Catalytic inhibition of laminar flames by transition metal compounds

Some of the most effective flame inhibitors ever found are metallic compounds. Their effectiveness, however, drops off rapidly with an increase of agent concentration, and varies widely with flame type. Iron pentacarbonyl, for example, can be up to two orders of magnitude more efficient than CF3Br for reducing the burning velocity of premixed laminar flames when added at low volume fraction; nevertheless, it is nearly ineffective for extinction of co-flow diffusion flames. This article outlines previous research into flame inhibition by metal-containing compounds, and for more recent work, focuses on experimental and modeling studies of inhibited premixed, counterflow diffusion, and co-flow diffusion flames by the present authors. The strong flame inhibition by metal compounds when added at low volume fraction is found to occur through the gas-phase catalytic cycles leading to a highly effective radical recombination in the reaction zone. While the reactions of these cycles proceed in some cases at close to collisional rates, the agent effectiveness requires that the inhibiting species and the radicals in the flame overlap, and this can sometimes be limited by gas-phase transport rates. The metal species often lose their effectiveness above a certain volume fraction due to condensation processes. The influence of particle formation on inhibitor effectiveness depends upon the metal species concentration, particle size, residence time for particle formation, local flame temperature, and the drag and thermophoretic forces in the flame.