Properties Of Aqueous Solutions Research Articles

Unravelling the structural and dynamical properties of concentrated aqueous ammonium nitrate solutions: MD simulation studies

ABSTRACT In this work, we present, the concentration-dependent solvation structure and dynamics of an ammonium nitrate (AN) ion pair in aqueous media by means of classical molecular dynamics simulations. Structural properties were investigated by computing the potentials of mean force (PMFs), radial distribution functions (RDFs), cluster size distribution functions, and hydrogen bond dynamics. The change in the depth of the contact ion pair (CIP) and solvent-separated ion pair minima (SSIP) is marginal, whereas for the solvent-assisted ion pair (SAIP) is more stable at lower salt concentrations. The marginal difference in the depth of the CIP minimum of the PMF is explained based on cluster size distribution and hydrogen bonding. The solvation structure of the ions is not affected by the salt concentration. Ab-initio and classical molecular dynamics simulations (both constrained and unconstrained) give similar results for the solvation structure around the cation and the anion. The spatial density distribution functions of the anions around the cations show that the anions occupy the space around the ammonium hydrogen atoms. Profound differences in dynamical properties are found in the case of concentrated solutions as compared to dilute solutions.

Self-Consistent Implementation of a Solvation Free Energy Framework to Predict the Salt Solubilities of Six Alkali Halides.

To assess the salt solubilities of six alkali halides in aqueous systems, we proposed a thermodynamic cycle and an efficient molecular modeling methodology. The Gibbs free energy changes for vaporization, dissociation, and dissolution were calculated using the experimental data of ionic thermodynamic properties obtained from the NBS tables. Additionally, the Marcus' and Tissandier's solvation free energy data for Li+, Na+, K+, Cl-, and Br- ions were compared with the conventional solvation free energies by substituting into our self-consistent thermodynamic cycle. Furthermore, Tissandier's absolute solvation free energy data were used as the training set to refit the Lennard-Jones parameters of OPLS-AA force field for ions. To predict salt solubilities, an assumption of a pseudo-solvent was proposed to characterize the coupling work of a solute with its environment from infinitely diluted to saturated solutions, indicating that the Gibbs energy change of solvation process is a function of ionic strength. Following the self-consistency of the cycle, the newly derived formulas were used to determine the salt solubilities by interpolating the intersection of Gibbs free energy of dissolution and the zero free energy line. The refined ion parameters can also predict the structure and thermodynamic properties of aqueous electrolyte solutions, such as densities, pair correlation functions, hydration numbers, mean activity coefficients, vapor pressures, and the radial dependences of the net charge at 298.15 K and 1 bar. Our method can be used to characterize the solid-liquid equilibria of ions or charged particles in aqueous systems. Furthermore, for highly concentrated strong electrolyte systems, it is essential to introduce accurate water models and polarizable force fields.

BSA-assisted ultrasound synthesis of water stable CsPbBr3 nanocrystals for sensitive fluorescent detection of hydrogen sulfide in human serum.

A bovine serum albumin (BSA)-assisted ultrasonication strategy was developed for the synthesis of CsPbBr3 nanocrystals (NCs) with stable fluorescence properties in aqueous solution. Such a preparation method is simple, fast and does not require complex equipment. The results show that the synthesized CsPbBr3 NCs are homogeneous in particle size and have good solubility and stability in water. The CsPbBr3 NCs have been utilized as fluorescence probe for rapid detection of hydrogen sulfide (H2S) in human serum. The reaction of H2S with the lead sites on the surface of CsPbBr3 NCs produces lead sulfide (PbS), resulting in the decrease of fluorometric intensity of CsPbBr3 NCs. Our designed fluorescent assay has a linear S2- detecting range of 10 ~ 800nM with a detection limit of 7.05nM. The assay was used to determineH2S in human serum with spiked recoveries ranging from 94.98% to 102.69%. This work opens new avenues for the application of halide lead perovskite in different biosensing areas.

