Water–Zinc (Copper) Methanesulfonate Systems: Thermodynamic Properties and Phase Equilibria

Belova, Ekaterina V.; Finkelshteyn, D. I.; Maksimov, Aleksey; Uspenskaya, I. A.

doi:10.1134/s0036024419110050

Cited by 9 publications

(10 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The results obtained are in good agreement with the observation that the change in water activity with temperature in such a narrow temperature range (15–35 °C) does not exceed the measurement standard uncertainty in a binary Zn(CH 3 SO 3 ) 2 –H 2 O system, while in the ZnCl 2 – H 2 O system, the activity of the components significantly depends on the temperature …”

Section: Resultssupporting

confidence: 87%

Phase Equilibria and Thermodynamic Properties in the Zinc Chloride–Zinc Methanesulfonate–Water System

2019

View full text Add to dashboard Cite

Obtained isothermal sections of the ZnCl 2 −Zn(CH 3 SO 3 ) 2 −H 2 O phase diagram at −10.8 and 25 °C (262.35 and 298.15 K) showed the Zn(CH 3 SO 3 ) 2 •4H 2 O hydrate to be stable under 25 °C in compositions with high ZnCl 2 content. The change of the solubility of the Zn(CH 3 SO 3 ) 2 •4H 2 O is slower with temperature than that of Zn(CH 3 SO 3 ) 2 •12H 2 O both in binary and ternary mixtures. The Laliberte model parameters were obtained for Zn(CH 3 SO 3 ) 2 −H 2 O and were used to predict density in the ternary aqueous solutions. Density and water activity of the aqueous solutions containing both ZnCl 2 and Zn(CH 3 SO 3 ) 2 were measured at several temperatures. The measured values were compared with predicted densities; the deviation does not exceed 2% for all compositions.

show abstract

Section: Resultssupporting

confidence: 87%

Phase Equilibria and Thermodynamic Properties in the Zinc Chloride–Zinc Methanesulfonate–Water System

2019

View full text Add to dashboard Cite

show abstract

“…Saturated vapor pressure measurements were performed by a static method at temperatures 15 °C/288.15 K, 25 °C/298.15 K, and 35 °C/308.15 K on an original apparatus, which was described in our previous works. − Because methanesulfonic acid is not volatile, according to Clegg and Brimblecombe, as well as its salts, the total pressure above a ternary solution would be almost the same as the saturated water vapor pressure (within the uncertainty stated for the method). The temperature of a vessel during measurement was maintained with a 0.02 K precision using a liquid thermostat (Julabo F25-MC) controlled by a second Pt resistance thermometer connected to the bridge.…”

Section: Methodsmentioning

confidence: 96%

“…To solve this equation(s) (eq 4) for the isotherm crosssection calculation, scripts in the MATLAB environment based on lsqnonlin.m were used, similar to the ones in Belova et al 18 The equations were solved for the metal concentration using varying H + concentrations (for an anion, electroneutrality balance is considered), except a small part of the Zn-(CH 3 SO 3 ) 2 •12H 2 O field (in this case, the Zn 2+ mole fraction variation was used instead of the H + one). These solubility constants were taken from Belova et al, 17 except Zn(CH 3 SO 3 ) 2 •12H 2 O, which was recalculated later using the reference state as in eq 4 (and not as a melted Zn(CH 3 SO 3 ) 2 •12H 2 O solution, as reported in Belova et al 17 ).…”

Section: Chemical Analysis Of the Liquid Phase And Wetmentioning

confidence: 99%

“…Binary PSC Parameters. Binary PSC parameters were set equal to the ones at 298.15 K reported in Belova et al 17 for Zn(CH 3 SO 3 ) 2 −H 2 O and Cu(CH 3 SO 3 ) 2 −H 2 O as well as that reported in Belova et al 16 for CH 3 SO 3 H−H 2 O without further re-evaluation.…”

Section: Chemical Analysis Of the Liquid Phase And Wetmentioning

confidence: 99%

“…As for the model of choice, on the one hand, the Pitzer model is one of the most widespread models for electrolyte solutions used, e.g., in the works by Charykova et al, Vielma, Kobylin et al, and Justel et al, and there is a compatibility with systems with some other anions (e.g., sulfate in the works by Charykova et al, Vielma, Kobylin et al, and Justel et al or nitrate in the works by Filippov et al and Sadowska& Libuś), making it possible to look for mixed acid MSA leaching agents. On the other hand, the Pitzer model has a limited workability for concentrated acid solutions, whereas the Pitzer–Simonson–Clegg model allows to predict properties for up to 40 mol·kg –1 MSA solutions in water, as it was reported by Belova et al There are binary parameters for the copper and zinc methanesulfonate–water system within this framework in Belova et al, as well as for some other 3d-metal methanesulfonate–water systems in Belova et al Thus, the goal of this work was to obtain a thermodynamic model that allows us to calculate adequately VLE and SLE in Cu(CH 3 SO 3 ) 2 –CH 3 SO 3 H–H 2 O and Zn(CH 3 SO 3 ) 2 –CH 3 SO 3 H–H 2 O systems at least at 298.15 K and check solubility constants obtained previously in limiting binary water–salt systems.…”

