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A spectroscopic study of molybdenum extracts in organic solutions of dibutyl hydrogen phosphate in equilibrium with aqueous nitric acid solutions

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Abstract

The Mo extracts prepared by contacting dibutyl hydrogen phosphate (HDBP, HA) dissolved in xylene or CCl4 with HNO3 solutions of various concentrations in a wide range of Mo concentrations, and also the third phase formed in the analogous extraction system with tridecane as diluent were examined by IR and UV spectroscopy. The data obtained confirm the conclusion that, at the ratios HDBP: Mo ≥ 4 in the extract, molybdenum is extracted in the form of the acidic salt MoO2(HA2)2. The spectroscopic data obtained at higher extract loading were interpreted assuming the formation of binuclear complexes (HA2)MoO2A2MoO2(HA2) and, at HDBP: Mo < 3, of complexes of hydroxomolybdenyl and/or dimolybdenyl, and finally of polymeric complexes with bridging Mo-O-Mo bonds. In strongly acidic media, coextraction of outer-sphere molecular HNO3 and the presence of coordinated nitrate ion in the extract (probably in the form of molybdenyl nitrate complexes) are observed. A multistep extraction mechanism involving formation in the aqueous phase of an asymmetric monomeric complex MoO2(OH)(H2O)(HA2) was suggested.

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Correspondence to N. D. Goletskii.

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Original Russian Text © N.D. Goletskii, B.Ya. Zilberman, Yu.S. Fedorov, E.A. Puzikov, A.A. Lumpov, L.G. Mashirov, G.V. Sidorenko, 2011, published in Radiokhimiya, 2011, Vol. 53, No. 6, pp. 522–533.

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Goletskii, N.D., Zilberman, B.Y., Fedorov, Y.S. et al. A spectroscopic study of molybdenum extracts in organic solutions of dibutyl hydrogen phosphate in equilibrium with aqueous nitric acid solutions. Radiochemistry 53, 619–632 (2011). https://doi.org/10.1134/S1066362211060099

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  • DOI: https://doi.org/10.1134/S1066362211060099

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