Physical properties of natural deep eutectic solvent and its application in remediation of heavy metal lead in soil

At present, solvent extraction is an effective method to remove heavy metals from soil, which has certain practical significance. The physical properties such as density, viscosity and conductivity of NADESs with different proportions synthesized based on the double solid components of glycolic acid (GA) and L-proline (L-PRO) and the physical properties of NADESs aqueous solution at the lowest eutectic point (3:1) were studied. The extraction effect of NADESs on soil heavy metal Pb2+ under different conditions was studied. The results showed that under the conditions of atmospheric pressure of 101.33 kPa, the lowest eutectic melting point, DESs concentration of 0.6 mol·L−1, extraction temperature of 313.15 K and extraction time of 4 h, the extraction rate of Pb2+ by NADESs was 95.28%. In addition, the internal structure of DESs was characterized by IR and NMR, which indicated that intermolecular hydrogen bonds were formed. and the interaction between DESs and Pb2+ was analyzed by quantum chemical calculation, which showed that the hydroxyl group of GA was more likely to form coordination bond with Pb2+, and chelation occurred between them. This kind of DESs provides a new idea for the removal of heavy metals in soil.

Green and facile preparation of hierarchical porous carbon with a 3D honeycomb-like structure for high-performance supercapacitors

The urgent need for sustainable energy development is contingent on pollution-free technologies, which has sparked widespread interest in exploring environmentally favorable methods employing inexpensive and abundant starting materials. In this study, 3D honeycomb-like hierarchical porous carbons were prepared using a green molten salt activation method, with renewable biomass waste cotonier catkin (CC) as the carbon source and non-toxic salt KHCO3 as the activating agent and were used as electrodes for supercapacitors. Specifically, the optimal CC-HPC-1:3 sample has a 3D honeycomb-like structure with a high specific surface area (970.5 m2 g−1) and a relatively applicable pore volume (0.54 cm3 g−1) as well as abundant multi-heteroatoms doping (nitrogen: 3.64 at. %, oxygen: up to 11.22 at. %). As anticipated, the CC-HPC-1:3 electrode exhibits intriguing electrochemical properties in aqueous solution, including an excellent specific capacitance of up to 284.5 F g−1 at 0.5 A g−1, good rate capacitive behavior (194.2 F g−1 retain at 10 A g−1) and low resistance. Notably, the assembled symmetric supercapacitors based on CC-HPC-1:3 carbon materials with a wide voltage window of 1.8 V result in a high energy density of 16.1 Wh kg−1 at 180 W kg−1 and good stability with a capacitance ratio >96 % after 10,000 cycles. Our work presented a very competitive strategy for synthesizing sustainable new green electrode materials for high-performance and low-cost energy storage devices due to the simple and environmentally friendly preparation of CC-HPC.

Effect of Recombinant Spidroins Self-Assembly on Rheological Behavior of Their Dispersions and Structure of Electrospun Nanofibrous Materials.

The effect of primary amino acid sequence in recombinant spidroins on their spatial organization is crucial for the fabrication of artificial fibers and fibrous materials. This study focuses on the rheological properties of aqueous and alcoholic solutions of recombinant analogs of natural spidroins (rS1/9 and rS2/12), as well as the structure of their films and nanofibrous materials. Non-Newtonian flow behavior of aqueous solutions of these proteins was observed at certain concentrations in contrast to their solutions in hexafluoroisopropanol. The secondary structure of recombinant spidroins was addressed by IR spectroscopy, whereas their self-organization in various solvents was studied by AFM and cryo-TEM. The influence of the solvent on the structure and properties of the films and nanofibrous materials produced by electrospinning has been established.

AIE-active dipyridinyltriphenylamine for dual-model visualization of latent fingerprints

The development of highly efficient latent fingerprints technology (LFPs) on different background remains extremely vital for forensic and criminal investigations. In this work, a pure organic molecular sensor (DPTPA1) was designed to image LFP with strong signal-to-noise ratio by optimizing the imaging technology. DPTPA1 exhibits aggregation-induced emission (AIE) properties in both aqueous solution and solid state. Two pyridine moieties and one aldehyde moiety were introduced as the end-capped units. DPTPA1 exhibits the typical solvatochromic effect whose maximum emission wavelengths red-shift from 410 nm to 540 nm with the increasing polarity of solvents. The obvious emission of DPTPA1 in the aqueous solution is observed around 500 nm (φ = 9.6%). Both cyanoacrylate glue fuming (CGF) and powder dusting (PD) methods were used to obtain the fluorescent images of LFP on glass, tinfoil, steel and plastic substrates. Among them, the CGF method can image the clear second level details of LFP on the glass and tinfoil. The PD method using DPTPA1-loaded silica gel material can obtain the high quality LFP images on the curved surface of all four substrates. This work provides a strategy for lowing the cost in the broad fields of LFPs imaging.

