ISSN:
1572-901X
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary [MoOCl5]2− aquates rapidly in solutions ofca. 5 M or less in HCl or MeSO3H to give an intermediate which changes to the well known ion, Mo2O 4aq 2+ at a lower rate. Solutions of molybdenum(V) in 12M MeSO3H, when diluted, also change at a similar rate to Mo2O 4 2+ . The rate of reaction, d[Mo2O 4 2+ ]/ dt=k[MoV] has a value of k=30.(1)s−1 at 0°C in 5.00 MMeSO3H. At constant ionic strength, k is nearly independent of acidity (5.2–0.5 M) and is only slightly affected by exchanging MeSO 3 − with Cl− orp-toluenesulfonate ion. At low ionic strength k increases dramatically. In 4.78 MMeSO3H, the activation parameters are: ΔH≠=72.68(29) kJ/mole, ΔS≠=16.63(8) jmole · K and k=5.01(5)×102s−1 at 0°C.18O measurements on the oxygen transfer between MoO aq 3+ and Mo2O 4aq. 2+ were partially inconclusive. A mechanistic interpretation is given to the kinetic results. The x-ray crystal structure of KMoOCl4(OH2)·H2O is reported.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00624469
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