Infrared chemiluminescence and laser-induced fluorescence studies of energy disposal by reactions of F and Cl atoms with H/sub 2/S (D/sub 2/S), H/sub 2/Se, H/sub 2/O (D/sub 2/O), and CH/sub 3/OH

Journal Article · Thu May 22 04:00:00 EDT 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100402a039· OSTI ID:5497638

Agrawalla, B S; Setser, D W

The vibrational energy disposal to HF (DF), HCl (DCl), SH (SD), and CH/sub 3/O and relative product formation rate constants were measured for the title reactions. The experiments were done in a fast-flow reactor with infrared emission and laser-induced fluorescence to observe nascent product state distributions for the diatomic hydride products. The CH/sub 3/O vibrational and HF (DF) rotational distributions are partially relaxed, but the nascent distributions for these cases were estimated. Laser-induced fluorescence measurements showed that the SH, SD, and CH/sub 3/O fragments received only 0.02-0.03 of the available energy. The (f/sub v/(HX)) values for group VI (group 16) hydrides, 0.45 (F + H/sub 2/S), 0.44 (F + D/sub 2/S), 0.48 (F + H/sub 2/Se), 0.42 (F + D/sub 2/O), 0.41 (Cl + H/sub 2/Se), and 0.37 (Cl + D/sub 2/S), are similar but distinctly smaller than for F and Cl atom reactions with group IV and VII (group 14 and 17) hydrides. The (f/sub R/(HX)) values, 0.18 (F + H/sub 2/S), 0.19 (F + H/sub 2/Se), and approx. 0.14 (F + D/sub 2/S), are typical for H-abstraction reactions with similar cross sections. The F + H/sub 2/O/D/sub 2/O systems were used to characterize the extent of secondary reactions in the fast-flow reactor. For high reagent concentrations and longer reaction times, S/sub 2/ was observed in the F/Cl + H/sub 2/S systems by LIF.

• Research Organization: Kansas State Univ., Manhattan
• OSTI ID: 5497638
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:11; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMILUMINESCENCE
CHLORINE
DATA
DEUTERIUM COMPOUNDS
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
EXPERIMENTAL DATA
FLUORESCENCE
FLUORINE
HALOGENS
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
HYDROXY COMPOUNDS
INFORMATION
KINETICS
LASERS
LUMINESCENCE
METHANOL
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
REACTION KINETICS
SULFIDES
SULFUR COMPOUNDS
VIBRATIONAL STATES