Critical Analysis of Published Physical Property Data for Aqueous Potassium Hydroxide. Collation into Detailed Models for Alkaline Electrolysis

Physical properties of aqueous KOH solutions are crucial to the design and operation of alkaline electrolyzers but have been scarcely and sometimes unreliably reported. Obtaining published data for various properties currently requires time-consuming searches and subsequent interpretation, interpolation, and extrapolation. This work collates and critically analyzes published data for a range of physical properties relevant to alkaline electrolysis, including the density, viscosity, conductivity, surface tension, oxygen/hydrogen solubility, oxygen/hydrogen diffusivity, and water vapor pressures of aqueous KOH solutions, as a function of temperature, KOH molarity, and pressure. Correlation functions, in the form of excel spreadsheets, have been developed to allow interpolation of the most reliable data and computation of desired quantities at specific temperatures, pressures, and KOH concentrations. Composite models incorporating these properties have been developed for automated computation of (i) diffusive gas crossover and (ii) gas production volumes, including (iii) water vapor content, and associated (iv) dissolved gas concentrations in the liquid electrolyte, as a function of KOH concentration, temperature, pressure, current density, and separator thickness and porosity. These spreadsheets are provided in the Supporting Information, as tools and reference points for researchers and practitioners in alkaline electrolysis.

Hybrid zipper-like chitosan-carboxymethyl cellulose-ferric adsorbents for tunable anion adsorption

Composite materials (CCFe and CGCFe) were prepared from carboxymethyl cellulose, chitosan, glutaraldehyde, and iron III species. The composite materials were characterized by FTIR, TGA, ICP-OES and SEM studies that provided evidence of cross-linking between chitosan and glutaraldehyde, along with variable iron doping and morphology of the composites. The equilibrium uptake study indicates that CGCFe surpassed the adsorption capacity of CCFe, where greater uptake was noted at lower versus higher temperatures (283 – 303 K). The monolayer adsorption capacity (Qm; mg g−1) of CGCFe for 2-naphthoxy acetic acid (S6) was 263 mg/g and 484 mg/g at alkaline and acidic pH conditions, according to the Sips and Langmuir isotherm models. The composite materials show limited discrimination of OSPW naphthenate components. Regeneration studies revealed that CGCFe retained 95% of its adsorption capacity after 5 cycles via a “zippering effect” in the presence of saline water. The enhanced regeneration and zipper-like structural transition of CGCFe represents a unique application of saline responsive supramolecular function driven by changes in ionic strength. This study advances the design of modular polysaccharide adsorbents according to the insight on the role of Fe (III) species, cross-linking effects, and biopolymer structure that relate to anion binding properties in aqueous solution.

Thermal hysteresis phenomena in aqueous xanthan gum solutions

The anionic hydrocolloid polysaccharide xanthan gum is widely used in the food and petroleum industries (among others) as a viscosity enhancement polymer due to its high viscosity at low concentrations and moderate temperatures. The physical properties of microbial polysaccharide xanthan gum aqueous solutions were investigated using temperature dependent viscosity measurements. Specifically, the effect of thermal history on the solution viscosity was investigated. Heating and cooling cycles were assessed in two ways, by using a “sawtooth” and “triangle” pattern, which essentially differed in the rates of cooling. The sawtooth method used a cooling rate of 2.0 °C min−1 whereas the triangle pattern had a cooling rate of 0.20 °C min−1. The sawtooth cooling rate was controlled by the speed at which the Peltier device could cool the sample, and the triangle rate was governed by the time required to measure the viscosity at each temperature on return to the initial value. Cycles measured using the sawtooth pattern for 16 mg/kg xanthan gum in water showed an 8–10% overall decrease in the viscosity over four complete cycles. Comparatively, at 320 mg/kg the xanthan gum solution showed a 25% decrease in viscosity over four cycles. The observed temperature dependent viscosity variation suggested minor modifications in the physical network structure of xanthan gum. When using a triangle heating/cooling pattern, the overall decrease in the xanthan gum solution viscosity was 5–7% for 16 mg/kg and only 10% change for 320 mg/kg solutions. The activation energy of viscous flow for the aqueous xanthan gum solutions by either method was ∼15.0 kJ/mol under all conditions. The data showed that temperature and heating cycles influence xanthan gum viscosity and thermal history, which depends more strongly on xanthan gum concentration than solution temperature.

