TY - JOUR
T1 - Dynamics of Reaction CH3CHI + O2Investigated via Infrared Emission of Products CO, CO2, and OH
AU - Ji, Ya Tsang
AU - Lee, Yuan-Pern
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/9/30
Y1 - 2021/9/30
N2 - The reaction CH3CHI + O2 has been commonly employed in laboratories to produce a methyl-substituted Criegee intermediate CH3CHOO, but the detailed dynamics of this reaction remain unexplored. We carried out this reaction by irradiating a flowing mixture of CH3CHI2 (∼70 mTorr) and O2 (∼4 and 8 Torr) at 308 or 248 nm and observed infrared emission of the products with a step-scan Fourier-transform spectrometer. Upon irradiation at 248 nm with O2 ∼4 Torr, a Boltzmann distribution of CO (v ≤ 4, J ≤ 25) with average vibrational energy (12 ± 2) kJ mol-1 and of OH (v = 1, J ≤ 5.5) were observed and assigned to be produced from the decomposition of CH3C(O)OH∗ to form CO + CH3OH and OH + CH3CO, respectively. The observed broadband emission of CO2 was simulated with two vibrational distributions of average energies (42 ± 3) and (114 ± 6) kJ mol-1 and assigned to be produced from the decomposition of CH3C(O)OH∗ and (methyl dioxirane)*, respectively. The results upon irradiation of the sample at 308 nm are similar, likely indicating a small fraction of energy partition into these products and rapid thermalization of CH3CHI*. Compared with reaction CH2I + O2, the title reaction yielded products with much less internal excitation, consistent with the expectation that these observed products receive much less fraction of available energy upon fragmentation when an additional methyl moiety was present in the parent. The large-v component of CO observed in experiments of CH2I + O2 at 248 nm, produced from secondary reaction HCO + O2, was absent in this work because the corresponding secondary reaction CH3CO + O2 in decomposition of CH3CHOO∗ produces α-lactone + OH or H2CO + CO + OH.
AB - The reaction CH3CHI + O2 has been commonly employed in laboratories to produce a methyl-substituted Criegee intermediate CH3CHOO, but the detailed dynamics of this reaction remain unexplored. We carried out this reaction by irradiating a flowing mixture of CH3CHI2 (∼70 mTorr) and O2 (∼4 and 8 Torr) at 308 or 248 nm and observed infrared emission of the products with a step-scan Fourier-transform spectrometer. Upon irradiation at 248 nm with O2 ∼4 Torr, a Boltzmann distribution of CO (v ≤ 4, J ≤ 25) with average vibrational energy (12 ± 2) kJ mol-1 and of OH (v = 1, J ≤ 5.5) were observed and assigned to be produced from the decomposition of CH3C(O)OH∗ to form CO + CH3OH and OH + CH3CO, respectively. The observed broadband emission of CO2 was simulated with two vibrational distributions of average energies (42 ± 3) and (114 ± 6) kJ mol-1 and assigned to be produced from the decomposition of CH3C(O)OH∗ and (methyl dioxirane)*, respectively. The results upon irradiation of the sample at 308 nm are similar, likely indicating a small fraction of energy partition into these products and rapid thermalization of CH3CHI*. Compared with reaction CH2I + O2, the title reaction yielded products with much less internal excitation, consistent with the expectation that these observed products receive much less fraction of available energy upon fragmentation when an additional methyl moiety was present in the parent. The large-v component of CO observed in experiments of CH2I + O2 at 248 nm, produced from secondary reaction HCO + O2, was absent in this work because the corresponding secondary reaction CH3CO + O2 in decomposition of CH3CHOO∗ produces α-lactone + OH or H2CO + CO + OH.
UR - http://www.scopus.com/inward/record.url?scp=85115967239&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.1c05610
DO - 10.1021/acs.jpca.1c05610
M3 - Article
C2 - 34524829
AN - SCOPUS:85115967239
SN - 1089-5639
VL - 125
SP - 8373
EP - 8385
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 38
ER -