Abstract
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 an X-band EPR spectrometer. Since the photolysis cell is irradiated perpendicularly to its axis, variable angles of incidence 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 symmetric chlorine dioxide (OCIO) in aqueous solution was considered as an example. The initial differential quantum yield obtained for OCIO photodecomposition in aqueous solution was Θ366 = 0.55 ± 0.04.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Jiany J.J.: Bruker Rep.148, 14–15 (2000)
Hunt R.E., Hill T.L.: J. Chem. Phys.15, 111–113 (1947)
Dignam M.J., Le Roy D.J.: J. Chem. Phys.26, 964–965 (1957)
Davies J.A., Manning P.P.: J. Am. Chem. Soc.79, 5148–5151 (1957)
Dunn R.C., Flanders B.N., Vaida V., Simon J.D.: Spectrochim. Acta48A, 1293–1301 (1992)
Zhang J., Aker P.: J. Phys. Chem.98, 765–767 (1994)
Bishenden E., Donaldson D.J.: J. Chem. Phys.101, 9565–9572 (1994)
Vaida V., Goudjil K., Simon J.D., Flanders B.N.: J. Mol. Liq.61, 133–152 (1994)
Vaida V., Simon J.D.: Science268, 1443–1448 (1995)
Roth M., Maul C., Gericke K.: J. Chem. Phys.107, 10582–10591 (1997)
Thøgersen J., Jepsen P.U., Thomsen C.L., Poulsen J.Aa., Byberg J.R., Keiding S.R.: J. Phys. Chem. A101, 3317–3323 (1997)
Hayes S.C., Philpott M.P., Mayer S.G., Reid P.J.: J. Phys. Chem. A103, 5534–5546 (1999)
Dunn R.C., Simon J.D.: J. Am. Chem. Soc.114, 4856–4860 (1992)
Thøgersen J., Thomsen C.L., Poulsen J.Aa., Keiding S.R.: J. Phys. Chem. A102, 4186–4191 (1998)
Mialocq J.C., Barat F., Gilles L., Hickel B., Lesigne B.: J. Phys. Chem.77, 742–749 (1973)
Nagai Y., Goodeve C.F.: Trans. Faraday Soc.27, 508–515 (1931)
Ingols R.S., Ridenour G.M.: J. AWWA1948, 1207–1227.
Adrian F.J., Bohandy J., Kim B.F.: J. Chem. Phys.85, 2692 (1986)
Kuhn H.J., Braslavsky S.E., Schmidt R.: Pure Appl. Chem.61, 205 (1989)
Lee J., Seliger H.H.: J. Chem. Phys.40, 519–523 (1964)
Kirk A.D., Namasivayam C.: Anal. Chem.55, 2429–2431 (1983)
Lide D.R. (ed.): Handbook of Chemistry and Physics 73rd edn., pp. 10–310. Boca Raton: CRC Press 1993.
Ditchburn R.W. (ed.): Light, 3rd edn. chapt. 15. London: Academic Press 1982.
Steiner E. (ed.): The Chemistry Maths Book. New York: Oxford University Press 1997.
Bowen E.J., Cheung W.M.: J. Chem. Soc.1932, 1200–1207.
Buxton G.V., Williams R.J.: Proc. Chem. Soc.1962, 141–142.
Churio M.S., Brusa M.A., Perissinotti L.J., Ghibaudi E., Coronel M., Colussi A.J.: Chem. Phys. Lett.232, 237–241 (1995)
Brusa M.A., Perissinotti L.J., Churio M.S., Colussi A.J.: J. Photochem. Photobiol. A101, 105–111 (1996)
Logan S.R.: J. Chem. Soc. Faraday Trans.86, 61–63 (1990)
Yordanov N.D.: Appl. Magn. Reson.6, 241–257 (1994)
Yordanov N.D., Ivanova M.: Appl. Magn. Reson.6, 347–357 (1994)
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Quiroga, S.L., Churio, M.S. & Perissinotti, L.J. Determination of differential quantum yields in solution by electron paramagnetic resonance spectroscopy. Appl Magn Reson 22, 115–131 (2002). https://doi.org/10.1007/BF03170527
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF03170527