Photochemical processes in solutions of uranyl perchlorate in acetone with participation of atmospheric oxygen
Abstract
The photochemical formation processes of the nanoclusters of tetra- and pentavalent uranium with organic ligands have been studied by the methods of electron and IR absorption under light-emitting diode irradiation (430 – 450 nm) of UO2(ClO4 ) ⋅ 5H2O solutions having different proportions of Ca(NO3 )2 and uranium in the presence and in the absence of oxygen. It has been found that in the systems UO2(ClO4 )2 ⋅ 5H2O in acetone, with the addition of calcium nitrate in acetone, their irradiation in sealed cells leads to photopolymerization of acetone, the excited uranyl complexes being catalysts of the process. During such reactions the photoexcited ions of uranyl are oxidizing one part of the organic molecule and then are oxidized by its other part up to U(VI). In this way the uranyl ions are catalysts of the light activated dismutation reaction. The reactions of both types may take place in the absence of oxygen as well. Spectra of the same samples irradiated in the cells with the access of atmospheric oxygen reveal the bands attributed to the tetra- and pentavalent uranium complexes, i. e. in the presence of oxygen there is a possibility for the reaction of the third type – sensibilized autooxidition of the organic reducing agent and the accompanying reduction of U(VI) up to U(V) and U(IV).
References
- Bernadiner M. N., Shurygin A. P. Ognevaya pererabotka i obezvrezhivanie promyshlennykh otkhodov. Mosc., 1990 (in Russ.).
- Karpenko V. I., Shushakova M. V., Ozherelʼev O. A. Tekhnologiya kataliticheskoi pererabotki zhidkikh radioaktivnykh organicheskikh otkhodov [Technology of catalytic processing of liquid radioactive organic wastes]. Izv. Tomsk. politekhnicheskogo univ. 2005. Vol. 308, No. 3. P. 88–91 (in Russ.).
- Zajogin А. P., Zajogin А. А., Komyak A. I., et al. Fotoobrazovanie i fotokataliticheskaya aktivnostʼ uranila v atsetonovykh rastvorakh [The photoformation and photocatalytic activity of uranyl in acetone solutions]. Zhurnal prikl. spektrosk. 2007. Vol. 74, No. 5. P. 565–568 (in Russ.).
- Umreiko D. S., Vilejshikova Е. V., Komyak А. I., et al. Electronic absorption spectra and photochemical (catalitic) activity of uranyl ion in perchlorate solutions in acetone with the addition of DMSO and DMF under optical irradiation. Vestnik BGU. Ser. 1, Fiz. Mat. Inform. 2014. No. 2. P. 3–7 (in Russ.).
- Umreiko D. S., Vilejshikova Е. V., Komyak A. I. A study of the effects exerted by the physical and chemical properties of the solutions of Mg, Na, and K on the photochemical formation processes of uranium complexes with organic ligands. Vestnik BGU. Ser. 1, Fiz. Mat. Inform. 2014. No. 3. P. 7–14 (in Russ.).
- Umreiko D. S., Vilejshikova E. V., Zajogin A. P., et al. Opredelenie fotokhimicheskoi aktivnosti iona uranila v atsetone pri svetovom obluchenii v prisutstvii primesei kationov metalla i anionov [Determination photochemical activity of uranyl ion in acetone under light illumination in the presence of the impurities of metal cations and anions]. Zhurnal prikl. spektrosk. 2015. Vol. 82, No. 3. P. 781–783 (in Russ.).
- Zherin I. I., Amelina G. N. Khimiya, teoriya urana i plutoniya [Chemistry, theory of uranium and plutonium]. Tomsk, 2010. P. 50 –56 (in Russ.).
- Garmash S. A. The formed reactiv oxygen species under the combined action of uranyl ions and physical factors. Fundamentalʼnye issled. 2012. No. 9, part 4. P. 961–954 (in Russ.).
- Buchachenko A. L., Khudyakov I. V. The photochemistry of uranyl: spin selectivity and magnetic effects. Usp. Khim. 1991. Vol. 60, No. 6. P. 1105–1127 (in Russ.).
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