MgCl2 Solutions Research Articles

Application of deep learning through group method of data handling for interfacial tension prediction in brine/CO2 systems: MgCl2 and CaCl2 aqueous solutions

Capillary/residual CO2 trapping is one of the main mechanisms of CO2 storage in underground formations. Therefore, it is required to estimate the brine/CO2 interfacial tension under different conditions. Although many methods have been proposed so far, the error of estimation is still high. This paper proposes a novel deep learning method to estimate the brine/CO2 interfacial tension at various temperatures, pressures, and salinities. The proposed method is a neural network with the Group Method of Data Handling (GMDH) learning method. The GMDH has the advantage of handling the structural and parametric optimization of the network automatically. The proposed method is tested on an experimental dataset of brine/CO2 interfacial tension with CalCl2 and MgCl2 salts. The results of the proposed method were compared with four of the best performing methods in the literature. The Average Absolute Percentage Error (AAPE) of the method on the training, testing and all data was 1.3 %, 2.95 %, 1.73 %, respectively, while the best method from the literature could reach an AAPE of 8.16 % on all data. Therefore, the proposed method performs far better than the existing methods. Also, a sensitivity analysis was done to determine the most influential inputs to estimate the output. The contribution of this work is to show the applicability of the GMDH method to construct more optimal data-driven models to estimate the brine/CO2 interfacial tension. Also, the utilized dataset is collected under a wide range of pressure, temperature and salinity conditions that increases the generality of the model.

Effect of Magnesium Chloride Solution as an Antifreeze Agent in Clay Stabilization during Freeze-Thaw Cycles

Freeze-thaw cycles significantly impact construction by altering soil properties and stability, which can lead to delays and increased costs. While soil-stabilizing additives are vital for addressing these issues, stabilized soils remain susceptible to volume changes and structural alterations, ultimately reducing their strength after repeated freeze-thaw cycles. This study aims to introduce a different approach by employing magnesium chloride (MgCl2) as an antifreeze and soil stabilizer additive to enhance the freeze-thaw resilience of clay soils. We investigated the efficiency of MgCl2 solutions at concentrations of 4%, 9%, and 14% on soil by conducting tests such as Atterberg limits, standard proctor compaction, unconfined compression, and freeze-thaw cycles under extreme cold conditions (−10 °C and −20 °C), alongside microstructural analysis with SEM, XRD, and FTIR. The results showed that MgCl2 reduces the soil’s liquid limit and plasticity index while enhancing its compressive strength and durability. Specifically, soil treated with a 14% MgCl2 solution maintained its volume and strength at −20 °C, with similar positive outcomes observed for samples treated with 14% and 9% MgCl2 solutions at −10 °C. This underlines MgCl2’s potential to enhance soil stability during initial stabilization and, most importantly, preserve it under cyclic freeze-thaw stresses, offering a solution to improve construction practices in cold environments.

Investigation of ionic liquid adsorption and interfacial tension reduction using different crude oils; effects of salts, ionic liquid, and pH

The results revealed the significant effect of NaCl, KCl, CaCl2, MgCl2, CaSO4, MgSO4, and Na2SO4 and pH values of 3.5–11 on the interfacial tension (IFT) reduction using three types of neutral, acidic, and basic crude oils, especially for acidic crude oil (crude oil II) as the pH was changed from 3.5 to 11 (due to saponification process). The findings showed the highest impact of pH on the IFT of crude oil II with a reducing trend, especially for the pH 11 when no salts exist. The results revealed that the salts except MgCl2 and CaCl2 led to a similar IFT variation trend for the case of distilled water/crude oil II. For the MgCl2 and CaCl2 solutions, a shifting point for IFT values was inevitable. Besides, the dissolution of 1-dodecyl-3-methyl imidazolium chloride ([C12mim][Cl]) with a concentration of 100–1000 ppm eliminates the effect of pH on IFT which leads to a reducing trend for all the examined crude oils with minimum IFT of 0.08 mN/m. Finally, the [C12mim][Cl] adsorption (under pH values) for crude oils using only Na2SO4 was measured and the minimum adsorption of 0.41 mg surfactant/g Rock under the light of saponification process was obtained.