Surface and foaming properties of an anionic CO2-switchable tail surfactant

Abstract CO2-switchable materials in general and CO2-switchable surfactants in particular are of great interest in environmental research. There is a great potential to make processes more environmentally friendly by enhancing reusability and circularity and thus reducing material costs and energy consumption by replacing common non-switchable surfactants with their switchable counterparts. Inspired by this, the present work deals with the surface and foaming properties of aqueous solutions of the novel anionic CO2-switchable tail surfactant sodium 4-(methyl(octyl)amino)butane-1-sulfonate. In the presence of N2, the unprotonated surfactant is able to stabilize foams. By switching, i.e. by protonating the CO2-responsive trialkyl amine group in the surfactants hydrocarbon chain, the amphiphilic nature of the surfactant is reduced which is indicated by an increase of the plateau surface tension and a higher CMC compared to the non-protonated surfactant. Furthermore, the ability of the protonated surfactant to stabilize foams is reduced.

Rheological properties and thickening effect of high molecular weight exopolysaccharide and intracellular polysaccharide from Schizophyllum commune

Edible and medicinal fungal polysaccharides with excellent biological activity and high viscosity are potential thickeners for food applications. In this study, the rheological properties of aqueous solutions of exopolysaccharide or fermentation broth polysaccharide (SCFP) and intracellular polysaccharide or mycelial polysaccharide (SCMP) obtained from liquid submerged fermentation of the fungus Schizophyllum commune (S. commune), and their thickening effects on coffee and fruit tea were investigated. The polysaccharide aqueous solutions behaved as pseudoplastic fluids, and their viscosity was concentration-dependent but not significantly affected by temperature (10–70 °C). The critical concentrations (c*) of SCFP and SCMP were 0.275 g/L and 0.356 g/L, respectively. The intensity of the thixotropic properties of the polysaccharide aqueous solutions was positively correlated with polysaccharide concentration. Both polysaccharide solutions exhibited solid-like viscoelastic behavior and formed weak gels, with enhanced gel strength at high concentrations and low temperatures. The viscosity at a shear rate of 50 s−1 (η50) of the 5 g/L SCFP- and SCMP-thickened coffee was 0.07 Pa·s, while that of SCFP- and SCMP-thickened fruit tea was 0.1 Pa·s and 0.08Pa·s, respectively, which were significantly higher than that of polysaccharide aqueous solutions (0.05 Pa·s for SCFP and SCMP). The yield stress values increased with increasing polysaccharide concentration, suggesting a potential role of for these polysaccharides in dysphagia management. Overall, SCFP and SCMP have significant potential for application in the food industry.

Use of Pitzer’s model to calculate thermodynamic properties of aqueous electrolyte solutions of sulfuric acid

Over this study we calculated the coefficients of activity of different species and the concentration in the presence of H+ ion when H2SO4 is alone in solution. The coefficient of average activity was calculated using the model of Pitzer. The constants of dissociation of these reactions were calculated from the values of the free standard energies. The reaction reaches a balance while producing H+, HSO4- and SO42-. The research reported here concentrated on the effect of some important operational parameters on dissolution process. The parameters were investigated and their ranges are as follows: initial molality ranging from 0.001 to 5 mol.kg-1 and temperatures between 25 and 200°C. Fortran 90 (Mathematical formula translating system) was used to perform all mathematical calculations. The numerical code can be used to calculate the molarity of ion H+ of an aqueous solution of sulfuric acid. The objective of the present work is to optimize the parameters of leaching such as activity of sulfuric acid on the dissociation phenomena.

