Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology
Abstract
:1. Introduction
Compound | Sp.gr. sym. | a, Å | b, Å | c, Å | β, ° | Reference |
---|---|---|---|---|---|---|
Lindbergite | C2/c | 11.995(5) | 5.632(2) | 9.967(7) | 128.34(4) | [5] |
α-MnC2O4·2H2O | C2/c | 12.016 | 5.632 | 9.961 | 128.37 | [11], PDF #00-025-0544 *** |
α-MnC2O4·2H2O | C2/c | 11.765(2) | 5.655(1) | 9.637(1) | 125.84(1) | [12] |
α′-MnC2O4·2H2O | C2/c | 11.998(4) | 5.647(6) | 9.985(3) | 128.34(4) | [7] |
α″-MnC2O4·2H2O | C2/c | 11.939(5) | 5.624(7) | 9.703(3) | 126.52(6) | [7] |
γ-MnC2O4·2H2O | P212121 | 6.262(4) | 13.585(5) | 6.091(4) | 90 | [13] |
Glushinskite * | C2/c | 12.688 | 5.400 | 9.959 | 129.44 | [3] |
α-MgC2O4·2H2O | C2/c | 12.689 | 5.391 | 9.977 | 129.82 | [8], PDF #00-026-1223 *** |
β-MgC2O4·2H2O | C2/c | 12.675 | 5.406 | 9.984 | 129.45 | [8] *** |
β-MgC2O4·2H2O | Fddd ** | 12.691(3) | 5.394(1) | 15.399(3) | 90 | [10] |
2. Results
2.1. Powder X-ray Diffraction
2.1.1. Evolution of Phase Composition of Precipitates on Change in Composition of the Initial Solution
2.1.2. Variations in Unit Cell Parameters
2.2. Scanning Electron Microscopy and EDX Spectroscopy
2.2.1. Chemical Composition of Precipitates and Its Dependence on Solution Composition
2.2.2. The Influence of Element Composition on Crystal Morphology
2.3. Thermodynamic Modelling
3. Discussion
4. Methods and Materials
4.1. Synthesis
4.2. Thermodynamic Modelling
4.3. Instrumental Methods
4.3.1. Powder X-ray Diffraction (PXRD)
4.3.2. Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray (EDX) Spectroscopy
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Humboldtine Group. Mineral Information, Data and Localities. Available online: www.mindat.org/min-43258.html (accessed on 21 November 2022).
- Zhemchuzhnikov, Y.A.; Ginzburg, A.I. Basics of Coal Petrology; USSR Academy of Sciences: Moscow, Russia, 1960. (In Russian) [Google Scholar]
- Wilson, J.; Jones, D.; Russel, J.D. Glushinskite, a Naturally Occurring Magnesium Oxalate. Mineral. Mag. 1980, 43, 837–840. [Google Scholar] [CrossRef]
- Wilson, M.J.; Jones, D. The Occurence and Significance of Manganese Oxalate in Pertusaria-Corallina (Lichens). Pedobiologia 1984, 26, 373–379. [Google Scholar]
- Atencio, D.; Coutinho, J.; Graeser, S.; Matioli, P.; Filho, L. Lindbergite, a New Mn Oxalate Dihydrate from Boca Rica Mine, Galiléia, Minas Gerais, Brazil, and Other Occurences. Am. Mineral. 2004, 89, 1087–1091. [Google Scholar] [CrossRef]
- Baran, E. Review: Natural Oxalates and Their Analogous Synthetic Complexes. J. Coord. Chem. 2014, 67, 3734–3768. [Google Scholar] [CrossRef]
- Puzan, A.N.; Baumer, V.N.; Lisovitskiy, D.V.; Mateychenko, P.V. Structure Disorder and Thermal Decomposition of Manganese Oxalate Dihydrate, MnC2O4·2H2O. J. Solid State Chem. 2018, 260, 87–94. [Google Scholar] [CrossRef]
