Abstract
Absolute quantum yields for the formation of OH radicals in the laser photolysis of aqueous solutions of NO3 -, NO2 - and H2O2 at 308 and 351 nm and as a function of pH and temperature have been measured. A scavenging technique involving the reaction between OH and SCN- ions and the time resolved detection by visible absorption of the (SCN)2 - radical ion was used to determine the absolute OH yields. The following results were obtained:
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NO -3 -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFWaam% cqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFZaWmcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKjYOcaqGGaGaam% iCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMdaaeaacqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqqHMoGr% daWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaWGubGaaiykai% abg2da9iabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiik% aiaaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqWFGaaica% qGLbGaaeiEaiaabchacaqGGaWaamWaaeaacaqGOaGaaeymaiaabIda% caqGWaGaaeimaiaabccacqGHXcqScaaI0aGaaGioaiaaicdacaqGPa% GaaeikamaalaaabaGaaeymaaqaaiaabkdacaqG5aGaaeioaaaacaqG% GaGaeyOeI0IaaeiiamaalaaabaGaaeymaaqaaiaadsfaaaGaaeykaa% Gaay5waiaaw2faaiaac6caaaaa!9673!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = 0.017 \pm 0.003 {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm 480{\text{)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\]
Selected experiments at 351 nm indicate that these results are essentially unchanged.
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NO -2 -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXc% qScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFXaqmcqWF% PaqkcqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacq% GHKjYOcaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMda% caqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8% hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab-D5aibqaba% GccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaaWcbaGae83N% d8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIdacqWFGaaicq% WFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaaeiiamaadmaa% baGaaeikaiaabgdacaqG1aGaaeOnaiaabcdacaqGGaGaeyySaeRaae% iiaiaabodacaqG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaa% baGaaeOmaiaabMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaae% aacaqGXaaabaGaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiilaaqa% aiaaiodacaaI1aGaaGymaiaabccacaqGUbGaaeyBaiaabQdacqWFGa% aicqqHMoGrdaWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaI% YaGaaGyoaiaaiIdacqWFGaaicqWFAoWscaGGPaGaeyypa0Jae8hiaa% Iae8hkaGIae8hmaaJae8Nla4Iae8hmaaJae8hnaqJae8NnayJae8hi% aaIaeyySaeRae8hiaaIae8hmaaJae8Nla4Iae8hmaaJae8hmaaJae8% xoaKJae8xkaKIae8hiaaIaaeOzaiaab+gacaqGYbGaaeiiaiaabsda% caqGGaGaeyizImQaaeiiaiaadchacaqGibGaaeiiaiaab2dacaqGGa% GaaeioaiaabYcaaeaacqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqqHMoGrdaWgaaWcbaGae83Nd8Kae83L% dGeabeaakiaacIcacaWGubGaaiykaiabg2da9iabfA6agnaaBaaale% aacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5aGaaGioaiab% -bcaGiab-P5aljaacMcacqWFGaaicaqGLbGaaeiEaiaabchacaqGGa% WaamWaaeaacaqGOaGaaeymaiaabIdacaqGWaGaaeimaiaabccacqGH% XcqScaqGGaGaaeinaiaabcdacaqGWaGaaeykaiaabIcadaWcaaqaai% aabgdaaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabcca% daWcaaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaaca% GGUaaaaaa!FC61!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.017 \pm 0.001) {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1560 }} \pm {\text{ 360)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.046 \pm 0.009) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 8,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm {\text{ 400)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\]
