Analysis of acetic acid gas phase reactivity: Rate constant estimation and kinetic simulations

Abstract

The gas phase reactivity of acetic acid was investigated combining first principle calculations with kinetic simulations. Rate constants for the unimolecular decomposition of acetic acid were determined integrating the 1D master equation over a Potential Energy Surface (PES) investigated at the M06-2X/aug-cc-pVTZ level. Energies were computed at the CCSD(T)/aug-cc-pVTZ level using a basis set size correction factor determined at the DF-MP2/aug-cc-pVQZ level. Three decomposition channels were considered: CO2 + CH4, CH2CO + H2O, and CH3 + COOH. Rate constants were computed in the 700–2100 K and 0.1–100 atm temperature and pressure ranges. The simulations show that the reaction is in fall off above 1200 K at pressures smaller than 10 atm. Successively, the PESs for acetic acid H-abstraction by H, OH, OOH, O2, and CH3 were investigated at the same level of theory. Rate constants were computed accounting explicitly for the formation of entrance and exit van der Waals wells and their collisional stabilization. Energy barriers were determined at the CASPT2 level for H-abstraction by OH of the acidic H, since it has a strong multireference character. The calculated rate constant is in good agreement with experiments and supports the experimental finding that at low temperatures it is pressure dependent. The calculated rate constants were used to update the POLIMI kinetic model and to simulate the pyrolysis and combustion of acetic acid. It was found that acetic acid decomposition and the formation of its direct decomposition products can be reasonably predicted. The formation of secondary products, such as H2 and C2 hydrocarbons, is underpredicted. This suggests that reaction routes not incorporated in the model may be active. Some hypotheses are formulated on which these may be.