Non-ideal Solution Research Articles

Nanoclustering in non-ideal ethanol/heptane solutions alters solvation dynamics.

Alcohol/alkane solutions widely used in chemical synthesis and as transportation fuels are highly non-ideal due to the nanoscale clustering of the amphiphilic alcohol molecules within the nonpolar alkanes. Besides impacting reactivity, such as combustion, non-ideal solutions are likely to exhibit unusual solvation dynamics on ultrafast time scales arising from the structurally heterogeneous nature of molecular-scale association. Using a convenient transition metal carbonyl vibrational probe [(C5H5)Mn(CO)3, CMT], linear absorption and nonlinear two-dimensional infrared (2D-IR) spectroscopy reveal composition-dependent solvation dynamics as reported by the frequency fluctuation correlation function in a series of ethanol/heptane solutions. Slow spectral diffusion with dilute ethanol indicates preferential solvation of the polar solute by the alcohol with a mechanism largely dominated by solvent exchange. Comparison with an ethanol/acetonitrile solution series yields no substantial preferential solvation or solvent exchange signatures in the linear or 2D-IR spectra. In ethanol/heptane solutions, increasing the ethanol concentration speeds up the solvation dynamics, which is largely consistent with a model that includes solvent exchange and single-solvent spectral diffusion. Detailed analysis of the deviation from the experimental time constants from the model's optimal parameters yields a remarkable resemblance of the concentration-weighted Kirkwood-Buff integrals for ethanol/heptane solutions. This trend indicates that solution non-ideality alters the spectral diffusion dynamics of the probe solute. Given that nanoscale clustering drives the non-ideality, these experiments reveal a dynamical consequence of nanoscale heterogeneity on the ultrafast dynamics of the solution. Refined understanding of the structural and dynamical aspects of mixed solvents will be necessary for predictive solution strategies in chemistry.

Thermodynamic assessment of evaporation during molten steel testing onboard the International Space Station

Evaporation control is a critical facility resource during solidification experiments that limits processing time and must be tracked to ensure facility health. A thermodynamic analysis was performed on a ternary FeCrNi sample processed onboard the International Space Station (ISS) using ESA Electromagnetic Levitation (EML) facility in a microgravity environment. A non-ideal solution-based mathematical model was applied for the overall sample mass loss prediction during this study. The overall sample mass loss prediction is consistent with the post-flight mass loss measurements. The species-specific findings from this study were validated using post-mission SEM-EDX surface evaluations by three different facilities. The bulk composition prediction was validated using SEM-EDX and wet chemical analysis. The non-ideal solution model was then applied to predict the composition of the dust generated during EML testing. The thicknesses of the deposited layer on the EML coil at various locations were also calculated using the geometry of the facility and results were validated with near-real-time dust layer predictions from toxicity tracking software developed by the German Space Center (DLR) Microgravity User Support Center (MUSC).

Diffusion-induced stress amplification in phase-transition materials for electrodes of lithium-ion batteries

This work sheds the light on the stress amplification in active material particles of electrodes caused by the localized lithium concentration inhomogeneity due to phase transitions. This is a significant issue usually neglected in the literature, as generally the ideal Fickian diffusion model is used to describe the lithium diffusion, which particularly fails when dealing with phase change materials, resulting in the underestimation of the stress. In turn, this results in the underestimation of the fracture behavior of the electrode and the battery degradation, ultimately.To overcome these limitations, this work proposes a mechanical-transport model where the lithium transport is modeled according to the non-ideal solution theory with an equivalent diffusion coefficient depending on the potential of the host material vs Li/Li+. The results show that the proposed model correctly describes the concentration distribution within the particle of phase-change materials (graphite is chosen as a case study), in agreement with the existent experimental measurements. The differences with respect to the traditional Fickian diffusion model is substantial as the stress is up to 85% higher with the proposed model and the concentration distribution can capture the inhomogeneity caused by phase transitions.

Separation of an azeotropic mixture through the use of organic solvent nanofiltration

Experimental data, along with theoretical modelling, are combined to explore the potential for the separation of an azeotropic polar/non-polar solvent mixture through an OSN membrane. A mixture of toluene/butanol was used for the model development, and then applied to toluene/ethanol, and toluene/heptane mixtures. Experimental data was obtained at various testing conditions to validate simulation results from a non-ideal solution diffusion transport model incorporating the Flory–Huggins ternary equations. Accounting for the effects of non-ideality in the feed and permeate solutions generated a better fit to the experimental data. The system of equations was solved using parameters obtained from mono component membrane data only. The model developed can be used as a pre screening check for the separation of a potential solvent mixture that an OSN membrane can offer prior to embarking upon an extensive experimental program.

