Osmotic pressure of aqueous electrolyte solutions via molecular simulations of chemical potentials: Application to NaCl

Smith, William R.; Moučka, Filip; Nezbeda, Ivó

doi:10.1016/j.fluid.2015.05.012

Cited by 24 publications

(27 citation statements)

References 59 publications

(117 reference statements)

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“…The osmotic pressure, Π, and the vapor pressure, P * (T, P, m), of aqueous NaCl solutions are directly related to the water activity in the solution, due to the requirement for the equality of its chemical potential. W.R. Smith et al [131] determined Π from the relevant thermodynamic relations for the water chemical potential and pure water phases. Π is given by Π(T, P, m) = − RT ln a H2O (T, P, m) v H2O (T, P, m)…”

Section: Water Chemical Potential and Related Propertiesmentioning

confidence: 99%

Recent progress in molecular simulation of aqueous electrolytes: force fields, chemical potentials and solubility

Moučka²,

2016

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Although aqueous electrolytes are among the most important solutions, the molecular simulation of their intertwined properties of chemical potentials, solubility and activity coefficients has remained a challenging problem, and has attracted considerable recent interest. In this perspectives review, we focus on the simplest case of aqueous sodium chloride at ambient conditions and discuss the two main factors that have impeded progress. The first is lack of consensus with respect to the appropriate methodology for force field (FF) development. We examine how most commonly used FFs have been developed, and emphasize the importance of distinguishing between "Training Set Properties" used to fit the FF parameters, and "Test Set Properties", which are pure predictions of additional properties. The second is disagreement among solubility results obtained, even using identical FFs and thermodynamic conditions. Solubility calculations have been approached using both thermodynamic-based methods and direct molecular dynamics-based methods implementing coexisting solution and solid phases. Although convergence has been very recently achieved among results based on the former approach, there is as yet no general agreement with simulation results based on the latter methodology. We also propose a new method to directly calculate the electrolyte standard chemical potential in the Henry-Law ideality model. We conclude by making recommendations for calculating solubility, chemical potentials and activity coefficients, and outline a potential path for future progress.

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Section: Water Chemical Potential and Related Propertiesmentioning

confidence: 99%

Recent progress in molecular simulation of aqueous electrolytes: force fields, chemical potentials and solubility

Moučka²,

2016

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“…The osmotic coefficient is a measure of the nonideal behavior of the solvent in a mixed solution. The usual definition of the osmotic coefficient (ϕ) is …”

Section: Data Investigatedmentioning

confidence: 99%

Data Analysis for Electrolyte Systems: A Method Illustrated on Alkali Halides in Water

et al. 2021

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In the recent years, the need to improve the thermodynamic models, particularly making them more precise and predictable for complex systems, has increased [Industrial Requirements for Thermodynamics and Transport PropertiesHendriksE. Hendriks, E. Ind. Eng. Chem. Res.2010491113111141 Industrial Requirements for Thermodynamic and Transport PropertiesKontogeorgisG. Kontogeorgis, G. Ind. Eng. Chem. Res.20216049875013 The complexity of electrolyte systems is due to the strong interactions between ions, the hydration forces that take place during salt dissociation, and the physical forces at high concentrations of solute. Consequently, the existing thermodynamic electrolyte models show some limitations and are far from being completely optimized for industrial simulations. Thermodynamics based on electrolyte mixtures and mixed solvents requires further development and research [PolingB. E. Poling, B. E. The Properties of Gases and LiquidsMcGraw-Hill Education2001The EleTher Joint Industrial Project (JIP) aims at promoting research in this field. A practical workflow is under development where the first stage consists in analyzing the data. The present work is part of this larger scope and presents a strategy to analyze the internal and external consistency of experimental data for electrolyte mixtures. The focus is on alkali halide salts in water. Internal consistency allows testing the quality of data by confronting them to each other and using the thermodynamic relationships between these data. For that purpose, the data are confronted with a model that was initially optimized and the deviations are analyzed. For this purpose, the electrolyte non-random two-liquid (eNRTL) thermodynamic model was selected. Some deviations are attributed to the model inadequacy (high temperature or high molalities). Others are to be attributed to data inconsistencies. On the other hand, the objective of external consistency is to evaluate the consistency between different systems of the same family. The Bromley model is used for this purpose, as it contains a single adjustable parameter. Investigating the trend of this parameter with type of compound or with temperature may provide valuable information regarding the underlying physics, in addition to identifying outliers.

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“…50 In molecular simulation it is possible to compute the osmotic pressure in the LR framework using equation 5. The procedure is well described in the work of Smith et al, 11 and was tested for NaCl aqueous systems. This approach requires the use of an Osmotic .…”

Section: • 39mentioning

confidence: 99%

“…10 Results are strongly dependent on the complexity of the model as well as to the appropriate treatment of the calculations (algorithms, sampling, and convergence of the results, etc.). 11 The sampling can become quite complicated when dealing with interfacial properties, due to the long time and length scales involved and also due to the different affinities of ions at the aqueous-hydrophobic interfaces. 12 , 13 , 14 There is a huge amount of work to derive accurate force field for molecular simulations at the atomistic level (all-atom force field).…”

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Thermodynamically Consistent Force Field for Coarse-Grained Modeling of Aqueous Electrolyte Solution

Nieto‐Draghi

Rousseau

2019

J. Phys. Chem. B

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We propose a thermodynamically consistent methodology to parameterize interactions between charged particles inside the dissipative particle dynamics (DPD) formalism. We used osmotic pressure experimental data as a function of the salinity in order to optimize the interaction parameters. Results for NaCl aqueous solution show that both mean osmotic and activity coefficients of individual ions allowed the determination of Na+–water, Cl––water, and Na+–Cl– DPD repulsion parameters. A simple linear relationship between the hydration-free energies of ions and the ion–water repulsion parameters that allows the parameterization of the complete series of halide and alkaline ions is proposed. Two strategies have been used to obtain the anion–cation interaction parameters for halide and alkaline ions. In the first one, the parameters are obtained based on the numerical optimization of the anion–cation repulsion parameter with respect to the experimental osmotic pressure data (with mean average deviations <4%). Second, we propose a predictive approach based on the free-energy difference of hydration energies of anions and cations in the spirit of the law of matching water affinities [with a mean absolute relative deviation of about 13%, better than 6% if small ions (Li+ and F–) are removed].

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Osmotic pressure of aqueous electrolyte solutions via molecular simulations of chemical potentials: Application to NaCl

Cited by 24 publications

References 59 publications

Recent progress in molecular simulation of aqueous electrolytes: force fields, chemical potentials and solubility

Recent progress in molecular simulation of aqueous electrolytes: force fields, chemical potentials and solubility

Data Analysis for Electrolyte Systems: A Method Illustrated on Alkali Halides in Water

Thermodynamically Consistent Force Field for Coarse-Grained Modeling of Aqueous Electrolyte Solution

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