Destruction Chemistry of Dimethyl Methylphosphonate in H₂/O₂/Ar FlameStudied by Molecular Beam Mass Spectrometry

Chemical Transformations in Inhibited Flames over Range of Stoichiometry

“…The ends of the thermocouple are welded to a 0.2-mm-diameter wire fabricated from the same material. Springs provide a steady stretching of the thermocouple and made it possible to prevent it from being deformed in the flame (Korobeinichev et al, 1996). Upon welding the surface of the thermocouple is coated with SiO 2 or Ceramobond 569 (Burton et al, 1992) to eliminate catalytic processes on its surface.…”

“…Mass spectrometry makes it possible to simultaneously detect in situ all flame components, a capability that is beyond the reach of any other method. Figure 1 shows the setup with molecular beam mass spectrometric sampling; for details, see (Korobeinichev et al, 1996). …”

“…The structure of hydrogen-oxygen flames seeded with trimethylphosphate (TMP) and Dimethylmethylphosphonate (DMMP) was determined using a kinetic model of OPCs destruction in flames involved 35 steps. This model was initially developed on the basis of experimental data on the structure of flames seeded with DMMP (Werner & Cool, 1999;Korobeinichev et al, 1996), thermochemical data obtained by Melius, and the mechanism proposed by Twarowski (Twarowski, 1993a(Twarowski, , 1993b(Twarowski, , 1995; it was tested by comparing the experimental and theoretical results on the structure of H 2 -O 2 -Ar flames seeded with TMP and DMMP (Korobeinichev et al, 1999b(Korobeinichev et al, , 2000(Korobeinichev et al, , 2001) at a pressure of 47 Torr and methane-oxygen flames seeded with TMP at 76 Torr (Korobeinichev et al, 2001). This model includes the mechanism developed by Twarowski (Twarowski, 1993a(Twarowski, , 1993b(Twarowski, , 1995 with modified rate constants from (Korobeinichev et al, 2000).…”

“…It was successfully applied to studying the combustion of OPCs at the Cornel University (USA) (Werner & Cool, 1999) and at the Institute of Chemical Kinetics and Combustion of the Siberian Division of the Russian Academy of Sciences (Korobeinichev et al, 1996).…”

Kinetic study of the combustion of organophosphorus compounds

“…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. Addition of trimethylphosphate (TMP) to *Current address: DCPR-CNRS, 1 rue Grandville, 54000 Nancy, France.…”