Reaction calorimetry and structural crystal properties of non-ideal binary rhabdophane solid solutions (Ce1−xREExPO4·nH2O)

Rhabdophane is a hydrous phosphate that commonly replaces monazite as a weathering product in critical mineral deposits during the alteration of rare earth elements (REE) bearing carbonatites and alkaline igneous complexes. It is an important host to the light (L)REE (i.e., La to Gd) but the stability and structure of binary solid solutions between the Ce and the other LREE endmembers have not yet been determined experimentally. Here we present room temperature calorimetric experiments that were used to measure the enthalpy of precipitation of rhabdophane (Ce1−xREExPO4·nH2O; REE = La, Pr, Nd, Sm, Eu, and Gd). The solids were characterized using X-ray diffraction, scanning electron microscopy, Raman spectroscopy, and the role of water in the rhabdophane structure was further determined using thermogravimetric analysis coupled with differential scanning calorimetry. The calorimetric experiments indicate a non-ideal behavior for all of the binary solid solutions investigated with an excess enthalpy of mixing (ΔHex) described by a 2- to 3-term Guggenheim parameters equation. The solid solutions were categorized into three groups: 1) binary Ce-La and Ce-Pr which display positive ΔHex values with a slight asymmetry; 2) binary Ce-Nd and Ce-Sm which display negative ΔHex values with a nearly symmetric shape; 3) Ce-Eu and Ce-Gd which display both negative and positive ΔHex values with nearly symmetric shape. The excess Gibbs energy (ΔGex) of the solid solutions was further investigated using a thermodynamic analysis approach of aqueous-solid solution equilibria and the optimization programs GEMS and GEMSFITS. The resulting ΔGex values combined with the calorimetric ΔHex values indicate that there is likely an excess entropy contribution implying important short-range structural modifications in the solid solutions dependent on the deviation of the REE ionic radii from the size of Ce3+. These observations corroborate with the trends in the Raman v1 stretching bands of the PO4-site. The excess molar volumes determined from X-ray diffraction analysis further indicate an overall asymmetric behavior in all of the studied binary solid solutions, which becomes increasingly important from La to Gd. The pronounced short-range order–disorder occurring in groups 2 and 3 solid solutions mimics some of the behavior observed from previous studies in anhydrous monazite solid solutions. This study highlights the potential to use the chemistry and the structural modifications of rhabdophane as potential indicators of formation conditions in geologic systems and permits improving our modeling capabilities of REE partitioning in critical minerals systems.

РАСЧЁТ ПАРОЖИДКОСТНОГО РАВНОВЕСИЯ НА ОСНОВЕ ТЕРМОДИНАМИЧЕСКИХ МОДЕЛЕЙ КОЭФФИЦИЕНТОВ АКТИВНОСТИ

The main thermodynamic models for calculating the activity coefficients of components of non-ideal solutions are considered. The need for an accurate assessment of vapor-liquid equilibrium when modeling mass transfer processes is shown

Temperature Dependence of Membrane Permeability Parameters for Five Cell Types Using Nonideal Thermodynamic Assumptions to Mathematically Model Cryopreservation Protocols.

