Dissolution Behavior and Thermodynamic of Metallic Oxides in ChCl-Urea Deep Eutectic Solvent AITranslate
Abstract AITranslate
Deep eutectic solvents （DESs），which are prepared from quaternary ammonium salts mixed with hydrogen bond donors （HBD） such as amides，alcohols and carboxylic acids，have been developed as a promising solvent for organic synthesis，extraction and separation of metal and metal electrodeposition due to their excellent physicochemical properties. Additionally，they can selectively dissolve valuable metal oxide such as zinc oxide and cuprous oxide，but are unable to dissolve gangue ingredients including ferric oxide，calcium oxide and aluminium oxide，which offers an effective way for the recovery of zinc from zinc-containing secondary resources such as steelmaking dust，zinc slag，zinc smelting fume，etc. But so far，there are very few studies on the dissolution of metal oxides in deep eutectic solvents，and the relevant data are very scarce. Thus，it is of great interest to measure the solubility of metal oxides in deep eutectic solvents systematically and to study their thermodynamics of dissolution. Here，the solubility of main metal oxides that present in steel-making dust，including ZnO，Cu2O，CuO，Ni2O3，Co2O3 and Fe3O4，in ChCl-urea DES was systematically measured by chemical method in the temperature range of 323~363 K. It was found that the solubility of these metal oxides in ChCl-urea DES varied widely. The solubilities of ZnO and Cu2O in ChCl-urea ranged from 0.1906% to 37.2683% and from 0.0220% to 3.1470% respectively，which were much higher than those of CuO （0.0045%~0.1803%），Ni2O3 （0.0070%~0.2574%），Co2O3 （0.0034%~0.1174%） and Fe3O4 （0.007%~0.0465%） in ChCl-urea DES. This demonstrated that ZnO and Cu2O had good solubility in ChCl-urea DES，while the rest of metal oxides were slightly soluble or insoluble in ChCl-urea DES，which was conducive to the selective dissolution of zinc from steel-making dust. With an increase of temperature from 323 to 363 K，the solubility of all metal oxides in ChCl-urea DES increased rapidly，but the degree of increase was different. The solubilities of ZnO and Cu2O increased by about 196 times and 143 times，while the solubilities of CuO，Ni2O3 and Co2O3 only increased by 40，36，34 and 66 times. The solubility of each metal oxide in ChCl-urea DES was correlated with temperature，and it was found that the relationship between the solubility of ZnO and temperature was parabolic，and the solubilities of other oxides were linear with temperature. By fitting them，the empirical equations of solubility for these metal oxides were regressed. The phase equilibrium relationships between metallic oxide and ChCl-urea DES were established，and the activity coefficient，excess Gibbs free energy，excess enthalpy and excess entropy of different metal oxide in ChCl-urea DES were respectively calculated according to the rules of solubility equilibrium. The activity coefficients of all metal oxides in ChCl-urea were greater than 1 except for that of ZnO at higher temperature （≥343 K），indicating that ChCl-urea solution of metal oxides largely had a positive deviation from the ideal solution. At the same temperature，the activity coefficient of ZnO in ChCl-urea DES was much smaller than that of other metallic oxide in ChCl-urea DES，indicating that interaction between ZnO and ChCl-urea was much stronger than those of other metal oxides with ChCl-urea DES. For the same metal oxide，the activity coefficient decreased with the increase of temperature，which was because the solubility of metal oxides increased with the increase of temperature，and the interaction of metal oxides and low eutectic solvents was enhanced. Based on the relationship between excess Gibbs free energy and activity coefficient，excess Gibbs free energy of various metal oxides in ChCl-urea DES at different temperatures could be obtained by calculating. The excess Gibbs free energy of zinc oxide in ChCl-urea DES was far smaller than that of other metal oxides. Moreover，excess Gibbs free energy of each metal oxide decreased with the increase of temperature，and the relationship between them was linear. Through linear fitting of the relationship between excess Gibbs free energy and temperature，the excess entropy and excess enthalpy of metal oxides in ChCl-urea DES were obtained. It was found that the excess enthalpy of metal oxide in ChCl-urea DES was larger compared to that in aqueous solution and high temperature molten salt，which might be due to the different structure and properties of ChCl-urea DES and aqueous solutions （or high temperature molten salt）. In addition，the excess enthalpy and excess Gibbs free energy of ZnO in ChCl-urea were also lower than those of other metal oxides，which was ascribed to the smaller activity coefficient of ZnO in ChCl-urea. This result indicated that the property and behavior of the solution obtained by ZnO dissolving in ChCl-urea were closer to the ideal solution compared to those of the solution formed by other metal oxide dissolving in ChCl-urea. Meanwhile，excess entropy of ZnO in ChCl-urea was 79 J⋅mol−1 and was relative lower，suggesting that the behavior of ChCl-urea solution containing ZnO was close to regular solution.
