Binary Solutions Research Articles

Single and Binary Adsorption of Benzene, Phenol, and p‐Nitrophenol: Effect of Physical Interactions

AbstractThis work aims at emphasizing the impact of different physical interactions such as intermolecular ones between co‐adsorbed molecules on the adsorption mechanisms in the liquid phase. Thus, the adsorption of a low concentration (5 ppm) of benzene, phenol, and p‐nitrophenol from aqueous medium in single and binary mixture solutions is studied. Two activated carbons were prepared from two different activating agents and used in this regard. The adsorbed amounts are determined by high‐performance liquid chromatography. The results showed the great importance of the aforementioned interactions in the adsorption of phenol, particularly the interactions with the co‐adsorbed compounds. Indeed, phenol was remarkably better retained in binary mixture solutions than in a single one.

The effect of Al on the corrosion resistance of binary Mg-Al solid solutions: Combining in-situ electrochemistry with combinatorial thin films

The effect of varying Al concentrations on the electrochemical corrosion resistance of binary Mg-Al solid solutions thin films under alkaline immersion conditions was investigated via a combination of in-situ flow-cell, scanning vibrating electrode technique and microscopy analysis. These spatially resolving characterization techniques are employed along the Al concentration gradient of the combinatorically grown thin films enabling efficient screening of the Al concentration dependent electrochemical corrosion behaviour. The analysis revealed an increasing corrosion resistance with increasing Al concentration, as a consequence of Al induced hydroxide reinforcement. Specifically, the addition of >4 wt.% Al decreases the corrosion current density in the range of 70–90 % compared to pure Mg.

Role of oxygen vacancy in high-entropy Cu1Zn1Al0.5Ce5Zr0.5Ox for CO2 hydrogenation reaction

High-entropy oxides (HEOs) have garnered significant attention in catalysis due to their excellent redox properties and superior stability. In this study, we prepared and investigated a high-entropy oxide, Cu1Zn1Al0.5Ce5Zr0.5Ox, to elucidate the impact of oxygen vacancy density on the CO2 hydrogenation reaction. Comparisons were made with binary or ternary solid solutions composed of the same cations present in this HEO, and possessing the same phase structure. The HEO exhibits a higher surface oxygen vacancy density as evidenced by Raman spectroscopy and XPS. The increased number of oxygen vacancies significantly increases the active sites and enhances the strength for CO2 adsorption. Combined with kinetic analysis, it is suggested that the enhanced CO2 adsorption leads to improved CO2 conversion on the HEO. Moreover, the formation of oxygen vacancies facilitates H2 dissociation and supply, which is pivotal for methanol formation on the HEO. The stability of the HEO Cu1Zn1Al0.5Ce5Zr0.5Ox surpasses that of the medium entropy oxide, showing no significant deactivation after 100 hours of reaction.

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.

Surface properties, aggregation behavior and wettability of the mixed system of fluorocarbon cationic surfactant and hydrocarbon anionic surfactant in dilute solutions

Traditional perfluorooctane sulfonic acid (PFOS) fluorocarbon surfactants endangered human health and environment. Therefore, an environmentally friendly quaternary ammonium cationic fluorocarbon surfactant (PFAS-IEt) was synthesized, and surface activities, aggregation behavior, adsorption properties and wettability of PFAS-IEt/sodium n-octyl sulfate (SOS) mixtures in dilute solutions were systematically investigated. The results demonstrated that PFAS-IEt possessed excellent surface activity in aqueous solution. Surprisingly, its surface tension was only 15.33 mN/m and critical micelle concentration (CMC) was 0.002 mol/L. It could be used as a potential substitute for PFOS. In addition, PFAS-IEt had the good synergistic effect with SOS. The PTFE plate with low surface energy could be completely wetted by the binary compound solution at low concentration (0.04 mol/L) (contact angle was 0°), which was superior to the reported long chain quaternary ammonium non-ionic fluorocarbon surfactants (MN-2C9F19 and EN-2C9F19).