Cryopreservation is the process of preserving biological matter at subzero temperatures for long-term storage. During cryopreservation, cells are susceptible to various injuries that can be mitigated by controlling the cooling and warming profiles and cryoprotective agent (CPA) addition and removal procedures. Mathematical modeling of the changing cell volume at different temperatures can greatly reduce the experiments needed to optimize cryopreservation protocols. Such mathematical modeling requires as inputs the cell membrane permeabilities to water and CPA and the osmotically inactive fraction of the cell. Since the intra- and extracellular solutions are generally thermodynamically nonideal, our group has been incorporating the osmotic virial equation to model the solution thermodynamics that underlie the cell volume change equations, adding the second and third osmotic virial coefficients of the grouped intracellular solute to the cell osmotic parameters that must be measured. In our previous work, we reported methods to obtain cell osmotic parameters at room temperature by fitting experimental cell volume kinetic data with equations that incorporated nonideal solution thermodynamics assumptions. Since the relevant cell volume excursions occur at different temperatures, the temperature dependence of the osmotic parameters plays an important role. In this work, we present a new two-part fitting method to obtain five cell-type-specific parameters (water permeability, dimethyl sulfoxide permeability, osmotically inactive fraction, and the second and third osmotic virial coefficients of the intracellular solution) from experimental measurements of equilibrium cell volume and cell volume as a function of time at room temperature and 0 °C for five cell types, namely, human umbilical vein endothelial cells (HUVECs), H9c2 rat myoblasts, porcine corneal endothelial cells (PCECs), the Jurkat T-lymphocyte cell line, and human cerebral microvascular endothelial cells (hCMECs/D3 cell line). The fitting method in this work is based on both equilibrium and kinetic cell volume data, enabling us to solve some technical challenges and expand our previously reported measurement technique to 0 °C. Finally, we use the measured parameters to model the cell volume changes for a HUVEC cryopreservation protocol to demonstrate the impact of the nonideal thermodynamic assumptions on predicting the changing cell volume during freezing and thawing.

Properties of aqueous electrolyte solutions at carbon electrodes: effects of concentration and surface charge on solution structure, ion clustering and thermodynamics in the electric double layer.

Surfaces are able to control physical-chemical processes in multi-component solution systems and, as such, find application in a wide range of technological devices. Understanding the structure, dynamics and thermodynamics of non-ideal solutions at surfaces, however, is particularly challenging. Here, we use Constant Chemical Potential Molecular Dynamics (CμMD) simulations to gain insight into aqueous NaCl solutions in contact with graphite surfaces at high concentrations and under the effect of applied surface charges: conditions where mean-field theories describing interfaces cannot (typically) be reliably applied. We discover an asymmetric effect of surface charge on the electric double layer structure and resulting thermodynamic properties, which can be explained by considering the affinity of the surface for cations and anions and the cooperative adsorption of ions that occurs at higher concentrations. We characterise how the sign of the surface charge affects ion densities and water structure in the double layer and how the capacitance of the interface-a function of the electric potential drop across the double layer-is largely insensitive to the bulk solution concentration. Notably, we find that negatively charged graphite surfaces induce an increase in the size and concentration of extended liquid-like ion clusters confined to the double layer. Finally, we discuss how concentration and surface charge affect the activity coefficients of ions and water at the interface, demonstrating how electric fields in this region should be explicitly considered when characterising the thermodynamics of both solute and solvent at the solid/liquid interface.

Influence of Surfactant Structure on Polydisperse Formulations of Alkyl Ether Sulfates and Alkyl Amidopropyl Betaines.

Surfactants provide detergency, foaming, and texture in personal care formulations, yet the micellization of typical industrial primary and cosurfactants is not well understood, particularly in light of the polydisperse nature of commercial surfactants. Synergistic interactions are hypothesized to drive the formation of elongated wormlike self-assemblies in these mixed surfactant systems. Small-angle neutron scattering, rheology, and pendant drop tensiometry are used to examine surface adsorption, viscoelasticity, and self-assembly structure for wormlike micellar formulations comprising cocoamidopropyl betaine, and its two major components laurylamidopropyl betaine and oleylamidopropyl betaine, with sodium alkyl ethoxy sulfates. The tail length of sodium alkyl ethoxy sulfates was related to their ability to form wormlike micelles in electrolyte solutions, indicating that a tail length greater than 10 carbons is required to form wormlike micelles in NaCl solutions, with the decyl homologue unable to form elongated micelles and maintaining a low viscosity even at 20 wt % surfactant loading with 4 wt % NaCl present. For these systems, the incorporation of a disperse ethoxylate linker does not enable shorter chain surfactants to elongate into wormlike micelles for single-component systems; however, it could increase the interactions between surfactants in mixed surfactant systems. For synergy in surfactant mixing, the nonideal regular solution theory is used to study the sulfate/betaine mixtures. Tail mismatch appears to drive lower critical micelle concentrations, although tail matching improves synergy with larger relative reductions in critical micelle concentrations and greater micelle elongation, as seen by both tensiometric and scattering measurements.

On the Elusive Links between Solution Microstructure, Dynamics, and Solvation Thermodynamics: Demystifying the Path through a Bridge over Troubled Conjectures and Misinterpretations.

