Probing the pyrolysis of ethyl formate in the dilute gas phase by synchrotron radiation and theory.

Abstract

The thermal decomposition of the atmospheric constituent ethyl formate was studied by coupling flash pyrolysis with imaging photoelectron photoion coincidence (iPEPICO) spectroscopy using synchrotron vacuum ultraviolet (VUV) radiation at the Swiss Light Source (SLS). iPEPICO allows photoion mass-selected threshold photoelectron spectra (ms-TPES) to be obtained for pyrolysis products. By threshold photoionization and ion imaging, parent ions of neutral pyrolysis products and dissociative photoionization products could be distinguished, and multiple spectral carriers could be identified in several ms-TPES. The TPES and mass-selected TPES for ethyl formate are reported for the first time and appear to correspond to ionization of the lowest energy conformer having a cis (eclipsed) configuration of the O=C(H)-O-C(H2 )-CH3 and trans (staggered) configuration of the O=C(H)-O-C(H2 )-CH3 dihedral angles. We observed the following ethyl formate pyrolysis products: CH3 CH2 OH, CH3 CHO, C2 H6 , C2 H4 , HC(O)OH, CH2 O, CO2 , and CO, with HC(O)OH and C2 H4 pyrolyzing further, forming CO + H2 O and C2 H2 + H2 . The reaction paths and energetics leading to these products, together with the products of two homolytic bond cleavage reactions, CH3 CH2 O + CHO and CH3 CH2 + HC(O)O, were studied computationally at the M06-2X-GD3/aug-cc-pVTZ and SVECV-f12 levels of theory, complemented by further theoretical methods for comparison. The calculated reaction pathways were used to derive Arrhenius parameters for each reaction. The reaction rate constants and branching ratios are discussed in terms of the residence time and newly suggest carbon monoxide as a competitive primary fragmentation product at high temperatures.