A Novel Microwave Sensor Based on Modified Rat-Race Coupler for Extracting Real Permittivity and Concentration of Binary Aqueous Solution

A Novel Microwave Sensor Based on Modified Rat-Race Coupler for Extracting Real Permittivity and Concentration of Binary Aqueous Solution

HSPiP, Computational, and Thermodynamic Model-Based Optimized Solvents for Subcutaneous Delivery of Tolterodine Tartrate and GastroPlus-Based In Vivo Prediction in Humans: Part I.

Tolterodine tartrate (TOTA) is associated with adverse effect, high hepatic access, varied bioavailability, slight aqueous solubility, and short half-life after oral delivery. Hansen solubility parameters (HSP, HSPiP program), experimental solubility (T = 298.2 to 318.2K and p = 0.1MPa), computational (van't Hoff and Apelblat models), and thermodynamic models were used to the select solvent(s). HSPiP predicted PEG400 as the most suitable co-solvent based on HSP values (δd = 17.88, δp = 4.0, and δh = 8.8 of PEG400) and comparable to the drug (δd = 17.6, δp = 2.4, and δh = 4.6 of TOTA). The experimental mole fraction solubility of TOTA was maximum (xe = 0.0852) in PEG400 confirming the best fit of the prediction. The observed highest solubility was attributed to the δp and δh interacting forces. The activity coefficient (ϒi) was found to be increased with temperature. The higher values of r2 (linear regression coefficient) and low RMSD (root mean square deviation) indicated a good correlation between the generated "xe" data for crystalline TOTA and the explored models (modified Apelblat and van't Hoff models). TOTA solubility in "PEG400 + water mixture" was endothermic and entropy-driven. IR (immediate release product) formulation can be tailored using 60% PEG400 in buffer solution for 2mg of TOTA in 0.25mL (dosing volume). The isotonic binary solution was associated with a pH of 7.2 suitable for sub-Q delivery. The approach would be a promising alternative with ease of delivery to children and aged patients.

Machine learning for determination of activity of water and activity coefficients of electrolytes in binary solutions

Activity of water and electrolytes in aqueous solutions is of utmost importance for multiple industrial applications. However, experimental determination of such values is time-consuming, while calculation of activity coefficients using numerical methods is challenging. By training neural networks models on literature data, one could predict activity of water and electrolytes easily, without requiring any experiment. In this paper, multiple descriptors (or features) are compared to predict activity coefficients of electrolytes and activity of water in electrolyte solutions. A neural network based on the Levenberg-Marquardt algorithm (LM-NN) showed high accuracy to calculate values, despite the small size of the training datasets. Both activity coefficients of electrolytes and activity of water in electrolyte solutions can be predicted accurately even on unseen data, using simple descriptors such as electrolyte concentration, ion sizes and charges. However, some discrepancies were observed due to the lack of representativeness of the training dataset. This could be solved by selecting training data sets that are similar (e.g. same group of the periodic table) to the unknown values, or by including available experimental data for the salt considered. The ability of the LM-NN to solve non-linear least square curve fitting problems makes it a good candidate to fit experimental activity coefficient data, with the advantage of simplicity as compared to e-NRTL or UNIQUAC methods. This method paves the way for accurate and quick determination of thermodynamic data for electrolyte solutions (and beyond) using machine learning, without necessitating large training datasets.

