There is much interest in the combustion mechanism of organophosphorus compounds (OPCs) due to their role as potential halon replacements in fire suppression. A continuing investigation of the inhibition activity of organophosphorus compounds under a range of equivalence ratios was performed experimentally and computationally, as measured by the burning velocity. Updates to a previous mechanism were made by the addition and modification of reactions in the mechanism for a more complete description of the recombination reactions. In this work, the laminar flame speed is measured experimentally and calculated numerically for a premixed propane/air flame, under a range of equivalence ratios, undoped and doped with dimethyl methylphosphonate (DMMP). A detailed investigation of the catalytic cycles involved in the recombination of key flame radicals is made for two equivalence ratios, lean and rich. From this, the importance of different catalytic cycles involved in the lean versus rich case is discussed. Although the importance of certain cycles is different under different stoichiometries, the OPCs are similarly effective across the range, demonstrating the robustness of OPCs as flame suppressants. In addition, it is shown that the phosphorus compounds are most active in the high temperature region of the flame. This may, in part, explain their high level of inhibition effectiveness.

Chemical inhibition of laminar propane flames by organophosphorus compounds has been studied experimentally, using a laboratory Mache Hebra nozzle burner and a flat flame burner with molecular beam mass spectrometry (MBMS), and with a computational flame model using a detailed chemical kinetic reaction mechanism. Both fuel-lean and fuel-rich propane flames were studied to examine the role of equivalence ratio in flame inhibition. The experiments examined a wide variety of organophosphorus compounds. We report on the experimental species flame profiles for tri-methyl phosphate (TMP) and compare them with the species flame profile results from modeling of TMP and di-methyl methyl phosphonate (DMMP). Both the experiments and kinetic modeling support and illustrate previous experimental studies in both premixed and non-premixed flames that inhibition efficiency is effectively the same for all of the organophosphorus compounds examined, independent of the molecular structure of the initial inhibitor molecule. The chemical inhibition is due to reactions involving the small P-bearing species HOPO 2 and HOPO that are produced by the organophosphorus compounds (OPCs). The ratios of the HOPO 2 and HOPO concentrations differ between the lean and rich flames, with HOPO 2 dominant in lean flames while HOPO dominates in rich flames. The resulting HOPO 2 and HOPO species profiles do not depend significantly on the initial source of the HOPO 2 and HOPO and thus are relatively insensitive to the initial OPC inhibitor. A more generalized form of the original Twarowski mechanism for hydrocarbon radical recombination is developed to account for the results observed, and new theoretical values have been determined for heats of formation of the important P-containing species, using the BAC-G2 method.

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