Phase equilibria and thermodynamic properties of phases in the manganese methanesulfonate – methanesulfonic acid – water system: experiment and calculations

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Abstract

The cross section of the phase diagram of the Mn(CH3SO3)2–CH3SO3H–H2O system at 298.15 K is obtained by the isothermal solubility method. The Mn(CH3SO3)2∙2H2O dihydrate is shown to be in equilibrium with solutions containing from 0 to 58 wt% acid. In this ternary system, the bulk properties of solutions at 298.15 K are obtained for a number of compositions, and in its subsystem Mn(CH3SO3)2–H2O they are obtained in the temperature range 288.15 K – 323.15 K. A semi-empirical Laliberté approach is used to describe the bulk properties. The water activities in the temperature range 288.15-323.15 K are calculated by the static method using the measurement results of the saturated vapor pressure. In the Mn(CH3SO3)2–CH3SO3H–H2 system, the possibility of estimating the solubility and activity of water using only the binary parameters of the Pitzer-Simonson-Clegg model for the liquid phase and the known solubility constant at 298.15 K is checked. It is shown that only binary parameters are insufficient for adequate prediction of solubility, it is necessary to take into account at least one parameter of ternary interaction.

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E. V. Belova

M. V. Lomonosov Moscow State University

Author for correspondence.
Email: catrine2@td.chem.msu.ru

Department of Chemistry

Russian Federation, Moscow

A. S. Kapelyushnikov

M. V. Lomonosov Moscow State University

Email: catrine2@td.chem.msu.ru

Department of Chemistry

Russian Federation, Moscow

I. A. Uspenskaya

M. V. Lomonosov Moscow State University

Email: catrine2@td.chem.msu.ru

Department of Chemistry

Russian Federation, Moscow

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2. Fig. 1. Differences between the calculated and experimental densities in the Mn(CH₃SO₃)₂–H₂O system at 288.15 (▲), 298.15 (●) and 308.15 K (☆). The solid and dashed lines indicate the standard and expanded errors, respectively.

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3. Fig. 2. Isothermal (298.15 K) section of the phase diagram of the Mn(CH₃SO₃)₂–CH₃SO₃H–H₂O system in mass fraction coordinates. Phases: L – liquid, Mn2W – Mn(CH₃SO₃)₂∙2H₂O. Black dotted and red lines – calculation of the solubility of Mn(CH₃SO₃)₂∙2H₂O (this work, without and with the triple interaction parameter, respectively), black solid lines – tie lines (see Table 3), ▲ – wet residues (see Table 3), ● – composition of the saturated solution (see Table 3). Solubility in the two-component system is given according to the data of [7].

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4. Fig. 3. Water activity in solutions of the Mn(CH₃SO₃)₂–CH₃SO₃H–H₂O system at 298.15 K. Symbols ● indicate experimental data (this work), symbols ▲ indicate water activities calculated using the PSC model with binary interaction parameters from [6, 7] (a) without taking into account the ternary interaction parameters and (b) taking into account the ternary interaction parameters.

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