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The reaction of CCl[sub 3] radicals and Cl atoms with hydrogen molecules

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.468627· OSTI ID:6605954
; ;  [1];  [2];  [3]
  1. Department of Chemistry, Columbia University, New York, New York 10027 (United States)
  2. RIKEN (The Institute of Physical and Chemical Research), Wako, Saitama, 351-01 (Japan)
  3. Department of Chemistry, Ben Gurion University, Beersheba (Israel)

A small amount of H atoms are observed as products of the reaction of Cl atoms generated by photodissociating Cl[sub 2] at 351 nm in the presence of H[sub 2]. A much larger H atom concentration is detected when a mixture of H[sub 2] and CCl[sub 4] is photodissociated at 193 nm with an average kinetic energy of 6.5[plus minus]0.5 kcal/mol. The reactant is shown to be the vibrationally hot CCl[sub 3] radical. In the reaction of CCl[sub 3] and Cl atoms with HD the atomic H/D product ratios are 1.47[plus minus]0.16 and 0.59[plus minus]0.11, respectively. The former result is in accord with the theory of Johnson [ital et] [ital al]. [J. Chem. Phys. [bold 94], 2749 (1991)] that for kinematic reasons the D end of the HD molecule is more reactive unless the HD molecule is strongly rotating. The F and Cl atoms which give H/D ratios less than 1 when reacting with HD are special cases for which higher [ital J] states of HD are still reactive.

OSTI ID:
6605954
Journal Information:
Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 102:8; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English