We build a fundamentally based bridge between the solute-induced microstructural perturbation of the species environment and the dynamic as well as thermodynamic responses of the fluid system, regardless of the state conditions, composition, nature of the solvent, and either the magnitude or the type of solute-solvent intermolecular-interaction asymmetries. For that purpose, we advance a fluctuation-based solvation formalism of fluid mixtures to provide meaningful descriptors of solvation phenomena, the microstructural signatures of their solute-solvent intermolecular interaction asymmetry, and the thermodynamic manifestations linked to the solution nonideality. The rigorous foundations afford us to address some crucial issues frequently invoked in the literature including the microstructural perturbation domain, its proper identification and molecular-based meaning toward the interpretation of the solvation process, and the potential impact of the local differential behavior between anions and cations on the actual salt-induced perturbation of the solvent microstructure. Indeed, we link the precisely characterized species solvation behavior to fundamental thermodynamic residual-property relations, and the dynamics associated with either the viscous flow or diffusive behavior of the solvent, to finally illustrate their outcome with experimental data of aqueous electrolyte solutions from the available literature. Ultimately, this effort provides a highly desirable unambiguous identification of the cause-effect connections between the microstructurally perturbed domains and the experimentally measured macroscopic solvation properties, including their effect on the dynamics of the solvent environment. More importantly, it lends a well-established solvation framework to bridge rigorously the microstructural details of the mixture, its dynamics, and its solvation thermodynamics to enhance our understanding of well-defined ranked Hofmeister series, i.e., by avoiding ad hoc conjectures and unsupported microscopic interpretations of solvation phenomena.

Osmotic and Gibbs–Donnan equilibrium for ions and neutral solutes

The general set of equations for the equilibrium of two solutions with a mixture of non-permeating and permeating ions and neutral solutes at each side of a permselective membrane is formulated using the principles of electroneutrality and mass conservation law for each solution, and equilibrium conditions: equality of electrochemical potentials at both sides of the membrane for each permeating solution component. There is at least one permeating neutral chemical species (solvent) in the system. The theory is in general valid for non-ideal solutions. The generalized Gibbs–Donnan (G–D) equilibrium coefficients depend on activities/fractions of all species at one side of the membrane, and charges of ions and partial molar volumes of all species. The equilibrium osmotic pressure across the membrane is also provided by the theory and can be calculated using the ratio of activities (or equivalently the G–D factor) of any permeating neutral solute (including solvent) or the ratios of activities (or equivalently the G–D factors) of any two permeating ions.

Kinetic effects during the plane-front and dendritic solidification of multicomponent alloys

A generalized model for the kinetics of a dendrite tip with a non-equilibrium interface is presented for multicomponent alloys. The model includes full coupling with thermodynamic databases to account for non-dilute non-ideal solutions, in addition to a full diffusion matrix in the liquid. The consequences of the computed non-equilibrium phase diagram boundaries on the dendrite tip kinetics are considered, and substantial deviations from existing theories are observed, especially in the case of zero solute drag. The model is applied to the rapid solidification of Inconel 718 (a nickel-based superalloy) and 316L (a stainless steel), which contain seven and five solute species, respectively. From the model, the phase diagram properties (i.e., partition coefficients and liquidus slopes) are able to be directly visualized as a function of velocity and observed to vary non-linearly and, in some cases, non-monotonically due to the combination of non-linear phase diagrams and kinetic effects. Finally, recent reports in the literature on the competition between the growth of ferrite and austenite from the melt in 316L are revisited with these new developments.

A non-ideal aim of redressing epistemic injustices in corruptive educational environments: Toward restorative epistemic justice

The most important and general aim of the education system is to edify students, epistemically speaking. However, it is a sad reality that the education system is sometimes a corruptive epistemic environment in which a variety of epistemic injustices occur. In this article, I first argue that the special character of educational institutions means that children sometimes suffer testimonial, participant, and hermeneutical betrayals as specifically educational variants of epistemic injustices. Next, I ask what our response should be to such epistemic injustices. I draw a distinction between an ‘ideal’ and a ‘non-ideal’ solution to these problems. I hold that consideration of (a) environmental bad luck and (b) children’s lack of control over their epistemic environments should lead us to favor a non-ideal solution to the problem of epistemic injustice in education. I propose that the non-ideal approach to epistemic injustice in education should focus not on the reduction or neutralization of our implicit prejudices, as has commonly been proposed in the literature, but on providing for the epistemic needs of those who suffer epistemic injustices in corruptive environments in two ways. First, we should aim to care for children who are afflicted by injustice by having their epistemic needs legitimately recognized by caring educators. Second, we should aim systemically to offer an educational curriculum for any child and teacher to develop critical imagination to care about the epistemic needs of those who are vulnerable to epistemic injustices. I conclude by explaining the acts of epistemic caring and critical imagining as parts of restorative epistemic justice that affords vulnerable children due recognition of their epistemic needs beyond merely knowing the mechanisms of implicit prejudices and the epistemic injustices associated with them.

