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

Plyasunov, Andrey V.; Korzhinskaya, V. S.; O’Connell, John P.

doi:10.1016/j.fluid.2019.06.012

Cited by 13 publications

(4 citation statements)

References 57 publications

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“…No errors were reported in this experimental data. The experimental results for v a were taken from ref . The reported error in v a reflects errors estimated from available experimental results or correlations fitted to experimental results.…”

Section: Resultsmentioning

confidence: 99%

Temperature, Pressure, and Concentration Derivatives of Nonpolar Gas Hydration: Impact on the Heat Capacity, Temperature of Maximum Density, and Speed of Sound of Aqueous Mixtures

Ashbaugh

Bukannan

2020

J. Phys. Chem. B

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The hydrophobic effect is an umbrella term encompassing a number of solvation phenomena associated with solutions of nonpolar species in water, including the following: a meager solubility opposed by entropy at room temperature; large positive hydration heat capacities; positive shifts in the temperature of maximum density of aqueous mixtures; increases in the speed of sound of dilute aqueous mixtures; and negative volumes of association between interacting solutes. Here we present a molecular simulation study of nonpolar gas hydration over the temperature range 273.15–373.15 K and a pressure range −500 to 1000 bar to investigate the interrelationships between distinct hydrophobic phenomena. We develop a new free energy correlation for the solute chemical potentials founded on the Tait equation description of the equation-of-state of liquid water. This analytical correlation is shown to provide a quantitatively accurate description of nonpolar gas hydration over the entire range of thermodynamic state points simulated, with an error of ∼0.02 k B T or lower in the fitted chemical potentials. Our simulations and the correlation accurately reproduce many of the available experimental results for the hydration of the solutes examined here. Moreover, the correlation reproduces the characteristic entropies of hydration, temperature dependence of the hydration heat capacity, perturbations in the temperature of maximum density, and changes in the speed of sound. While negative volumes of association result from pairwise interactions in solution, beyond the limits of our simulations performed at infinite dilution, we discuss how our correlation could be supplemented with second virial coefficient information to expand to finite concentrations. In total, this work demonstrates that many distinct phenomena associated with the hydrophobic effect can be captured within a single thermodynamically consistent correlation for solute hydration free energies.

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Section: Resultsmentioning

confidence: 99%

Temperature, Pressure, and Concentration Derivatives of Nonpolar Gas Hydration: Impact on the Heat Capacity, Temperature of Maximum Density, and Speed of Sound of Aqueous Mixtures

Ashbaugh

Bukannan

2020

J. Phys. Chem. B

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“…It makes sense to reduce the problem of estimation of φ 2 ∞ to the problem of estimation of the function A 12 ∞ , defined as where V 2 ∞ is the infinite dilution partial molar volume of a solute and κ T = 1/ρ 1 * ( ∂ρ 1 * / ∂P ) T , which is the isothermal compressibility of pure solvent. The dimensionless quantity, A 12 ∞ , is linearly related to the spatial integral of the molecular solute-water direct correlation function at infinite dilution arising in Fluctuation Solution Theory. − This function was advocated by O’Connell , for use in predicting/correlating the thermodynamic properties of species in dilute solutions. ,,− Values of ϕ 2 ∞ can be calculated with an isothermal integration over density of the A 12 ∞ function , …”

Section: Methods Of Estimation Of φ2 ∞ For Aqueous Hydroxidesmentioning

confidence: 93%

“…The A 12 ∞ function is convenient for representation of the temperature and water density dependence of the thermodynamic properties of a dilute solute, as it is a smooth, continuous, and finite function at all conditions, including at the pure-solvent critical point. The temperature dependence of A 12 ∞ is understandable: it increases with temperature at low water densities and decreases at high water densities. ,, At all temperatures A 12 ∞ = 1 at ρ 1 * = 0.…”

Section: Methods Of Estimation Of φ2 ∞ For Aqueous Hydroxidesmentioning

confidence: 99%

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Predicting Solubility of Oxides of Metals and Metalloids in Supercritical Water

Plyasunov

2019

Ind. Eng. Chem. Res.

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The solubility of oxides of metals and metalloids in water can be considered as a reaction of hydration with the formation of hydroxides species, like Al(OH) 3 •H 2 O, Si(OH) 4 , B(OH) 3 , etc. Calculation of solubility requires, along with the equilibrium constant of the dissolution reaction in the ideal gas state, knowledge of the fugacity coefficients, φ 2 ∞ , for aqueous species. This work describes simple ways of estimating fugacity coefficients for such species in water of various pressures/densities, based on the stoichiometry of hydroxides or the corresponding-states correlation. The method is verified by satisfactorily predicting the solubility of quartz, SiO 2 , at 647.1−773 K, and the pressure dependence of solubility of corundum, Al 2 O 3 , at 973 K in water up to 2000 MPa. A few experimental data points, if available, may significantly improve the accuracy of the proposed method.

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High-temperature water–olivine interaction and hydrogen liberation in the subarc mantle

Zelenski

Plyasunov

Kamenetsky

et al. 2022

Contrib Mineral Petrol

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

Cited by 13 publications

References 57 publications

Temperature, Pressure, and Concentration Derivatives of Nonpolar Gas Hydration: Impact on the Heat Capacity, Temperature of Maximum Density, and Speed of Sound of Aqueous Mixtures

Temperature, Pressure, and Concentration Derivatives of Nonpolar Gas Hydration: Impact on the Heat Capacity, Temperature of Maximum Density, and Speed of Sound of Aqueous Mixtures

Predicting Solubility of Oxides of Metals and Metalloids in Supercritical Water

High-temperature water–olivine interaction and hydrogen liberation in the subarc mantle

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