Production of electronically-excited species by photoselection of pathways (POP). Final report, February 1, 1978-June 30, 1979. [F + HBr. -->. HF + Br]

Technical Report · Sun Jul 01 04:00:00 EDT 1979

DOI:https://doi.org/10.2172/5878912· OSTI ID:5878912

Polanyi, J. C.

The reaction studied with a view to observing POP was F + HBr ..-->.. HF + Br(/sup 2/P/sub 3/2/)(k/sub H/) and ..-->.. HF + Br* (/sup 2/P/sub 1/2/)(k/sub H/*). The findings were: (1) With thermal reagent beams (300K) the ratio k/sub H/*/k/sub H/ = 0.06. (2) Irradiation of the beam crossing point with 10/sup 8/ W/cm/sup 2/ of 943 cm/sup -1/ CO/sub 2/ TEA-laser radiation gave rise to no detectable change in Br*/Br despite the possibility of some transfer from the F(/sup 2/P/sub 3/2/) + HBr to the F*(/sup 2/P/sub 1/2/) + HBr potential energy surface. (3) A careful study of the effect on k/sub H/*/k/sub H/ of a change in the ratio F*/F in the reagents showed that (despite favorable electronic correlation) increased F*/F is not associated with increased Br*/Br. (4) Using supersonic seeded beams of F the collision energy, T, for F + HBr could be varied from T = 1 to 14 kcal mole/sup -1/, the effect of increasing T was to decrease S/sub r/(T) and S/sub r/*(T) (S/sub r/ is the reactive cross section) approximately equally, i.e. Br*/Br not equal to fn.(T). (5) The thermal reactions F + DBr ..-->.. DF + Br(k/sub D/) and ..-->.. DF + Br*(k/sub D/*) gave k/sub D/*/k/sub D/ approx. = 0.01.

• Research Organization: Toronto Univ., Ontario (Canada). Dept. of Chemistry
• OSTI ID: 5878912
• Report Number(s): COO-4644-4
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COLLISIONS
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELEMENTS
FLUORINE
HALOGENS
HYDROBROMIC ACID
HYDROGEN COMPOUNDS
INORGANIC ACIDS
KINETICS
LASER RADIATION
MOLECULE COLLISIONS
NONMETALS
PHOTOCHEMICAL REACTIONS
RADIATIONS
REACTION KINETICS