Sorption from Solution: A Statistical Thermodynamic Fluctuation Theory.

Given an experimental solid/solution sorption isotherm, how can we gain insight into the underlying sorption mechanism on a molecular basis? Classifying sorption isotherms, for both completely and partially miscible solvent/sorbate systems, has been useful, yet the molecular foundation of these classifications remains speculative. Isotherm models, developed predominantly for solid/gas sorption, have been adapted to solid/solution isotherms, yet how their parameters should be interpreted physically has long remained ambiguous. To overcome the inconclusiveness, we establish in this paper a universal theory that can be used for interpreting and modeling solid/solution sorption. This novel theory shares the same theoretical foundation (i.e., the statistical thermodynamic fluctuation theory) not only with solid/gas sorption but also with solvation in liquid solutions and solution nonidealities. The key is the Kirkwood-Buff χ parameter, which quantifies the net self-interaction (i.e., solvent-solvent and sorbate-sorbate interactions minus solvent-sorbate interaction) via the Kirkwood-Buff integral in the same manner as the solvation theory and, unlike the Flory χ, is not limited to the lattice model. We will demonstrate that the Kirkwood-Buff χ is the key not only to isotherm classification but also to generalizing our recent statistical thermodynamic gas (vapor) isotherm, which is capable of fitting most of the solid/solution isotherm types.

Chemical short-range order in liquid Ni–Cu

Neutron diffraction in combination with isotopic substitution on the zero-scatterer 62Ni43 63Cu57 shows indications for chemical short-range order in the stable liquid as evidenced by oscillations in the concentration–concentration structure factor S CC(q). This points towards a non-ideal solution behavior of Ni–Cu contrary to common believe but in agreement with measurements of free enthalpy of mixing. The temperature dependence of S CC at small momentum transfer provides evidence of critical compositional fluctuations in Ni43Cu57 melts.

Sedimentation velocity FDS studies of antibodies in pooled human serum.

The biotech industry has great interest in investigating therapeutic proteins in high concentration environments like human serum. The fluorescence detection system (Aviv-FDS) allows the performance of analytical ultracentrifuge (AUC) sedimentation velocity (SV) experiments in tracer or BOLTS protocols. Here, we compare six pooled human serum samples by AUC SV techniques and demonstrate the potential of this technology for characterizing therapeutic antibodies in serum. Control FDS SV experiments on serum alone reveal a bilirubin-HSA complex whose sedimentation is slowed by solution nonideality and exhibits a Johnston-Ogston (JO) effect due to the presence of high concentrations of IgG. Absorbance SV experiments on diluted serum samples verify the HSA-IgG composition as well as a significant IgM pentamer boundary at 19s. Alexa-488 labeled Simponi (Golimumab) is used as a tracer to investigate the behavior of a therapeutic monoclonal antibody (mAb) in serum, and the sedimentation behavior of total IgG in serum. Serum dilution experiments allow extrapolation to zero concentration to extract so, while global direct boundary fitting with SEDANAL verifies the utility of a matrix of self- and cross-term phenomenological nonideality coefficients (ks and BM1) and the source of the JO effect. The best fits include weak reversible association (~ 4 × 103M-1) between Simponi and total human IgG. Secondary mAbs to human IgG and IgM verify the formation of a 10.2s 1:1 complex with human IgG and a 19s complex with human IgM pentamers. These results demonstrate that FDS AUC allows a range of approaches for investigating therapeutic antibodies in human serum.

Solubility of carbon dioxide in water: Some useful results for hydrate nucleation.

