The effect of flame structure

As the important effect of temperature on NO formation is discussed in the following sections, it is useful to remember that flame structure can play a most significant role in determining the overall NOx emitted. For premixed systems like those obtained on Bunsen and flat flame burners and almost obtained in carbureted spark-ignition engines, the temperature, and hence the mixture ratio, is the prime parameter in determining the quantities of NOx formed. Ideally, as in equilibrium systems, the NO formation should peak at the stoichiometric value and decline on both the fuel-rich and fuel-lean sides, just as the temperature does. Actually, because of kinetic (nonequilibrium) effects, the peak is found somewhat on the lean (oxygen-rich) side of stoichiometric. 

However, in fuel-injection systems where the fuel is injected into a chamber containing air or an air stream, the fuel droplets or fuel jets bum as diffusion flames, even though the overall mixture ratio may be lean and the final temperature could correspond to this overall mixture ratio. The temperature of these diffusion flames is at the stoichiometric value during part of the burning time, even though the excess species will eventually dilute the products of the flame to reach the true equilibrium final temperature. Thus, in diffusion flames, more NO, forms than would be expected from a calculation of an equilibrium temperature based on the overall mixture ratio. The reduction reactions of NO are so slow that in most practical systems the amount of NO formed in diffusion flames is unaffected by the subsequent drop in temperature caused by dilution of the excess species. 

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