KeyWords AITranslate
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Basic Information:
DOI：10.13373/j.cnki.cjrm.XY22110018
Chinese Library Classification Number:TF803.2
Citation Information:
Deep eutectic solvents （DESs），which are prepared from quaternary ammonium salts mixed with hydrogen bond donors （HBD） such as amides，alcohols and carboxylic acids，have been developed as a promising solvent for organic synthesis，extraction and separation of metal and metal electrodeposition due to their excellent physicochemical properties. Additionally，they can selectively dissolve valuable metal oxide such as zinc oxide and cuprous oxide，but are unable to dissolve gangue ingredients including ferric oxide，calcium oxide and aluminium oxide，which offers an effective way for the recovery of zinc from zinc-containing secondary resources such as steelmaking dust，zinc slag，zinc smelting fume，etc. But so far，there are very few studies on the dissolution of metal oxides in deep eutectic solvents，and the relevant data are very scarce. Thus，it is of great interest to measure the solubility of metal oxides in deep eutectic solvents systematically and to study their thermodynamics of dissolution. Here，the solubility of main metal oxides that present in steel-making dust，including ZnO，Cu2O，CuO，Ni2O3，Co2O3 and Fe3O4，in ChCl-urea DES was systematically measured by chemical method in the temperature range of 323~363 K. It was found that the solubility of these metal oxides in ChCl-urea DES varied widely. The solubilities of ZnO and Cu2O in ChCl-urea ranged from 0.1906% to 37.2683% and from 0.0220% to 3.1470% respectively，which were much higher than those of CuO （0.0045%~0.1803%），Ni2O3 （0.0070%~0.2574%），Co2O3 （0.0034%~0.1174%） and Fe3O4 （0.007%~0.0465%） in ChCl-urea DES. This demonstrated that ZnO and Cu2O had good solubility in ChCl-urea DES，while the rest of metal oxides were slightly soluble or insoluble in ChCl-urea DES，which was conducive to the selective dissolution of zinc from steel-making dust. With an increase of temperature from 323 to 363 K，the solubility of all metal oxides in ChCl-urea DES increased rapidly，but the degree of increase was different. The solubilities of ZnO and Cu2O increased by about 196 times and 143 times，while the solubilities of CuO，Ni2O3 and Co2O3 only increased by 40，36，34 and 66 times. The solubility of each metal oxide in ChCl-urea DES was correlated with temperature，and it was found that the relationship between the solubility of ZnO and temperature was parabolic，and the solubilities of other oxides were linear with temperature. By fitting them，the empirical equations of solubility for these metal oxides were regressed. The phase equilibrium relationships between metallic oxide and ChCl-urea DES were established，and the activity coefficient，excess Gibbs free energy，excess enthalpy and excess entropy of different metal oxide in ChCl-urea DES were respectively calculated according to the rules of solubility equilibrium. The activity coefficients of all metal oxides in ChCl-urea were greater than 1 except for that of ZnO at higher temperature （≥343 K），indicating that ChCl-urea solution of metal oxides largely had a positive deviation from the ideal solution. At the same temperature，the activity coefficient of ZnO in ChCl-urea DES was much smaller than that of other metallic oxide in ChCl-urea DES，indicating that interaction between ZnO and ChCl-urea was much stronger than those of other metal oxides with ChCl-urea DES. For the same metal oxide，the activity coefficient decreased with the increase of temperature，which was because the solubility of metal oxides increased with the increase of temperature，and the interaction of metal oxides and low eutectic solvents was enhanced. Based on the relationship between excess Gibbs free energy and activity coefficient，excess Gibbs free energy of various metal oxides in ChCl-urea DES at different temperatures could be obtained by calculating. The excess Gibbs free energy of zinc oxide in ChCl-urea DES was far smaller than that of other metal oxides. Moreover，excess Gibbs free energy of each metal oxide decreased with the increase of temperature，and the relationship between them was linear. Through linear fitting of the relationship between excess Gibbs free energy and temperature，the excess entropy and excess enthalpy of metal oxides in ChCl-urea DES were obtained. It was found that the excess enthalpy of metal oxide in ChCl-urea DES was larger compared to that in aqueous solution and high temperature molten salt，which might be due to the different structure and properties of ChCl-urea DES and aqueous solutions （or high temperature molten salt）. In addition，the excess enthalpy and excess Gibbs free energy of ZnO in ChCl-urea were also lower than those of other metal oxides，which was ascribed to the smaller activity coefficient of ZnO in ChCl-urea. This result indicated that the property and behavior of the solution obtained by ZnO dissolving in ChCl-urea were closer to the ideal solution compared to those of the solution formed by other metal oxide dissolving in ChCl-urea. Meanwhile，excess entropy of ZnO in ChCl-urea was 79 J⋅mol−1 and was relative lower，suggesting that the behavior of ChCl-urea solution containing ZnO was close to regular solution.
quote
| GB/T 7714-2015 | [1] Xiao Chen, Cunying Xu, Jianru Li, et al. Dissolution Behavior and Thermodynamic of Metallic Oxides in ChCl-Urea Deep Eutectic Solvent[J]. Chinese Journal of Rare Metals, 2024, 48(12): 1713-1720. DOI:10.13373/j.cnki.cjrm.XY22110018. |
| MLA | [1] Xiao Chen, et al., "Dissolution Behavior and Thermodynamic of Metallic Oxides in ChCl-Urea Deep Eutectic Solvent." Chinese Journal of Rare Metals, vol. 48, no. 12, 2024, pp. 1713-1720, https://doi.org/10.13373/j.cnki.cjrm.XY22110018. |
| APA | [1] Xiao Chen, Cunying Xu, Jianru Li, Yixin Hua, Qibo Zhang, & Min Zheng. (2024). Dissolution Behavior and Thermodynamic of Metallic Oxides in ChCl-Urea Deep Eutectic Solvent. Chinese Journal of Rare Metals, 48(12), 1713-1720. https://doi.org/10.13373/j.cnki.cjrm.XY22110018 |
| IEEE | [1] Xiao Chen, Cunying Xu, Jianru Li, Yixin Hua, Qibo Zhang, and Min Zheng, "Dissolution Behavior and Thermodynamic of Metallic Oxides in ChCl-Urea Deep Eutectic Solvent," Chinese Journal of Rare Metals, vol. 48, no. 12, pp. 1713-1720, 2024, doi: 10.13373/j.cnki.cjrm.XY22110018. keywords: {deep eutectic solvent;ChCl-urea;metal oxide;solubility;thermodynamics} |