Experimental and Computational Investigation on the Gas Phase Reaction of Ethyl Formate with Cl Atoms

The rate coefficient for the gas-phase reaction of Cl atoms with ethyl formate was measured over the temperature range of 268-343 K using relative rate methods, with ethyl chloride as a reference compound. The temperature dependent relative rate coefficients for the ethyl formate + Cl reaction were measured, and the modified Arrhenius expression k(ethyl formate)(268-343) = (2.54 +/- 0.57) x 10(-23) T-4.1 exp {-(981 +/- 102)/T} cm(3) molecule(-1) s(-1) was obtained with 2 sigma error limits. The room temperature rate coefficient for the title reaction is (9.84 +/- 0.79) x 10(-12) cm(3) molecule(-1) s(-1), which is in good agreement with reported values. To complement the experimental measurement, computational methods were used to calculate the rate coefficient for the ethyl formate + Cl reaction atoms using canonical variational transition state theory (CVT) with small curvature tunneling (SCT) and the CCSD (T)/cc-pVDZ//M062X/6-31+g(d,p) level of theory. The temperature dependent Arrhenius expression was obtained to be 2.97 x 10(-18) T-2.4 exp[-(390/T)] cm(3) molecule(-1) s(-1) over the temperature range of 200-400 K. The thermodynamic parameters and branching ratio were calculated. Also, the atmospheric lifetime and global warming potentials (GWPs) were calculated for ethyl formate.