In this paper, the solubility of carbon dioxide (CO2) in water along the isobar of 400 bar is determined by computer simulations using the well-known TIP4P/Ice force field for water and the TraPPE model for CO2. In particular, the solubility of CO2 in water when in contact with the CO2 liquid phase and the solubility of CO2 in water when in contact with the hydrate have been determined. The solubility of CO2 in a liquid-liquid system decreases as the temperature increases. The solubility of CO2 in a hydrate-liquid system increases with temperature. The two curves intersect at a certain temperature that determines the dissociation temperature of the hydrate at 400bar (T3). We compare the predictions with T3 obtained using the direct coexistence technique in a previous work. The results of both methods agree, and we suggest 290(2)K as the value of T3 for this system using the same cutoff distance for dispersive interactions. We also propose a novel and alternative route to evaluate the change in chemical potential for the formation of hydrates along the isobar. The new approach is based on the use of the solubility curve of CO2 when the aqueous solution is in contact with the hydrate phase. It considers rigorously the non-ideality of the aqueous solution of CO2, providing reliable values for the driving force for nucleation of hydrates in good agreement with other thermodynamic routes used. It is shown that the driving force for hydrate nucleation at 400bar is larger for the methane hydrate than for the carbon dioxide hydrate when compared at the same supercooling. We have also analyzed and discussed the effect of the cutoff distance of dispersive interactions and the occupancy of CO2 on the driving force for nucleation of the hydrate.

A Multi-Criteria Decision-Making Approach for Warehouse Location Selection using TOPSIS

This research makes use of the Method for Order of Preference by Similarity to Ideal Solution, also known as the TOPSIS approach, in order to discover the most suitable site for a company's warehouse. Following the establishment of the criteria for the selection of the warehouse location, weights were allotted to each of the criteria. The min-max method was utilized to do data normalization once it had been collected for each prospective location. After constructing the decision matrix with the weighted normalized values and determining the ideal and non-ideal solutions for each criterion, the results were then presented. Following the calculation of the Euclidean distance between each potential location and the ideal and non-ideal solutions, the TOPSIS formula was used to determine the relative proximity between each of the potential locations. The site of the potential location that was the highest relative closeness to the optimum solution was chosen to be the optimal location for the warehouse. By employing this strategy, the company will be able to make an educated decision regarding the location of their warehouse, which will, in the long run, result in improved operational efficiency and cost savings.

Derivation of expressions for interdiffusion and intrinsic diffusion flux in presence of chemical potential gradient in a multicomponent system with composition dependent molar volume

Abstract It has been generally accepted and often mentioned in the text books that gradient in chemical potential of a species is the fundamental driving force for its diffusion. However, a general derivation of the interrelation between the diffusion flux of a component and chemical potential gradients in a non-ideal solution is lacking. Although there have been various studies in the literature reporting such interrelations for a binary system, they all assume constant molar volume. In a non-ideal system though molar volume changes with composition. Hence, in the present work, kinetic theory is used to derive a relation between diffusion flux and the chemical potential gradients for a multicomponent system with composition dependent molar volume. It is shown that the velocity of the marker as measured in a diffusion couple experiment should consist of the drift velocity (UN) due to change in molar volume accompanied by diffusion as well as the Kirkendall velocity caused by vacancy equilibration process. For the assumption of volume change occurring only in the direction of diffusion, the Kirkendall velocity is same as the marker velocity measured in a diffusion couple. However, if the lattice is allowed to relax in all directions, the contribution of UN to the marker velocity can be significant. This is shown to be as high as 20% for Cu in a Cu-Ni diffusion couple.

Thermodynamic modeling of aqueous lithium salt solutions with association electrolyte nonrandom two-liquid activity coefficient model

The high charge density of lithium ion and the resulting strong association phenomena make thermodynamic modeling of aqueous lithium electrolyte solutions extremely challenging. In this study, the association electrolyte nonrandom two-liquid activity coefficient model of Lin et al. (AIChE J. 2022, 68(2), e17422) is utilized to correlate and predict thermodynamic properties and solubility behavior of aqueous single electrolyte solutions of LiCl, LiBr, LiI, and LiNO3, and their mixed electrolyte solutions. Capturing self-association of water, cross-association of ion and water for hydration, and cross-association of cation and anion for ion-pairing, the association model accurately represents the literature experimental data up to saturation concentrations and at the temperature ranging from 263 K to 523 K. This study further investigated the effect of anions of the lithium salts, and re-confirmed that the order of solution non-ideality as LiI > LiBr > LiCl > LiNO3 because the anions with stronger association strengths are more likely to form ion pairs and thus lower the mean ionic activity coefficients.