Development of the detailed mechanism of pyrolysis and combustion of triphenyl phosphate: New quantum chemistry calculations and experimental data on structure of the H2/O2/Ar flame doped with TPP
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Abstract
A possible method for a flammability reduction of the polymeric materials is the introduction of flame retardants into their composition. An effective search for optimal flame retardants and an understanding of their inhibition mechanisms requires the extensive information on the chemistry of their transformation in flames. A new data on chemical flame structure of a premixed H2/O2/Ar flame doped with 1000 ppm of triphenyl phosphate (TPP) at a pressure of 1 atm was obtained with a molecular-beam mass-spectrometry technique. Among intermediate products of the TPP decomposition were identified: several large phosphorus containing compounds, small phosphorus containing species (PO, PO2, HOPO, HOPO2), cyclic hydrocarbons (benzene, toluene, phenol), phenyl and phenoxy radicals. The detailed kinetic mechanism proposed earlier for the thermal degradation of TPP was updated with several new reactions including reactions with common flame radicals H/OH/CH3. Reaction rate constants were calculated using the Rice-Ramsberger-Kassel-Marcus theory and potential energy surfaces obtained by the DLPNO-CCSD(T)/cc-pVQZ//ωb97xd/6-31G(d) method. A comparison between experimental data and simulation results with the new model has shown a satisfactory qualitative and quantitative agreement, which confirmed that, the TPP decomposition occurs in flame according to the proposed scheme.
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The mission of the journal is to publish high quality work from experimental, theoretical, and computational investigations on the fundamentals of combustion phenomena and closely allied matters. While submissions in all pertinent areas are welcomed, past and recent focus of the journal has been on:
Development and validation of reaction kinetics, reduction of reaction mechanisms and modeling of combustion systems, including:
Conventional, alternative and surrogate fuels;
Pollutants;
Particulate and aerosol formation and abatement;
Heterogeneous processes.
Experimental, theoretical, and computational studies of laminar and turbulent combustion phenomena, including:
Premixed and non-premixed flames;
Ignition and extinction phenomena;
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Flame structure;
Instabilities and swirl;
Flame spread;
Multi-phase reactants.
Advances in diagnostic and computational methods in combustion, including:
Measurement and simulation of scalar and vector properties;
Novel techniques;
State-of-the art applications.
Fundamental investigations of combustion technologies and systems, including:
Internal combustion engines;
Gas turbines;
Small- and large-scale stationary combustion and power generation;
Catalytic combustion;
Combustion synthesis;
Combustion under extreme conditions;
New concepts.
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