The Solubilities of NiO , Co3 O 4, and Ternary Oxides in Fused Na2 SO 4 at 1200°K
Abstract
The solubilities of the oxides and in molten have been established as a function of activity at 1200°K. A reference electrode of in a mullite tube was used as a sodium activity probe for the melt. A second reference electrode of Pt, (air)/zirconia served as an oxygen activity probe for . The combination of measurements of the sodium probe and oxygen probe in the melt provided the activity in directly, and eliminated the necessity for any bare metal electrode. Saturated melts were analyzed by atomic absorption spectroscopy for the dissolved metal contents. The observed dependences of the solubilities of and in on the activities of sodium oxide are in agreement with those predicted from the Na‐Ni‐S‐O and N‐Co‐S‐O phase stability diagrams, respectively. Activity coefficients were calculated for the solute species. Preliminary measurements were made of the aluminum contents in melts saturated with and in an alumina crucible. The unusual dependences of aluminum content on salt basicity suggested the existence of the ternary oxides and . While the preliminary aluminum measurements were not considered reliable, a theoretical model was developed to predict the expected solubility behavior for a ternary oxide in .
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For metal oxides with multiple valences available for the metal (e.g., cobalt, chromium and iron oxides), solubilities depend on the metal oxidation states, which in turn depend on the oxygen partial pressure.
“For metal oxides with multiple valences available for the metal (e.g., cobalt, chromium and iron oxides), solubilities depend on the metal oxidation states, which in turn is dependent on the oxygen partial pressure [68, 69, 74, 75].”
From A review on molten sulfate salts induced hot corrosion (2021) · cites this paper as [69]
Dissolution of metal oxides in molten Na2SO4 is divided into basic dissolution at log(aNa2O) values above the solubility minimum and acid dissolution at values below the solubility minimum.
“The dissolution is divided into two categories based on the melt basicity. Basic dissolution (Eq. (5, 7-10)) occurs at log(aNa2O) values above the basicity value for the solubility minimum of the metal oxide and acid dissolution Eq. (6, 11-14)) refers to the solubility reaction at basicity values below the solubility minimum [67-69].”
From A review on molten sulfate salts induced hot corrosion (2021) · cites this paper as [69]
The dissolution of metal oxides in molten Na2SO4 is closely related to melt basicity.
“The reaction involving the dissolution of metal oxides is closed related to the melt basicity.”
From A review on molten sulfate salts induced hot corrosion (2021) · cites this paper as [69]
The solubilities and dissolution mechanisms of metal oxides in molten Na2SO4 depend on the value of -log(aNa2O).
“As discussed below, the solubilities and dissolution mechanisms of metal oxides in molten Na2SO4 are dependent on the value of -log(aNa2O).”
From A review on molten sulfate salts induced hot corrosion (2021) · cites this paper as [69]
Once the protective oxide layer contacts the fused salt, dissolution of various oxides such as NiO, Co3O4, Fe2O3, Fe3O4 and Cr2O3 takes place.
“Once the protective oxide layer comes into contact with the fused salt, the dissolution of various oxides, e.g., NiO, Co3O4, Fe2O3, Fe3O4 and Cr2O3, takes place.”
From A review on molten sulfate salts induced hot corrosion (2021) · cites this paper as [69]
The base metals Fe, Ni, Co, and Cr are not stable when in contact with fused sulfate salts, so electrochemical reactions take place to achieve chemical equilibrium.
“Since the base metal, e.g., Fe, Ni, Co, Cr, is not stable when it is in contact with the fused sulfate salts [67, 69, 82], electrochemical reactions take place to achieve the chemical equilibrium.”
From A review on molten sulfate salts induced hot corrosion (2021) · cites this paper as [69]
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- Authors
- Gupta, D. K., & Rapp, R. A.
- Affiliations
- The Ohio State University (US)
- ORCID
- Gupta, Dilip K.
- Venue
- Journal of The Electrochemical Society
- Publisher
- The Electrochemical Society
- Published
- 1980-10-01
- Volume
- 127
- Issue
- 10
- Pages
- 2194-2202
- ISSN
- 0013-4651 (ISSN-L)
- 1945-7111
- OpenAlex
- W2159005406
- Cited by
- 94
- References
- 0
- Citations by year
- 2026: 1 · 2025: 2 · 2024: 2 · 2023: 2 · 2022: 4 · 2021: 3 · 2020: 1 · 2019: 2 · 2018: 3 · 2017: 1 · 2016: 2 · 2015: 4 · 2014: 1 · 2013: 1
- FWCI
- 3.25
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- Journal of The Electrochemical Society (publishedVersion)
- Funders
- National Science Foundation
- Topics
- Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Molten salt chemistry and electrochemical processes
- Physical Sciences › Engineering › Mechanical Engineering › Metallurgical Processes and Thermodynamics
- Physical Sciences › Materials Science › Ceramics and Composites › Glass properties and applications
- Keywords
- ternary oxides, molten salts, sodium activity, oxygen activity, reference electrode, activity coefficients, phase stability diagram, molten salt electrolysis
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