Abstract

The solubility of molybdenum trioxide (MoO3(s)) in aqueous solutions has been investigated experimentally at 250°, 300°, and 350°C and saturated water vapor pressure, and total Na concentrations ranging from 0 to 3 molal (m). Results of these experiments show that the solubility of MoO3(s) increases with increasing temperature and at 350°C can reach several thousand parts per million at high salinity (>1 m NaCl). At low Na+ activity, MoO3(s) dissolves dominantly as HMoO4 whereas at high Na+ activity, the dominant species is NaHMoO40. The two dissolution reactions are  
MoO3(s)+H2O=HMoO4+H+
(1)
and  
MoO3(s)+H2O+Na+=NaHMoO40+H+.
(2)
The values of the logarithms of the equilibrium constants for reaction (1) are –5.20 ± 0.12, –5.31 ± 0.17, and –5.50 ± 0.09 at 250°, 300°, and 350°C, respectively, and for reaction (2) the values are –3.40 ± 0.11, –3.25 ± 0.19, and –2.97 ± 0.09 for the same temperatures. In combination, these equilibrium constants yield equilibrium constants for the reaction relating the two aqueous species:  
Na++HMoO4=NaHMoO40.
(3)

The values of the logarithms of the equilibrium constants for reaction (3) are 1.80 ± 0.16, 2.06 ± 0.25, and 2.53 ± 0.13 at 250°, 300°, and 350°C, respectively. Calculations, based on the results of this study and thermodynamic data available for other species, suggest strongly that in ore-forming hydrothermal systems, molybdenum is transported mainly as NaHMoO40 and deposits as molybdenite in response to cooling and possibly a reduction in fO2.

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