ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT.
This paper presents thermodynamic calculations to identify optimal conditions for reducing oxygen-containing molybdenum and carbon compounds, suitable precursors for the electrochemical synthesis of molybdenum and molybdenum carbides in molten salts. A thermodynamic analysis of the high-tem...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2024
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-6682025-01-28T08:27:07Z ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. Kuleshov, Serhii Novoselova, Inessa Omel’chuk, Anatoliy molybdenum carbides, electrochemical synthesis, oxygen-containing compounds of molybdenum and carbon, thermodynamic analysis. This paper presents thermodynamic calculations to identify optimal conditions for reducing oxygen-containing molybdenum and carbon compounds, suitable precursors for the electrochemical synthesis of molybdenum and molybdenum carbides in molten salts. A thermodynamic analysis of the high-temperature electrochemical synthesis (HTES) of molybdenum carbide was carried out based on calculations and analysis of thermochemical decomposition voltages of molybdenum and carbon oxygen-containing compounds. The analysis have showed that the following pairs of compounds can be used as synthesis precursors for the electrochemical production of molybdenum carbides in the a wide range of cathodic current density: (1) BaMoO4–Li2CO3; (2) MoO2–CO2; (3) MoO2–CaCO3; (4) Li2MoO4–Li2CO3; (5) K2MoO4–Na2CO3; (6) MgMoO4–CO2; (7) CaMoO4–СaCO3; (8) ВaMoO4–ВaCO3; (9) Na2MoO4–Na2CO3; (10) СаMoO4–СО2; (11) Li2MoO4–СО2; (12) MoO2–Li2CO3; (13) ВаMoO4–СО2. The difference in the equilibrium potentials of molybdenum and carbon deposition from them does not exceed 0.2 V. For the first time, thermodynamic calculations have shown that alkali/alkaline earth metal cations, which are part of carbonates and molybdates composition, have an inverse effect on the potentials of carbon and molybdenum deposition from the corresponding compounds, depending on their polarization (electrostatic) force (Z/r2, where Z is the charge number of the cation, r is the cation radius). The higher the polarization force of the cation, the less energy consumption is required for the electrolytic deposition of carbon or molybdenum. It has been shown that the cathodic decomposition potentials of NaCl and KCl are more negative compared to the synthesis precursor compounds, which makes it possible to use an equimolar mixture of NaCl–KCl as a background electrolyte. The specified temperature range of 700–750 °C ensures the stability of the electrolytic bath and the completeness of the reaction of formation of molybdenum carbides. Thermodynamic analysis of the HTES of molybdenum carbides allowed one to select the optimal compositions of pairs of synthesis precursors and background electrolyte, to propose minimum regimes of temperature and energy consumption for the electrolysis with the maximum of current yield for the final product due to the prevention of side reactions. V.I.Vernadsky Institute of General and Inorganic Chemistry 2024-07-26 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/668 10.33609/2708-129X.90.6.2024.59-70 Ukrainian Chemistry Journal; Vol. 90 No. 6 (2024): Ukrainian Chemistry Journal; 59-70 Украинский химический журнал; Том 90 № 6 (2024): Ukrainian Chemistry Journal; 59-70 Український хімічний журнал; Том 90 № 6 (2024): Ukrainian Chemistry Journal; 59-70 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/668/333 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
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| datestamp_date |
2025-01-28T08:27:07Z |
| collection |
OJS |
| language |
English |
| topic_facet |
molybdenum carbides electrochemical synthesis oxygen-containing compounds of molybdenum and carbon thermodynamic analysis. |
| format |
Article |
| author |
Kuleshov, Serhii Novoselova, Inessa Omel’chuk, Anatoliy |
| spellingShingle |
Kuleshov, Serhii Novoselova, Inessa Omel’chuk, Anatoliy ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. |
| author_facet |
Kuleshov, Serhii Novoselova, Inessa Omel’chuk, Anatoliy |
| author_sort |
Kuleshov, Serhii |
| title |
ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. |
| title_short |
ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. |
| title_full |
ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. |
| title_fullStr |
ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. |
| title_full_unstemmed |
ELECTROCHEMICAL SYNTHESIS OF MOLYBDENUM CARBIDES IN MOLTEN SALTS: THEROMODYNAMIC ASPECT. |
| title_sort |
electrochemical synthesis of molybdenum carbides in molten salts: theromodynamic aspect. |
| description |
This paper presents thermodynamic calculations to identify optimal conditions for reducing oxygen-containing molybdenum and carbon compounds, suitable precursors for the electrochemical synthesis of molybdenum and molybdenum carbides in molten salts. A thermodynamic analysis of the high-temperature electrochemical synthesis (HTES) of molybdenum carbide was carried out based on calculations and analysis of thermochemical decomposition voltages of molybdenum and carbon oxygen-containing compounds. The analysis have showed that the following pairs of compounds can be used as synthesis precursors for the electrochemical production of molybdenum carbides in the a wide range of cathodic current density: (1) BaMoO4–Li2CO3; (2) MoO2–CO2; (3) MoO2–CaCO3; (4) Li2MoO4–Li2CO3; (5) K2MoO4–Na2CO3; (6) MgMoO4–CO2; (7) CaMoO4–СaCO3; (8) ВaMoO4–ВaCO3; (9) Na2MoO4–Na2CO3; (10) СаMoO4–СО2; (11) Li2MoO4–СО2; (12) MoO2–Li2CO3; (13) ВаMoO4–СО2. The difference in the equilibrium potentials of molybdenum and carbon deposition from them does not exceed 0.2 V. For the first time, thermodynamic calculations have shown that alkali/alkaline earth metal cations, which are part of carbonates and molybdates composition, have an inverse effect on the potentials of carbon and molybdenum deposition from the corresponding compounds, depending on their polarization (electrostatic) force (Z/r2, where Z is the charge number of the cation, r is the cation radius). The higher the polarization force of the cation, the less energy consumption is required for the electrolytic deposition of carbon or molybdenum. It has been shown that the cathodic decomposition potentials of NaCl and KCl are more negative compared to the synthesis precursor compounds, which makes it possible to use an equimolar mixture of NaCl–KCl as a background electrolyte. The specified temperature range of 700–750 °C ensures the stability of the electrolytic bath and the completeness of the reaction of formation of molybdenum carbides. Thermodynamic analysis of the HTES of molybdenum carbides allowed one to select the optimal compositions of pairs of synthesis precursors and background electrolyte, to propose minimum regimes of temperature and energy consumption for the electrolysis with the maximum of current yield for the final product due to the prevention of side reactions. |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2024 |
| url |
https://ucj.org.ua/index.php/journal/article/view/668 |
| work_keys_str_mv |
AT kuleshovserhii electrochemicalsynthesisofmolybdenumcarbidesinmoltensaltstheromodynamicaspect AT novoselovainessa electrochemicalsynthesisofmolybdenumcarbidesinmoltensaltstheromodynamicaspect AT omelchukanatoliy electrochemicalsynthesisofmolybdenumcarbidesinmoltensaltstheromodynamicaspect |
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2025-09-24T17:43:57Z |
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2025-09-24T17:43:57Z |
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