- Walter-Levy, L.; Perrotey, J.; Visser, J.W. Crystal Systems of Magnesium Oxalates and Chlorooxalates. Bull. Soc. Chim. Fr. 1971, 757–761. (In French) [Google Scholar]
- Dubernat, J.; Pezerat, H. Fautes d’empilement Dans Les Oxalates Dihydratés Des Métaux Divalents de La Série Mangésienne (Mg, Fe, Co, Ni, Zn, Mn). J. Appl. Crystallogr. 1974, 7, 387–393. [Google Scholar] [CrossRef]
- Chen, X.-A.; Song, F.-P.; Chang, X.-A.; Zang, H.-G.; Xiao, W.-Q. A New Polymorph of Magnesium Oxalate Dihydrate. Acta Crystallogr. Sect. E Struct. Rep. Online 2008, 64, m863. [Google Scholar] [CrossRef] [Green Version]
- Deyrieux, R.; Berro, C.; Peneloux, A. Studies on Oxalates of Some Bivalent Metals. III.—Crystal-Structure of Dihyrated Manganese, Cobalt, Nickel and Zinc Oxalates—Polymorphism of Dihydrated Cobalt and Nickel Oxalates. Bull. la Société Chim. Paris 1973, 1, 25–34. [Google Scholar]
- Soleimannejad, J.; Aghabozorg, H.; Hooshmand, S.; Ghadermazi, M.; Attar Gharamaleki, J. The Monoclinic Polymorph of Catena-Poly[[Diaquamanganese(II)]-μ-Oxalato-Κ4O1,O2:O1′,O2′]. Acta Crystallogr. Sect. E 2007, 63, m2389–m2390. [Google Scholar] [CrossRef]
- Lethbridge, Z.A.D.; Congreve, A.F.; Esslemont, E.; Slawin, A.M.Z.; Lightfoot, P. Synthesis and Structure of Three Manganese Oxalates: MnC2O4·2H2O, [C4H8(NH2)2][Mn2(C2O4)3] and Mn2(C2O4)(OH)2. J. Solid State Chem. 2003, 172, 212–218. [Google Scholar] [CrossRef]
- Holland, T.J.B.; Redfern, S.A.T. UNITCELL: A Nonlinear Least-Squares Program for Cell-Parameter Refinement and Implementing Regression and Deletion Diagnostics. J. Appl. Crystallogr. 1997, 30, 84. [Google Scholar] [CrossRef] [Green Version]
- Fichtner-Schmittler, H. On Some Features of X-ray Powder Patterns of OD Structures. Krist. Technol. 1979, 14, 1079–1088. [Google Scholar] [CrossRef]
- Vlasov, D.Y.; Frank-Kamenetskaya, O.V.; Zelenskaya, M.S.; Sazanova, K.V.; Rusakov, A.V.; Izatulina, A.R. The Use of Aspergillus Niger in Modeling of Modern Mineral Formation in Lithobiotic Systems. In Aspergillus Niger: Pathogenicity, Cultivation and Uses; Braun, E., Ed.; Nova Science Publishers, Inc.: New York, NY, USA, 2020; p. 197. ISBN 978-1-53618-080-0. [Google Scholar]
- Mehta, K.D.; Das Mukhopadhyay, C.; Pandey, B. Leaching of Copper, Nickel and Cobalt from Indian Ocean Manganese Nodules by Aspergillus Niger. Hydrometallurgy 2010, 105, 89–95. [Google Scholar] [CrossRef]
- Acharya, C.; Kar, R.N.; Sukla, L.B.; Misra, V.N. Fungal Leaching of Manganese Ore. Trans. Indian Inst. Met. 2004, 57, 501–508. [Google Scholar]
- Mulligan, C.N.; Kamali, M.; Gibbs, B.F. Bioleaching of Heavy Metals from a Low-Grade Mining Ore Using Aspergillus Niger. J. Hazard. Mater. 2004, 110, 77–84. [Google Scholar] [CrossRef]
- Mohanty, S.; Ghosh, S.; Nayak, S.; Das, A.P. Bioleaching of Manganese by Aspergillus Sp. Isolated from Mining Deposits. Chemosphere 2017, 172, 302–309. [Google Scholar] [CrossRef]
