Dilute Salt Solutions Research Articles

Spontaneous Production of H2O2 at the Liquid-Ice Interface: A Potential Source of Atmospheric Oxidants.

We present experimental evidence for the spontaneous production of hydrogen peroxide (H2O2) at the liquid-ice interface during the freezing of dilute salt solutions. Specifically, sample solutions containing NaCl, NaBr, NH4Cl, and NaI at concentrations between 10-6 and 10-1 M were subjected to freezing-melting cycles and then analyzed for H2O2 content. The relationship between the production rate of H2O2 and the salt concentration follows that of the Workman-Reynolds freezing potential (WRFP) values as a function of the salt concentration. Our results suggest that H2O2 is formed at the liquid-ice interface from the self-recombination of hydroxyl radicals (OH·), produced from the oxidation of hydroxide anions due to the high electric field generated at the aqueous-ice interface under the WRFP effect. Furthermore, the involvement of O2 likely acting as an electron capturer could promote to produce more OH radicals and hydroperoxyl radicals (HO2·), thus enhancing the production of H2O2 at the liquid-ice interface. Overall, this study suggests a novel mechanism of H2O2 formation in ice via its spontaneous production at the liquid-ice interface, induced by the Workman-Reynolds effect.

Hofmeister effect driven dynamic-bond cross-linked dialdehyde xylan hydrogels with rapid response and robust mechanical properties for expanding stent

The biomedical field urgently needs for programmable stent materials with nontoxic, autonomous self-healing, injectability, and suitable mechanical strength, especially self-expanding characteristics. However, such materials are still lacking. Herein, based on gelatin and dialdehyde-functionalized xylan, we synthesized 3D-printable, autonomous, self-healing, and mechanically robust hydrogels with a reversible Schiff base crosslink network. The hydrogels exhibited excellent mechanical properties and automatic healing properties at room temperature. The solid mechanical properties originate from the Schiff base, hydrogen bonding interactions, and xylan nanoparticle reinforcement of the polymer networks. As a proof of concept, the Hofmeister effect enabled the hydrogel to contract in highly concentrated salt solutions. In contrast, the same hydrogel expanded and relaxed in dilute salt solutions (quick response within 10 s), showing ionic stimulus-response and excellent shape memory characteristics, which demonstrated that the prepared hydrogel could be used as self-expanding artificial vascular stents. In particular, good biocompatibility was confirmed by cytotoxicity and compatibility tests, and ex vivo arterial experiments further indicated the feasibility of these artificial vascular scaffolds (the expansion force reached 1.51 N). Combined with its ionic stimuli-responsive shape memory ability, the strong mechanical, self-healing, 3D-printable, and biocompatibility properties make this hydrogel a promising material for artificial stents in various biomedical applications.

Neural network analysis of safe life of the oil and gas industrial structures

Purpose is to study safe life of industrial (metal) structures under long-time operation in the corrosive-active media of oil and gas wells with the help of neural network analysis. Methods. The MATLAB system (MATrix LABoratory) was selected as the tool environment for interface modelling; the system is developed by Math Works Inc. and is a high-level programming language for technical computations. Of the three existing learning paradigms, we used the “with teacher” learning process, as we believed that a neural network had correct answers (network outputs) for each input example. The coefficients were adjusted so that the network gave answers being as close as possible to the known correct answers. Findings. An artificial neural network has helped obtain a generalized diagram of the expected areas of high viscoplastic characteristics of carbon steels used to manufacture metal structures in the oil and gas industry. While applying the trained neural networks, generalized dependences of the corrosion rates of structural steels on the parameters of media with different concentrations of chlorine ions, sulphate ions, hydrogen sulphide, carbon dioxide, carbon dioxide, and oxygen ions were obtained; they were the basis to predict corrosion behaviour of steels. Originality. For the first time, the possibility of applying neural network modelling to predict local corrosion damage of structural pipe steels has been shown in terms of the “steel 20 – oxygen and chloride-containing medium” system. For the first time, the technological possibility has been demonstrated to use neural network analysis for engineering predictive assessment of corrosion activity of binary systems of simulated solutions, which are most often found under industrial conditions of the oil and gas sector of the economy. Practical implications. The proposed technology of using the neural network analysis will make it possible to expand a range of predicted values beyond experimental data, i.e. to predict the value of Vcor in very dilute or concentrated salt solutions within the acidified and neutral pH ranges. It should be noted that the error of the prediction results shown by the neural network will increase along with distancing from the scope of experimental data.