Thermodynamic properties of aqueous lanthanum sulfate solutions taking into account the association

Thermodynamic properties (the mean activity coefficients, γ±, and the relative apparent molar enthalpies, φL) of lanthanum sulfate aqueous solutions, strongly deviating from the Debye-Hückel limiting law even at lowest experimentally accessible concentrations, can easily and quantitatively be reproduced assuming the formation of two sulfate complexes, LaSO4+ and LaSO42-, whose existence was established in numerous complex formation studies. The analysis was carried out using a simple SIT model for the activity coefficients of ions with only the electrostatic Debye-Hückel terms. Excellent agreement between measured values of γ± and φL and the values of equilibrium constants was obtained by using the following values of equilibrium constants and enthalpy changes of reactions of formation of LaSO4+ (La3++SO42-⇄ LaSO4+) and La(SO4)2- (La3++2SO42-⇄ La(SO4)2-): log10K1o = 3.65 ± 0.05; log10K2o = 5.63 ± 0.2, ΔrH1o = 17.6 ± 1.0 kJ mol−1; ΔrH20 = 28.1 ± 4.0 kJ mol−1. The agreement with literature data is excellent for log10K1o and ΔrH1o and satisfactory for log10K2o and ΔrH2o. With these log10K1o, log10K2o, ΔrH1o and ΔrH2o results the experimental γ± and φL values are reproduced quantitatively.

Physical characterization of genipin complexes coupled with multivariate data analysis to assess formed pigments

The potential of electrophoretic mobility and dynamic light scattering (DLS) was investigated to assess pigment formation in aqueous solution after the genipin reaction with different amino acids by separate. Absorbance, mobility, hydrodynamic size, polydispersity index, and conductivity of the aqueous solutions were measured after the reaction. Only complexes derived from genipin and leucine, tyrosine, arginine, lysine, and glycine developed dark blue colors. From all measured variables, complex size was correlated with their blue color intensity, and darkest blue complexes showed the highest hydrodynamic size (1073–4179 nm). Moreover, size pigments below 1 µm were obtained for all amino acids at different concentrations of genipin and amino acid, except for arginine. A partial least squares (PLS) model for size was built and exhibited a good ability to describe the distribution in blue complexes formed after the reaction of genipin and excess of amino acid (mM): (R2adj = 0.88; RMSE = 0.94). Electrophoretic mobility and DLS coupled with multivariate analysis is a useful tool as it can give reliable assessment of the physical properties of aqueous solutions of genipin pigments.

Triple Hydrophilic Statistical Terpolymers via RAFT Polymerization: Synthesis and Properties in Aqueous Solutions.

In this work, we report the synthesis of novel triple hydrophilic statistical terpolymers consisting of three different methacrylate monomers with varying degrees of responsivity to solution conditions. Terpolymers of the type poly(di(ethylene glycol) methyl ether methacrylate-co-2-(dimethylamino)ethylmethacrylate-co-oligoethylene glycol methyl ether methacrylate), P(DEGMA-co-DMAEMA-co-OEGMA), and of different compositions, were prepared by using the RAFT methodology. Their molecular characterization was carried out using size exclusion chromatography (SEC) and spectroscopic techniques, including 1H-NMR and ATR-FTIR. Studies in dilute aqueous media by dynamic and electrophoretic light scattering (DLS and ELS) show their potential responsiveness regarding changes in temperature, pH, and kosmotropic salt concentration. Finally, the change in hydrophilic/hydrophobic balance of the formed terpolymer nanoparticles during heating and cooling was studied using fluorescence spectroscopy (FS) in conjunction with pyrene giving additional information on the responsiveness and internal structure of the self-assembled nanoaggregates.

Transport of chemical species alongside magnetic pseudoplastic nanomaterial through a porous surface

Pseudoplastic fluids are non-Newtonian fluids with intriguing uses in current research and industry. Among many other extant models, the Sutterby fluid model is an essential viscoelastic fluid model that demonstrates shear thinning and shear thickening properties in high polymer aqueous solutions by manifesting viscous and elastic aspects during deformation. The magneto hydrodynamic effects of Sutterby nanofluid on porous elastic surfaces in the presence of chemical processes are examined in this theoretical study. By using similarity transformation, the mathematical model of a governed problem is converted into a collection of differential equations. A shooting strategy is used to solve these nonlinear coupled ordinary differential equations. The velocities, temperatures, and chemical species concentrations of fluids are graphically shown. Physical quantities of importance, such as local heat and mass flow, are visually represented using bar charts. Heat and mass transport, as well as chemical species concentration, decrease with Hartman number in both suction and injection. Chemical concentration of governed fluid rises for homogeneous reactions but drops for heterogeneous reactions. Temperature and concentration of fluid increases for thermophoresis parameter but decreases for Brownian motion parameter, also the effects of injection are much stronger and higher than suction.

