FTIR spectroscopic study of the mechanism for the gas-phase reaction between ozone and tetramethylethylene

Journal Article · Thu Feb 12 04:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100288a035· OSTI ID:7043646

Niki, H; Maker, P D; Savage, C M; Breitenbach, L P; Hurley, M D

Long-path FTIR spectroscopic product studies were made of mixtures containing part-per-million concentrations of O/sub 3/ and (CH/sub 3/)/sub 2/C double bonded C(CH/sub 3/)/sub 2/ (TME) in 700 Torr of O/sub 2/-N/sub 2/ to determine the formation and reactions of the dimethyl-substituted Criegee intermediate (CH/sub 3/)/sub 2/COO expected from O/sub 3/ + TME ..-->.. (CH/sub 3/)/sub 2/COO + (CH/sub 3/)/sub 2/C double bonded O. The observed stoichiometry, ..delta..-(TME)/..delta..(O/sub 3/), was typically 1.7, and among the products were CO, CO/sub 2/, HCHO, CH/sub 3/OH, CH/sub 3/OOH, CH/sub 3/C(double bonded O)OH, CH/sub 3/C(double bonded O)OOH, (CH/sub 3/)/sub 2/C double bonded O, CH/sub 3/C(double bonded O)CHO, CH/sub 3/C(double bonded O)OCH/sub 3/, CH/sub 3/C(double bonded O)CH/sub 2/(OH), and products tentatively identified as (CH/sub 2/)/sub 2/C(OH)-C(CH/sub 3/)/sub 2/OOH AND CH/sub 3/C(double bonded O)CH/sub 2/(OOH). In addition, /sup 16/O- and /sup 18/O-labeled products were identified in /sup 18/O/sub 3/-TME-air mixtures, and the effects of added HCHO, CH/sub 3/CHO, and NO/sub 2/ (or /sup 15/NO/sub 2/) on the product distribution were determined. The results indicate that ca. 25% of the (CH/sub 3/)/sub 2/COO moiety formed was thermally stable, and that the remainder largely dissociated to yield the following free radicals, i.e., (CH/sub 3/)/sub 2/COO ..-->.. CH/sub 3/C(OOH)double bonded CH/sub 2/ ..-->.. CH/sub 3/C(double bonded O)CH/sub 2/ + HO. The HO-initiated oxidation of TME was shown to account for the excess consumption of TME over O/sub 3/ as well as for some of the major products observed.

• Research Organization: Ford Motor Co., Dearborn, MI
• OSTI ID: 7043646
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:4; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
FLUIDS
GASES
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
OZONE
RADICALS
SPECTRA
STOICHIOMETRY
YIELDS