Nucleation Curves of Ice in Dilute Salt Solutions

Nucleation Curves of Ice in Dilute Salt Solutions

Interactions between γ-alumina surfaces in water and aqueous salt solutions

Particle agglomeration is relevant to numerous industrial applications and consumer products. The present work explores interactions between and agglomeration of gamma (γ)-alumina nanoparticles in pure water and dilute aqueous salt solutions. To characterize surface- and salt-specific effects, potential of mean force (PMF) profiles between γ-alumina surfaces ([110] and [100] facets) are extracted using classical molecular dynamics (MD) simulations. Supporting experiments are conducted using dynamic light scattering (DLS) to investigate agglomeration at the macroscale. The ion pairs considered are sodium chloride, ammonium acetate, barium nitrate, and barium acetate; sampling a broad range of the Hofmeister series. As particle surfaces approach contact, free-energy fluctuations of the PMF profiles reflect structural adjustments of the intervening aqueous phase. We extract values for the cohesive energy from the MD results, and parse the resultant effective pair interactions into van der Waals and electrostatic contributions. Molecular scale findings from simulations correlate with hydrodynamic radii of γ-alumina nanoparticles, obtained from DLS experiments. The results highlight the applicability of molecular simulations to identify the origins of macroscale observables.

Experimental analysis of the impact of ionic concentration and type on shale’s stability: dilute vs. concentrated salt solutions

ABSTRACT Wellbore instability in shale formations is one of the most bothersome problems leading to significant changes in shale’s petrophysical, mechanical, and chemical properties, and could cost billions of dollars annually. Drilling fluid’s ionic composition is one of the factors affecting wellbore stability. This paper investigates the impact of chemical osmosis, ionic diffusion, and diffusion osmosis on the stability of shale, identify the critical salt concentration, and examine the impact of ionic type and concentration on shale’s stability. Experimental methods include utilisation of two different shale cores (I and II), in which each core is cut into several samples, to conduct linear expansion and gravimetric measurement tests using different salt solutions (KCl, NaCl, and CaCl2) of various salt concentrations. Results show that the critical salt concentrations of shale I and II is 8 w/w%. Chemical osmosis is found to be a reliable method for water extraction out of shale if the critical salt concentration value is not surpassed. Beyond this value, ionic diffusion and diffusion osmosis in shale I and II were adversely affecting shale’s stability through swelling. The swelling and gravimetric ions and water uptake tests showed that shale is a leaky semi-permeable membrane, and that chemical osmosis could be jeopardised by ionic transport into shale. In this study, the cation type (Na+, K+, Ca+2) that makes up the salt was varied. The impact of cation type on the stability of shale was clear as the anion type was fixed. Since both cations and anions tend to diffuse into shale in the presence of a concentration gradient, it is proposed for future work to study the combined impact of cation and anion types on shale’s stability by varying the anion and cation types.

Complexes of Charged-Neutral Block Copolymers and Surfactants: Process-Dependent Features and Long-Term Stability of Their Aqueous Dispersions

Aqueous dispersions of charged-neutral block copolymers (poly(acrylamide)-b-poly(acrylate)) complexed with an oppositely charged surfactant (dodecyltrimethylammonium) have been prepared by different approaches: the simple mixing of two solutions (MS approach) containing the block copolymer and surfactant, with their respective simple counterions, and dispersion of a freeze-dried complex salt prepared in the absence of simple counterions (CS approach). The CS particles were investigated under different conditions: dispersion of a CS in salt-free water and dispersion of a CS in a dilute salt solution, the latter condition yielding dispersions with the same composition as the MS process. Additionally, aged dispersions (up to 6 months) and dispersed complexes of the polyacrylate homopolymer and dodecyltrimethylammonium surfactant were evaluated. By employing different characterization techniques, it was seen that dispersions prepared by the MS approach display nanometric spherical particles with disordered cores, and poor colloidal stability, partially caused by the absence of surface charge (ζ-potential close to zero). Oppositely, anisometric particles were formed in CS dispersions and were large enough to sustain micellar cubic cores. The CS particles presented long-time colloidal stability, partially due to a net negative surface charge, but the stability varied with the length of the neutral block composing the corona. Our results demonstrate that all dispersed particles are metastable structures, with physicochemical properties strongly dependent on the preparation procedure, thus making these particles suitable for fundamental studies and potential applications where accurate control of their properties, including size, shape, internal structure, and stability, is desired.

