoxide. DFT would decompose through a mechanism in stages and initiated by the homolytic breakdown of one of the peroxidic bonds of the molecule, with the formation of the corresponding intermediate biradical. The concentration studied was very low, so that the effects of secondary reactions of decomposition induced by free radicals originated in the reaction medium can be considered minimal or negligible. The activation parameters for the unimolecular thermal decomposition reaction of the DFT are ΔH# = 30.52 ± 0.3 kcal•mol −1 and ΔS# = −6.38 ± 0.6 cal•mol −1 K −1. The support for a step-by-step mechanism instead of a process concerted is made by comparison with the theoretically calculated activation energy for the thermal decomposition of 1,2,4,5-tetroxane.

show abstract

Energetic Materials Trends in 5‐ and 6‐Membered Cyclic Peroxides Containing Hydroperoxy and Hydroxy Substituents

Gamage

Stiasny²,

Kratz

et al. 2016

Eur J Inorg Chem

View full text Add to dashboard Cite

Ten peroxide compounds based upon the 3,6-di-(hydroperoxy)-1,2-dioxane, 2-hydroxy-6-hydroperoxy-1,2-dioxane, 3,5-di(hydroperoxy)-1,2-dioxolane, and 3-hydroxy-5-hydroperoxy-1,2-dioxolane skeletons have been synthesized, structurally characterized, and fully evaluated for their energetic materials properties. The solid-state structures of these compounds are dominated by hydrogen bonding interactions involving the hydroperoxy and hydroxy groups. Energetic materials testing [a]

show abstract

Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

Cited by 7 publications

References 42 publications

Thermal decomposition of 3,6-diphenyl-1,2,4,5-tetroxane in nitromethane solution

Thermal decomposition of 3,6-diphenyl-1,2,4,5-tetroxane in nitromethane solution

Thermal Decomposition of Diphenyl Tetroxane in Chlorobenzene Solution

Energetic Materials Trends in 5‐ and 6‐Membered Cyclic Peroxides Containing Hydroperoxy and Hydroxy Substituents

Contact Info

Product

Resources

About