- Seh-Bardan, B.J.; Othman, R.; Wahid, S.A.; Husin, A.; Sadegh-Zadeh, F. Bioleaching of Heavy Metals from Mine Tailings by Aspergillus Fumigatus. Bioremediat. J. 2012, 16, 57–65. [Google Scholar] [CrossRef]
- Matzapetakis, M.; Karligiano, N.; Bino, A.; Dakanali, M.; Raptopoulou, C.P.; Tangoulis, V.; Terzis, A.; Giapintzakis, J.; Salifoglou, A. Manganese Citrate Chemistry: Syntheses, Spectroscopic Studies, and Structural Characterizations of Novel Mononuclear, Water-Soluble Manganese Citrate Complexes. Inorg. Chem. 2000, 39, 4044–4051. [Google Scholar] [CrossRef]
- Rusakov, A.; Kuzmina, M.A.; Izatulina, A.R.; Frank-Kamenetskaya, O. V Synthesis and Characterization of (Ca, Sr)[C2O4]∙nH2O Solid Solutions: Variations of Phase Composition, Crystal Morphologies and in Ionic Substitutions. Crystals 2019, 9, 654. [Google Scholar] [CrossRef] [Green Version]
- Pearce, K.N. Formation Constants for Magnesium and Calcium Citrate Complexes. Aust. J. Chem. 1980, 33, 1511–1517. [Google Scholar] [CrossRef]
- Filatov, S.K.; Krivovichev, S.V.; Bubnova, R.S. General Crystal Chemistry; Saint Petersburg State University: Saint Petersburg, Russian, 2018. (In Russian) [Google Scholar]
- Eriksson, G. An Algorithm for the Computation of Aqueous Multicomponent, Multiphase Equilibria. Anal. Chim. Acta 1979, 112, 375–383. [Google Scholar] [CrossRef]
- Ingri, N.; Kakolowicz, W.; Sillén, L.G.; Warnqvist, B. High-Speed Computers as a Supplement to Graphical Methods—V: HALTAFALL, a General Program for Calculating the Composition of Equilibrium Mixtures. Talanta 1967, 14, 1261–1286. [Google Scholar] [CrossRef] [PubMed]
- Haynes, W.M. (Ed.) CRC Handbook of Chemistry and Physics, 95th ed.; CRC Press: Boca Raton, FL, USA, 2014. [Google Scholar]
- Hummel, W.; Mompean, F.J. Chemical Thermodynamics of Compounds and Complexes of U, Np, Pu, Am, Tc, Se, Ni and Zr With Selected Organic Ligands, 1st ed.; Illemassene, M., Perrone, J., Eds.; Elsevier: Amsterdam, The Netherlands, 2005. [Google Scholar]
- Roof, R.B. INDX: A Computer Program to Aid in the Indexing of X-ray Powder Patterns of Crystal Structures of Unknown Symmetry; U.S. Department of Energy Office of Scientific and Technical Information: Oak Ridge, TN, USA, 1968.
Series | Lindbergite | Glushinskite | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
a, Å | b, Å | c, Å | β, ° | b, Å | ||||||
k * 103 | m | k * 103 | m | k * 103 | m | k * 102 | m | k * 103 | y (100%) = m + 100k | |
S | 3.7 | 11.974 | −1.1 | 5.640 | 1.3 | 9.722 | 1.6 | 126.48 | −5.0 | 5.386 |
N | 4.6 | 12.007 | −2.2 | 5.642 | 1.6 | 9.739 | 2.0 | 126.53 | 5.387 | |
SC | 4.6 | 11.998 | −1.7 | 5.642 | 1.7 | 9.744 | 1.8 | 126.52 | −3.4 | 5.400 |
NC | 5.9 | 11.999 | −2.1 | 5.640 | 2.0 | 9.734 | 2.3 | 126.55 | −2.2 | 5.390 |
Series | Lindbergites, Mg/(Mg + Mn)% | Glushinskites, Mn/(Mg + Mn)% | ||
---|---|---|---|---|
Solution | Crystal | Solution | Crystal | |
