KCl System Research Articles

Determination and Correlation of Phase Equilibria of Quaternary System KCl–KH2PO4–CO(NH2)2–H2O and Its Ternary Subsystems at 323.15 and 333.15 K

Determination and Correlation of Phase Equilibria of Quaternary System KCl–KH2PO4–CO(NH2)2–H2O and Its Ternary Subsystems at 323.15 and 333.15 K

Microporous Ag/AgCl on a Titanium Scaffold for Use in Capillary Reference Electrodes.

AgCl-coated silver fabricated with the thermal-electrolytic method can be used to prepare more reproducible reference electrodes than Ag/AgCl prepared with alternative methods such as electrolytic and chemical AgCl deposition or thermal fabrication. However, thermal-electrolytic fabrication requires a scaffold material upon which to build the layers upon. Platinum and rhodium have been used for this purpose as they are mechanically strong and chemically inert, but their cost is prohibitive for wider application. Herein, we report the stability of Ag/AgCl reference electrodes built atop a titanium scaffold using the thermal-electrolytic method and the use of these Ti/Ag/AgCl constructs in capillary-based reference electrodes. Electrochemical characterization shows that the probable presence of small amounts of oxygen at the Ti/Ag interface does not affect the reference electrode performance; in particular, over a wide pH range, the half-cell potential is pH independent. The electrical resistance of the Ti/Ag/AgCl/KCl system is dominated by the charge transfer resistance at the interface of the AgCl to KCl solution but is kept very small by the large AgCl surface area and a high solution concentration of chloride. The resulting high exchange current minimizes the effect of system impurities on the reference half-cell potential. Capillary-based reference electrodes comprising Ti/Ag/AgCl show exceptionally low potential drifts (as low as 0.03 ± 2.01 μV/h) and standard deviations of the potential at or below ±0.5 mV over a 60 h period. These capillary-based reference electrodes are suitable for very small sample volumes while still providing a free-flowing liquid junction that prevents reference electrode contamination.

Phase Equilibria of Quaternary System KCl + BaCl2 + SrCl2 + H2O and Its Ternary Systems at 323 K

Phase Equilibria of Quaternary System KCl + BaCl2 + SrCl2 + H2O and Its Ternary Systems at 323 K

Sorption behavior of three aromatic acids (benzoic acid, 1-naphthoic acid and 9-anthroic acid) on biochar: Cosolvent effect in different liquid phases

Influence of the cosolvent on the sorption of organic acids on biochar has not been well understood. For this purpose, the sorption (log Km, L kg−1) of three aromatic acids (benzoic acid (BA, pKa = 4.20), 1-naphthoic acid (1-NAPA, pKa = 3.70), and 9-anthroic acid (9-ANTA, pKa = 3.65) was evaluated as a function of methanol volume fraction (fc = 0.0, 0.25, and 0.5), liquid pH (2.5 and 7.0), ionic composition (CaCl2 and KCl) and ionic strength (0.005 M, 0.5 M, and 1 M CaCl2). A giant Miscanthus-derived biochar (ZPC of 2.86) was used as the sorbent. For all solutes, the sorption coefficients (log Km) measured at pH 2.5 (i.e., pH < pKa) tended to decrease with increasing fc, as expected from the cosolvency model, while the result obtained at pH 7.0 was not fully explained by the same model. The log Km of 1-NAPA in the CaCl2 system was always greater than in the KCl system (p < 0.05) and the impact became pronounced at high pH (>pKa) with increasing fc. Increasing the Ca2+ concentration at fc = 0.0 (from 0.005 M to 1 M) enhanced the value by 0.32 log unit of Km. These phenomena indicate a significant role of dissolved Ca2+ in the liquid phase, most likely due to the formation of cation bridges between aromatic carboxylates and the biochar surface (i.e., [R-COO--Ca2+]-{Biochar−}). A decrease in the dielectric constant of the methanol mixture could fortify the formation of this bridge. Regardless of the degree of cosolvency power (σ), as the number of aromatic rings of solutes increases, Km decreases in the order BA > 1-NAPA > 9-ANTA, where fc = 0.0. In conclusion, the sorption potential of biochar can be significantly weakened by increasing pH and fc, and in the absence of a divalent cation.

