Combustion and Flame, Vol.140, No.1-2, 103-115, 2005
Flame inhibition by phosphorus-containing compounds over a range of equivalence ratios
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 inhibition reactions. Reaction pathways for HOPO2 + H and HOPO + H are analyzed using the BAC-G2 approach. A new reaction pathway for HOPO2 + H = PO2 + H2O has been identified which results in a higher rate constant than that reported in the literature. In this work, the laminar flame speed is measured experimentally and calculated numerically for a premixed propane/air flame at 1 atm, 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, fuel lean and fuel rich. From this, the importance of different catalytic cycles involved in the lean versus rich case is discussed. The chemical kinetic model indicates that the HOPO2 <----> PO2 inhibition cycle is more important in the lean flame than the rich. 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. (C) 2004 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords:flame inhibition;organophosphorus compounds;laminar flame speed;detailed chemical kinetic modeling