Modeling Solid—Solution Reactions in Low-Temperature Aqueous Systems
Abstract
The effect of substitutional impurities on the stability and aqueous solubility of a variety of solids is investigated. Stoichiometric saturation, primary saturation and thermodynamic equilibrium solubilities are compared to pure phase solubilities. Contour plots of pure phase saturation indices (SI) are drawn at minimum stoichiometric saturation, as a function of the amount of substitution and of the excess-free-energy of the substitution. SI plots drawn for the major component of a binary solid-solution generally show little deviation from pure phase solubility except at trace component fractions greater than 1%. In contrast, trace component SI plots reveal that aqueous solutions at minimum stoichiometric saturation can achieve considerable supersaturation with respect to the pure trace-component end-member solid, in cases where the major component is more soluble than the trace. Field or laboratory observations of miscibility gaps, spinodal gaps, critical mixing points or distribution coefficients can be used to estimate solid-solution excess-free-energies, when experimental measurements of thermodynamic equilibrium or stoichiometric saturation states are not available. As an example, a database of excess-free-energy parameters is presented for the calcite, aragonite, barite, anhydrite, melanterite and epsomite mineral groups, based on their reported compositions in natural environments.
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The rhombohedral (Ca,Mn)CO3 solid solutions as a complete series has a0 < 2 at 25 °C.
“The rhombohedral (Ca,Mn)CO3 solid solutions as a complete series has a0 < 2 (25 °C) [15, 16].”
From Dissolution and solubility of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] at 25 °C (2021) · cites this paper as [16]
Two-parameter Guggenheim expansion equations (subregular models) were effectively applied to fit experimental solubilities of (Sr,Ca)CO3-H2O, (Ba,Sr)CO3-H2O, and (Ca,Mg)CO3-H2O systems.
“The two-parameter Guggenheim expansion equations (“subregular” models) were effectively applied to fit the experimental solubilities of (Sr,Ca)CO3-H2O, (Ba,Sr)CO3-H2O, and (Ca,Mg)CO3-H2O systems [16].”
From Dissolution and solubility of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] at 25 °C (2021) · cites this paper as [16]
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Dissolution and solubility of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] at 25 °C
Zhu, Y., Nong, P., Mo, N., Zhu, Z., Deng, H., Tang, S., Yang, H., Zhang, L., & Wang, X. (2021) · Geochemical Transactions · doi:10.1186/s12932-021-00075-1 · Cited by 11 · see citing works
“The a0 parameter was calculated from the miscibility gap [15] to be a0 < 2 at 25 °C [16].”
BackgroundMethodSoltan, M. E., & Rashed, M. N. (2000) · International Journal of Environmental Studies · doi:10.1080/00207230008711273 · Cited by 5 · see citing works
“The carbonates of divalent Fe, Mn, Zn, Cd, Co, Sr, Pb and UO2 are all less soluble than calcite and, in fact, the Fe, Mn, Zn, Cd, Pb and UO2 carbonates are over 100 times less soluble [24].”
BackgroundImplementation of isotopes into coupled hydrogeochemical modeling
Marinoni, M. (2018) · doi:10.70675/e590713azb574z4ca6zaa41zdbf158d5a014
“For each end-member, the following mass action law is verified at thermodynamic equilibrium (P. D. Glynn 1990): 1,...,EM EM EMEM EM EMEM EM EM EM TOT Q Q Q K EM N Xssa x Xss (5.6) where QEM is the ion activity product of the species involved in the precipitation of the mineral/endmember EM, KEM is…”
BackgroundMethodInfluentialBöttcher, M. E., & Gehlken, P. L. (1995) · Neues Jahrbuch für Mineralogie - Abhandlungen Journal of Mineralogy and Geochemistry · doi:10.1127/njma/169/1995/81
- Authors
- Glynn, P. D.
- Affiliations
- United States Geological Survey (US)
- Corresponding author
- Glynn, Pierre D.
- ORCID
- Glynn, Pierre D.
- Venue
- ACS Symposium Series
- Publisher
- American Chemical Society
- Published
- 1990-12-07
- Pages
- 74-86
- ISSN
- 0097-6156 (ISSN-L)
- 1947-5918
- OpenAlex
- W2506226771
- Cited by
- 22
- References
- 0
- Citations by year
- 2021: 1 · 2018: 2 · 2015: 1 · 2013: 1 · 2012: 1
- FWCI
- 8.22
- Type
- conference paper
- Language
- en
- Open access
- closed
- Locations
- ACS symposium series (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
- Physical Sciences › Chemical Engineering › Filtration and Separation › Chemical and Physical Properties in Aqueous Solutions
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Keywords
- solid-solution reaction, substitutional impurities, water solubility, saturation index, excess free energy, supersaturation, miscibility gap, distribution coefficient, calcite, aragonite, barite, anhydrite, melanterite, epsomite, mineral solubility
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