Research on stress corrosion cracking behavior of stainless steel bellows expansion joints used in GIS equipment

This article conducts metallographic structure, martensite content, Vickers hardness, and stress corrosion performance tests on two commonly used stainless steel bellows expansion joints with different materials and geometric parameters in the power grid. The material properties and stress corrosion sensitivity of 304 and 316 stainless steel bellows are compared. The results indicate that the martensite content is highest at the peak position and lowest at the trough position in the bellows. As the curvature radius of the bellows decreases, the martensite content increases at the same position. Under the same conditions, the content of deformed martensite in 304 stainless steel is much higher than that in 316 stainless steel. After soaking in boiling MgCl2 solution for 7 days, the stress corrosion crack length of 304 stainless steel bellows is greater than that of 316 stainless steel. As the curvature radius of the ripple decreases, the crack length of 304 stainless steel bellows increases from 1.38 mm to 11.39 mm, while the crack length of 316 stainless steel bellows only increases from 0.32 mm to 7.32 mm.

Microstructural and mechanical analysis of magnesium chloride stabilization in highly plastic swelling clayey soils

In recent years, there has been an increasing interest in investigating the use of non-traditional additives for stabilizing problematic soils. As the demand for eco-friendly alternatives to cement rises, magnesium chloride, a widely used deicer and dust suppressor, has emerged as a potential choice. This study aims to provide a comprehensive understanding of the microstructural changes that occur and affect the macro behavior of treated bentonite (B) and yellow marl (YM). To achieve this, MgCl2 solution was added to the soils at 3, 6, 9, and 12 percent by dry weight of the soil, and samples were cured for 7, 14, and 28 days at 5°C, 25°C, and 35°C. The mechanical properties of the treated soils were then evaluated using the unconfined compression test, direct shear test, and pressure chamber test (SWCC), while microstructural analysis techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDAX), and Fourier transform infrared spectroscopy (FTIR) were employed to examine the mechanism of MgCl2 stabilization. The results indicate that adding MgCl2 and extending the curing period significantly increased both soils' unconfined compressive strength (UCS). However, the UCS value decreased for treated samples cured at temperatures higher than 25°C due to an incomplete cation exchange process and the reduction of apparent cohesion. A part of the gained strength from apparent cohesion and matric suction in the unsaturated samples was lost when the samples reached full saturation during the direct shear test. Changes in the particle size, pore size, and pore void distribution due to the MgCl2 stabilization affected the SWCCs of the treated soils. Microstructural analyses revealed the formation of magnesium hydration products, such as magnesium silicate hydrate (M-S-H) and magnesium aluminate hydrate (M-A-H), which contributed to the strength increase by increasing grain size, filling the pores, binding fine particles within coarse grains, and forming a flocculated structure through recrystallization of MgCl2 and the formation of cementitious gel. Additionally, for B, adding MgCl2 led to soil flocculation through ion exchange, while for YM, the same process occurred due to the greater surface tension of the saline solution encircling the particles.

Impact of MgCl2 on the mechanical properties of alite pastes at mesoscale and nanoscale

AbstractWhile the MgCl2 mixing alite paste causes degradation of the modulus and hardness of C–S–H formed, the underlying degradation mechanism needs to be better understood. This study comprehensively analyzed the mechanical properties of alite pastes mixed with MgCl2 solutions, examining the effects at both mesoscale and nanoscale. The in situ X‐ray diffraction analysis revealed that the formation of brucite occurred at a very early age together with the formation of portlandite, which may induce a loosened packing density of C−S−H and served as the primary cause of modulus and hardness degradation. We used Bayesian statistical models to fit the nanoindentation data of C−S−H. By extrapolation at a packing fraction equal to unity, we were able to extract elastic properties (modulus and hardness) of the C−S−H nanograins. The nanoscale C−S−H elastic modulus showed no significant alterations in the mechanical properties of the C−S−H nanostructures. Atomistic simulations also suggested that Mg2+ ions preferably substitute interlayer Ca rather than intralayer Ca in C−S−H, and the Mg docking in CSH induced a very modest volume contraction.