Solubility Measurement and Calculation of the Quaternary System KCl–KBr–NaCl–NaBr–H2O at 323.15 K

Solubility Measurement and Calculation of the Quaternary System KCl–KBr–NaCl–NaBr–H₂O at 323.15 K

Solid–Liquid Equilibria in the Quinary System KCl–KBr–NaCl–NaBr–H2O at 298.15 K and Its Application

Solid–Liquid Equilibria in the Quinary System KCl–KBr–NaCl–NaBr–H₂O at 298.15 K and Its Application

Beryllium solubility and hydrolysis in dilute to concentrated CaCl2 solutions: thermodynamic description in cementitious systems

The solubility and hydrolysis of Be(II) was investigated from undersaturation conditions in alkaline, dilute to concentrated CaCl2 solutions (0.05–3.5 M). Experiments were performed with α-Be(OH)2(cr) under Ar atmosphere at T = (22 ± 2)°C. Aqueous Be speciation was further investigated by means of molecular dynamics (MD) calculations. For the most diluted CaCl2 systems (0.05 and 0.25 M), a solubility minimum is observed at pHm ≈ 9.5 {with [Be(II)] ≈ 10−7 M}, consistent with solubility data previously reported in NaCl and KCl solutions. Above this pHm, and at higher CaCl2 concentrations, a steep increase in the solubility with a slope of ∼ +2 is observed, hinting towards the predominance of the moiety [Be(OH)42–] in the aqueous phase. In NaCl and KCl systems, this hydrolysis species prevails only above pHm ∼ 13, thus supporting the formation of ternary complex/es Ca–Be(II)–OH(aq) in CaCl2 solutions. The analysis of solubility data in combination with MD calculations underpin the key role of the complex Ca2[Be(OH)4]2+ in alkaline to hyperalkaline systems containing Ca. In combination with our previous work in NaCl–NaOH and KCl–KOH systems, complete chemical, thermodynamic and (SIT) activity models are derived for the first time for the system Be2+–Ca2+–Na+–K+–H+–Cl––OH––H2O(l). This model provides an accurate and robust tool for the evaluation of Be(II) solubility and speciation in a diversity of geochemical conditions, including source term calculations of beryllium in the context of repositories for nuclear waste disposal with a high cement inventory.

Experimental study and thermochemical assessment of the reciprocal system Li+, K+//Cl−, CO32−

In this work a new thermodynamic dataset of the reciprocal system Li+, K+//Cl−, CO32− was generated by using Calphad method with FactSage. After collecting and analyzing the available thermodynamic data in the literature, experiments were designed to improve the comprehensiveness of the new database. Specifically, Differential Thermal Analysis (DTA) was used (1) to confirm the eutectic temperature of the K2CO3–KCl system, (2) to check the solid solubility in the K2CO3–Li2CO3 system and (3) to measure the phase equilibria of the diagonal sections (i.e. Li2CO3–(KCl)2 and K2CO3–(LiCl)2) in the reciprocal system. In addition, the heat capacity of the intermediate compound LiKCO3 was measured by three types of Differential Scanning Calorimetry (DSC) and its phase transformation was studied by High temperature X-ray Diffractometry (HTXRD). Based on the literature data and the present experimental results, the thermodynamic data on pure LiCl, all sub-binary systems and the reciprocal system were reassessed in the new database, which can be used to calculate and predict the thermodynamic properties of the salt mixtures in the reciprocal system Li+, K+//Cl−, CO32− more precisely and reliably.

Redox Polymer-Regulated Hysteresis in Ion Current Rectification through AAO Membranes and Single Nanopipettes

