Fourier transform infrared study of the kinetics and mechanisms for the Cl-atom- and HO-radical-initiated oxidation of glycoaldehyde

Journal Article · Thu Apr 09 04:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100292a038· OSTI ID:6538023

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

The Cl-atom- and HO-radical-initiated oxidation of CH/sub 2/(OH)CHO was studied by the FTIR spectroscopic method in the steady-state photolyses (lambda greater than or equal to 300 nm) of mixtures containing ppm concentrations of CH/sub 2/(OH)CHO and Cl/sub 2/, and CH/sub 2/(OH)CHO and C/sub 2/H/sub 5/ONO, respectively, in 700 Torr of N/sub 2/-O/sub 2/. HCHO and CHO-CHO were observed as major initial products in both the Cl and HO reactions. In the presence of added NO/sub 2/, the former product was partially replaced by a transient species identified as CH/sub 2/(OH)C(double bond O)OONO/sub 2/, while the CHO-CHO yield remained unchanged. The results are consistent with the occurrence of reactions 1a and 1b followed by the subsequent oxidation of the ensuring radicals CH/sub 2/(OH)C(double bond O) and CH(OH)CHO, i.e., CH/sub 2/(OH)CHO +Cl (or HO) ..-->.. CH/sub 2/(OH)C(double bond O) + HCl (or H/sub 2/O) (1a), CH/sub 2/(OH)CHO +Cl (or HO) ..-->.. CH(OH)CHO + CHl (or H/sub 2/O) (1b). Values for k/sub 1b//(k/sub 1a/ + k/sub 1b/) were determined to be 0.35 and 0.22 for the Cl and HO reactions, respectively. Relative rate constants of k(Cl + CH/sub 3/CHO)/k(Cl+CH/sub 2/(OH)CHO) = 0.9 and k(HO+CH/sub 3/CHO)lt. slashK(HO+CH/sub 2/(OH)CHO) = 1.6 were also obtained.

• Research Organization: Ford Motor Co., Dearborn, MI
• OSTI ID: 6538023
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:8; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ALDEHYDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORINE
DATA
DECOMPOSITION
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
FOURIER TRANSFORM SPECTROMETERS
GASES
HALOGENS
HYDROXYL RADICALS
INFORMATION
INFRARED SPECTRA
KINETICS
LOW PRESSURE
MEASURING INSTRUMENTS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
SPECTRA
SPECTROMETERS
STEADY-STATE CONDITIONS
YIELDS