Probing molecular interactions of an anti-epileptic drug, sodium valproate in aqueous MgCl2 solutions

Study of the physicochemical properties of anti-epileptic drugs in the presence of cosolutes in aqueous solutions has been a subject of interest of researchers because of their interaction with biological membranes to employ their effect. Such properties provide complete information regarding solute-solute and solute-solvent type interactions. As electrolytes are essential components of biological systems, therefore the study of drug-electrolyte chemistry is important to understand the mechanism of drug action at the molecular level and hence useful in drug design and development processes. Therefore, in the current report, the density and sound velocity of an anti-epileptic drug sodium valproate (SV) in aqueous and in aqueous solutions of an electrolyte viz. MgCl2 (mB = 0.024, 0.047, 0.070 mol kg−1) at different temperatures (288.15, 298.15, 308.15, and 318.15 K) and at a pressure of 0.101 MPa were measured along with 1H NMR spectroscopy. Various volumetric and acoustical parameters such as apparent molar volume (Vφ) and isentropic compressibility (Kφ) of the solute, apparent molar volume (Vφ°) and isentropic compressibility (Kφ°) of solute at infinite dilution, apparent molar expansibility (Eφ°) and their double derivatives (∂2Vφ°/∂T2)P, transfer volumes (∆trVφ°), hydration number (nH), acoustic impedance (Z), intermolecular free length (Lf), Wada's constant (W) and Rao's constant (R) were calculated from density and sound velocity data. The variation in all these parameters with cosolute concentration indicates the existence of hydrophilic/ionic-ionic interactions at lower concentrations but hydrophobic-ionic interactions at higher concentrations of MgCl2. The 1H NMR spectroscopic results also support the existence of hydrophobic-ionic interactions at higher concentrations of MgCl2. The decrease in electrostriction but increase in hydrophobic hydration of solute molecules has also been seen with rise in temperature.

Hydrolysis behavior and mechanistic insights of CaMg2InX (X = 0.1, 0.3, 0.5, 0.7) ternary alloy for sustainable hydrogen production

The hydrolysis behavior of CaMg2In0.1, CaMg2In0.3, CaMg2In0.5, and CaMg2In0.7 ternary alloys in an MgCl2 solution following casting and hydrogenation were investigated. The hydrolysis mechanism of these alloys is elucidated through an analysis of microstructure, phase composition, and kinetics before and after hydrolysis. The nucleation-growth Avrami model is employed to accurately model the hydrolysis kinetics, revealing improved hydrolysis yields and reaction rates following hydrogenation. Notably, CaMg2In0.1 has demonstrated exceptional hydrolysis characteristics, exhibiting a yield of 1140 mL/g, an initial hydrolysis rate of 113 mL/g·s, and an activation energy of 24.3 ± 1.7 kJ·mol−1. The yield of H-CaMg2In0.1 further escalates to 1800 mL/g with a rate of 221 mL/g·s, attributed to the formation of Ca4Mg3H14 and In phases subsequent to the hydrogenation of In2Ca and Mg3In phases in the alloy. These newly formed phases act as catalysts and actively participate in the hydrolysis process, providing active sites for hydrogen production, thus enhancing hydrolysis yields and kinetics. It is observed that with increasing In content, the order of hydrolysis performance of the alloy is as follows: CaMg2In0.1 > CaMg2In0.3 > CaMg2In0.5 > CaMg2In0.7, consistent with the trend after hydrogenation. These findings indicate that the addition of In significantly enhances the hydrolysis performance of CaMg2 alloys, offering a promising strategy for preparing magnesium-based alloys with high yields and favorable kinetic properties.

Reexpansion of charged nanoparticle assemblies in concentrated electrolytes

Electrostatic forces in solutions are highly relevant to a variety of fields, ranging from electrochemical energy storage to biology. However, their manifestation in concentrated electrolytes is not fully understood, as exemplified by counterintuitive observations of colloidal stability and long-ranged repulsions in molten salts. Highly charged biomolecules, such as DNA, respond sensitively to ions in dilute solutions. Here, we use non-base-pairing DNA-coated nanoparticles (DNA-NP) to analyze electrostatic interactions in concentrated salt solutions. Despite their negative charge, these conjugates form colloidal crystals in solutions of sufficient divalent cation concentration. We utilize small-angle X-ray scattering (SAXS) to study such DNA-NP assemblies across the full accessible concentration ranges of aqueous CaCl2, MgCl2, and SrCl2 solutions. SAXS shows that the crystallinity and phases of the assembled structures vary with cation type. For all tested salts, the aggregates contract with added ions at low salinities and then begin expanding above a cation-dependent threshold salt concentration. Wide-angle X-ray scattering (WAXS) reveals enhanced positional correlations between ions in the solution at high salt concentrations. Complementary molecular dynamics simulations show that these ion-ion interactions reduce the favorability of dense ion configurations within the DNA brushes below that of the bulk solution. Measurements in solutions with lowered permittivity demonstrate a simultaneous increase in ion coupling and decrease in the concentration at which aggregate expansion begins, thus confirming the connection between these phenomena. Our work demonstrates that interactions between charged objects continue to evolve considerably into the high-concentration regime, where classical theories project electrostatics to be of negligible consequence.