Nanopore technology has promising potential in fields such as high-density energy conversion, stochastic chemical sensing, logic operation and neuromorphic computing, separation and fundamental nanoelectrochemistry due to its rich ion transport features and easy fabrication. Understanding the ion transport dynamics at the solid-liquid interface is essential for further technological advancements. Ion current rectification (ICR) and its time-dependent hysteresis have been found to arise from the asymmetric nanointerfaces (geometry, together with surface charges in polarity and density). While various nanostructures can be fabricated and surface charges can be modified, active controls in ICR and hysteresis during transport applications are lacking. Here, we report actively controlled transport hysteresis in ion current rectification though PEDOT-modified single nanopipettes and anodic aluminum oxide (AAO) membranes. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) provides high conductivity and chemical stability, low operating voltages, and enhanced performances in hydrophilicity, processability, and flexibility. The PEDOT:PSS aqueous dispersion is crosslinked inside a nanopipette or assembled onto one side of the AAO surface. Oxidation and reduction reversibly switch the PEDOT between the positive and neutral form, and thus modulate the space charge in nanopores or across the AAO membranes, correspondingly, the ion transport behaviors. The amplitude and polarity of ICR and the scale of hysteresis through a nanopore or AAO membrane have been altered by oxidizing/reducing the PEDOT substrate by adjusting the external electrical field. In contrast, the surface charge varying on pH, ionic strength, and electrolyte type is commonly adopted in ion transport studies but cannot be externally regulated in real-time. Interestingly, negative differential resistance (NDR) is also found in the PEDOT-modified nanopores in simple KCl systems without external pressure differential or concentration gradients. The NDR peak position and magnitude can be easily adjusted by controlling the redox states of the PEDOT fillings. Figure 1

Electrochemical synthesis of Co–Pr intermetallic compounds by the co-reduction of Co(II) and Pr(III) ions in a molten LiCl–KCl eutectic

For effective recovery of the fission element Pr from spent nuclear fuel (SNF) by using molten salt electrolysis technology, the electrochemical behavior of Pr(III) on inert Mo electrode in the molten LiCl–KCl system was investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques, indicating that the reduction of Pr(III) on the Mo electrode is a one-step reaction process with three electrons. Subsequently, electrochemical methods were used to reveal and calculate the kinetic and thermodynamic parameters of the Pr(III) ion reduction process. The co-reduction reaction of Pr(III) and Co(II) ions was explored, and five different CoxPry intermetallic compounds were detected. Meanwhile, only one Co2Pr intermetallic compound was obtained by galvanostatic and potentiostatic electrolysis with the best electrochemical parameters, and the thermodynamic properties of the Co2Pr intermetallic compound were calculated at different temperatures. The co-reduction product was verified using X-ray diffraction (XRD), and the composition was determined by scanning electron microscopy (SEM) with energy spectrum analysis (EDS) and X-ray photoelectron spectroscopy (XPS). In addition, the produced Co2Pr intermetallic compound has magnetic properties with a saturation magnetization of 10.3 emu/g.

Correction of the 3D Computer Model of the Phase Diagram for the LiCl–PrCl3–KCl System Using Thermoanalytical Curves

A spatial (3D) computer model of an isobaric phase diagram of the LiCl–PrCl3–KCl system was designed. The model was assembled of 66 surfaces and 27 phase regions, of which 31 surfaces and 14 phase regions degenerate to verticals or vertical planes because of the limited solubilities of the initial chlorides and their compounds. Published experimental isothermal sections and thermoanalytical curves for 33 salt melts were used to improve the quality of the 3D model. The results can be used to improve the molten-salt refining technology of nuclear fuel waste.

Correction of the 3D Computer Model of the Phase Diagram for the LiCl–PrCl3–KCl System Using Thermoanalytical Curves

Correction of the 3D Computer Model of the Phase Diagram for the LiCl–PrCl3–KCl System Using Thermoanalytical Curves

First-principles-derived transport properties of Molten chloride salts

Molten salts have many applications ranging from a heat transfer medium in both generation IV nuclear reactor designs and the solar industry to thermal storage systems. While molten salts show promising properties for these applications, there still exists a knowledge gap for the transport properties of molten salts at elevated temperatures. This work uses ab initio Molecular Dynamics to investigate the transport properties of KCl, LiCl, KCl-LiCl eutectic, NaCl, MgCl2, and NaCl-MgCl2 eutectic molten salt systems. The properties presented here are the diffusion coefficient, viscosity, and isochoric heat capacity. These properties are compared to experimental data where available and other computational work in cases where no experimental data is available. This is the first work to explore timescales over 100 ps via AIMD for the determination of transport properties in molten salts.

