Time-resolved, broadband UV-absorption spectrometry measurements of Criegee intermediate kinetics using a new photolytic precursor: unimolecular decomposition of CH₂OO and its reaction with formic acid

Abstract

We present a time-resolved broadband cavity-enhanced UV-absorption spectrometer apparatus that we have constructed and utilized for temperature- and pressure-dependent kinetic measurements of formaldehyde oxide (CH₂OO) reactions. We also introduce and utilize a new photolytic precursor, bromoiodomethane (CH₂IBr), which photolysis at 213 nm in presence of O₂ produces CH₂OO. Importantly, this precursor appears to be free from secondary reactions that may regenerate CH₂OO in kinetic experiments. The unimolecular decomposition rate coefficient of CH₂OO has been measured over wide pressure (5-400 Torr) and temperature (296-600 K) ranges and master equation simulations of the decomposition kinetics have been performed using MESMER program. The MESMER simulations of the experimental data with the calculated zero-point energy corrected transition state energy 85.9 kJ mol^-1 for decomposition required no adjustment and returned 〈ΔE〉_down = 123.2 × (T/298 K)^0.74 cm^-1 for temperature-dependent exponential-down model of the collisional energy transfer in He. A very good agreement between results of simulations and experiments is obtained. The results are compared with the previously reported unimolecular decomposition study by Stone et al. (Phys. Chem. Chem. Phys., 2018, 20, 24940-24954). Current master equation simulations suggest about 61% decomposition yield for the predominant H₂ + CO₂ channel, whereas the yields of two other channels, H₂O + CO, and HCO + OH, are sensitive on the parameters involved in the simulations. The kinetics of CH₂OO reaction with formic acid has also been investigated as function of pressure (5-150 Torr) and temperature (296-458 K). The bimolecular rate coefficient for CH₂OO + HCOOH reaction shows a negative temperature dependency, decreasing from (1.0 ± 0.03) × 10^-10 cm³ molecule^-1 s^-1 at 296 K to (0.47 ± 0.05) × 10^-10 cm³ molecule^-1 s^-1 at 458 K with an Arrhenius activation energy of -4.9 ± 1.6 kJ mol^-1, where statistical uncertainties shown are 2σ. Estimated overall uncertainty in the measured rate coefficients is about ±20%. Current bimolecular rate coefficient at room temperature agrees with the previously reported rate coefficients from the direct kinetic experiments. The reaction is found to be pressure independent over the range between 5 and 150 Torr at 296 K in He.