Experimental and kinetic studies of the chemical role of CO 2 in hydrocarbon reactions were conducted in a fuel-rich CH 4 flat flame with air ratios varying from 0.60 to 0.74. Unburned hydrocarbons (CH 4 , C 2 H 2 , C 2 H 4 , and C 2 H 6 ) in O 2 /CO 2 combustion were found to be lower than those in air combustion. The differences in the CH 4 oxidation characteristics between the air and O 2 /CO 2 combustion were caused by the chemical role of CO 2 in the reaction R1 (CO 2 + H → CO + OH), R2 (CH 2 (S) + CO 2 → CH 2 O + CO), and higher third body efficiencies of CO 2 at an air ratio (= 0.62 where the concentrations of reactants were high. The role of CO 2 in R1, R2, and the higher third body efficiencies of CO 2 decreased the rate of CH 4 oxidation during the early stage of combustion, where O 2 was present. Even though R2 did not directly compete with the main chain branching reaction R3 (H + O 2 → H + OH) for H radicals, like R1 did, R2 changed the hydrocarbon reaction pathway, thereby decreasing the rate of R4 (CH 3 + HO 2 → CH 3 O + OH) which had negative sensitivity in CH 4 oxidation. However, we found that R1 and R2 advance CH 4 oxidation in the last stage of combustion where O 2 was mostly consumed. This is attributed to the fact that the reactions R1 and R2 were able to advance without the presence of O 2 , and that R1 produced OH radicals that were active in hydrocarbon oxidation in the specific temperature range and R2 enhanced hydrocarbon oxidation when the rate of R4 was insignificant. Although R1 was the dominant reaction to reduce unburned hydrocarbons in the O 2 /CO 2 combustion, the role of R2 was significant at  = 0.62. Meanwhile, when the air ratio was 0.74 where concentrations of reactants were relatively low, the chemical role of CO 2 is to only decrease the rate of CH 4 oxidation due to the presence of an excessive amount of O 2 .

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