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H2O2-photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWF5aqocqWF4aaocqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFZaWmcqWFPaqkcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaae% iiaiaabEdacaqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaa% Iae8hiaaIae8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaa% WcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIda% cqWFGaaicqWFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaae% iiamaadmaabaGaaeikaiaabAdacaqG2aGaaeimaiaabccacqGHXcqS% caqGGaGaaeymaiaabMdacaqGWaGaaeykaiaabIcadaWcaaqaaiaabg% daaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabccadaWc% aaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaacaGGSa% aabaGaaG4maiaaiwdacaaIXaGaaeiiaiaab6gacaqGTbGaaeOoaiab% -bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikai% aaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWF% GaaicqWFOaakcqWFWaamcqWFUaGlcqWF5aqocqWF2aGncqWFGaaicq% GHXcqScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWF0aancqWFPaqk% cqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKj% YOcaqGGaGaamiCaiaabIeacaqGGaGaaeypaiaabccacaqG3aGaaeil% aaqaaiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGi% ab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bca% Giab-bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaai% ikaiaadsfacaGGPaGaeyypa0JaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaaGOmaiaaiMdacaaI4aGae8hiaaIae8NMdS% Kaaiykaiab-bcaGiaabwgacaqG4bGaaeiCaiaabccadaWadaqaaiaa% bIcacaqG1aGaaeioaiaabcdacaqGGaGaeyySaeRaaeiiaiaabgdaca% qG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaabaGaaeOmaiaa% bMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaaeaacaqGXaaaba% GaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiOlaaaaaa!F3D0!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.98 \pm 0.03) {\text{for }}p{\text{H }} \leqslant {\text{ 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(660 }} \pm {\text{ 190)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.96 \pm 0.04) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(580 }} \pm {\text{ 160)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\]
Together with the absorption coefficients and an assumed actinic flux within atmospheric droplets of twice the clear air value, the partial photolytic lifetimes (τOH) of these molecules at 298 K are estimated as 10.5 d, 5.4 h and 30.3 h for NO3 -, NO2 - and H2O2, respectively. These lifetimes will increase by a factor of two (NO3 -, NO2 -) and by 15% (H2O2) at T=278 K. Using average ambient concentrations in tropospheric aqueous droplets, the photolytic OH source strengths from these species are calculated to be 2.8×10-11, 1.3×10-11 and 1.4×10-11 mol 1-1 s-1 for NO3 -, NO2 - and H2O2 respectively.
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References
Amichai, O. and Treinin, A., 1969, The reactivity of O(3P) in aqueous solution, Chem. Phys. Lett. 3, 611–617.
Baxendale, J. H. and Wilson, J. A., 1956, The photolysis of hydrogen peroxide at high light intensities, Trans. Faraday Soc. 53, 344–356.
Baxendale, J. H., Bevan, P. L. T., and Scott, D. A., 1968, Pulse radiolysis of aqueous thiocyanate and iodide solutions, Trans. Faraday Soc. 64, 2389–2397.
Behar, D., Bevan, P. L. T., and Scholes, G., 1972, Pulse radiolysis of aqueous thiocyanate solutions. Nature of the intermediate transient species, J. Phys. Chem. 76, 1537–1542.
Bott, A. and Zdunkowski, W., 1987, Electromagnetic energy within dielectric spheres, Optical Soc. Am. A 4, 1361–1365.
Bufalini, J. J., Lancaster, H. T., Namie, G. R., and Gay, B. W.Jr., 1979, Hydrogen peroxide formation from the photooxidation of formaldehyde and its presence in rainwater, J. Environ. Sci. Health, Part A 14, 135–141.
Chameides, W. and Davis, D. D., 1982, The free radical chemistry of cloud droplets and its impact upon the composition of rain, J. Geophys. Res. 87, 4863–4877.
Finlayson-Pitts, B. J. and Pitts, James N.Jr., 1986a, Atmospheric Chemistry, Wiley-Interscience, New York, pp. 667–724.
Finlayson-Pitts, B. J. and Pitts, James N.Jr., 1986b, Atmospheric Chemistry, Wiley-Interscience, New York, p. 134.
Graedel, T. E., 1980, Atmospheric photochemistry, in O. Hutzinger (ed.), Handbook of Environmental Chemistry, vol. 2A, Springer, New York, pp. 107–143.
Graedel, T. E. and Weschler, C. J., 1981, Chemistry within aqueous atmospheric aerosols and raindrops, Rev. Geophys. Space Phys. 19, 505–539.
