Journal Details

1. Experimental and computational investigation on the gas phase reaction of ethyl formate with Cl atoms.”.

M. Balaganesh, M. R. Dash, B. Rajakumar J. Phys. Chem, 2014, 118(28), 5272-5278

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 kethyl formate(268–343) = (2.54 ± 0.57) × 10–23 T4.1 exp {−(981 ± 102)/T} cm3 molecule–1 s–1 was obtained with 2σ error limits. The room temperature rate coefficient for the title reaction is (9.84 ± 0.79) × 10–12 cm3 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 × 10–18 T2.4 exp[−(390/T)] cm3 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.