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Pulse Radiolysis Study of Concentrated Sulfuric Acid Solutions; Formation Mechanism, Yield and Reactivity of Sulfate Radicals

DOI: 10.1039/ft9928801653

Source and publish data:

Journal of the Chemical Society - Faraday Transactions p. 1653 - 1658 (1992)

Update date:2022-08-11

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Authors:

Jiang, Pei-YunJiang, Pei-Yun

Katsumura, YosukeKatsumura, Yosuke

Nagaishi, RyujiNagaishi, Ryuji

Domae, MasahumiDomae, Masahumi

Ishikawa, KenichiIshikawa, Kenichi

et al.et al.

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Article abstract of DOI:10.1039/ft9928801653

In the pulse radiolysis of concentrated sulfuric acid solutions, the absorption spectrum and the molar absorption coefficient (1600 dm3 mol-1 cm-1) of the sulfate radical are unchanged up to 10 mol dm-3 H2SO4, suggesting that the sulfate radical exists in the dissociated form (SO4-).Two formation processes for the sulfate radical have been directly demonstrated in sulfuric acid and hydrogensulfate solutions: a fast one completed in the duration of the electron pulse, and a slow one occuring over a microsecond time range.For sulfate solutions only the fast formation process is observed.In sulfuric acid solutions the slow formation process is OH + HSO4- -> H2O + SO4- (4.7 x 105 dm3 mol-1 s-1) and OH + H2SO4 -> HSO4 + H2O -> SO4- + H3O+ (1,4 x 107 dm3 mol-1 s-1) and the fast formation process is the direct action of radiation on sulfuric acid with a G value of (2.7 +/- 0.4) x 10-2 molecule eV-1.The yields of (OH + SO4-) and H can be quantified as: G(OH + SO4-) = 2.9fw + 2.7fs and G(H) = 3.7fw + 2.7fs.The yields of SO4- have also been evaluated and the decay kinetics and reactions of the sulfate radical studied.

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