Kinetics and mechanism of hydrogen peroxide oxidation by silver(III) in aqueous alkaline media
Journal of the Chemical Society, Dalton Transactions, ISSN: 1472-7773, Issue: 4, Page: 749-753
1983
- 25Citations
- 5Usage
- 4Captures
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Metrics Details
- Citations25
- Citation Indexes25
- 25
- CrossRef8
- Usage5
- Abstract Views5
- Captures4
- Readers4
Article Description
The oxidation of hydrogen peroxide by AgIII in strongly alkaline media has been studied by stopped-flow spectrophotometry in the temperature range 6-45 °C at a total ionic strength of 1.2 mol dm-3 (NaClO4). The reaction is first order in [AgIII], [HO2-], and [OH-] with a third-order rate constant of (4.2 ± 0.6) × 105 dm6 mol-2 s-1 at 25 °C. The form of the rate law and the activation parameters (ΔH‡ = 25 ± 5kJ mol-1, ΔS‡ = -113 ± 5 J K-1 mol-1) suggest the formation of a five-co-ordinate intermediate of the form [Ag(OH)4O2]3-. Although kinetic results do not distinguish between a oneor two-electron transfer, a change in stoicheiometry from Δ[AgIII]/Δ[HO2-] = 1 at high [HO2-] to 2 at excess [AgIII] leads to the conclusion that a bivalent silver intermediate is produced.
Bibliographic Details
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=37049113205&origin=inward; http://dx.doi.org/10.1039/dt9830000749; https://xlink.rsc.org/?DOI=dt9830000749; https://digitalcommons.uri.edu/chm_facpubs/965; https://digitalcommons.uri.edu/cgi/viewcontent.cgi?article=1966&context=chm_facpubs; https://dx.doi.org/10.1039/dt9830000749; https://pubs.rsc.org/en/content/articlelanding/1983/dt/dt9830000749
Royal Society of Chemistry (RSC)
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