Liquid–liquid equilibria of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate and sodium citrate/tartrate/acetate aqueous two-phase systems at 298.15 K: Experiment and correlation

Binodal curves of the aqueous 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) + sodium citrate (Na₃C₆H₅O₇), [Bmim]BF₄ + sodium tartrate (Na₂C₄H₄O₆) and [Bmim]BF₄ + sodium acetate (NaC₂H₃O₂) systems have been determined experimentally at 298.15 K. The Merchuk equation was used to correlate the binodal data. The effective excluded volume (EEV) values obtained from the binodal model for these three systems were determined. The binodal curves and EEV both indicate that the salting-out abilities of the three salts follow the order: Na₃C₆H₅O₇ > Na₂C₄H₄O₆ > NaC₂H₃O₂. The liquid–liquid equilibrium (LLE) data were obtained by density determination and binodal curves correlation of these systems. Othmer–Tobias and Bancraft, and Setschenow equations were used for the correlation of the tie-line data. Good agreement was obtained with the experimental tie-line data with both models.     

Liquid-liquid equilibrium of novel aqueous two-phase systems and evaluation of salting-out abilities of salts

Binodal data are beneficial to the design of aqueous two-phase extraction and the establishment of thermodynamic models. For the 2-propanol + Li₂SO₄/Na₂SO₄/ (NH₄)₂SO₄/K₃PO₄ + water systems and 1-propanol + K₃PO₄/K₃C₆H₅O₇/(NH₄)₃C₆H₅O₇ + water systems, binodal data were determined at 298.15 K. The binodal data were correlated by a theoretical equation on the basis of statistical geometry. The salting-out abilities of salts and the phase-separation abilities of alcohols were evaluated by the effective excluded volume of salt and the binodal curves plotted in molality. A simple Hofmeister series of cations and anions were obtained. The organic salt, K₃C₆H₅O₇, shows as high a salting-out ability as K₃PO₄.      

Study of the composition and properties of products formed in interaction of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> with proton-containing reagents

Composition and properties were studied of products formed in treatment of solid Na₂CO₃ with aqueous solutions containing acetic and citric acids with mass fractions of 0.40–0.60 and 0.33–0.49, respectively, at a Na₂CO₃/H _x An molar ratio of 2–6, where H _x An = CH₃COOH and H₃(C₆H₅O₇). It was found that the content of water in the systems under study and the strength of an acid affect the yield of the double salt of carbonic acid, Na₂CO₃·NaHCO₃·2H₂O and the composition of derivative proton-containing compounds. It is noted that sodium sesquicarbonate can be formed both by the crystallization mechanism and via a transformation of the primary structure of sodium carbonate. In the resulting powder-like products, water introduced with the acid solution is predominantly consumed for formation of crystal hydrates of carbonate-containing and derivative proton-containing compounds. The hygroscopic point of the resulting salt formulations was determined to be at a level of 70–75%. It was noted that sesquicarbonate-containing salt formulation formed in “dry” neutralization of sodium carbonate by acid solutions can be regarded as a builder for obtaining synthetic household detergents.     

Solubility in K+-Na+-Mg 4 2− aqueous solution at T = 298.15 K

In the salt solubility predictions for K⁺-Na⁺-Mg ₄ ^2? aqueous solution the treatment of thermodynamic data of three-component systems at T = 298.15 K involved the application of the Extended Pitzer’s ion-interaction model for the pure and mixed electrolyte solutions and criteria of phase equilibrium. Osmotic coefficients data of three-component systems were revised according to recently published parameters of the solutions NaCl(aq) and KCl(aq) that served as reference standards in isopiestic measurements. Parameters of the extended ion-interaction model of K₂SO₄(aq) are determined by treatment of experimental and predicted values of osmotic coefficient in supersaturated region obtained by the Zdanovskii-Stokes-Robinson rule. Results of salt solubility prediction were compared to experimental solubility data from literature. The agreement between calculated and experimental solubility data in the systems K₂SO₄ + MgSO₄ + H₂O, Na₂SO₄ + MgSO₄ + H₂O, and Na₂SO₄ + K₂SO₄ + H₂O at T = 298.15 K, was excellent.     