One-step electrolytic reduction desulfurization of Sb2S3 in different molten salts

A comparative analysis of different molten salt systems was conducted, including NaCl−KCl, NaCl−CaCl2, NaCl−Na2CO3, NaCl−KCl−CaCl2, and NaCl−KCl−Na2CO3. The phase diagrams, thermal stability, and solubility of Sb2S3 in molten salt systems were investigated. Based on the distribution of the element antimony, current efficiency, energy consumption, and the characterization of the residue, the most suitable molten salt for the electrical reduction of Sb2S3 was verified. The results show that all molten salt systems have good thermal stability and can realize the electrolytic reduction of Sb2S3. The system with CaCl2 is not conducive to the dissolution of Sb2S3, and the system with Na2CO3 can react with Sb2S3. In addition, the current efficiency of the NaCl−KCl system is the highest (75.68%), and the energy consumption ratio is the lowest (2.18 kW·h/kg).

Phase Equilibrium and Crystallization Process of the Ternary System KCl-(NH2)2CO-H2O at Different Temperatures

The phase equilibriums of the ternary system KCl-(NH2)2CO-H2O at 303.15 K, 323.15 K, 333.15 K, and 343.15 K were studied using the isothermal dissolution equilibrium method, in which the composition of equilibrium solid phase was determined by Schreinemaker’s wet residue method and X-ray diffraction (XRD) method. It was found that the ternary system is a simple cosaturated system, without the formation of neither double salt nor solid solution. Wilson and NRTL models were employed to correlate in the solubility data of the system at experimental temperatures. The maximum values of RAD and RMSD of the Wilson model were 2.18 × 10−2 and 0.83 and those of the NRTL model were 1.69 × 10−2 and 0.40, respectively. The two models were utilized to forecast solubility data at various temperatures, and the obtained outcomes were in line with the literature data. Based on the experimental solubility data at 343.15 K, the cooling crystallization process of the system was monitored online by focused beam reflectance measurement (FBRM) and particle video microscope (PVM). The crystal products were characterized by XRD, scanning electron microscope (SEM), and energy dispersive spectrometry (EDS). The results showed that the precipitation of (NH2)2CO occurred during the crystallization process, and this was followed by KCl. KCl was formed on the surface of (NH2)2CO crystal. The crystal was a simple mixture containing KCl and (NH2)2CO.

Study on diffusion kinetics of chromium and nickel electrochemical co-deposition in a NaCl–KCl–NaF–Cr2O3–NiO molten salt

Abstract The process of preparing surface composite by molten salt co-deposition is the result of the mass transfer of active particles in molten salt, electrochemical reduction, and solid diffusion. In this study, we prepared Cr–Ni alloy/low-carbon steel surface composites in NaCl, KCl, NaF, Cr2O3, and NiO melt salt system successfully, and analyzed the entire diffusion dynamics process, aiming to find out the limiting links and provide ideas for further improving the preparation efficiency. The results show that chromium and nickel ions are simultaneously reduced on the cathode surface through two and one steps, respectively. And an alloy layer with Fe content of 64.52 wt%, Ni content of 28.96 wt%, and Cr content of 6.52 wt% is formed on the surface of low-carbon steel substrate. The average diffusion coefficients of chromium and nickel atoms in the surface composites are 1.16 × 10−14 and 1.44 × 10−14 m2·s−1. The mass transfer process in molten salt is the limiting link in the whole preparation process.

The System KCl–CaCO3–MgCO3 at 3 GPa

Inclusions in mantle minerals and xenoliths from kimberlites worldwide derived from depths exceeding 100 km vary in composition from alkali-rich saline to carbonatitic. Despite the wide distribution of these melts and their geochemical importance as metasomatic agents that altered the mineralogy and geochemistry of mantle rocks, the P-T range of stability of these melts remains largely undefined. Here we report new experimental data on phase relations in the system KCl–CaCO3–MgCO3 at 3 GPa obtained using a multianvil press. We found that the KCl–CaCO3 and KCl–MgCO3 binaries have the eutectic type of T-X diagrams. The KCl-calcite eutectic is situated at K2# 56 and 1000 °C, while the KCl-magnesite eutectic is located at K2# 79 and 1100 °C, where K2# = 2KCl/(2KCl + CaCO3 + MgCO3) × 100 mol%. Just below solidus, the KCl–CaCO3–MgCO3 system is divided into two partial ternaries: KCl + magnesite + dolomite and KCl + calcite–dolomite solid solutions. Both ternaries start to melt near 1000 °C. The minimum on the liquidus/solidus surface corresponds to the KCl + Ca0.73Mg0.27CO3 dolomite eutectic situated at K2#/Ca# 39/73, where Ca# = 100∙Ca/(Ca + Mg) × 100 mol%. At bulk Ca# ≤ 68, the melting is controlled by a ternary peritectic: KCl + dolomite = magnesite + liquid with K2#/Ca# 40/68. Based on our present and previous data, the KCl + dolomite melting reaction, expected to control solidus of KCl-bearing carbonated eclogite, passes through 1000 °C at 3 GPa and 1200 °C at 6 GPa and crossovers a 43-mW/m2 geotherm at a depth of 120 km and 37-mW/m2 geotherm at a depth of 190 km.

