Flash-photolysis Study of Potassium Hydroxide Solutions†

Abstract

Flash-photolysis experiments of KOH solutions ([KOH>0.03 M) are carried out in hydrogen- and air-saturated solutions; the formation of hydrated electrons is observed in hydrogen-saturated solutions, but the formation of O₂·^- and O₃·^- is observed in the presence of molecular oxygen and a reaction mechanism supported by kinetic computer simulations of the results is proposed.

References

1. D. N. Nikogosyan and H. Görner, J. Photochem. Photobiol. B: Biol., 1992, 13, 219.
2. J. Barret and J. H. Baxendale, Trans. Faraday Soc., 1960, 56, 37; U. Sokolov and G. Stein, J. Chem. Phys., 1965, 44, 2189, 3329; Radiation Chemistry in Aqueous Systems, ed. G. Stein, Weizmann Science Press, Jerusalem, 1968, pp. 83–89, and references cited therein.
3. E. J. Hart and M. Anbar, in The Hydrated Electron, Wiley–Interscience, New York, 1970; D. Phillips, in Photochemistry, The Chemical Society, London, 1973, vol. 4, part II, p. 366 and references cited therein.
4. K.-D. Asmus and J. H. Fendler, J. Phys. Chem., 1969, 73, 1583.
5. G. O. Schenck and N. Getoff, Proc. Int. Conf. Photochem., 1967, 2, 720.
6. J. W. Boyle, J. A. Ghormley, C. J. Hochanadel and J. F. Riley, J. Phys. Chem., 1969, 73, 2886.
7. E. San Román, P. F. Aramendía and H. J. Schumacher, An. Asoc. Quím. Argent., 1980, 70, 887.
8. G. L. Hug, Nat. Stand. Ref. Data Ser. (U.S. Nat. Bur. Stand.), 1981, 69, 30 and references cited therein.
9. K. Schmidt and E. J. Hart, ACS Adv. Chem., 1968, 81, 267 and references cited therein.
10. K. Sehested, J. Holcman, E. Bjerbakke and E. J. Hart, J. Phys. Chem., 1982, 86, 2066.
11. R. E. Bühler, J. Staehelin and J. Hoigné, J. Phys. Chem., 1984, 88, 2560.
12. G. Czapski and L. M. Dorfman, J. Phys. Chem., 1964, 68, 1169.
13. G. E. Adams, J. W. Boag and B. D. Michael, Nature (London), 1965, 205, 898.
14. G. E. Adams, J. W. Boag and B. D. Michael, Proc. R. Soc. London, A, Math. Phys. Sci., 1966, 289, 321.
15. L. J. Heidt and B. R. Landl, J. Chem. Phys., 1964, 41, 176.
16. B. H. J. Bielski, Methods Enzymol., 1984, 105, 81; B. H. J. Bielski and R. L. Araudi, Anal. Biochem., 1983, 133, 170.
17. P. Neta, R. E. Nuie and A. B. Ross, J. Phys. Chem. Ref. Data, 1988, 17, 1027.
18. Fahataziz and A. B. Ross, Selected Specific Rates of Reactions of Transients from Water in Aqueous Solutions. Part II. Hydroxyl Radical and Perhydroxyl Radical and their Radical Ions. NSRDSNBS 59, National Bureau of Standards, Washington DC, 1977.
19. G. V. Buxton, C. L. Greenstock, W. P. Helman and A. B. Ross, J. Phys. Chem. Ref. Data, 1988, 17, 513.
20. M. C. GonzalezD. O. MártireInt. J. Chem. Kin., in the press.