Abstract—
Coquimbite Al\({\text{Fe}}_{3}^{{3 + }}\)[SO4]6(H2O)12⋅6H2O (sample from the Javier Mine, Peru) has been studied by thermal and electron microprobe analysis, X-ray powder diffraction, Raman spectroscopy, and Mössbauer spectroscopy. The enthalpy of formation of the coquimbite from elements ∆fH0(298.15 K) = −11 118 ± 40 kJ/mol was determined by the method of solution calorimetry in melt of lead borate 2PbO∙B2O3 on a Setaram (France) Calvet microcalorimeter. The value of its absolute entropy S0(298.15 K) = 1248.3 ± 3.0 J/(mol K) was estimated, the entropy of formation ∆fS0(298.15 K) = − 5714.0 ±3.0 J/mol K), and the Gibbs energy of formation from elements ∆fG0(298.15 K) = −9411 ± 40 kJ/mol were calculated. The values of the enthalpy and Gibbs energy of formation of aluminocoquimbite Al2\({\text{Fe}}_{2}^{{3 + }}\)[SO4]6(H2O)12⋅6H2O from elements were estimated at −11 540 ± 29 and −9830 ± 29 kJ/mol, respectively.
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REFERENCES
S. Ackermann, B. Lazic, T. Armbruster, S. Doyle, K.‑D. Grevel, and J. Majzlan, “Thermodynamic and crystallographic properties of kornelite [Fe2(SO4)3 ~ 7.75H2O] and paracoquimbite [Fe2(SO4)3·9H2O],” Am. Mineral. 94, 1620–1628 (2009).
S. K. Dedushenko and Yu. D. Perfiliev, “On the correlation of the 57Fe Mössbauer isomer shift and some structural parameters of a substance,” Hyperfine Inter. 243, # 15 (2022).
F. Demartin, C. Castellano, C. A. Gramaccioli, and I. Campostrini, “Aluminum-for-iron substitution, hydrogen bonding, and a novel structure-type in coquimbite-like minerals,” Can. Mineral. 48, 323–333 (2010a).
F. Demartin, C. Castellano, C. A. Gramaccioli, and I. Campostrini, “Aluminocoquimbite, AlFe (SO4)3·9H2O, a new aluminum iron sulfate from Grotta Dell’allume, Vulcano, Aeolian Islands, Italy,” Can. Mineral. 48, 1465–1468 (2010b).
M. D. Dyar, E. R. Jawin, E. Breves, G. Marchand, M. Nelms, M. D. Lane, S. A. Mertzman, D. L. Bish, and J. L. Bishop, “Mössbauer parameters of iron in phosphate minerals: Implications for interpretation of Martian data,” Am. Mineral. 99, 914–942 (2014).
J. H. Fang and P. D. Robinson, “Crystal structure and mineral chemistry of hydrated ferric sulfates. I. The crystal structure of coquimbite,” Am. Mineral. 55, 1534–1540 (1970).
R. L. Frost, Ž. Ž. Gobac, A. López, Y. Xi, R. Scholz, C. Lana, and R. M. F. Lima, “Characterization of the sulphate mineral coquimbite, a secondary iron sulphate from Javier Ortega mine, Lucanas Province, Peru – Using infrared, Raman spectroscopy and thermogravetry,” J. Mol. Struct., No. 1063, 251–258 (2014).
B. Hemingway, R. R. Seal, and Chou I. -M. II, “Thermodynamic data for modeling acid mine drainage problems: Compilation and estimation of data for selected soluble iron-sulfate minerals,” U.S. Geol. Surv, Open-File Rept. 02–161, (2002).
IMA List of Minerals. http://cnmnc.main.jp/IMA_Master_List_(2021–11).pdf.
I. A. Kiseleva, “Thermodynamic properties and stability of pyrope,” Geokhimiya, No. 6, 845–854 (1976).
I. A. Kiseleva, L. P. Ogorodova, N. D. Topor, and O. G. Chigareva, “Thermochemical studies of the CaO–MgO–SiO2 System,” Geokhimiya, No. 12, 1811–1825 (1979).