Different patterns of germination inhibition by carvacrol and thymol in Bacillus subtilis spores.

This study aimed to clarify how the phenolic monoterpene carvacrol and its structural isomer thymol both as essential oil components (EOCs) inhibit the germination of Bacillus subtilis spore. Germination was evaluated by the OD600 reduction rate in a growth medium and phosphate buffer containing either l-alanine (l-Ala) system or l-asparagine, d-glucose, d-fructose plus KCl (AGFK) system. The germination of the wild-type spores in the Trypticase Soy broth (TSB) was found to be greatly inhibited by thymol than by carvacrol. Such a difference in the germination inhibition was confirmed by the dipicolinic acid (DPA) release from germinating spores in the AGFK buffer system, but not in the l-Ala system. Similar to the wild-type spores, no difference in the inhibitory activity between the EOCs was also indicated with the gerB, gerK-deletion mutant spores in the l-Ala buffer system and the above substantial difference was also done with the gerA-deleted mutant spores in the AGFK. Fructose was found to release spores from the EOC inhibition and inversely even stimulated. Increased concentrations of glucose and fructose partially suppressed the germination inhibition by carvacrol. The results obtained should contribute to the elucidation of the control effects of these EOCs on bacterial spores in foods.

Analysis of the Raw Material Inventory Control to Improve Cost Efficiency PT Pupuk Indonesia

&lt;em&gt;&lt;span&gt;World commodity prices rose due to the pandemic, the energy crisis in Europe and several countries that have policies to stop their exports, the increase in the price of KCL and DAP raw materials due to export restrictions carried out by Russia and China. The data analysis techniques used are collecting data containing information on raw material inventory in 2021, processing inventory control data based on company policies, calculating inventory costs using a just in time system, data analysis and drawing conclusions KCL needs 53,627 frequency of purchases 4 times the total inventory costs of Rp. 460,827,437. 20 times the total cost of supply Rp. 202,764,072. 1 time the total cost of supply Rp. 921,654,874. 11 times the total cost of inventory is Rp. 276,496,462. The needs of 69,138 DAP purchase frequency 6 times the total cost of inventory Rp. 829,043,491. 24 times the total cost of inventory Rp. 404,573,224. 5 times the total cost of supply Rp. 890,061,092 and 11 times the total cost of supply Rp. 606,859,835. The biggest saving value on KCL raw materials is to make a frequency of purchases as much as 20 times, inventory costs borne by the company Rp. 202,764,072 so as to save costs of Rp. 718,890,802. Meanwhile, DAP raw materials can make purchases as much as 24 times with inventory costs borne by the company of Rp. 404,573,224, so that the company can save costs of Rp. 1,618,292,894.&lt;/span&gt;&lt;/em&gt;

Experiments on Vapor Pressure of KCl at Different Molar Fractions in Mixtures of KCl + K2SO4.

The objective of this paper is to measure the vapor pressure of potassium chloride (KCl) in its mixture with potassium sulfate (K2SO4). Evaporation behavior of pure salts of KCl, K2SO4, and their mixtures at different molar fractions were examined using a simultaneous thermogravimetric analyzer (STA) at different temperatures with a pair of crucibles (outer: platinum; inner: alumina). The dependence of the vapor pressure of KCl on its molar fraction in mixtures of KCl + K2SO4 was obtained on the basis of relative pressure. Results show that vapor pressure of KCl is increased to 1.2 times when a small amount of K2SO4 (molar fraction from 0.05 to 0.20) is added. Evaporation of KCl will be inhibited by K2SO4 when the molar fraction of K2SO4 is higher than 0.27, which is its fraction in the eutectic system of KCl + K2SO4. Vapor pressure of KCl decreases significantly with increasing molar fractions of K2SO4 at its inhibition scope.