S | 50 | 71 | 25 | 22 |
N | 40 | 53 | 35 | 22 |
SC | 50 | 61 | 30 | 31 |
NC | 40 | 39 | 40 | 34 |
Origin | Series/Reference | a, Å | b, Å | c, Å | β, ° | n/m | |
---|---|---|---|---|---|---|---|
Lindbergite MnC2O4·2H2O | |||||||
Synthetic | S (our data) | α″ | 11.974(1) | 5.640(1) | 9.722(1) | 126.48(1) | 2.072 |
α′ | 11.975(1) | 5.641(1) | 9.973(1) | 128.40(1) | 1.933 | ||
Synthetic | N (our data) | α″ | 12.007(1) | 5.642(1) | 9.739(1) | 126.53(1) | 2.071 |
α′ | 12.008(1) | 5.643(1) | 9.989(1) | 128.51(1) | 1.931 | ||
Synthetic | SC (our data) | α″ | 11.998(1) | 5.642(1) | 9.744(1) | 126.52(1) | 2.069 |
α′ | 11.996(1) | 5.642(1) | 9.982(1) | 128.36(1) | 1.936 | ||
Synthetic | NC (our data) | α″ | 11.999(1) | 5.640(1) | 9.734(1) | 126.55(1) | 2.070 |
α′ | 11.999(1) | 5.642(1) | 9.974(1) | 128.34(1) | 1.939 | ||
Synthetic | PDF-2 #00-057-0602 (STAR) * | 11.995(5) | 5.632(2) | 9.967(7) | 128.34(4) | 1.940 | |
Synthetic | PDF-2 #01-086-6854 (STAR) * | 11.939(5) | 5.624(1) | 9.703(3) | 126.52(6) | 2.068 | |
Mineral | [5] | 11.995(5) | 5.632(2) | 9.967(7) | 128.34(4) | 1.940 | |
Synthetic (single crystal) | [12] | 11.765(2) | 5.655(1) | 9.637(1) | 125.84(1) | 2.085 | |
Glushinskite MgC2O4·2H2O | |||||||
Synthetic | S (our data) | C2/c | 12.695(1) | 5.386(1) | 9.985(1) | 129.46(1) | 2.001 |
Fddd | 12.695(1) | 5.389(1) | 15.415(1) | 90 | |||
Synthetic | N (our data) | C2/c | 12.675(1) | 5.387(1) | 9.978(1) | 129.47(1) | 1.998 |
Fddd | 12.676(1) | 5.384(1) | 15.405(1) | 90 | |||
Synthetic | SC (our data) | C2/c | 12.709(1) | 5.400(1) | 9.998(1) | 129.46(1) | 2.000 |
Fddd | 12.705(1) | 5.397(1) | 15.433(1) | 90 | |||
Synthetic | NC (our data) | C2/c | 12.695(1) | 5.390(1) | 9.983(1) | 129.47(1) | 2.000 |
Fddd | 12.698(1) | 5.390(1) | 15.413(1) | 90 | |||
Synthetic | PDF-2 #00-028-0625 (INDEXED) *, **** | 12.675 | 5.406 | 9.984 | 129.45 | 1.998 | |
Mineral | [3] **, **** | 12.688 | 5.400 | 9.959 | 129.44 | 2.005 | |
Synthetic (single crystal) | [10] *** | 12.691(3) | 5.394(1) | 15.399(3) | 90 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Korneev, A.V.; Izatulina, A.R.; Kuz’mina, M.A.; Frank-Kamenetskaya, O.V. Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology. Int. J. Mol. Sci. 2022, 23, 14734. https://doi.org/10.3390/ijms232314734
Korneev AV, Izatulina AR, Kuz’mina MA, Frank-Kamenetskaya OV. Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology. International Journal of Molecular Sciences. 2022; 23(23):14734. https://doi.org/10.3390/ijms232314734
Chicago/Turabian StyleKorneev, Anatolii V., Alina R. Izatulina, Mariya A. Kuz’mina, and Olga V. Frank-Kamenetskaya. 2022. "Solid Solutions of Lindbergite–Glushinskite Series: Synthesis, Ionic Substitutions, Phase Transformation and Crystal Morphology" International Journal of Molecular Sciences 23, no. 23: 14734. https://doi.org/10.3390/ijms232314734