Section: Introductionmentioning

confidence: 95%

See 2 more Smart Citations

Phase Equilibria in Water–Methanesulfonic Acid–Copper (Zinc) Methanesulfonate: Experiments and Modeling

Belova,

Kapelushnikov,

Novikov

et al. 2024

J. Chem. Eng. Data

View full text Add to dashboard Cite

An isothermal solubility method was used to obtain an isothermal cross section at 298.15 K for Cu(CH3SO3)2–CH3SO3H–H2O and Zn(CH3SO3)2–CH3SO3H–H2O systems. Up to 35 wt % of methanesulfonic acid (MSA), Cu(CH3SO3)2·4H2O is the only stable crystal hydrate in the first system. At 298.15 K, the solubility decreases from 39.1 wt % of Cu(CH3SO3)2 in pure water to 5.1 wt % of Cu(CH3SO3)2 in a solution of MSA with 39.0 wt % of CH3SO3H. In the other system, Zn(CH3SO3)2·12H2O is a stable form in solutions with less than 5.5 wt % of CH3SO3H. At a higher acid content, Zn(CH3SO3)2·4H2O precipitates, and it is a stable form in equilibrium with a liquid phase with up to 56.5 wt % of MSA. At this concentration, its solubility decreases to 5 wt %. Water vapor pressure was measured in the 288.15–308.15 K range to calculate water activity. The Pitzer–Simonson–Clegg model was used for liquid phase modeling. Ternary parameters were evaluated. As was shown, they are necessary for a correct solubility prediction, but the water vapor pressure is predicted with less difference without ternary parameters.

show abstract

Methanesulfonic Acid (MSA) in Hydrometallurgy

Binnemans

Jones

2022

J. Sustain. Metall.

View full text Add to dashboard Cite

This paper reviews the properties of methanesulfonic acid (MSA) and its potential for use in hydrometallurgy. Although MSA is much less known than sulfuric, hydrochloric or nitric acid, it has several appealing properties that makes it very attractive for the development of new circular flowsheets in hydrometallurgy. Unlike other organic acids such as acetic acid, MSA is a very strong acid (pKa = − 1.9). In addition, it is very stable against chemical oxidation and reduction, and has no tendency to hydrolyze in water. In terms of its environmental impact, MSA has low toxicity and is biodegradable. In nature, it is part of the geochemical sulfur cycle. A useful property is the high solubility of its salts in water: methanesulfonate salts have a much higher solubility in water than sulfate salts. Additionally, MSA and its salts are compatible with the electrowinning of metals because the anode reaction involves the formation of oxygen gas (unlike chlorine gas formation in chloride electrolytes) and no cathodic reduction of the anion occurs (unlike nitrate reduction in nitrate electrolytes). MSA is particularly interesting for lead hydrometallurgy, where it offers more environment-friendly alternatives to HBF4 and H2SiF6. However, MSA can also be adopted in all hydrometallurgical processes that require strong Brønsted acids. It can be used in the metallurgy of copper, zinc, cobalt, nickel, and rare earths, as well as in the recycling of metals from end-of-life products. Although MSA itself is a non-oxidizing acid, in combination with hydrogen peroxide it yields strongly oxidizing lixiviants that can leach copper from chalcopyrite or dissolve metallic silver. The global production of MSA is expected to increase rapidly in the near future thanks to both the industrialization of a new sustainable synthesis process and its many applications (cleaning fluids, electrolytes for electroplating, redox-flow batteries, catalysts in organic synthesis, and as a solvent for high-molecular-weight polymers). As a result, MSA will become more widely available and a lower price will make it an increasingly attractive option. Graphical Abstract

show abstract

Water–Zinc (Copper) Methanesulfonate Systems: Thermodynamic Properties and Phase Equilibria

Cited by 9 publications

References 13 publications

Phase Equilibria and Thermodynamic Properties in the Zinc Chloride–Zinc Methanesulfonate–Water System

Phase Equilibria and Thermodynamic Properties in the Zinc Chloride–Zinc Methanesulfonate–Water System

Phase Equilibria in Water–Methanesulfonic Acid–Copper (Zinc) Methanesulfonate: Experiments and Modeling

Methanesulfonic Acid (MSA) in Hydrometallurgy

Contact Info

Product

Resources

About