Flash photolysis of chlorine dioxide in aqueous solution

Mialocq, J.C.; Barat, F.; Gilles, L.; Hickel, B.; Lesigne, B.

doi:10.1021/j100625a003

Cited by 32 publications

(12 citation statements)

References 3 publications

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“…Photodecomposition of OC10 in aqueous solution results in the production of HCI and HCIO3; CI 2, and 02 are minor products. Neither the final products nor the radical intermediates (C1, O, CIO and CIOO) absorb significantly at 366 nm under their concentrations in this system [13][14][15].…”

Section: Introductionmentioning

confidence: 80%

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Determination of differential quantum yields in solution by electron paramagnetic resonance spectroscopy

2002

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Quantitative kinetic studies on the photochemistry of paramagnetic species in solution may be carried out by electron paramagnetic resonance (EPR) spectroscopy. A cylindrical cell can be used as photochemical reactor, but the internal diameter should be less than 1.7 mm in order to achieve the resonance of an aqueous sample in an X-band (9-10 GHz ) spectrometer. In this paper we present a detailed analysis of the fractions of incident light that are reflected, transmitted and absorbed by a liquid solution in a quartz cylindrical cell placed in the optical cavity of ah X-band EPR spectrometer. Since the photolysis cell is irradiated perpendicularly to its axis, variable angles of incidente have been considered to calculate the transmission and reflection coefficients from Fresnel equations. Polarization of light has been also taken into account in the evaluation of the coefficients. The procedure proposed here is adequate for the evaluation of the absorbed light in the determination of quantum yields. The continuous photolysis at 366 nm of symmet¡ chlorine dioxide (OC10) in aqueous solution was considered as an example. The initial differential quantum yield obtained for OC10 photodecomposition in aqueous solution was I• ~--0.55___0.04.

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Section: Introductionmentioning

confidence: 80%

“…Although studies on the photolysis of OC10 have increased since it was determined as one of the main processes related to the destruction of the stratospheric ozone, most of the works on this topic refer to the primary processes [5][6][7][8][9][10][11][12][13][14][15]:…”

Section: Introductionmentioning

confidence: 99%

Determination of differential quantum yields in solution by electron paramagnetic resonance spectroscopy

2002

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“…While this reaction is one of the possible fragmentation * To whom correspondence should be addressed. (1) channels in condensed-phase photolysis of chlorine dioxide, [22][23][24][25][26][27][28][29] it does not seem to be feasible in the thermally induced decomposition. In support of this statement, it should be remembered that slightly acidic solutions of chlorine dioxide can be stored in the dark without apparent concentration loss for several months.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Mechanism of Catalytic Decomposition and Oxidation of Chlorine Dioxide by the Hypochlorite Ion

et al. 2001

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The oxidation of ClO(2) by OCl(-)is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO(2)]/dt = 2k(OCl)[ClO(2)][OCl(-)]. The rate constant (T = 298 K, mu = 1.0 M NaClO(4)) and activation parameters are k(OCl) = 0.91 +/- 0.02 M(-1) s(-1), DeltaH = 66.5 +/- 0.9 kJ/mol, and DeltaS(++) = -22.3 +/- 2.9 J/(mol K). In alkaline solution, pH > 9, the primary products of the reaction are the chlorite and chlorate ions and consumption of the hypochlorite ion is not observed. The hypochlorite ion is consumed in increasing amounts, and the production of the chlorite ion ceases when the pH is decreased. The stoichiometry is kinetically controlled, and the reactants/products ratios are determined by the relative rates of the production and consumption of the chlorite ion in the ClO(2)/OCl(-) and HOCl/ClO(2)(-) reactions, respectively.

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“…triplet state formation was then calculated by exciting deaerated solutions of BP and potassium ferrocyanide with 265 nm light in separate experiments and comparing the yields of the BP triplet state and egq formed, respectively. Assuming a quantum yeld of 0.52 for eiq formation(Mialocq et al, 1980), a quantum yield of 0.19 k 0.02 was calculated for the BP triplet state.…”

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confidence: 99%

Laser Flash and Steady‐state Photolysis of Benoxaprofen in Aqueous Solution*

Navaratnam¹,

Hughes²,

Parsons³

et al. 1985

Photochem & Photobiology

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Abstract— On laser flash photolysis of aqueous solutions of benoxaprofen (BP), the BP triplet state is produced with a quantum yield of 0.19. One other unidentified species is also formed probably in a yield less than 0.02. Identical observations were made in alcoholic solution. The effect of potential hydrogen donors, isopropanol and histidine, on the kinetic reactivity of the BP triplet state, showed that for isopropanol the rate constant is slow (< 8 × 103 dm3 mol‐1 s‐1) if it occurs at all, whilst no reactivity with histidine could be seen. In oxygen uptake experiments, it was deduced that singlet oxygen is produced via the BP triplet state with a quantum yield of 0.18. There was no evidence for superoxide anion radical production. In other steady‐state photolysis experiments using high performance liquid chromatography, the quantum yield for loss of BP was determined to be 0.20, while the quantum yield for the only observed product, decarboxylated benoxaprofen, was estimated as 0.18. The involvement of the two major processes, i.e. singlet oxygen formation and BP decarboxylation, in BP phototoxicity is discussed.

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Flash photolysis of chlorine dioxide in aqueous solution

Cited by 32 publications

References 3 publications

Determination of differential quantum yields in solution by electron paramagnetic resonance spectroscopy

Determination of differential quantum yields in solution by electron paramagnetic resonance spectroscopy

Kinetics and Mechanism of Catalytic Decomposition and Oxidation of Chlorine Dioxide by the Hypochlorite Ion

Laser Flash and Steady‐state Photolysis of Benoxaprofen in Aqueous Solution*

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