New Approach for Enhancing Sensitivity in Liquid‐Gated Nanowire FET Biosensors Under Optical Excitation

AbstractThe results obtained for liquid‐gated (LG) nanowire (NW) field‐effect transistor (FET) sensors analyzed in divalent ion (MgCl2) solutions, which play a crucial role in the human body, are reported. Liquid‐gated NW FET sensors fabricated in‐house are investigated using I–V characteristics and noise spectroscopy in a wide range of voltages and different intensities of optical infrared irradiation. A new effect is revealed under the influence of external optical excitation. The effect allows for the control of characteristic times of single‐trap phenomena: capture time to a single trap, emission time from the trap, and its ratio represented by the dimensionless ratio parameter (R‐factor). These parameters enabled an improvement in sensor sensitivity. The findings open prospects for controlling charge states in LG NW FET structures to optimize new parameters for achieving ultrahigh sensitivity in biosensors.

Full recycling of MgCl2 wastewater generated in rare earth extraction and separation process by spray pyrolysis

Wastewater recycling is the desired goal of the rare earth separation plants for current ecological requirements and economic benefit. The MgCl2 wastewater generated during rare earth extraction and separation process was treated by spray pyrolysis for the first time to achieve full recycling. The kinetic of spray pyrolysis process and the mechanism affecting the activity of MgO powder were investigated. The results showed that the rate determining step of MgCl2 solution spray pyrolysis was transformed from a chemical reaction control to a diffusion process control after the temperature exceeded 1073 K. The MgO powder prepared by spray pyrolysis was rough and porous, the embedding of Cl made MgO grains severely distorted, producing more defects. Meanwhile, polycrystalline basic magnesium chloride likewise had more defects. These two points resulted a higher density of defects of MgO powders, and causing higher activity. Moreover, at a temperature of 1173 K, MgCl2 concentration of 300 g/L and N2 flow rate of 40 L/min, the thermal decomposition rate of MgCl2 reached 99.54%, the alkalinity of the powder reached 0.045 mol/g, and the iodine absorption value reached 102.72 mg I2/g MgO. Meanwhile, the high purity hydrochloric acid with a concentration of 6.70 mol/L was obtained.

Simultaneous removal of triadimefon and dinotefuran by a new biochar-based magnesium oxide composite in water: Performances and mechanism

In recent years, the ecological security has been seriously threatened by the residues of pesticides in the environment. In this study, a new biochar-based magnesium oxide composite (MTBC) was successfully prepared using Traditional Chinese Medicine residues and MgCl2 solution, and then applied for the removal of triadimefon (TDF) and/or dinotefuran (DIN) in water. Batch experiments results indicated that 86.42 and 87.86 % of TDF and DIN removals could be obtained by MTBC within 120 min, respectively. The TDF adsorption process was proved to be well fitted with the pseudo-second-order kinetic, Elovich, liquid film diffusion, Intra-particle diffusion and Langmuir isothermal models. The TDF adsorption by MTBC was a spontaneous endothermic reaction, and chemical adsorption process was dominant. The inhibitory of the coexisting anions on TDF removal followed the order of SO42−＜Cl−＜HPO43−＜HCO3–. Both TDF and DIN could be simultaneously removed by MTBC at the certain concentrations levels. The possible removal mechanism for the adsorption of TDF and DIN by MTBC was proposed, both TDF and DIN were rapidly distributed and adsorbed on MTBC surface, then diffused into the interior pores structure and were finally adsorbed on MTBC through various reaction processes. The TDF removal process might be involved with hydrogen bonding, π-π interaction, pore filling and electrostatic interaction, while DIN removal might be involved with hydrogen bonding, pore filling and electrostatic interaction. These findings suggested that biochar-based magnesium oxide composite was an effective adsorbent for the remediation of agricultural effluents containing TDF and DIN.

