An Experimental Study of the Solubility and Speciation of MoO3(s) in Hydrothermal Fluids at Temperatures up to 350°C
Linbo Shang, Anthony E. Williams‐Jones, Xin‐Song Wang, A. Timofeev, Ruizhong Hu, Xian‐Wu Bi
Abstract
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.