Interfacial Tensions, Solubilities, and Transport Properties of the H<sub>2</sub>/H<sub>2</sub>O/NaCl System: A Molecular Simulation Study

Rooijen, W. A. van; Habibi, Parsa; Xu, Ke; Dey, Poulumi; Vlugt, Thijs J. H.; Hajibeygi, Hadi; Moultos, Othonas A.

doi:10.1021/acs.jced.2c00707

Cited by 40 publications

(66 citation statements)

References 144 publications

(386 reference statements)

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“…In our recent work, we proposed the Madrid-Transport force field, , which uses a scaled charge of q = ±0.75 and that is able to reproduce transport properties, such as the viscosities and diffusion coefficients of water and ions in the whole concentration range. This force field has also been able to reproduce transport properties in the presence of hydrogen . It should be mentioned that the introduction of scaled charges improves a number of properties of electrolytes but deteriorates the value of the free energy of solvation (although it can be corrected via theoretical corrections).…”

Section: Introductionmentioning

confidence: 99%

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property

Blazquez

Abascal

Lagerweij

et al. 2023

J. Chem. Theory Comput.

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In this work, we computed electrical conductivities under ambient conditions of aqueous NaCl and KCl solutions by using the Einstein−Helfand equation. Common force fields (charge q = ±1 e) do not reproduce the experimental values of electrical conductivities, viscosities, and diffusion coefficients. Recently, we proposed the idea of using different charges to describe the potential energy surface (PES) and the dipole moment surface (DMS). In this work, we implement this concept. The equilibrium trajectories required to evaluate electrical conductivities (within linear response theory) were obtained by using scaled charges (with the value q = ±0.75 e) to describe the PES. The potential parameters were those of the Madrid-Transport force field, which accurately describe viscosities and diffusion coefficients of these ionic solutions. However, integer charges were used to compute the conductivities (thus describing the DMS). The basic idea is that although the scaled charge describes the ion−water interaction better, the integer charge reflects the value of the charge that is transported due to the electric field. The agreement obtained with experiments is excellent, as for the first time electrical conductivities (and the other transport properties) of NaCl and KCl electrolyte solutions are described with high accuracy for the whole concentration range up to their solubility limit. Finally, we propose an easy way to obtain a rough estimate of the actual electrical conductivity of the potential model under consideration using the approximate Nernst−Einstein equation, which neglects correlations between different ions.

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Section: Introductionmentioning

confidence: 99%

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property

Blazquez

Abascal

Lagerweij

et al. 2023

J. Chem. Theory Comput.

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“…Concerning phase equilibrium between air and saturated brines, no specific model has been found in the literature probably due to the lack of experimental data, although molecular simulation is more and more used as a complementary tool to experiments in this field [14]. Nevertheless, we can mention the modeling work recently proposed by Chabab et al on N 2 + brine and O 2 + brine systems with the Soreide and Whitson equation of state [15].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen and air storage in salt caverns: a thermodynamic model for phase equilibrium calculations

Kiemde

Ferrando²,

Hemptinne³

et al. 2023

STET

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When storing gas in a salt cavern, it occupies most of the excavated volume, but the lower part of the cavern inevitably contains residual brine, in contact with the gas. The design of hydrogen and compressed air storage in salt caverns requires to have a thermodynamic model able to accurately predict both phase properties such as densities, and phase equilibrium (gas solubility and water content of the vapour phase). This work proposes a parameterization of the e-PPC-SAFT equation of state in this context. Experimental data of pure components and mixtures of light gas + pure water and light gas + salted water are reviewed and used to fit pure component parameters for hydrogen, nitrogen, oxygen, and the brine, and binary interaction parameters between H2, O2, N2 + water and H2, O2, N2 + ions (Na+ and Cl−), for temperature ranging from 273 to 473 K and salinities up to NaCl saturation (6 mol/kg). The model developed delivers good accuracy in reproducing data: the average deviation between experiments and calculated data is between 3% and 9% for gas solubility in saturated brine. More interestingly, the model has been validated on its capability to predict data not included in the parameterization database, including the composition of the vapor phase, and its extension to a mixture, such as air. Finally, it has been used in a case study of Compressed Air Energy Storage (CAES) to evaluate the water content of the gas produced during injection-withdrawing cycles.

