Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility

An investigation has been carried out to understand the solution chemistry of the Cu-NH<sup>−</sup>-SO<sub>4</sub><sup>−2</sup> system, focusing on the effect of pH on the solubility of copper in the solution and maximizing the Cu(I):Cu(II) ratio. A Pourbaix diagr...

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Main Authors: Zulqarnain Ahmad Ali, Joshua M. Werner
Format: Article
Language:English
Published: MDPI AG 2024-10-01
Series:Waste
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Online Access:https://www.mdpi.com/2813-0391/2/4/22
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author Zulqarnain Ahmad Ali
Joshua M. Werner
author_facet Zulqarnain Ahmad Ali
Joshua M. Werner
author_sort Zulqarnain Ahmad Ali
collection DOAJ
description An investigation has been carried out to understand the solution chemistry of the Cu-NH<sup>−</sup>-SO<sub>4</sub><sup>−2</sup> system, focusing on the effect of pH on the solubility of copper in the solution and maximizing the Cu(I):Cu(II) ratio. A Pourbaix diagram for the Cu-N-S system has also been created using the HSC Chemistry software for a wide range of Cu-NH<sub>3</sub> species, unlike most other studies that focused only on Cu(NH<sub>3</sub>)<sub>4</sub><sup>2+</sup> and Cu(NH<sub>3</sub>)<sub>5</sub><sup>2+</sup> (Cu(II)) as the dominant species. The Pourbaix diagram demonstrated that the Cu(I) exists as Cu(NH<sub>3</sub>)<sub>2</sub><sup>+</sup>, while the Cu(II) species are present in the system as Cu(NH<sub>3</sub>)<sub>4</sub><sup>2+</sup> and Cu(NH<sub>3</sub>)<sub>5</sub><sup>2+</sup>, depending upon the Eh and pH of the solution. Copper precipitation was observed in the electrolyte at pH values less than 8.0, and the precipitation behavior increased as the pH became acidic. The highest Cu(I):Cu(II) ratio was observed at higher pH values of 10.05 due to the higher solubility of copper at higher alkaline pH. The maximum Cu(II) concentration can be achieved at 4.0 M NH<sub>4</sub>OH and 0.76 M (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>. In the case of low pH, the highest Cu(I):Cu(II) ratio obtained was 0.91 against the 4.0 M and 0.25 M concentrations of NH<sub>4</sub>OH and (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>, respectively. Meanwhile, at high pH, the maximum Cu(I):Cu(II) ratio was 15.11 against the 0.25 M (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> and 4.0 M NH<sub>4</sub>OH. Furthermore, the low pH experiments showed the equilibrium constant (K) K < 1, and the high pH experiments demonstrated K > 1, which justified the lower and higher copper concentrations in the solution, respectively.
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spelling doaj-art-8df58e6e7c4b491b877c9393abe987d22024-12-27T14:59:28ZengMDPI AGWaste2813-03912024-10-012439741310.3390/waste2040022Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper SolubilityZulqarnain Ahmad Ali0Joshua M. Werner1Mining Engineering Department, University of Kentucky, Lexington, KY 40506, USAMining Engineering Department, University of Kentucky, Lexington, KY 40506, USAAn investigation has been carried out to understand the solution chemistry of the Cu-NH<sup>−</sup>-SO<sub>4</sub><sup>−2</sup> system, focusing on the effect of pH on the solubility of copper in the solution and maximizing the Cu(I):Cu(II) ratio. A Pourbaix diagram for the Cu-N-S system has also been created using the HSC Chemistry software for a wide range of Cu-NH<sub>3</sub> species, unlike most other studies that focused only on Cu(NH<sub>3</sub>)<sub>4</sub><sup>2+</sup> and Cu(NH<sub>3</sub>)<sub>5</sub><sup>2+</sup> (Cu(II)) as the dominant species. The Pourbaix diagram demonstrated that the Cu(I) exists as Cu(NH<sub>3</sub>)<sub>2</sub><sup>+</sup>, while the Cu(II) species are present in the system as Cu(NH<sub>3</sub>)<sub>4</sub><sup>2+</sup> and Cu(NH<sub>3</sub>)<sub>5</sub><sup>2+</sup>, depending upon the Eh and pH of the solution. Copper precipitation was observed in the electrolyte at pH values less than 8.0, and the precipitation behavior increased as the pH became acidic. The highest Cu(I):Cu(II) ratio was observed at higher pH values of 10.05 due to the higher solubility of copper at higher alkaline pH. The maximum Cu(II) concentration can be achieved at 4.0 M NH<sub>4</sub>OH and 0.76 M (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>. In the case of low pH, the highest Cu(I):Cu(II) ratio obtained was 0.91 against the 4.0 M and 0.25 M concentrations of NH<sub>4</sub>OH and (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>, respectively. Meanwhile, at high pH, the maximum Cu(I):Cu(II) ratio was 15.11 against the 0.25 M (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> and 4.0 M NH<sub>4</sub>OH. Furthermore, the low pH experiments showed the equilibrium constant (K) K < 1, and the high pH experiments demonstrated K > 1, which justified the lower and higher copper concentrations in the solution, respectively.https://www.mdpi.com/2813-0391/2/4/22e-wastecopper-ammonium-sulfate systemCu(I):Cu(II) maximizationpHcopper solubility
spellingShingle Zulqarnain Ahmad Ali
Joshua M. Werner
Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility
Waste
e-waste
copper-ammonium-sulfate system
Cu(I):Cu(II) maximization
pH
copper solubility
title Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility
title_full Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility
title_fullStr Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility
title_full_unstemmed Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility
title_short Optimization of Copper-Ammonia-Sulfate Electrolyte for Maximizing Cu(I):Cu(II) Ratio Using pH and Copper Solubility
title_sort optimization of copper ammonia sulfate electrolyte for maximizing cu i cu ii ratio using ph and copper solubility
topic e-waste
copper-ammonium-sulfate system
Cu(I):Cu(II) maximization
pH
copper solubility
url https://www.mdpi.com/2813-0391/2/4/22
work_keys_str_mv AT zulqarnainahmadali optimizationofcopperammoniasulfateelectrolyteformaximizingcuicuiiratiousingphandcoppersolubility
AT joshuamwerner optimizationofcopperammoniasulfateelectrolyteformaximizingcuicuiiratiousingphandcoppersolubility