Shock tube/laser absorption studies of the decomposition of methyl formate

Reaction rate coefficients for the major high-temperature methyl formate (MF, CH3OCHO) decomposition pathways, MF → CH3OH + CO (1), MF → CH2O + CH2O (2), and MF → CH4 + CO2 (3), were directly measured in a shock tube using laser absorption of CO (4.6 μm), CH2O (306 nm) and CH4 (3.4 μm). Experimental conditions ranged from 1202 to 1607 K and 1.36 to 1.72 atm, with mixtures varying in initial fuel concentration from 0.1% to 3% MF diluted in argon. The decomposition rate coefficients were determined by monitoring the formation rate of each target species immediately behind the reflected shock waves and modeling the species time-histories with a detailed kinetic mechanism [12]. The three measured rate coefficients can be well-described using two-parameter Arrhenius expressions over the temperature range in the present study: k1 = 1.1 × 1013 exp(−29556/T, K) s−1, k2 = 2.6 × 1012 exp(−32052/T, K) s−1, and k3 = 4.4 × 1011 exp(−29 078/T, K) s−1, all thought to be near their high-pressure limits. Uncertainties in the k1, k2 and k3 measurements were estimated to be ±25%, ±35%, and ±40%, respectively. We believe that these are the first direct high-temperature rate measurements for MF decomposition and all are in excellent agreement with the Dooley et al. [12] mechanism. In addition, by also monitoring methanol (CH3OH) and MF concentration histories using a tunable CO2 gas laser operating at 9.67 and 9.23 μm, respectively, all the major oxygen-carrying molecules were quantitatively detected in the reaction system. An oxygen balance analysis during MF decomposition shows that the multi-wavelength laser absorption strategy used in this study was able to track more than 97% of the initial oxygen atoms in the fuel.