Experimental and simulation studies on the improvement of coal dust pollution by an aqueous solution of sodium α-alkenylsulfonate and amino acid-based surfactants

The use of surfactants is crucial for the prevention and control of coal dust pollution in coal mining operation areas, yet there still exist many challenges in the control of coal dust pollution. In this paper, the green biomass-based amino acid surfactant sodium myristoyl glutamate (SMG) and the anionic surfactant sodium α-alkenyl sulfonate (AOS) were selected to investigate the improvement of coal dust wettability by single and binary solutions from the macroscopic and microscopic perspectives. Molecular simulations were used to reveal the microscopic mechanism of the wettability of coal dust by the different solutions. Experimental measurements showed that the contact angle of the AOS + SMG aqueous solution was as low as 13.8° on a coal surface. Coating the coal dust with the AOS + SMG solution reduced the surface tension by 12.02% compared to coating the coal with a single component solution. Additionally, the use of the binary AOS + SMG solution increased the hydrophilic group content in the coating by 11.77% compared to a single component solution, and the linkage between hydrophilic groups was enhanced, which pulls the water molecules to wet the coal dust. These research results should provide a new way to promote more environmentally friendly coal dust pollution control technology.

Size effects on spinodal decomposition

Abstract We examine the influence of grains size on the stability of polycrystalline coherent binary solid solutions. By assuming that the grains are isotropic, we find that the tendency for instability decreases as the radius of the grains decrease. We also find that a temperature-dependent critical grain radius exists below which the tendency for instability vanishes and the grains are stable, with respect to infinitesimal composition fluctuations, for any initial composition. We find that the critical grain radius decreases monotonically as the temperature decrease. If the radius of the grains is smaller than the minimum critical grain radius the grains are stable for any temperature and initial composition.

Physiochemical study of 1-methyl imidazole trifluoro methane sulfonate ionic liquid in aqueous and aqueous amino acid solutions at different temperatures

The experimental density and speed of sound of 1-methyl imidazole trifluoro methane sulfonate ionic liquid in aqueous binary ([MIm][OTf]+H2O) solution and aqueous ternary ([MIm][OTf] + 0.05 mol.kg−1 aqueous glycine) solution are reported in the dilute concentration range (0.06 to 0.16 mol.kg−1) at the temperature between 288.15 and 318.15 K with 5K interval and at atmospheric pressure. These density (ρ) and speed of sound (u) data are utilized to derive various significant thermophysical parameters namely apparent molar volume of solute (Vϕ), isentropic compressibility of solution (κs) and apparent molar isentropic compressibility of solute (KS,ϕ). The limiting apparent molar volume (Vϕ0) and limiting apparent molar isentropic compressibility (KS,ϕ0) of [MIm][OTf] are estimated by extrapolation methods. By using Vϕ0and KS,ϕ0data of the studied binary and ternary systems, the values of transfer volumes i.e. volume changes due to transfer (ΔtrVϕ0)and transfer compressibility i.e. compressibility changes due to transfer(ΔtrKsϕ0) from aqueous to aqueous amino acid solution are estimated. The observed ΔtrVϕ0and ΔtrKsϕ0values are temperature dependent. The outcomes of this investigation are framed within the context of solute-solute and solute-solvent interactions.

Optimization and modelling of magnesium oxide (MgO) photocatalytic degradation of binary dyes using response surface methodology

Textile industry dye effluent contains a mixture of different kinds of dyes. Many times, photocatalysis is targeted as a solution for the treatment of dye effluent from the textile industry. Many researches have been published related to the photocatalysis of single textile dyes but in the real-world scenario, effluent is a mixture of dyes. Magnesium oxide (MgO) is used as a photocatalyst to treat a mixture (binary solution) of Methylene blue (MB) and Methylene violet (MV) along with individual MB and MV dyes in this article. MgO shows remarkable photocatalytic activity at about 93 and 88% for MB and MV dye in binary solution within 135 min. Furthermore, to study the influence of process parameters, experiments are designed with the help of the central composite design (CCD), and Response surface methodology (RSM) is used to study the interactions between parameters. For this study, five parameters are selected i.e., Photocatalyst dosage, initial concentration of both dyes, time of exposure to the light source, and pH of the binary solution. The photocatalytic process is also optimized and finally optimization of process parameters is validated with an experiment. The result of the validation experiment is very close to the predicted photocatalytic activity.

