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Suppression of inhibition of substrate photodegradation by scavengers of hydroxyl radicals: the solvent-cage effect of bromide on nitrate photolysis |
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| Authors: | Radharani Das Binay K Dutta Valter Maurino Davide Vione Claudio Minero |
| Institution: | 1. Dipartimento di Chimica Analitica, Università di Torino, Via P. Giuria 5, 1025, Torino, Italy 2. Department of Chemical Engineering, Haldia Institute of Technology, ICARE complex, Haldia, 721657, India 3. Chemical Engineering Department, Universiti Technologi Petronas, 31750, Tronoh, Perak Darul Ridzuan, Malaysia |
| Abstract: | In this paper we show that bromide scavenges the ·OH radicals formed upon photolysis of nitrate, before they leave the solvent cage. Bromide can thus inhibit the in-cage recombination between ·OH and ·NO2. The consequence is an increased generation of ·NO2 and nitrite and of Br2 ?· + ·OH, compared to ·OH alone in the absence of bromide. We show that this effect compensates for the lower reactivity of Br 2 ?· compared to ·OH toward certain organic substrates, e.g. phenol and tryptophan. Our findings could lead to a deep revision of the present views of the role of bromide in saltwater photochemistry. |
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