Abstract
The potentiometric titration technique has been used to study molybdenum(VI) equilibria in 1.0 mol dm–3 sodium nitrate and at 25 °C. Numerical treatment of the data indicates that the ‘best’ model includes the species [HMoO4]–, H2MoO4, [Mo7O24]6–, [Mo7O23(OH)]5–, [Mo7O22(OH)2]4–[Mo7O21(OH)3]3–, [Mo8O26]4–, and [Mo10O34]8– whose formation constants, log βpq, are, respectively, 3.92, 8.09, 52.49, 57.57, 61.33, 64.96, 73.18, and 79.15. Evidence is given for the existence of a high-molecular-weight species even though computational limitations preclude its identification. A ‘slow’ region of equilibrium has also been found and its kinetics studied. The reaction mechanism is discussed; the rate constants of the forward and backward reaction, k1 and k–1, are 642 ± 300 dm6 mol–2 s–1 and (2.51 ± 1.00)× 10–5 s–1, respectively. Further evidence for the co-ordination numbers of the protonated forms of the molybdate ion is given.
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