Densities, Excess Molar Volumes and Excess Refractive Indices for Binary Solutions of D2O and H2O

Densities, Excess Molar Volumes and Excess Refractive Indices for Binary Solutions of D2O and H2O

Characterizing boiling behaviors in water/ethanol binary droplet impact on a heated plate

This work experimentally investigates the transition boiling behaviors of water/ethanol binary droplets impact on a heated smooth aluminum alloy plate with a high-speed imaging system, forming a more finely defined impact behavior regime map. The dynamic Leidenfrost point temperature exhibits a non-monotonic variation trend with ethanol fraction. Binary droplets exhibit two characteristic boiling behaviors at specific temperatures (Ts) and droplet compositions (Φe), including corona boiling and prompt boiling, distinguished by the elevation of a crown-shaped thick liquid lamella and the prompt generation of numerous secondary droplets from the contact line, respectively. Both boiling behaviors are featured with the violent breakup of parent droplet into about 10 or more fragment droplets (secondary droplets with D ≥ 0.3 mm) and the short residence times on the wall, while exhibiting different splash angle distributions of satellite droplets (secondary droplets with D < 0.3 mm). Characteristic parameter analysis of the two boiling behaviors is conducted to provide qualitative mechanistic explanations. Corona boiling occurs at Φe = 25% & 50% with a lower temperature range (Ts ≤ 200 ℃), the liftoff of the liquid layer is attributed to the combined effect of decelerated wetting speed caused by evaporation and the vapor-induced lift. Prompt boiling occurs at Φe = 25% & 50% with Ts ≥ 220 °C and Φe = 75% with Ts < 200 °C, the intensity of the bubble cloud determines whether the central part of the droplet forms a jet or a liquid bulk filled with microbubbles. This work will provide some new insights into the boiling behaviors and the regulation of secondary atomization of binary solution droplets impact studies.

Employing supramolecular chemistry strategies for the separation of mixtures of anisole and bromoanisole isomers

AbstractIn the present work, host compounds trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylate (H1), trans-α,α,α’,α’-tetraphenyl-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol (H2) and trans-α,α,α’,α’-tetra(p-chlorophenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol (H3) were assessed for their host ability for anisole (ANI) and 2-, 3- and 4-bromoanisole (2-, 3- and 4-BA). It was demonstrated that H3 formed complexes with each of these guest species, while H1 and H2 only possessed the ability to enclathrate ANI. When H3 was crystallized from equimolar binary guest solutions, a significantly enhanced host affinity was observed for ANI and 3-BA. As examples, equimolar binary ANI/2-BA and 2-BA/3-BA solutions afforded complexes that demonstrated a near-complete H3 selectivity towards ANI (97.5%) and 3-BA (94.5%), respectively. Furthermore, from H3 crystallization experiments in binary ANI/2-BA, ANI/4-BA, 3-BA/2-BA and 3-BA/4-BA mixtures, where the molar guest amounts were varied sequentially, were calculated significant selectivity coefficients (K values), so much so that H3 may be used to separate very many of the guest anisole mixtures prepared in this work, through supramolecular chemistry strategies, which serves as a greener separation protocol compared with tedious and energy intensive fractional distillations. Thermal analyses were also used to investigate the relative stabilities of each of the single solvent complexes.

Theoretical and practical investigation of ion-ion association in electrolyte solutions.

In this study, we present a new equation of state for electrolyte solutions, integrating the statistical associating fluid theory for variable range interactions utilizing the generic Mie form and binding Debye-Hückel theories. This equation of state underscores the pivotal role of ion-ion association in determining the properties of electrolyte solutions. We propose a unified framework that simultaneously examines the thermodynamic properties of electrolyte solutions and their electrical conductivity, given the profound impact of ion pairing on this transport property. Using this equation of state, we predict the liquid density, mean ionic activity coefficient, and osmotic coefficient for binary NaCl, Na2SO4, and MgSO4 aqueous solutions at 298.15K. Additionally, we evaluate the molar conductivity of these systems by considering the fraction of free ions derived from our equation of state in conjunction with two advanced electrical conductivity models. Our results reveal that, while ion-ion association has a minimal influence on the modification of the predicted properties of sodium chloride solutions, their impact on sodium and magnesium sulfate solutions is considerably more noticeable.

