Thermodynamic Properties of Coquimbite and Aluminocoquimbite

Yu. D. Gritsenko; Гриценко Ю. Д.; L. P. Ogorodova; Огородова Л. П.; M. F. Vigasina; Вигасина М. Ф.; D. A. Kosova; Косова Д. А.; S. K. Dedushenko; Дедушенко С. К.; L. V. Melchakova; Мельчакова Л. В.; D. A. Ksenofontov; Ксенофонтов Д. А.

doi:10.31857/S0016752523050059

Thermodynamic Properties of Coquimbite and Aluminocoquimbite

Authors: Gritsenko Y.D.¹^,2, Ogorodova L.P.¹, Vigasina M.F.¹, Kosova D.A.³, Dedushenko S.K.⁴, Melchakova L.V.¹, Ksenofontov D.A.¹
Affiliations:
1. Geological Faculty, Lomonosov Moscow State University
2. Fersman Mineralogical Museum, Russian Academy of Sciences
3. Chemical Faculty, Lomonosov Moscow State University
4. NUST MISIS
Issue: Vol 68, No 6 (2023)
Pages: 622-628
Section: Articles
URL: https://journals.rcsi.science/0016-7525/article/view/134816
DOI: https://doi.org/10.31857/S0016752523050059
EDN: https://elibrary.ru/ELQGOT
ID: 134816

Cite item

Full Text

Open Access
Restricted Access

Access granted
Restricted Access

Subscription Access

Abstract

Coquimbite AlFe3+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 Al2Fe3+2[SO4]6(H2O)12⋅6H2O from elements were estimated at −11 540 ± 29 and −9830 ± 29 kJ/mol, respectively.

Keywords

coquimbite, X-ray powder diffraction, Raman spectroscopy, Mössbauer spectroscopy, thermal analysis, Calvet microcalorimetry, enthalpy, entropy, Gibbs energy

References

Киселева И.А. (1976) Термодинамические свойства и устойчивость пиропа. Геохимия. (6), 845-854.
Киселева И.А., Огородова Л.П., Топор Н.Д., Чигарева О.Г. (1979) Термохимическое исследование системы СаО–MgO–SiO2. Геохимия. (12), 1811-1825.
Котельников А.Р., Кабалов Ю.К., Зезюля Т.Н., Мельчакова Л.В., Огородова Л.П. (2000) Экспериментальное изучение твердого раствора целестин-барит. Геохимия. (12), 1286-1293.
Kotel’nikov A.R., Kabalov Yu.K., Zezyulya T.N., Mel’chakova L.V., Ogorodova L.P. (2000) Experimental study of celestine-barite solid solution. Geochem. Int. (12), 1181-1187.
Наумов Г.Б., Рыженко Б.Н., Ходаковский И.Л. (1971) Справочник термодинамических величин (для геологов). М.: Атомиздат. 239 с.
Огородова Л.П., Киселева И.А., Мельчакова Л.В., Вигасина М.Ф., Спиридонов Э.М. (2011) Калориметрическое определение энтальпии образования пирофиллита. ЖФХ. (9), 1609-1611.
Ackermann S., Lazic B., Armbruster T., Doyle S., Grevel K.-D., Majzlan J. (2009) Thermodynamic and crystallographic properties of kornelite [Fe2(SO4)3 ~ 7.75H2O] and paracoquimbite [Fe2(SO4)3·9H2O]. Am. Mineral. 94, 1620-1628.
Dedushenko S.K., Perfiliev Yu.D. (2022) On the correlation of the 57Fe Mössbauer isomer shift and some structural parameters of a substance Hyperfine Interactions. 243, № 15.
Demartin F., Castellano C., Gramaccioli C.A., Campostrini I. (2010a) Aluminum-for-iron substitution, hydrogen bonding, and a novel structure-type in coquimbite-like minerals. Canad. Mineral. 48, 323-333.
Demartin F., Castellano C., Gramaccioli C.A., Campostrini I. (2010b) Aluminocoquimbite, AlFe (SO4)3·9H2O, a new aluminum iron sulfate from Grotta Dell’allume, Vulcano, Aeolian Islands, Italy. Canad. Mineral. 48, 1465-1468.
Dyar M.D., Jawin E.R., Breves E., Marchand G., Nelms M., Lane M.D., Mertzman S.A., Bish D.L., Bishop J.L. (2014) Mössbauer parameters of iron in phosphate minerals: Implications for interpretation of martian data. Am.Mineral. 99, 914-942.
Fang J.H., Robinson P.D. (1970) Crystal structure and mineral chemistry of hydrated ferric sulfates. I. The crystal structure of coquimbite. Am. Mineral. 55, 1534-1540.
Frost R.L., Gobac Ž.Ž., López A., Xi Y., Scholz R., Lana C., Lima R.M.F. (2014) 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. 1063, 251-258.
Hemingway B., Seal R.R., II, Chou I.-M. (2002) Thermodynamic data for modeling acid mine drainage problems: Compilation and estimation of data for selected soluble iron-sulfate minerals. U.S. Geol. Survey, Open-File Report, 02-161, 13 p.
IMA list of minerals. http://cnmnc.main.jp/IMA_Master_ List_(2021-11).pdf.
Majzlan J., Navrotsky A., McCleskey R.B., Alpers C.N. (2006) Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5. Eur. J. Mineral.
Majzlan J., Dordevié T., Kolitsch U. (2010) Hydrogen bonding in coquimbite, nominaly Fe2(SO4)3⋅9H2O, and the relationship between coquimbite and paracoquimbite. Miner. Petrol. 100, 241-248.
Majzlan J., Alpers C.N., Koch C.B., McCleskey R.B., Myneni S.C.B., Neil J.M. (2011) 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.
Mauro D., Biagioni C., Pasero M., Skogby H., Zaccarini F. (2020) Redefinition of coquimbite, Al Fe3(SO4)6(H2O)12⋅6H2O. Mineral. Magaz. 84, 275-282.
Ogorodova L.P., Melchakova L.V., Kiseleva I.A., Belitsky I.A. (2003) Thermochemical study of natural pollucite. Thermochim. Acta 403, 251–256.
Poitras J.T., Cloutis E.A., Salvatore M.R., Mertzman S.A., Applin D.M., Mann P. (2018) Mars analog minerals’ spectral reflectance characteristics under Martian surface conditions. Icarus. 306, 50-73.
Robie R.A., Hemingway B.S. (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 pascals) pressure and at higher temperatures. U S Geol. Surv. Bull. 2131.
Robinson P.D., Fang J.H. (1971) Crystal structure and mineral chemistry of hydrated ferric sulfates. II. The crystal structure of paracoquimbite. Am. Mineral. 56, 1567-1572.
Turenne N., Parkinson A., Applin D.M., Mann P., Cloutis E.A., Mertzman S.A. (2022) Spectral reflectance properties of minerals exposed to Martian surface conditions: Implications for spectroscopy-based mineral detection on Mars. Planet. Space Sci. 210, 105377.
www.happysloth.ru: Левин Д.М., Дедушенко С.К. Программа для ЭВМ “Happy Sloth”. Реестр программ для ЭВМ. № 2016660090.
Yang Z., Giester G. (2018) Structure refinement of coquimbite and paracoquimbite from the Hongshan Cu–Au deposit, NW China. Eur.J. Mineral. 30, 849-858.