Correlation and prediction of thermodynamic properties of dilute solutes in water up to high T and P. III. Polar and aromatic solutes H2S, C6H6, C7H8, CH3SH, SO2, HCN, acetone, NH3, CH3NH2, CH3OH, C2H5OH, phenol

Plyasunov, Andrey V.; Korzhinskaya, V. S.

doi:10.1016/j.fluid.2020.112872

Cited by 4 publications

(2 citation statements)

References 85 publications

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“…The calculated values of A 12 ∞ and φ 2 ∞ are shown in Figure for two species, Al(OH) 3 (a) and Al(OH) 3 · 2H 2 O (b), at 773 and 1573 K at various water densities. The temperature and density dependence of these functions for “hydroxides” is typical for neutral species, similar to the results for nonpolar , and polar “gaseous” species.…”

Section: Resultssupporting

confidence: 76%

Thermodynamic Modeling of Solubility of Corundum in Water at Supercritical Conditions

Plyasunov

Zyubina

2022

ACS Earth Space Chem.

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The dissolution of corundum, Al2O3, in water is considered as a set of reactions of hydration of the solid phase with the formation of various charge-neutral aqueous Al species. Methods of quantum chemistry (QC) were used to compute the thermodynamic properties of several Al forms in the ideal gas state. The combination of QC results with estimated values of fugacity coefficients of these species in water permits the evaluation of the concentrations of various Al forms over corundum and thus the calculation of the total solubility of solid Al2O3 in supercritical water. It was found that the minimum set of species dominating the Al speciation over corundum in the very wide temperature (from 647 up to 2000 K) and pressure (up to 7000 MPa) ranges consists of at least five species: Al(OH)3, its hydrates Al(OH)3 · H2O, Al(OH)3 · 2H2O, Al(OH)3 · 3H2O, and the dimer Al2(OH)6. For all species, the values of the entropies and heat capacities in the gaseous state are taken from QC computations; for two out of five forms (Al(OH)3 · H2O and Al(OH)3 · 3H2O), the enthalpies of formation at 298.15 K and 0.1 MPa were adjusted to provide agreement of experimental and calculated values of solubility of corundum; for other three species, the QC enthalpy values were accepted. The calculated values of solubility of Al2O3 in water at supercritical temperatures are in satisfactory agreement with experimental data. According to the proposed model, the solubility of corundum increases strongly with temperature. Speciation of Al changes with both the temperature and water density: on an isotherm, an increase in the water density shifts the speciation toward the prevalence of the form with a higher content of water; on an isochore, the increase in temperature leads to a quick dehydration of Al species. As a result, at low supercritical temperatures, the dominating forms are the di- and trihydrate, Al(OH)3 · 2H2O and Al(OH)3 · 3H2O, while at temperatures above 1300 K, Al(OH)3, the dimer Al2(OH)6, and the monohydrate Al(OH)3 · H2O.

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Section: Resultssupporting

confidence: 76%

Thermodynamic Modeling of Solubility of Corundum in Water at Supercritical Conditions

Plyasunov

Zyubina

2022

ACS Earth Space Chem.

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“…Calculated values of A 12 ∞ and log 10 φ 2 ∞ for the monomer (solid lines) and dimer (dashed lines) are presented in Figures and , respectively, at temperatures 673 (blues lines) and 1273 K (red lines). Similar to the behavior of A 12 ∞ for volatile compounds (like CO 2 , H 2 S, etc. ), the values of the A 12 ∞ function slightly increase with temperature at low densities of water and notably decrease with temperature at high densities of water.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamic Modeling of the Solubility of Quartz in Water up to High Temperatures and Pressures

Plyasunov

Zyubina

2021

ACS Earth Space Chem.

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Available data on speciation of silica in aqueous solutions show that the main forms of silica are the monomer Si(OH)4 and the dimer Si2O(OH)6, with shares of higher polymers growing with an increase of temperature and the total concentration of silica in solution. Thermodynamic properties of the monomer and dimer in the ideal gas state are determined from the quantum-chemical calculations. The fugacity coefficients of these species in water up to water densities of 1200 kg m–3 and temperatures of up to 1350 K are estimated from an empirical correlation based on the stoichiometry of hydroxide species. The fine-tuning of the model is made by comparing calculations with the experimental solubility and speciation data. It was found that to match the speciation results reported as the share of the monomer, it is necessary to consider polymerization of silica beyond the dimer, which can be achieved without increasing the number of fitting parameters. The resulting model reproduces well the experimental results on the solubility of quartz in water, on the distribution of silica between the vapor and liquid phases of water at subcritical temperatures, and on the speciation of silica in water in equilibrium with quartz.

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Correlation and prediction of thermodynamic properties of dilute solutes in water up to high T and P. IV. Simple fluids He, Ne, Ar, Kr, Xe, Rn, H2, N2, O2, CO, CH4 - Re-parametrization

Plyasunov

Korzhinskaya

2021

Fluid Phase Equilibria

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Correlation and prediction of thermodynamic properties of dilute solutes in water up to high T and P. III. Polar and aromatic solutes H2S, C6H6, C7H8, CH3SH, SO2, HCN, acetone, NH3, CH3NH2, CH3OH, C2H5OH, phenol

Cited by 4 publications

References 85 publications

Thermodynamic Modeling of Solubility of Corundum in Water at Supercritical Conditions

Thermodynamic Modeling of Solubility of Corundum in Water at Supercritical Conditions

Thermodynamic Modeling of the Solubility of Quartz in Water up to High Temperatures and Pressures

Correlation and prediction of thermodynamic properties of dilute solutes in water up to high T and P. IV. Simple fluids He, Ne, Ar, Kr, Xe, Rn, H2, N2, O2, CO, CH4 - Re-parametrization

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