Molecular and electrostatic origins of mixed salt partitioning phenomena in uncharged poly(ethylene oxide)-based membranes

Despite the increasing interest in membranes for water purification and resource recovery from aqueous electrolyte mixtures, few studies rigorously investigate the influence of salt solution composition (e.g., mole fraction and total salt concentration) on membrane material properties such as partition coefficients. Here, we systematically investigate the influence of solution composition on the partitioning of ionic species from binary aqueous salt solutions into crosslinked poly(ethylene glycol) diacrylate membranes at fixed ionic strength. These results are compared to partition coefficients observed for pure salt solutions. We observe large systematic deviations between the pure salt and mixed salt ion partition coefficients, indicating that the single salt partition coefficients that are often reported do not describe the more complex and realistic mixed salt scenario. Free energy calculations from molecular dynamics simulations, coupled with equilibrium thermodynamic modeling, indicate that mixed salt partitioning trends result from (i) different ions exhibiting different affinities for the membrane and (ii) the constraint of global electrical neutrality within the membrane. With this physical insight, we develop a simple approach to predicting the concentration of various ions in a membrane equilibrated with a mixed salt solution which requires no adjustable parameters.

Hydrogen bond complexation of ethanol with chlorobenzene: FTIR studies

ABSTRACT FTIR spectral studies has been carried out on ethanol (EtOH), chlorobenzene (PhCl) and their binary solutions at various EtOH/PhCl mole fractions. The bonded O − H stretching region has been deconvoluted into four Gaussian peaks centring at 3543.6, 3489.4, 3406.3 and 3254.3 cm−1. The first and the last peaks have been assigned to the hydroxyl stretching bands of dimer and tetramer, while the remaining two to the trimer bands. The presence of dimer in liquid PhCl has been confirmed by the experimental C − Cl stretching bands. Experimentally, two C − Cl stretching bands have been observed, which fall outside the 1096–1089 cm−1 range reported for chlorobenzenes in literature. The positional changes in O − H , C H 3 , C H 2 , C − H and C − Cl stretching bands in the spectrum of the solutions have been analysed in terms of heteromolecular H-bond interactions. This analysis shows that the classical O − H ⋯ Cl hydrogen bonds are the dominant interaction forces.

Guest-induced supramolecular helices and its application in L-Arg detection and L-Arg controlled reversible morphology modulation

A novel AIE supramolecular polymer (BPK) was synthesized by bis(2-hydroxy-1-naphthaldehyde) terephthalo hydrazone functionalized pillar [5]arene and cross-linked using a bis(4.4-dipyridinium salt)cross-linker via host-guest complexation. BPK exhibited strong aggregation-induced emission (AIE) in binary solutions of DMSO/H2O. BPK could be an AIE-based sensor with specific fluorescence sensing ability for L-Arg in water. The detection limit of BPK for L-Arg was 3.95 × 10−7 M, and other amino acids did not interfere with the sensing process. Moreover, in a pure DMSO solvent, BPK can self-assemble into a fibrous structure of the right-hand spiral by guest-induced supramolecular helices. At 80 % water content, BPK undergoes a morphological transformation into supramolecular polymer. Intriguingly, BPK exhibits a reversible transformation from a polymer to a nanosphere through the alternating addition of trifluoroacetic acid and arginine. Additionally, the fluorescence of BPK demonstrates an "on-off" switch. This phenomenon is attributed to the formation and disruption of intermolecular hydrogen bonds. The reversible manipulation of polymer materials' morphology and optical properties holds significant potential in biomedicine and smart materials.

Study of structuredness and hydrogen bonding in binary solutions using microwave technique

Study of structuredness and hydrogen bonding in binary solutions using microwave technique