Physico-chemical properties of MnCO3–CaCO3 and MnO–CaO solid solutions
Abstract
MnCO3–CaCO3 has been shown to form a continuous phase isomorphous with calcite as the Mn concentration is varied across the whole range of composition from CaCO3 to MnCO3. Magnetic susceptibility and e.p.r. studies show that the manganese-containing carbonate is paramagnetic, and diffuse reflectance spectroscopy confirms octahedral coordination for the Mn2+ ions.The decomposition of the MnxCa1–xCO3 phase to form the oxide has been investigated at five compositions between x= 0 and x= 1 with a view to preparing MnxCa1–xO solid solutions in a finely divided state. It is shown that this can be achieved by controlled decomposition in vacuo at 925 K. X-ray powder diffraction confirms the expected variation of unit-cell parameter with Mn content in the cubic MnxCa1–xO phase. A special Gouy cell was devised to determine magnetic susceptibility without exposure to the atmosphere. The temperature range studied (77–300 K) included the Néel temperature for MnO, and attenuation of superexchange interactions as Ca2+ ions replace Mn2+ ions is manifested by a rapid decrease of the Weiss constant and by a decrease of linewidth in the e.p.r. spectrum. Mn2+ is present in the high-spin 6S5/2 state (µ= 5.9µB) in all the solid solutions.The transformation of carbonate to oxide has been followed by diffuse reflectance spectroscopy in vacuo. MnxCa1–xCO3(x= 0.65) is shown to decompose rapidly at 675–750 K, but there is evidence for an intermediate state to be passed before the MnxCa1–xO solid solution is produced.
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Several works reported componential ranges from total miscibility between CaCO3 and MnCO3 to restricted solid solubilities with diverse miscibility gaps.
“Several works reported componential ranges from the total miscibility between CaCO3 and MnCO3 to restricted solid solubilities with diverse ranges of miscibility gaps [57, 58].”
From Dissolution and solubility of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] at 25 °C (2021) · cites this paper as [58]
Unit-cell parameters are reported to show a linear behavior across the series.
“However, unit-cell parameters are re-”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Fubini and Stone 1983
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- Authors
- Fubini, B., & Stone, F. S.
- ORCID
- Fubini, Bice
- Venue
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 1983
- Volume
- 79
- Issue
- 5
- Pages
- 1215
- ISSN
- 0300-9599 (ISSN-L)
- OpenAlex
- W1987126305
- Cited by
- 36
- References
- 0
- Citations by year
- 2025: 1 · 2024: 1 · 2023: 1 · 2022: 1 · 2021: 2 · 2016: 1 · 2012: 2
- FWCI
- 1.55
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the Chemical Society Faraday Transactions 1 Physical Chemistry in Condensed Phases (publishedVersion)
- Institutional Research Information System University of Turin (University of Turin) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Electronic, Optical and Magnetic Materials › Magnetic and transport properties of perovskites and related materials
- Physical Sciences › Materials Science › Materials Chemistry › Solid-state spectroscopy and crystallography
- Physical Sciences › Chemistry › Inorganic Chemistry › Inorganic Chemistry and Materials
- Keywords
- manganese carbonate, manganese oxide, paramagnetism, Weiss constant, superexchange, Néel temperature, lattice parameters, magnetic susceptibility, electron spin resonance
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