The primary process ClO sub 3 sup minus (+h. nu. ) yields ClO sup minus + O sub 2 in the photolysis of aqueous ClO sub 3 sup minus solutions

Journal Article · Thu Jan 24 04:00:00 EST 1991 · Journal of Physical Chemistry; (USA)

OSTI ID:5760128

Klaening, U K ^[1]; Sehested, K ^[2]

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1. Aarhus Univ. (Denmark)
2. Risoe National Lab., Roskilde (Denmark)

The quantum yield, {Phi}{sub 1}, in the primary process ClO{sub 3}{sup {minus}}(+hv) {yields} ClO{sup {minus}} + O{sub 2} (1) and the sum of the quantum yields {Phi}{sub 2} + {Phi}{sub 3} in the primary processes ClO{sub 3}{sup {minus}} (+hv) {yields} ClO{sub 2} + O{sup {minus}} (2) and ClO{sub 3}{sup {minus}} {yields} ClO{sub 2}{sup {minus}} + O({sup 3}P) (3) were measured in the steady-state photolysis of aqueous ClO{sub 3}{sup {minus}} solutions at 214 and 229 nm. The ratio of the yields of ClO{sup {minus}} and ClO{sub 3}{sup {minus}} in the reactions ClO{sub 2} {yields} ClO{sup {minus}} + O{sub 2} and ClO{sub 2} + O{sup {minus}} {yields} (4) was determined by {gamma}-radiolysis of aqueous solutions of ClO{sub 2} at varying pH. The finding that the ratio between the yields of ClO{sup {minus}} and ClO{sub 3}{sup {minus}} in reactions 4 equals the ratio between {Phi}{sub 1} and the quantum yields, {Phi}{sub 0} = 1 {minus} {Phi}{sub 1}{minus}{phi}{sub 2}{minus}{phi}{sub 3}, for ClO{sub 3}{sup {minus}} returning to the ground state is taken as evidence that process 1 results from a cage-back reaction. This result combined with recent studies of the radiolysis of KClO{sub 3} crystals suggest that the primary processes in the photolysis of aqueous ClO{sub 3}{sup {minus}} originate in a common process by which O{sup {minus}} is expelled from ClO{sub 3}{sup {minus}} upon photoexcitation.

• OSTI ID: 5760128
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 95:2; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500* -- Photochemistry
400600 -- Radiation Chemistry
AQUEOUS SOLUTIONS
CHALCOGENIDES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
CHLORINE OXIDES
DATA
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
G VALUE
GAMMA RADIATION
HALOGEN COMPOUNDS
INFORMATION
IONIZING RADIATIONS
MIXTURES
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PH VALUE
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADIOLYSIS
SOLUTIONS