Nature of Luminescence and Pharmacological Activity of Sulfaguanidine.

Sulfonamides are one of the oldest groups of veterinary chemotherapeutic agents. Physico-chemical properties, the concentration and the nature of the environment are the factors responsible for the distribution of sulfonamides in the living organism. Although these drug compounds have been in use for more than half a century, knowledge about their behavior is still limited. Physiological activity is currently attributed to the sulfanyl radical. Our study is devoted to the spectral properties of aqueous solutions of sulfaguanidine, in which the formation of complexes with an H-bond and a protonated form takes place. The nature of the fluorescent state of sulfaguanidine was interpreted using computational chemistry, the electronic absorption method and the luminescence method. The structure of sulfaguanidine includes several active fragments: aniline, sulfonic and guanidine. To reveal the role of fragments in the physiological activity of the studied antibiotic, we calculated and compared the effective charges of the fragments of aniline and sulfaguanidine molecules. Chromophore groups were identified in molecules, which determine the intermolecular interaction between a molecule and a proton-donor solvent. The study also revealed the impact of sulfone and guanidine groups, as well as complexation, on the effective charge of the antibiotic fragment responsible for physiological activity and luminescent ability.

Horizontally Asymmetric Nanochannels of Graphene Oxide Membranes for Efficient Osmotic Energy Harvesting.

Reverse electrodialysis (RED) directly harvests renewable energy from salinity gradients, and the achievable potential power heavily relies on the ion exchange membranes. Graphene oxides (GOs) are considered a solid candidate for the RED membrane because the laminated GO nanochannels with charged functional groups provide an excellent ionic selectivity and conductivity. Yet, a high internal resistance and poor stability in aqueous solutions limit the RED performance. Here, we develop a RED membrane that concurrently achieves high ion permeability and stable operation based on epoxy-confined GO nanochannels with asymmetric structures. The membrane is fabricated by reacting epoxy-wrapped GO membranes with ethylene diamine via vapor diffusion, overcoming the swelling properties in aqueous solutions. More importantly, the resultant membrane exhibits asymmetric GO nanochannels in terms of both channel geometry and electrostatic surface charges, leading to the rectified ion transport behavior. The demonstrated GO membrane exhibits the RED performance up to 5.32 W·m-2 with >40% energy conversion efficiency across a 50-fold salinity gradient and 20.3 W·m-2 across a 500-fold salinity gradient. Planck-Nernst continuum models coupled to molecular dynamics simulations rationalize the improved RED performance in terms of the asymmetric ionic concentration gradient within the GO nanochannel and the ionic resistance. The multiscale model also provides the design guidelines for ionic diode-type membranes configuring the optimum surface charge density and ionic diffusivity for efficient osmotic energy harvesting. The synthesized asymmetric nanochannels and their RED performance demonstrate the nanoscale tailoring of the membrane properties, establishing the potentials for 2D material-based asymmetric membranes.

High-temperature and high-pressure thermodynamic properties of aqueous zinc sulfate solutions

A new method has been proposed to estimate the osmotic and activity coefficients of aqueous electrolyte solutions under non-ambient conditions on the basis of the Pitzer ion-interaction approach using the volumetric data. Following this method, a compact set of Pitzer ion-interaction parameters, valid within the temperature range 293.15 - 373.15 K, and pressure range 0.1 - 10 MPa have been obtained for aqueous ZnSO4 solutions. These parameters helped evaluate the osmotic and activity coefficients of this system to 3.0 mol∙kg−1. The pressure dependences of osmotic and activity coefficients have also been estimated using the equations derived by Rogers and Pitzer (1982). The results obtained by the method proposed in this research agree very well with those calculated using Rogers and Pitzer approach. The advantage of the method proposed here is that it directly provides a compact set of Pitzer ion-interaction parameters required for describing the osmotic and activity coefficients, in contrast to the other method. This study also provided important insight into the ion-association behavior of aqueous ZnSO4 solution with respect to temperature and pressure. Further, the apparent molar enthalpies have been estimated using appropriate temperature derivatives of the Pitzer ion-interaction parameters obtained in this study.