INFLUENCE OF SPACE CHARGE BREAKDOWN ON THE PERFORMANCE OF ELECTROMEMBRANE SYSTEMS

It is known that the existing methods of using electromembrane systems (EMS) do not allow the most efficient water treatment and water treatment at overlimiting current modes, which is why there is a need to determine the operating parameters of electrodialysis plants to prevent complex destructive effects, it is essential limiting mass transfer, and reducing the efficiency of EMS. In addition, in practice, a contradiction is found in practice - an increase in the potential jump in the existing EMS does not provide an intensification of the transfer of salt ions under overlimiting current modes. The article is devoted to the study of the influence of one of the destructive phenomena - the breakdown of the space charge on the performance of electromembrane systems in highly diluted salt solutions. The aim of this work is a theoretical assessment of the effect of space charge breakdown on the transport of salt ions in electromembrane systems. A mathematical model based on the Nernst-Planck and Poisson equations has been developed. The process of electrodialysis desalination of a NaCl solution located in a flow chamber between an anion exchange membrane (AEM) and a cation exchange membrane (CEM) is considered. The solution flow is directed from bottom to top. Numerical modeling of the effect of space charge breakdown on EMS performance in highly dilute salt solutions has been carried out. The new mathematical model and software have been developed for numerical simulation of the effect of space charge breakdown on EMS performance in highly dilute salt solutions. In this work, using a 2D mathematical model and the formula for the current-voltage characteristic of the desalination channel, the effect of space charge breakdown on the transfer of salt ions in electromembrane systems at various values of the potential jump was determined for the first time. The ranges of currents are determined, which correspond to a high and slight increase in the performance of electromembrane systems, as well as a range of currents in which there is no increase. The obtained results can be used to determine the optimal value of the potential jump according to the criterion of maximum productivity. The results obtained can be applied to the design of industrial EMC to intensify mass transfer and increase productivity.

Application of Electrolyzed Water in the Food Industry: A Review

Electrolyzed water is a novel disinfectant and cleaner that has been widely utilized in the food sector for several years to ensure that surfaces are sterilized, and that food is safe. It is produced by the electrolysis of a dilute salt solution, and the reaction products include sodium hydroxide (NaOH) and hypochlorous acid. In comparison to conventional cleaning agents, electrolyzed water is economical and eco-friendly, easy to use, and strongly effective. Electrolyzed water is also used in its acidic form, but it is non-corrosive to the human epithelium and other organic matter. The electrolyzed water can be utilized in a diverse range of foods; thus, it is an appropriate choice for synergistic microbial control in the food industry to ensure food safety and quality without damaging the organoleptic parameters of the food. The present review article highlights the latest information on the factors responsible for food spoilage and the antimicrobial potential of electrolyzed water in fresh or processed plant and animal products.

Controlling the Ion Transport Number in Solvent-in-Salt Solutions.

Solvent-in-salt (SIS) systems present promising materials for the next generation of energy storage applications. The ion dynamics is significantly different in these systems from that of ionic liquids and diluted salt solutions. In this study, we analyze the ion dynamics of two salts, Li-TFSI and Li-FSI, in highly concentrated aqueous and acetonitrile solutions. We performed high-frequency dielectric measurements covering the range of up to 50 GHz and molecular dynamics simulations. The analysis of the conductivity spectra provides the characteristic crossover time between individual charge rearrangements and the normal charge diffusion regime resulting in DC conductivity. Analysis revealed that the onset of normal charge diffusion occurs at the scale of ∼1.5-3.5 Å, comparable to the average distance between the ions. Based on the idea of momentum conservation, distinct ion correlations were estimated experimentally and computationally. The analysis revealed that cation-anion correlations can be suppressed by changing the solvent concentration in SIS systems, leading to an increase of the light ion (Li+ in our case) transport number. This discovery suggests a way for improving the light cation transport number in SIS systems by tuning the solvent concentration.

