Some simple, highly reactive, inorganic chlorine derivatives in aqueous solution. Their formation using pulses of radiation and their role in the mechanism of the Fricke dosimeter
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 69, 1597-1607
- https://doi.org/10.1039/f19736901597
Abstract
In aqueous solution OH radicals react with chloride ions to form initially ClOH–, the rate constant being 4.3 ± 0.4 × 109 l. mol–1 s–1. The rate constant for the dissociation of ClOH– back to OH radicals and chloride ions is 6.1 ± 0.8 × 109 s–1. ClOH– is converted to chlorine atoms via the reaction, ClOH–+ H+→ Cl + H2O (k= 2.1 ± 0.7 × 1010 l. mol–1 s–1 at an ionic strength of unity), the rate constant for the reverse reaction being 1.3 × 103 l. mol–1 s–1(0.3–3.0 × 103 l. mol–1 s–1). Chlorine atoms combine with chloride ions to form Cl– 2(k= 2.1 × 1010 l. mol–1 s–1), the rate constant for the dissociation of Cl– 2 back to chlorine atoms and chloride ions being 1.1 ± 0.4 × 105 s–1. The absorption spectra of ClOH– and Cl– 2 have been measured in the range 230–450 nm. Cl– 2 absorption has a maximum at 340 nm where the extinction coefficient is 8.8 ± 0.5 × 103 l. mol–1 cm–1, whereas ClOH– has a maximum at 350 nm with an extinction coefficient of 3.7 ± 0.4 × 103 l. mol–1 cm–1. The reactions of chlorine atoms and Cl– 2 with ferrous ions have also been investigated and the constants are 5.9 ± 0.6 × 109 and 1.4 ± 0.2 × 107 l. mol–1 s–1(ionic strength = 0.1 mol l.–1) respectively. The effect of chloride ions on the mechanism of the Fricke dosimeter is discussed.Keywords
This publication has 0 references indexed in Scilit: