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

Abstract

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) T(4.1) exp {-(981 ± 102)/T} cm(3) 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) 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 × 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.

Kinetic parameters for the reaction of OH radical with cis-CHFCHCHF2, trans-CHFCHCHF2, CF2CHCHF2 and CF2CCHF: Hybrid meta DFT and CVT/SCT/ISPE calculations

“…The minimum energy path (MEP) was obtained by intrinsic reaction coordinate (IRC) calculations to verify that the transition state connects the designated local minima for the respective reactants and products. To improve the accuracy of calculated reaction energetics, single-point energy calculations were carried out for all the stationary points at M a n u s c r i p t 6 coupled-cluster with single and double and perturbative triple excitations (CCSD(T)) [20][21][22] combined with the correlation-consistent polarized valence triple-zeta (cc-pVTZ) [23] basis set method using the optimized geometries obtained at the M06-2X/6-31+G(d,p) level of theory…”

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCFCF2

“…[35][36][37]44 The ether functionality in CF 3 OCFQCF 2 thus appears responsible for an additional product channel, yet the proposed HF elimination route 8,9 is not expected to be dependent on the presence or absence of the oxygen atom.…”

“…The energies obtained for the above reactions are again in good agreement with analogous reactions described in the literature. 25,[34][35][36][37] The minor adduct, CF 3 OCF(OH)-C F 2 , has access to similar decomposition routes (see Fig. 3, see Fig.…”

Theoretical studies on atmospheric chemistry of HFE-347mcc3: reactions with OH radicals and Cl atoms

“…The 6‐31 + G(d,p) was chosen because the same basis set was used for developing the model functional. Previous works have shown that the M06‐2X hybrid density functional provides reliable results for thermo chemistry and kinetics . The M06‐2X is a hybrid meta‐DFT method with a high percentage of HF exchange, and it has broadest applicability with average mean absolute errors of about 1.3, 1.2 and 0.5 kcal mol −1 , respectively, for thermochemical, barrier height and non‐covalent interaction calculations .…”