Sr2+ and Ba2+ salts induced conformational structure of sodium polyacrylate PAA investigated by molecular dynamics simulations

The shrinkage of sodium-poly(acrylate) PAA in divalent salt (strontium chloride (SrCl2) and barium chloride (BaCl2) solutions is investigated by atomistic molecular dynamics (MD) simulations to study the salt effect on PAA structure. The salt concentration (Cs) was varied in the range of 0 < Cs < 1 M for fully charged PAA. The PAA radius-of-gyration (Rg) decreases with Cs in the presence of both the divalent salts in qualitative agreement with experiments. The PAA chain stiffness calculated in persistence length (Lp) decreases over the entire range of Cs. At lower Cs, the PAA chains don't form aggregate, while at higher salt concentrations, PAA chains undergo self-association in both the divalent salts. The PAA-Water H-bonds decreases with Cs significantly in the presence of BaCl2 as compared to SrCl2. The PAA-Na+ radial distribution function (RDF) shows a decrease in its coordination number with Cs. The distribution of salt-ions around PAA shows that the Ba2+ condensation onto PAA is more significant than Sr2+ because of a greater coordination number for the former than the latter. Overall, the present study significantly advanced the molecular-level understanding of PAA microstructure in the dilute divalent metal salt solution.

Hofmeister Effect Mediated Strong PHEMA-Gelatin Hydrogel Actuator.

Hydrogels have become popular in biomedical applications, but their applications in muscle and tendon-like bioactuators have been hindered by low toughness and elastic modulus. Recently, a significant toughness enhancement of a single hydrogel network has been successfully achieved by the Hofmeister effect. However, little has been conducted for the Hofmeister effect on the hybrid hydrogels, although they have a special network structure consisting of two types of polymer components. Herein we fabricated hybrid poly(2-hydroxyethyl methacrylate) (PHEMA)-gelatin hydrogels with high mechanical performance and stimuli response. An ideal bicontinuous phase separation structure of the PHEMA (rigid) and gelatin (ductile) was observed with embedded microdisc-like gelatin in the three-dimensional polymeric network of PHEMA. A significant enhancement of mechanical performance by the Hofmeister effect was attributed to the salting-out-induced stronger and closer interphase interaction between PHEMA and gelatin. A superior comprehensive mechanical performance with fracture elongation over 650%, tensile strength of 5.2 MPa, toughness of 13.5 MJ/m3, and modulus of 45.6 MPa was achieved with the salting-out effect. More specifically, the synergy of phase separation and Hofmeister effect enable the hydrogel to contract with an enhanced modulus in high-concentration salt solutions, while the same hydrogel swells and relaxes in dilute solutions, exhibiting an ionic stimulus response and excellent shape-memory properties like those of most artificial muscle. This is manifested in highly stretched, twisted, and knotted hydrogel strips that can rapidly recover their original shape in a dilute salt solution. The high strength and modulus, ionic stimuli response, and shape memory property make the hybrid hydrogel a promising material for bioactuators in various biomedical applications.

Water Dynamics and Structure of Highly Concentrated LiCl Solutions Investigated Using Ultrafast Infrared Spectroscopy.

In highly concentrated salt solutions, the water hydrogen bond (H-bond) network is completely disrupted by the presence of ions. Water is forced to restructure as dictated by the water-ion and ion-ion interactions. Using ultrafast polarization-selective pump-probe (PSPP) spectroscopy measurements of the OD stretch of dilute HOD, we demonstrate that the limited water-water H-bonding present in concentrated lithium chloride solutions (up to four waters per ion pair) is, on average, stronger than that occurring in bulk water. Furthermore, information on the orientational dynamics and the angular restriction of water H-bonded to both water oxygens and chloride anions was obtained through analysis of the frequency-dependent anisotropy decays. It was found that, when the salt concentration increased, the water showed increasing restriction and slowing at frequencies correlated with strong H-bonding. The angular restriction of the water molecules and strengthening of water-water H-bonds are due to the formation of a water-ion network not present in bulk water and dilute salt solutions. The structural evolution of the ionic medium was also observed through spectral diffusion of the OD stretch using 2D IR spectroscopy. Compared to bulk water, there is significant slowing of the biexponential spectral diffusion dynamics. The slowest component of the spectral diffusion (13 ps) is virtually identical to the time for complete reorientation of HOD measured with the PSPP experiments. This result suggests that the slowest component of the spectral diffusion reflects rearrangement of water molecules in the water-ion network.