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“…This is consistent with the increase of viscosities as a function of NaB(OH) 4 molalities as the self-diffusivities of gasses and viscosities of the solution are inversely related. 40,41 As shown in Figure 6b, the self-diffusivities of H 2 have an Arrhenius relation with respect to the temperature (D Hd 2 ∝ exp[−A/T]). These findings are consistent with other simulations and experiments for gas diffusion in aqueous solutions.…”

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confidence: 97%

“…The fitting constants of eq 12 for the self-diffusivities of H 2 are listed in Table 4. This empirical correlation has also been used to model the selfdiffusivities of H 2 in aqueous NaCl solutions 40 for a wide range of temperatures (298−523 K) and concentrations (0−6 mol NaCl/kg water).…”

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confidence: 99%

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Thermodynamic and Transport Properties of H₂/H₂O/NaB(OH)₄ Mixtures Using the Delft Force Field (DFF/B(OH)₄^–)

Habibi

Postma

Padding

et al. 2023

Ind. Eng. Chem. Res.

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Sodium borohydride (NaBH4) has a high hydrogen (H2 ) gravimetric capacity of 10.7 wt %. NaBH4 releases H2 through a hydrolysis reaction in which aqueous NaB(OH)4 is formed as a byproduct. NaB(OH)4 strongly influences the thermophysical properties of aqueous solutions (i.e., densities, viscosities, and electrical conductivities) and the hydrolysis reaction kinetics and conversion of NaBH4. Here, molecular dynamics (MD) simulations are performed to compute viscosities, electrical conductivities, and self-diffusivities of H2 , Na+, and B(OH)4 – for a temperature and concentration range of 298–353 K and 0–5 mol NaB(OH)4/kg water, respectively. Continuous fractional component Monte Carlo (CFCMC) simulations are used to compute the solubilities of H2 and activities of water in aqueous NaB(OH)4 solutions for the same temperature and concentration range. A new force field is developed (Delft force field of B(OH)4 –: DFF/B(OH)4 –) in which B(OH)4 – is modeled as a tetrahedral structure with a scaled charge of −0.85. The OH group in B(OH)4 – is modeled as a single interaction site. This force field is based on TIP4P/2005 water and the Madrid-2019 Na+ force field. The MD simulations can accurately capture the densities and viscosities within 2.5% deviation from available experimental data at 298 K up to a concentration of 5 mol NaB(OH)4/kg water. The computed electrical conductivities deviate by ca. 10% from experimental data at 298 K for the same concentration range. Based on the molecular simulations results, engineering equations are developed for shear viscosities, self-diffusivities of H2, Na+, and B(OH)4 –, and solubilities of H2, which can be used to design and model NaBH4 hydrolysis reactors.

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Interfacial Tensions, Solubilities, and Transport Properties of the H₂/H₂O/NaCl System: A Molecular Simulation Study

Cited by 40 publications

References 144 publications

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property

Hydrogen and air storage in salt caverns: a thermodynamic model for phase equilibrium calculations

Thermodynamic and Transport Properties of H₂/H₂O/NaB(OH)₄ Mixtures Using the Delft Force Field (DFF/B(OH)₄^–)

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Interfacial Tensions, Solubilities, and Transport Properties of the H2/H2O/NaCl System: A Molecular Simulation Study

Cited by 40 publications

References 144 publications

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property

Hydrogen and air storage in salt caverns: a thermodynamic model for phase equilibrium calculations

Thermodynamic and Transport Properties of H2/H2O/NaB(OH)4 Mixtures Using the Delft Force Field (DFF/B(OH)4–)

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Product

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Interfacial Tensions, Solubilities, and Transport Properties of the H₂/H₂O/NaCl System: A Molecular Simulation Study

Thermodynamic and Transport Properties of H₂/H₂O/NaB(OH)₄ Mixtures Using the Delft Force Field (DFF/B(OH)₄^–)