ABSTRACTGibbs free energies of formation (ΔG°ƒ) for several
structurally related U(VI) minerals are estimated by summing the Gibbs
energy contributions from component oxides. The estimated ΔG°f values are used to construct activity-activity (stability)
diagrams, and the predicted stability fields are compared with observed
mineral occurrences and reaction pathways. With some exceptions, natural
occurrences agree well with the mineral stability fields estimated for the
systems Sio2-Cao-Uo3-UOH2O and
Co2-caO-UO3-H2O providing confidence in
the estimated thermodynamic values. Activity-activity diagrams are sensitive
to small differences in ΔG°f values, and mineral compositions must be known accurately,
including structurally bound H2O. The estimated ΔG°f values are not considered reliable for a few minerals for two
major reasons: (1) the structures of the minerals in question are not
closely similar to those used to estimate the ΔG°f* values of the component oxides, and/or (2) the minerals in
question are exceptionally fine grained, leading to large surface energies
that increase the effective mineral solubilities.