Flame inhibition by phosphorus-containing compounds in lean and rich propane flames

Abstract

Chemical inhibition of laminar propane flames by organophosphorus compounds has been studied experimentally and computationally 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 experimental species flame profiles for tri-methyl phosphate (TMP) and compare them with modeled species flame profile results of TMP and di-methyl methyl phosphonate (DMMP). Both experiments and kinetic modeling indicate that inhibition efficiency is effectively the same for all of the organophosphorus compounds examined, independent of the molecular structure of the initial inhibitor molecule. Chemical inhibition is due to reactions involving small P-bearing species HOPO 2 and HOPO produced by the organophosphorus compounds (OPCs). Ratios of HOPO 2 and HOPO concentrations differ between lean and rich flames, with HOPO 2 dominant in lean flames while HOPO dominates in rich flames. Resulting HOPO 2 and HOPO species profiles do not significantly depend 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 Twarowski mechanism is developed to account for the results observed, and new theoretical values are determined for heats of formation of the important P-containing species, using the BAC-G2 method.