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Electron transfer reaction rates and equilibria of the carbonate and sulfate radical anions

Authors
Journal
International Journal of Radiation Applications and Instrumentation Part C Radiation Physics and Chemistry
1359-0197
Publisher
Elsevier
Publication Date
Volume
38
Issue
5
Identifiers
DOI: 10.1016/1359-0197(91)90065-a

Abstract

Abstract Electron transfer reactions of the carbonate radical anion with azide, bromide, and hypochlorite ions have been studied by pulse radiolysis. From the equilibrium Br .- 2 + CO 2- 3 ⇆ 2Br - + CO .- 3 and the known redox potential for Br .- 2/2Br - = 1.62V vs NHE we derive E = 1.59V for CO .- 3/CO 2- 3. From this value and the equilibrium CO .- 3 + ClO - ⇆ CO 2- 3 + ClO . we derive E = 1.41V for ClO ./ClO -. The equilibrium reaction SO .- 4 + Cl - ⇆ SO 2- 4 + Cl . was studied by laser photolysis, by using 248 nm excitation of S 2O 2- 8 to produce SO .- 4 and examining the rate of reaction of this radical with Cl - in the presence of varying concentrations of SO 2- 4. By modeling the reactions taking place in this system, we derive the rate constant for the reaction of Cl . with SO 2- 4 (2.5 × 10 8dm 3mol -1s -1 at 0.1 mol dm -3 ionic strength), and from the known rate constant for reaction of SO .- 4 with Cl - (4.7 × 10 8dm 3mol -1s -1 at the same ionic strength) we derive the equilibrium constant. From the known redox potential for Clf .- 2/Cl - = 2.41V we derive E = 2.43V for SO .- 4/SO 2- 4.

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