Pyrolysis of Triethyl Phosphate

Zegers, E.J.P.; Fisher, Elizabeth M.

doi:10.1080/00102209808952064

Cited by 30 publications

(32 citation statements)

References 7 publications

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“…1. Ratio of alcohol and alkene amount formed in the pyrolysis of DEMP [9], TEP [10], and DIMP [11] in flow reactor under 1 atm. Curves are model predictions.…”

Section: Unimolecular Decompositionsmentioning

confidence: 99%

“…Zegers and Fisher measured rates of the six-center elimination for DEMP [9], TEP [10], and DIMP [11] by following decay of the reactant in pyrolysis between 700 K and 900 K. Rates are in good agreement with ester decomposition into acid and alkene involving the same kind of transition state [11]. However, measurements of ester decomposition show that the pre-exponential factor A for such a six-member transition state is between 3.10 12 and 10 13 s ‫1מ‬ [11,19].…”

Section: Unimolecular Decompositionsmentioning

confidence: 99%

“…Experimental results [9][10][11] were obtained in an atmospheric pressure flow reactor, with the reactant diluted in nitrogen. Measured products were ethylene and ethanol in the reaction of DEMP and TEP, and propene and i-propanol in the reaction of DIMP.…”

Section: Unimolecular Decompositionsmentioning

confidence: 99%

“…Measured products were ethylene and ethanol in the reaction of DEMP and TEP, and propene and i-propanol in the reaction of DIMP. Because heterogeneous effects change the ratio between the products [9][10][11], the initial load used for the calculations was the amount extrapolated to t ‫ס‬ 0 at the lower temperature studied. This assumption supposes that heterogeneous reactions are independent of temperature and play a role in the entrance section of the flow reactor but may be neglected downstream.…”

Section: Unimolecular Decompositionsmentioning

confidence: 99%

“…In pyrolysis, below 1000 K, L'Homme et al [7] determined products of the reaction of alkyl phosphates; Durig et al [8] compared reactivity of six compounds and proposed a decomposition mechanism by unimolecular eliminations. Zegers and Fisher studied thermal decomposition of diethyl methyl phosphonate (DEMP) [9], triethylphosphonate (TEP) [10], and diisopropyl methyl phosphonate (DIMP) [11] in the range 700-900 K. They measured the rate of unimolecular reaction of reactants and proposed mechanisms based on successive molecular eliminations. In combustion conditions, Werner and Cool [12] and Korobeinichev et al [13] studied the addition of dimethyl methyl phosphonate (DMMP) in a H 2 /O 2 flame; both measured phosphorus-containing intermediates and products.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Kinetic study of the combustion of organophosphorus compounds

Glaude

Curran

Pitz

et al. 2000

Proceedings of the Combustion Institute

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“…1. Ratio of alcohol and alkene amount formed in the pyrolysis of DEMP [9], TEP [10], and DIMP [11] in flow reactor under 1 atm. Curves are model predictions.…”

Section: Unimolecular Decompositionsmentioning

confidence: 99%

Section: Unimolecular Decompositionsmentioning

confidence: 99%

Section: Unimolecular Decompositionsmentioning

confidence: 99%

Section: Unimolecular Decompositionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Kinetic study of the combustion of organophosphorus compounds

Glaude

Curran

Pitz

et al. 2000

Proceedings of the Combustion Institute

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Probing Phosphorus Nitride (P≡N) and Other Elusive Species Formed upon Pyrolysis of Dimethyl Phosphoramidate

Liang

Hemberger

Levalois-Grützmacher

et al. 2017

Chemistry A European J

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The thermal behavior of organophosphorus compounds is intricate and poorly understood but crucial for understanding gas-phase flame inhibition, syntheses of thermally active phosphorus-based reactive precursors, catalytic combustion, incineration of toxic nerve gases, and astrochemistry. In this work, the pyrolysis of dimethyl phosphoramidate was investigated using photoion photoelectron coincidence spectroscopy in combination with vacuum ultraviolet synchrotron radiation. This technique enables isomer-selective detection of reactive intermediates, which are crucial in the understanding of the decomposition process. Combined with quantum chemical calculations, the experimental results permit the formulation of a comprehensive pyrolysis reaction pathway for dimethyl phosphoramidate, consisting of several reactive phosphorus species on four possible decomposition pathways. Compared to the decomposition of dimethyl methyl phosphonate, which leads exclusively to the formation of PO radicals, substitution of the methyl with an amino group most notably yields phosphorus nitride (P≡N). This mostly favored reaction pathway involves the subsequent loss of methanol and formaldehyde to yield three PONH tautomers, which eliminate water to generate P≡N. The thermally induced production of PN species and its possible role in flame inhibition has not previously been reported. In addition, the adiabatic ionization energy of O=P(OCH ) NH was determined to be 9.79±0.02 eV.

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Direct measurement of reaction rate for decomposition of diisopropyl methylphosphonate at high temperature using shock tube and laser absorption

Rahman

Higgs

Ninnemann

et al. 2022

Int J of Chemical Kinetics

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Diisopropyl methylphosphonate (DIMP) is an organophosphorus compound used as a simulant for the chemical weapon Sarin. One of the means of destruction of Sarin is incineration at high temperature, which requires a clear understanding of the high‐temperature reaction kinetics of Sarin. In this work, we study the reaction rate for thermal decomposition of DIMP in the temperature range of 762–1059 K at a pressure near 1 atm. Test conditions are carefully chosen to minimize interferences from other reactions and intermediates formed during the decomposition process. The experimental rates obtained have been fitted for the Arrhenius rate expression to get the rate parameters of the reaction r1, DIMP (C7H17O3P) = IMP (C4H11O3P) + propene (C3H6) as r1(s−1)badbreak=1015.058±0.5e−false(47497±1935(calmol)false)/RT\begin{equation*} {r_1}\;( {{s^{ - 1}}} ) = {10^{15.058 \pm 0.5}}\;{e^{ - ( {47497 \pm 1935( {\frac{{cal}}{{mol}}} )} )/RT}} \end{equation*}The rate obtained in this work extended the temperature range of previous measurements (up to 800 K) and can be used in reaction kinetic models for combustion of DIMP.

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Pyrolysis of Triethyl Phosphate

Cited by 30 publications

References 7 publications

Kinetic study of the combustion of organophosphorus compounds

Kinetic study of the combustion of organophosphorus compounds

Probing Phosphorus Nitride (P≡N) and Other Elusive Species Formed upon Pyrolysis of Dimethyl Phosphoramidate

Direct measurement of reaction rate for decomposition of diisopropyl methylphosphonate at high temperature using shock tube and laser absorption

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