1986•Journal of the Chemical Society Faraday Transactions 2 Molecular and Chemical PhysicsRequires access

Photoreduction of water sensitised by Rose Bengal

Andrew Mills, Carl A. Lawrence, Peter L. Douglas

Open publisher page 33 citations

Abstract

Rose Bengal was used to sensitise the photoreduction of water in aqueous ethanol solution (5 % EtOH v/v; pH 4.4)via both a reductive and an oxidative quenching mechanism, using EDTA and methyl viologen, respectively, as quenchers of its triplet state. In the presence of EDTA (which acts as both tiplet quencher and sacrificial electron donor) the photoreduction of water sensitised by Rose Bengal was inefficient for a number of reasons, including a low triplet quenching rate constant (8 × 103 dm3 mol–1 s–1) and a rapid disproportionation reaction involving the protonated semi-reduced dye radicals. In the presence of methyl viologen (triplet quencher) and EDTA (sacrificial electron donor) the photoreduction of water sensitised by Rose Bengal was inefficient due to a low cage-escape yield (ϕ≈ 5 × 10–2) following the primary electron-transfer step, a fast back reaction (k 1 × 108 dm3 mol–1 s–1) and formation of a complex between the dye and methyl viologen (K= 6400 ± 300 dm3 mol–1). The complexed form of Rose Bengal appeared able to photosensitise, inefficiently, the photoreduction of methyl viologen in the presence of EDTA, without exhibiting problems of dye fade.

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What this paper is about

Rose Bengal was used to sensitise the photoreduction of water in aqueous ethanol solution (5 % EtOH v/v; pH 4.4)via both a reductive and an oxidative quenching mechanism, using EDTA and methyl viologen, respectively, as quenchers of its triplet state. In the presence of EDTA (which acts as both tiplet quencher and sacrificial electron donor) the photoreduction of water sensitised by Rose Bengal was inefficient for a number of reasons, including a low triplet quenching rate constant (8 × 103 dm3 mol–1 s–1) and a rapid disproportionation reaction involving the protonated semi-reduced dye radicals. In the presence of methyl viologen (triplet quencher) and EDTA (sacrificial electron donor) the photoreduction of water sensitised by Rose Bengal was inefficient due to a low cage-escape yield (ϕ≈ 5 × 10–2) following the primary electron-transfer step, a fast back reaction (k 1 × 108 dm3 mol–1 s–1) and formation of a complex between the dye and methyl viologen (K= 6400 ± 300 dm3 mol–1). The complexed form of Rose Bengal appeared able to photosensitise, inefficiently, the photoreduction of methyl viologen in the presence of EDTA, without exhibiting problems of dye fade.

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Available abstract

Rose Bengal was used to sensitise the photoreduction of water in aqueous ethanol solution (5 % EtOH v/v; pH 4.4)via both a reductive and an oxidative quenching mechanism, using EDTA and methyl viologen, respectively, as quenchers of its triplet state. In the presence of EDTA (which acts as both tiplet quencher and sacrificial electron donor) the photoreduction of water sensitised by Rose Bengal was inefficient for a number of reasons, including a low triplet quenching rate constant (8 × 103 dm3 mol–1 s–1) and a rapid disproportionation reaction involving the protonated semi-reduced dye radicals. In the presence of methyl viologen (triplet quencher) and EDTA (sacrificial electron donor) the photoreduction of water sensitised by Rose Bengal was inefficient due to a low cage-escape yield (ϕ≈ 5 × 10–2) following the primary electron-transfer step, a fast back reaction (k 1 × 108 dm3 mol–1 s–1) and formation of a complex between the dye and methyl viologen (K= 6400 ± 300 dm3 mol–1). The complexed form of Rose Bengal appeared able to photosensitise, inefficiently, the photoreduction of methyl viologen in the presence of EDTA, without exhibiting problems of dye fade.

Key concepts: Rose bengal, Chemistry, Photochemistry, Disproportionation, Quenching (fluorescence), Protonation, Viologen, Radical

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