Abstract
The method of laser photoelectron emission from metals in electrolyte solutions has been used to measure the rate constants w3 for the electrochemical reduction of simple organic radicals R to carbanions R−. The following empirical rule has been established: the changes in the standard redox potential E° for R−/R in series of organic radicals are equal to the changes in the potential corresponding to individual values of w3. On the basis of this rule and the value of E° for CH3 −/CH3 E° values were obtained for C2H5, n-C3H7, n-C4H9, CH2OH, CH3CHOH, (CH3)2COH, CH2Cl, CHF2, CHFCl, CHCl2, CF2Cl, CFCl2, CF3, CCl3, C6H5, C6Cl5, and a scale of pK for the CH acids conjugate to R−. Consideration is given to the nature of the changes in E° and pK on passing from aqueous solutions to solutions in water-dioxane mixtures and in acetonitrile.
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P. Taffel and A. Henglein, Farad. Disc. Chem. Soc.,63, 124 (1978).
V. A. Benderskii, A. G. Krivenko, and V. A. Kurmaz, Electrokhimiya,22, 644 (1986).
V. A. Benderskii and A. G. Krivenko, Dokl. Akad. Nauk SSSR,291, 1395 (1987).
V. A. Benderskii, A. G. Krivenko, and G. V. Simbirtseva, Élektrokhimiya,23, 748 (1986).
V. A. Benderskii, A. G. Krivenko, V. A. Kurmaz, and G. V. Simbirtseva, Élektrokhimiya,22, 915 (1986).
D. Hidridge, Electrochemistry of Metals in Nonaqueous Solutions [Russian translation], Izd. Mir, Moscow (1974), pp. 161–163.
R. A. Marcus, Ann. Rev. Phys. Chem.,15, 155 (1964).
O. A. Reutov and I. P. Beletskaya, CH Acids [in Russian], Izd. Nauka, Moscow, 1980, Chap. 1.
K. E. Edgecomb and J. B. Russe, Can. J. Chem.,62, 2887 (1984).
K. Bowden and A. F. Cockerill, J. Chem. Soc. B, No. 1, 179 (1970).
B. B. Damaskin, O. A. Petrii, and V. V. Batrakov, Adsorption of Organic Compounds on Electrodes [in Russian], Izd. Nauka, Moscow, 1968, Chap. 3.
M. H. Abraham, J. Chem. Soc. Faraday Trans. 1,69, 1375 (1973).
V. A. Benderskii and A. A. Ovchinnikov, Physical Chemistry. Current Problems. Vol. 1 [in Russian], Izd. Khimiya, Moscow, 1989, p. 159.
V. A. Benderskii, A. G. Krivenko, and E. A. Ponomarev. Élektrokhimiya,26, No. 3, 318 (1989).
D. S. Marynick and D. A. Dixon, Proc. Nat. Acad. Sci. USA,74, 410 (1977).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1508–1514, July, 1990.
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Benderskii, V.A., Krivenko, A.G. & Simbirtseva, G.V. Photoelectrochemical pK Scale for weak CH-acids. Russ Chem Bull 39, 1363–1368 (1990). https://doi.org/10.1007/BF00957839
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DOI: https://doi.org/10.1007/BF00957839