Effect of osmotic ballast properties on the performance of a concentration gradient battery

A concentration gradient battery (CGB) is an energy storage system comprised of a series of concentrated and dilute salt solution compartments, separated by ion exchange membranes (IEMs). The battery is charged by electrodialysis (ED), which increases the concentration gradient between these solutions, and discharged by reverse electrodialysis (RED), which allows these solutions to mix. In both ED and RED, water moves by osmosis from dilute to concentrated compartments, reducing the CGB faradaic and energy efficiency. A promising approach to mitigate osmosis is to use an osmotic ballast in the dilute solution to balance the osmotic pressure and reduce faradaic energy losses. The objective of this study was to investigate the impact of ballast properties (i.e., size, structure, end-group) on the faradaic and round-trip efficiency of the CGB. To accomplish this objective, we tested seven sugar and five glycol compounds as osmotic ballasts in a closed-loop cell. Results show that ballasts with high molecular weight generally resulted in higher faradaic efficiency and lower water transport compared with low molecular weight ballasts. Data also indicates that ballast with a cyclic structure (instead of linear), non-planar structure (instead of planar), and lower number of methyl end-groups led to lower water transport. Of all ballasts tested, sucrose performed best in terms of reducing non-ideal water transport (by 109%) and enhancing both faradaic and round-trip efficiencies (from 47.4% to 77.7% and 25.5% to 38.1%, respectively) compared with the non-ballasted CGB. Our results contribute to fundamental understanding of the impact of solute properties on water and small organic molecule transport in ion exchange membranes and indicate that ballasted CGBs can be further improved through development of optimized ballasts and selection of optimum membrane-ballast pairs. The improved understanding of ballast impact on CGB performance could be used for evaluation of potential ballast benefits in other membrane-based systems that may be impacted by osmosis such as the acid-base flow battery, waste heat recovery using RED, ED purification processes, osmotically assisted processes, and redox flow batteries.

Nucleation Curves of Ice in Dilute Salt Solutions

Nucleation Curves of Ice in Dilute Salt Solutions

Utilization of Ultrafine Gas Bubbles to Investigate the Jones-Ray Effect of Diluted Salt Solutions.

The cause of the Jones-Ray effect has been controversially debated for years. Ultrafine gas bubbles were employed to lessen the surface excess of the surface-active impurities adsorbing to the air/water interface of the salt solutions, which would lead to a direct shift in surface tension observable by the Wilhelmy plate method. It was concluded in this study that once the surface excess of the inevitable impurities in the salts is lessened by the introduction of ultrafine gas bubbles, which possess great air/water interfacial area, the Jones-Ray effect becomes nonobservable. Therefore, our finding hypothesized that the Jones-Ray effect might not originate from salts.

Preservation of Lemuru (Sardinella lemuru) by Salting and Drying Methods at Istana Muncar Ikan SMEs of Banyuwangi District

Lemuru (Sardinella lemuru)is the most catches in Banyuwangi. This fish called pelagic fish that swim on the surface of the sea. The abundance of lemuru catch makes this fish have a role and benefit for the society. However, fish is also quickly to spoil after harvesting. Without the preservation process, the fish is only suitable for consumption within a day after being caught. Various preservation methods have been carried out, one of which is salting and drying aimed to reduce the moisture content in the fish body, so that didn’t give chance for microorganism to breed and didn’t affect the fish quality. This study was used descriptive method with data collection techniques through primary data and secondary data. Data collection carried out with observation, interview, active participation and literature study. Research result in Istana Muncar Ikan Banyuwangi SMEs included raw material used in food processing in SMEs was lemuru (Sardinella lemuru) obtained from Muncar Port. The fish was treated with brining method by soaking fish of dilute salt solution of 30-35% from total weight of fish. After brining, drying process was carried out under the sun for 1 day and dried salted fish produced, has distinctive smell, salty taste, normal colour, also good shape. Salt content of 13-17% by weight of salted dried fish.