Isotope effects accompanying δ2 H, δ18 O and δ17 O analyses of aqueous saline solutions using cavity ring-down laser spectroscopy.

The presence of substantial amounts of dissolved salts creates serious difficulties in isotope analyses of water samples using conventional isotope ratio mass spectrometry. Although nowadays laser-based instruments are increasingly used for this purpose, a comprehensive assessment of isotope effects associated with direct analyses of aqueous saline solutions using this technology is lacking. Here we report the results of laboratory experiments aimed at quantifying isotope effects associated with direct, δ2 H, δ18 O and δ17 O analyses of single-salt solutions and double-salt mixtures prepared with a water of known isotopic composition. Three single-salt solutions (NaCl, CaCl2 and MgSO4 ) and two double-salt mixtures (NaCl + CaCl2 and NaCl + MgSO4 ) were prepared and investigated for a wide range of molalities. The triple-isotope composition of the prepared solutions was analysed with the aid of a Picarro L2140-i Cavity Ring-Down Spectroscopy analyser. The NaCl and CaCl2 solutions revealed small negative salt effects, independent of molality and comparable with measurement uncertainty. The MgCl2 solution showed the highest salt effects, reaching saturated solution ca. +2.7‰ (2 H), -3.5‰ (18 O) and -1.7‰ (17 O). Salt effects for the double-salt mixtures generally mirrored the effects observed for the single-salt solutions. The observed salt effects are discussed in the context of processes occurring during the injection of the salt solutions into the vaporizer unit of the CRDS analyser. The presented study has demonstrated feasibility of direct, triple-isotope analyses of aqueous salt solutions using a Picarro L2140-i CRDS analyser for a broad range of salinities up to saturated conditions. Large uncertainties of 17 O-excess determinations for solutions forming hydrated salts preclude the use of this parameter for interpretation purposes.

Comparative Investigation of the Microstructure of MgCl2 Aqueous Solutions Using Different X-ray Scattering Sources, Raman Spectroscopy, and Atomistic Simulations.

Aqueous solutions of magnesium chloride (MgCl2(aq)) are often used to test advances in the theory of electrolyte solutions because they are considered an ideal strong 2:1 electrolyte. However, there is evidence that some ion association occurs in these solutions, even at low concentrations. Even a small ion-pairing constant can have a significant impact on the chemical speciation of ions, so it is important to determine whether ion pairing actually occurs. In this study, MgCl2(aq) with concentrations ranging from 1 to 35% was studied using three methods: X-ray scattering (XRS) with the Shanghai Synchrotron Radiation Facility (SSRF) and silver-anode laboratory sources, Raman spectroscopy, and molecular dynamics (MD) simulations with the COMPASS-II and Madrid force fields. XRS results were analyzed in the framework of PDF theory to obtain the reduced structure function F(Q) and the reduced pair distribution function G(r). The F(Q) values from synchrotron radiation and laboratory sources both showed that the tetrahedral hydrogen bonds in bulk water were destroyed with the increased MgCl2 concentration. The results of G(r) indicated that the main peaks centered at 2.05 and 2.80 Å can be ascribed to the interactions of Mg-O and O-O, respectively. The peak at 3.10 Å is attributed to the combined effect of O-O and Cl-O. By comparing the structural information on MgCl2 solution obtained from the two light sources, it was found that both SSRF and silver-anode laboratory sources can reflect the above-mentioned structural information on MgCl2 solution. The radial distribution function (RDF) obtained from MD simulations of MgCl2 solutions assigned the peaks at 2.0, 2.8, and 3.2 Å to the Mg-O, O-O, and Cl-O interatomic pairs, respectively. The decrease in the O-O coordination number confirms that the hydrogen-bonding network of water is disrupted by increasing MgCl2 observed by X-ray scattering. The proportion of Mg-Cl contact ion pairs gradually increases with MgCl2 concentration as does the coordination number. Raman spectroscopy results show that the bond type changes from double donor double acceptor (DDAA) to single donor-single acceptor (DA) with increasing concentration, providing explicit details of the hydrogen-bond evolution in the aqueous solution.

