Kinetics of the rapid monomer–dimer equilibration of molybdenum(VI) in aqueous perchloric acid solutions
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 6,p. 500-505
- https://doi.org/10.1039/dt9750000500
Abstract
The monomer–dimer equilibration of molybdenum(VI) in 0·2–3·0M perchloric acid solutions, I= 3·0M(LiClO4), has been studied at 25 °C. Spectrophotometric measurements are consistent with the presence of a monomeric species, [HMoO3]+, and dimeric species, [H2Mo2O6]2+ and [H3Mo2O6]3+, in agreement with previous work by Krumenacker. Evidence for the further monomeric species [H2MoO3]2+ has been obtained. Kinetic studies using the temperature-jump technique indicate a major pathway (i) for equilibration, with rate constant K1=[HMoO3]++[HMoO3]+ [graphic omitted] [H2Mo2O6]2+(i)(1·71 ± 0·10)× 105 l mol–1s–1 and k–1=(3·20 ± 0·20)× 103s–1. The equilibration(ii), appears to contribute [H2MoO3]2++[HMoO3]+ [graphic omitted] [H3Mo2O6]3+(ii) to a small extent with k2=(0·3 ± 0·3)× 105 l mol–1s–1 and k–2=(30 ± 20) s–1.Keywords
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