A. R. Kotel’nikov, Yu. K. Kabalov, T. N. Zezyulya, L. V. Mel’chakova, and L. P. Ogorodova, “Experimental study of celestine-barite solid solution,” Geochem. Int., No. 12, 1181–1187 (2000).
J. Majzlan, C. N. Alpers, C. B. Koch, R. B. McCleskey, S. C.B. Myneni, and J. M. Neil, “Vibrational, X-ray absorption, and Mőssbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California,” Chem. Geol. 284, 296–305 (2011).
J. Majzlan, T. Dordevié, and U. Kolitsch, “Hydrogen bonding in coquimbite, nominaly Fe2(SO4)3·9H2O, and the relationship between coquimbite and paracoquimbite,” Miner. Petrol. 100, 241–248 (2010).
J. Majzlan, A. Navrotsky, R. B. McCleskey, and C. N. Alpers, “Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5,” Eur. J. Mineral. 18 (2), 175–186 (2006).
D. Mauro, C. Biagioni, M. Pasero, H. Skogby, and F. Zaccarini, “Redefinition of coquimbite, AlFe3(SO4)6(H2O)12·6H2O,” Mineral. Mag. 84, 275–282 (2020).
G. B. Naumov, B. N. Ryzhenko, and I. L. Khodakovsky, A Reference Book of Thermodynamic Values (for Geologists) (Atomizdat, Moscow, 1971) [in Russian].
L. P. Ogorodova, I. A. Kiseleva, L. V. Melchakova, M. F. Vigasina, and E. M. Spiridonov, “Calorimetric Determination of the Enthalpy of Formation for Pyrophyllite,” Russ. J. Phys. Chem. A 85 (9), 1609–1611 (2011).
L. P. Ogorodova, L. V. Melchakova, I. A. Kiseleva, and I. A. Belitsky, “Thermochemical study of natural pollucite,” Thermochim. Acta 403, 251–256 (2003).
J. T. Poitras, E. A. Cloutis, M. R. Salvatore, S. A. Mertzman, D. M. Applin, and P. Mann, “Mars analog minerals’ spectral reflectance characteristics under Martian surface conditions,” Icarus 306, 50–73 (2018).
R. A. Robie and B. S. Hemingway, “Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 pascals) pressure and at higher temperatures,” US Geol. Surv. Bull., No. 2131, (1995).
P. D. Robinson and J. H. Fang, “Crystal structure and mineral chemistry of hydrated ferric sulfates. II. The crystal structure of paracoquimbite,” Am. Mineral. 56, 1567–1572 (1971).
N. Turenne, A. Parkinson, D. M. Applin, P. Mann, E. A. Cloutis, and S. A. Mertzman, “Spectral reflectance properties of minerals exposed to Martian surface conditions: Implications for spectroscopy–based mineral detection on Mars,” Planet. Space Sci. 210, 105377 (2022).
Z. Yang and G. Giester, “Structure refinement of coquimbite and paracoquimbite from the Hongshan Cu–Au deposit, NW China,” Eur. J. Mineral. 30, 849–858 (2018).
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The thermal equipment and mass spectrometer are installed at and belong to the Chemical Faculty of Lomonosov Moscow State University, and the diffractometer, scanning electron microscope, Raman microscope, and Calvet microcalorimeter are installed at and belong to the Geological Faculty of Lomonosov Moscow State University.
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Translated by E. Kurdyukov
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Gritsenko, Y.D., Ogorodova, L.P., Vigasina, M.F. et al. Thermodynamic Properties of Coquimbite and Aluminocoquimbite. Geochem. Int. 61, 643–649 (2023). https://doi.org/10.1134/S0016702923050051
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DOI: https://doi.org/10.1134/S0016702923050051