Molecular dynamics simulation of hydrogen diffusion into brine: Implications for underground hydrogen storage

Underground hydrogen storage has been the subject of extensive research recently. Hydrogen diffusion coefficient into brine critically affects hydrogen loss. However, the available data pertain to hydrogen diffusivity in pure water or NaCl solutions, with rare interpretations of temperature and salinity effects. In this paper, molecular dynamics simulations at realistic conditions were conducted to calculate these coefficients in various brines, particularly those containing divalent salts. The results indicate lower diffusivities at higher salinities and lower temperatures, the value being 7.29 × 10−9 m2/s at 323 K, increasing to 10.2 × 10−9 m2/s at 353 K for 1 molal NaCl solution. The diffusion coefficient decreases up to 38 % as the salinity increases from 1 to 5 molal. Besides, hydrogen diffusivity in MgCl2 solution is up to 60 % smaller than in NaCl solutions at the same molality. Radial distribution functions and hydrogen bond analyses confirm the results. This research provides new data for estimating hydrogen loss in aquifers or water-saturated caprocks.

Thermodynamic characterization of aqueous solutions of NaCl, KCl, MgCl2 and CaCl2: volumetric, acoustic, viscometric and computational analysis

The volumetric and acoustic properties of alkali and alkaline earth metal salts are ubiquitous in numerous biological and non-biological processes and accurate formulation of their thermophysical properties is a fundamental prerequisite for complete exploration of their diverse applications. To meet this purpose, in this investigation, we herewith report the systematic data of densities ρ, speed of sound u and viscosity η of aqueous binary solutions of the prominent alkali and alkaline earth metal salts viz. NaCl, KCl, MgCl2, and CaCl2 at seven different temperatures T = (288.15–318.15 K) and ambient pressure over the wide concentration range of (0.002–1) mol∙kg−1.These experimental data have been further employed to obtain some important thermodynamic parameters, viz, the apparent molar volume of solute Vϕ, limiting apparent molar volume of solute Vϕ0, isentropic compressibility of solution κS, apparent molar isentropic compression of the solute KS,ϕ, limiting apparent molar isentropic compression of solute KS,ϕ0 and apparent molar expansibility Eϕ0. Further, the coefficient of thermal expansion α*, the second-order derivative of limiting apparent molar volume ∂2Vϕ0/∂T2, Jones-Dole equation viscosity A, B, D coefficients, temperature derivative of B coefficient i.e. dB/dT, activation parameters for viscous flow and hydration number nH have also been computed. The results obtained have been used to elucidate different interactions taking place in the aqueous electrolytic solutions. To corroborate the experimental results, quantum chemical calculations were performed using density functional theory (DFT) by Gaussian software package. The calculations included an analysis of molecular orbitals, with particular emphasis on the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

EIS and relaxation times analysis of the electric double layer construction on Pt cathode surface in MgCl2 molten salt hydrate

The electric double layer on Pt cathode surface in the process of cathodic polarization was analyzed with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), Raman spectroscopy, and Scanning electron microscope (SEM) in magnesium chloride (MgCl2) solution and MgCl2 molten salt hydrate (MSH). The effects of KCl on the structure of MgCl2 molten salt hydrate and electrode reaction were discussed. EIS data were fitted to propose the equivalent electric circuits to simulate the structure of electric double layers on Pt electrodes. Distribution of relaxation times (DRT) analysis was estimated to identify each process for MgCl2 solution and MgCl2 molten salt hydrate on the Pt cathode. The results show that the solution transforms into MSHs as the water content in the solution decreases. The solution and molten salt exhibit different double-layer properties. The movement of hydrated ions has greater resistance in MSHs which leads to the reduction of electrode reaction rate. The DRT and EIS results demonstrate that H+ and hydrated Mg2+ are simultaneously adsorbed on the Pt surface to form a double electric layer in MgCl2 solution or MSHs. In the MgCl2 MSHs, H+, H2O, and compact hydrated Mg2+ on the Pt electrode surface form a double layer. KCl plays an important role in changing the structure of MgCl2 molten salt hydrate, increasing the active H2O, and offering H+ adsorbed on the Pt surface.