Multifunctional poly(methacrylate ester)s-based terpolymer cryogels with basic amino groups: Correlation of elasticity and structural properties with composition

Dual-responsive cryogel-structured materials open up a whole new field of bio-applications. Either dimethylaminoethyl methacrylate (DMAEMA) as a carrier of basic amino groups or glycidyl methacrylate (GMA) as a carrier of epoxy rings was introduced into hydroxypropyl methacrylate (HPMA) skeleton. pH/thermo-responsive cationic terpolymer cryogels were successfully prepared by varying the feeding DMAEMA/GMA mol percent ratio from 80/0 to 0/80. The presence of GMA imparts hydrophobic character that reduces swelling and provides additional crosslinks leading to a significant increase in the flexibility. Reducing the polymerization temperature below the freezing point of the solvent resulted in harder and non-brittle cryogels. Up to 48% reduction in hydration was observed for terpolymer cryogels containing 70 mol% DMAEMA upon increasing pH of bathing medium from 2.1 to 8.0. This trend confirmed pH-modulated swelling of amine-containing terpolymer gels, and pH-dependent transition point was found to be 7.7. Oscillating swelling/deswelling in response to pH cycles was studied. The water transport was strongly affected by incorporation of hydrophobic component GMA and protonation of amine functional groups. The swelling mechanism was shifted from anomalous to diffusion controlled with increasing GMA and overall swelling processes followed Schott second order dynamic equation. Lower equilibrium volume swelling at constant temperature was achieved by increasing GMA content of the terpolymers. In low temperature range, while DMAEMA-rich terpolymer gels were swollen, swelling decreased significantly when the gels were enriched in GMA and the temperature was raised above 55 °C. Regardless of salt type and Na+ or K+ hydrated ion radii, a significant difference was observed in salt-sensitive swelling in dilute salt solution (below about 10−3 M), which is controlled by the amount of DMAEMA in terpolymer structure. This study would provide novel ideas for the design of (meth)acrylate ester-based cationic terpolymer cryogels and elucidate the relationship between the gel matrix and their special swelling behavior.

Salt-solution-infused thin-film condenser for simultaneous anti-frost and solar-assisted atmospheric water harvesting

Frost is undesirable in many applications. Previous methods of defrosting are either energy intensive or ineffective in the long term. Meanwhile, frost is a valuable freshwater source whose production is delayed due to the solid state and lengthy accumulation of frost. Here, a salt-solution-infused thin-film condenser (SSTFC) is proposed for anti-frost at low energy consumption and simultaneous freshwater production. The SSTFC is composed of a highly permeable lower layer for salt solution infusion and an ultrathin hydrophobic top layer for constraining the infused solution and incorporating condensed vapor into the underlying solution at various low temperatures. The gradually diluted salt solution can be passively transported for regeneration and freshwater production by solar energy. The regenerated salt solution can be pumped back to the SSTFC for continuous operation of the system. Energy consumption can be saved by >50% compared to conventional methods.

Ion correlations drive charge overscreening and heterogeneous nucleation at solid–aqueous electrolyte interfaces

Classical electrical double layer (EDL) models are foundational to the representation of atomistic structure and reactivity at charged interfaces. An important limitation to these models is their dependence on a mean-field approximation that is strictly valid for dilute aqueous solutions. Theoretical efforts to overcome this limitation are severely impeded by the lack of visualization of the structure over a wide range of ion concentration. Here, we report the salinity-dependent evolution of EDL structure at negatively charged mica-water interfaces, revealing transition from the Langmuir-type charge compensation in dilute salt solutions to nonclassical charge overscreening in highly concentrated solutions. The EDL structure in this overcharging regime is characterized by the development of both lateral positional correlation between adsorbed ions and vertical layering of alternating cations and anions reminiscent of the structures of strongly correlated ionic liquids. These EDL ions can spontaneously grow into nanocrystalline nuclei of ionic compounds at threshold ion concentrations that are significantly lower than the bulk solubility limit. These results shed light on the impact of ion cooperativity that drives heterogeneous nonclassical behaviors of the EDL in high-salinity conditions.