Holleman, A. F. and Wiberg, E., 1971, Lehrbuch der anorganischen Chemie, De Gruyter, Berlin, p. 365.
Hunt, J. P. and Taube, H., 1952, The photochemical decomposition of hydrogen peroxide. Quantum yields, tracer and fractionation effects, J. Am. Chem. Soc. 74, 5999–6002.
Kelly, T. J., Stedman, D. H., and Kok, G. L., 1978, Measurement of H2O2 and HNO3 in rural air, Geophys. Res. Lett. 6, 375–378.
Kok, G. L., 1978, Ambient air measurements of hydrogen peroxide in the California south coast air basin, Environ. Sci. Technol. 12, 1077–1080.
Kok, G. L., 1980, Measurements of hydrogen peroxide in rainwater, Atmos. Environ. 14, 653–656.
Likens, G. E., Wright, R. F., Galloway, J. N., and Butler, T. J., 1979, Acid rain, Sci. Am. 241, 43–51.
Madronowich, J., 1987, J. Geophys. Res. 92, 9740–9752.
Meyertein, D. and Treinin, A., 1961, Absorption spectra of NO3 - in solution, Trans. Faraday Soc. 57, 2104–2112.
Noyes, R. M., 1954, Kinetics of competitive processes when reactive fragments are produced in pairs, J. Am. Chem. Soc. 77, 2042–2045.
Noyes, R. M., 1956, Models relating molecular reactivity and diffusion in liquids, J. Am. Chem. Soc. 78, 5486–5490.
Okita, T., 1968, Concentrations of sulphate and other inorganic materials in fog and cloudwater and in aerosol, J. Met. Soc. Japan 46, 120–127.
Radojevic, M., 1986, Nitrite in rainwater, Atmos. Environ. 20, 1309–1310.
Spicer, C. W., 1977, The fate of nitrogen oxides in the atmosphere, Adv. Envir. Sci. Technol. 7, 163–261.
Strehlow, H. and Wagner, I., 1982, Flash photolysis of nitrite ions in aqueous solutions, Z. Phys. Chem. Neue Folge 132, 151–160.
Strickler, S. J. and Kasha, M., 1963, Solvent effects on the electronic absorption spectrum of nitrite ion, J. Am. Chem. Soc. 85, 2899–2901.
Taylor, R. C. and Cross, P. C., 1949, Light absorption of aqueous hydrogen peroxide solutions in the near ultraviolet region, J. Am. Chem. Soc. 71, 2266–2268.
Volman, D. H. and Chen, J. C., 1959, The photochemical decomposition of hydrogen peroxide in aqueous solutions of allyl alcohol at 2537 Å, J. Am. Chem. Soc. 81, 4141–4144.
Wagner, I., Strehlow, H., and Busse, G., 1980, Flash photolysis of nitrate ions in aqueous solutions, Z. Phys. Chem. Neue Folge 123, 1–33.
Warneck, P. and Wurzinger, C., 1988, Product quantum yields for the 305 nm photodecomposition of NO3 - in aqueous solution, J. Phys. Chem. 92, 6278–6283.
Zafiriou, O. C. and Bonneau, R., 1987, Wavelength-dependent quantum yield of OH radical formation from photolysis of nitrite ion in water, Photochem. Photobiol. 45, 723–727.
Zellner, R. and Herrmann, H., 1990, Absolute OH quantum yields in the photolysis of nitrite ions and its temperature dependence, Ber. Bunsenges. Phys. Chem., in preparation.
Zepp, R. G., Hoigné, J., and Bader, H., 1987, Nitrate-induced photooxidation of trace organic chemicals in water, Environ. Sci. Technol. 21, 443–450.
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Zellner, R., Exner, M. & Herrmann, H. Absolute OH quantum yields in the laser photolysis of nitrate, nitrite and dissolved H2O2 at 308 and 351 nm in the temperature range 278–353 K. J Atmos Chem 10, 411–425 (1990). https://doi.org/10.1007/BF00115783
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DOI: https://doi.org/10.1007/BF00115783