Despite great efforts over the past decades, thermodynamic modeling of electrolytes in mixed solvents is still a challenge today. The existing frameworks based on activity coefficient models are data‐driven and require expert knowledge to be parameterized. It has been suggested that predictive capabilities could improved through development an electrolyte equation state. In this work, Cubic Plus Association (CPA) Equation State extended handle mixtures containing by including electrostatic...

The static permittivity is the most important physical property for thermodynamic models that account electrostatic interactions between ions. measured in mixtures containing electrolytes reduced due to kinetic depolarization and reorientation of dipoles electrical field surrounding Kinetic may explain 25-75% observed decrease solutions salts, but since this a dynamic property, effect should not be included modeling electrolytes. has, however, been ignored relation modeling, authors have...

The thermodynamics of electrolyte solutions has been investigated by many scientists throughout the last century. While several theories have presented, most popular models for electrostatic interactions are based on Debye–Hückel and mean spherical approximation (MSA) theories. In this paper we investigate differences between MSA theories, comparisons numerical results Helmholtz energy its derivatives with respect to temperature, volume composition presented. investigation shows that...

In this study, we present a new equation of state for electrolyte solutions, integrating the statistical associating fluid theory variable range interactions utilizing generic Mie form and binding Debye–Hückel theories. This underscores pivotal role ion–ion association in determining properties solutions. We propose unified framework that simultaneously examines thermodynamic solutions their electrical conductivity, given profound impact ion pairing on transport property. Using state,...

This study presents a novel model to predict the electrical conductivity of multisalt electrolyte solutions by incorporating corrections ideal behavior due relaxation and electrophoretic effects. The performance is evaluated comparing its predictions with experimental data 24 aqueous solutions. comparison reveals good agreement for an ionic strength below 1 mol/L without adjusting any parameter fit data. However, tends overestimate molar at higher strengths. discrepancy attributed neglect...

An extensive comparison of SRK, CPA, and PC-SAFT for the speed sound in normal alkanes has been performed. The results reveal that captures curvature better than cubic EoS, but accuracy is not satisfactory. Two approaches have proposed to improve PC-SAFT's sound: (i) putting data into parameter estimation; (ii) both universal constants regression estimation. shown second approach can significantly (3.2%) prediction while keeping acceptable primary properties, i.e. vapor pressure (2.1%)...

The static permittivity is a key property for describing solutions containing polar and hydrogen bonding compounds. However, the precise relationship between molecular dielectric properties not well-established. Here we show that relative at zero frequency (static permittivity) can be modeled simultaneously with thermodynamic properties. calculated from an extension of framework developed by Onsager, Kirkwood, Fröhlich to associating mixtures. are cubic-plus-association (CPA) equation state...

It has been almost one century since Onsager developed the limiting law of equivalent conductivity electrolyte solutions. Thenceforth, many models have developed; however, they not assessed thoroughly and systematically. This paper comprehensively investigates accuracy reliability six models, namely, Debye–Hückel–Onsager (DHOLL), extended (DHOEE), smaller ion shell (DHOSiS), along with simplified full mean spherical approximation (MSA, MSA-Simple), Quint–Viallard (QV). To this aim, we...

A new electrical conductivity model is developed for unassociated electrolyte solutions based on the Debye-Hückel-Onsager theory. In this model, we assume that a single cation and anion with their crystallographic ionic radii are in continuum medium of solvent(s). We compare predictions experimental measurements binary 1:1, 2:1, 1:2, 2:2, 1:3, 3:1, 2:3, 3:2, 3:3, 1:4, 2:4 aqueous temperature range 273.15-373.15 K. Our results good agreement data. An extension was formulated to incorporate...

Piperazine is an amine which used both as activator or promoter, but also active component in CO2 capture solvents. High concentrations are being formulated to draw benefit of the PZ properties. This results a risk precipitation and other solid phases during capture. It could be process, it result unforeseen situations potential hazardous operation, clogging, equipment failure etc. Security process needs focus. Flow assurance requires additional attention, especially due phenomenon. entails...

The Cubic-Plus-Association (CPA) equation of state (EoS) has already been proven to be a successful model for phase equilibrium calculations systems containing glycols. In the present work, we interface thermodynamic property package (ThermoSystem), based on CPA, with Aspen HYSYS through CAPE-OPEN standards. We, then, simulate certain binary and multicomponent where experimental data are available in literature which critical process design natural gas dehydration units by triethylene glycol...

The effect of a concentration-dependent relative static permittivity (RSP) and viscosity on the predictions equivalent conductivity models is studied. full version simplified mean spherical approximation along with four Debye-Hückel-Onsager (DHO) based are used to predict nine 1:1 aqueous electrolyte solutions at 25°C. Three DHO have been developed in this study by combining electrophoretic relaxation effects that previously presented literature. To investigate RSP predictions, we three...

The Born equation is a seminal model to study the solvation process of ions in solution, devised originally for at infinite dilution. Diverse modifications have been proposed literature since publication original work by Max 1920, with varying degrees success. In this work, we analyze and discuss various equation. We verify their performance Gibbs Free Energy, Enthalpy, Entropy using data from comprehensive database 143 charges −4 +4 26 different solvents. show how radius natural consequence...

This study presents a new equation of state (EOS) for charged hard sphere fluids that incorporates ion-ion association. The EOS is developed using the Debye-Hückel (DH) theory, reference cavity approximation, and Wertheim's theory. Predictive accuracy evaluated by comparing model's predictions with Monte Carlo simulations various hard-sphere fluids. assessment focuses on mean ionic activity coefficient, individual osmotic coefficients. results demonstrate good agreement between model...

Thermodynamic stability is regularly quantified using the enthalpy of formation (ΔfH) and Gibbs free energy (ΔfG). Although knowledge these properties crucial for many applications, literature data are often missing solids. We evaluate harmonic approximation (HA) prediction ΔfH ΔfG at constant volume pressure, based on phonon calculations. Using density functional theory to carry out calculations, we show that HA excellently describes temperature-dependence 14 compounds; mean absolute error...

The performance of four implicit solvent models for associative and two non-associative electrolyte solutions has been compared analyzed the mean ionic activity coefficient (MIAC) in solution. Two these are based on a chemical approach (Fisher-Levin-Guillot-Guissani (FLGG) Ebeling-Grigo (EG)), one them is reference cavity approximation (Zhou-Yeh-Stell (ZYS)). last thermodynamic perturbation theory (Binding spherical approximation, BiMSA). Models without ion-pairing also consist hard sphere...

Abstract Crystalline solids play a fundamental role in host of materials and technologies, ranging from pharmaceuticals to renewable energy. The thermodynamic properties these are crucial determinants their stability therefore behavior. advent large density functional theory databases with has stimulated research on predictive methods for properties, especially the enthalpy formation Δ f H . Increasingly sophisticated artificial intelligence machine learning (ML) models have primarily driven...

This Response addresses critiques raised about the Binding Debye–Hückel (BiDH) theory [Naseri Boroujeni et al., J. Chem. Phys. 159, 154503 (2023)] by Simonin and Bernard [J.-P. O. Bernard, 161, 057102 (2024)]. The questioned foundational framework of (DH) theory, relevance ion pairing in primitive model fluids, accuracy BiDH compared to mean spherical approximation model. Through a systematic rebuttal, supported extensive literature review comparison with Monte Carlo simulation data, this...