AuthorTRUJILLO REBOLLO, ANDRES.
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PublisherThe University of Arizona.
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AbstractThe equilibrium and the kinetics of the reaction of Mo (VI) with 8-hydroxyquinoline; 8-hydroxyquinaldine; KELEX 100; LIX63; and LIX65N were studied by solvent extraction. From the equilibrium studies it was concluded that in weakly acidic solution (pH 5 to 6) the overall extraction reaction is (UNFORMATTED TABLE FOLLOWS) MoO₄²⁻ + 2H⁺ + 2HL(o) ↔ (K(ex)) MoO₂L ₂(o) + 2H₂O (TABLE ENDS) where HL is the monoprotic bidentate ligand, "(o)" refers to the organic phase, and K(,ex) is the extraction constant. It was concluded that the complexation reaction requires four protons to convert molybdate into molybdenyl. The extractions constants for LIX63 and 8-hydroxyquinaldine, corrected for the side reaction of the ligand and metal, are 10¹⁶·⁴³ and 10¹⁴·⁴⁰, respectively. In the case of LIX65N, the plot of log(D) vs pH has a maximum at pH 1.0, which was explained qualitatively in terms of protonation of the ligand and molybdic acid at low pH. The extraction constant for the reaction of molybdic acid and the neutral ligand was estimated to be 100,000. The kinetics of extraction Mo (VI) with LIX63, 8-hydroxyquinoline, 8-hydroxyquinaldine, and Kelex 100 were studied in this work. In all cases, except 8-hydroxyquinoline, the rate-determining step of the reaction involves the formation of a 1:1 complex between the neutral ligand and several Mo(VI) species differing in the degree of protonation. The rate-determining step for the reaction of Mo(VI) with 8-hydroxyquinoline involves the formation of a 1:2 complex. The rate constant for the reaction of HMoO₄ with 8-hydroxyquinaldine is four orders of magnitude smaller than the corresponding value reported in the literature for 8-hydroxyquinoline. The slower reaction with 8-hydroxyquinaldine was attributed to the presence of the methyl group next to the nitrogen atom of the ligand which hinders its binding with molybdenum in the rate determining step of the reaction.