Effect of MgCl2 on CO2 sequestration as hydrates in marine environment: A thermodynamic and kinetic investigation with morphology insights

Oceanic hydrate-based CO2 sequestration (HBCS) holds great promise for achieving carbon neutrality. However, the presence of inorganic salts, particularly MgCl2 besides NaCl, in seawater can significantly impact the formation rate and the stability of CO2 hydrate. In this study, experimental investigations were conducted to examine the thermodynamics, kinetics, and the resulting morphological features of CO2 hydrate in the presence of MgCl2, covering mass fractions ranging from 0 to 5.0 wt%. The experimental findings reveal that MgCl2 exerts a thermodynamic inhibitory effect with its inhibitory capacity increasing with higher mass fractions. The solubility model of CO2 in MgCl2 solution was modified, demonstrating a gradual weakening of CO2 solubility as MgCl2 mass fraction increases. Additionally, the growth kinetics of CO2 hydrate decreases with increasing MgCl2 mass fraction. Regarding CO2 hydrate morphology, it was observed that at low mass fractions of MgCl2 (<1.0 wt%), a dense hydrate film rapidly formed at the gas-liquid interface after CO2 hydrate nucleation, hindering the further conversion of CO2 into hydrate. Conversely, at higher mass fractions (>3.0 wt%), CO2 hydrate exhibits a more porous and slurry-like structure, facilitating more gas-liquid contact and mass transfer, thereby enhancing the conversion of CO2 into hydrate. During hydrate dissociation, a salt-removal effect associated with CO2 hydrate formation was observed, leading to the accumulation of concentrated electrolyte (MgCl2) and facilitating CO2 hydrate dissociation. These findings have implications for understanding the CO2 hydrate formation and dissociation in the presence of MgCl2 relevant in the subsea environment and can contribute to the development of effective hydrate-based CO2 sequestration strategies.

Analyzing ion uptake in ion-exchange membranes using ion association model

Predicting ion uptake and selectivity in ion-exchange membranes is desired for many applications, yet a suitable physical description defining the most appropriate ion-specific parameters is still challenging. Here, we systematically develop an ion-association-based approach to modeling ion uptake in ion-exchange membranes from solutions of symmetric and non-symmetric salts. The model treats association in an ion-specific manner, self-consistently accounting for equilibria between free ions in solution and within the membrane phase (salt injection) and between free and associated species within the membrane (association equilibria), subjects to overall membrane electroneutrality. The resulting models, including different possible association equilibria, were employed to fit the reported data for Nafion 117 and CR61 cation-exchange membranes in equilibrium with NaCl, MgCl2, CaCl2, and Na2SO4 single-salt solutions. The results are compared with the previously reported fits to the Manning condensation model, which shows that both models produce similarly good fits for NaCl, MgCl2, and CaCl2 solutions in the 0.01 to 1 M range. However, the greater flexibility and specificity of the association model allow addressing deviations observed for Na2SO4 solutions and for CaCl2 above 1 M as free-ion paring and possible formation of charged NaSO4- and CaCl+ pairs, respectively. The results demonstrate the present model may be a sound non-mean-field alternative to the Manning condensation model, capable of addressing ion-specificity and multiple modes of association.

Effects of solution concentration and water amount on hydrogenation performance of MgH2

Hydride hydrolysis reaction is a promising method for on-site hydrogen production with high capacity. However, ensuring a certain amount of water and the formation of a passivation layer in the produced material is crucial to interrupt the reaction. In this experimental study, multiple hydrolysis experiments using chloride solutions at concentrations of 0.1 M, 0.5 M, and 1 M were investigated. Hydrolysis kinetics curves were measured at different temperatures. The resulting hydrolyzed products underwent analysis of phase and morphology using XRD and SEM scanning techniques, and the hydrolysis mechanism was examined. The results demonstrated that the hydrolysis activation energy for the 0.1 M, 0.5 M, and 1 M MgCl2 solutions was determined to be 42.62 ± 7, 37.4 ± 0.6, and 27.1 ± 0.5 kJ/mol, respectively, establishing the impact of concentration on the hydrolysis kinetics. Moreover, water reduction tests conducted under the original conditions revealed that using 0.1 M FeCl3 and 0.1 M AlCl3 solutions with 5 mL water yielded a hydrolysis yield of 1500 mL/g, and the conversion rate can reach 97 % in 2 mL of water in 0.5 M FeCl3 solution. These remarkable hydrolysis properties of MgH2 are significant for the study of related magnesium-based alloy hydrides.