Sodium di­hydrogen tris­(cyclo­propane­carboxyl­ate)

The title acid salt, Na⁺·C₄H₅O₂^?·2C₄H₆O₂, contains finite anions in which two cyclo­propanoic acid mol­ecules are hydrogen bonded to a cyclo­propanoate residue. Each such anion interacts with four different Na⁺ cations.     

Polyol-Metall-Komplexe. XIII [1]. Na2[Be(C4H6O3)2] · 5H2O und Na2[Pb(C4H6O3)2] · 3H2O – zwei homoleptische Bis-polyolato-metallate mit Beryllium und mit Blei

Polyol Metal Complexes. XIII. Na₂[Be(C₄H₆O₃)₂] · 5H₂O and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O – Two Homoleptic Bis Polyolato Metallates with Beryllium and with Lead Na₂[Be(C₄H₆O₃)₂] · 5H₂O ( 1 ) and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O ( 2 ) crystallize from concentrated, alkaline aqueous solutions. The polyol anhydroerythritol is deprotonated twice in the mononuclear, homoleptic complex anions. The preference of beryllium for the binding of cis-furanoid diols is shown. In 2 , a stereochemically active lone pair at the central atom is the reason for the construction of low dimensional aggregates from three plumbate and three sodium ions.     

Sodium citrate dihydrate doped with Mn3+ ions

Sodium citrate dihydrate doped with Mn³⁺ ions, namely trisodium(I) managnese(III) citrate(3−) dihydrate, [Na₃Mn_0.011(C₆H₅O₇)(H₂O)₂]_n, was obtained during attempts to prepare some complex Mn^III citrates from a concentrated strong alkaline solution containing Na⁺, Mn³⁺ and citrate ions. The compound is isostructural with the recently described Na₃(C₆H₅O₇)·2H₂O [Fischer & Palladino (2003). Acta Cryst. E 59 , m1080–m1082]. The essential difference between these two structures is the presence of a very small proportion (0.205 wt%) of Mn³⁺ ions, which are positioned at the special 4e Wyckoff position in C2/c, where they are in a highly distorted octahedral environment of O atoms from two citrate anions.     

All Organic Sodium‐Ion Batteries with Na4C8H2O6

Developing organic compounds with multifunctional groups to be used as electrode materials for rechargeable sodium‐ion batteries is very important. The organic tetrasodium salt of 2,5‐dihydroxyterephthalic acid (Na₄DHTPA; Na₄C₈H₂O₆), which was prepared through a green one‐pot method, was investigated at potential windows of 1.6–2.8 V as the positive electrode or 0.1–1.8 V as the negative electrode (vs. Na⁺/Na), each delivering compatible and stable capacities of ca. 180 mAh g^?1 with excellent cycling. A combination of electrochemical, spectroscopic and computational studies revealed that reversible uptake/removal of two Na⁺ ions is associated with the enolate groups at 1.6–2.8 V (Na₂C₈H₂O₆/Na₄C₈H₂O₆) and the carboxylate groups at 0.1–1.8 V (Na₄C₈H₂O₆/Na₆C₈H₂O₆). The use of Na₄C₈H₂O₆ as the initial active materials for both electrodes provided the first example of all‐organic rocking‐chair SIBs with an average operation voltage of 1.8 V and a practical energy density of about 65 Wh kg^?1.     

Effect of Antioxidants on Stability of Aqueous Solutions of Selenurea and on Properties of Lead Selenide Films Obtained with These Antioxidants

Spectrophotometric method was used to study the kinetics of the process in which aqueous solutions of selenurea of various compositions are oxidized. Significant differences between the stabilities of selenurea solutions were revealed in relation to the selenurea concentration and also to the acidity, or alkalinity of a medium. It was shown that the stability of selenurea solutions is affected by additives of various antioxidants: sodium sulfite Na₂SO₃, ascorbic acid C₆H₈O₆, hydroxylamine chloride NH₂OH·HCl, hydrazine hydrate N₂H₄·H₂O, and tin chloride SnCl₂·2H₂O. It was found that using a 1 : 1 mixture of antioxidants Na₂SO₃ and C₆H₈O₆ substantially raises their antioxidant activity and stabilizes the aqueous solutions of selenurea during up to five days. A hydro-chemical precipitation in the acetate—ethylenediamine reaction system in the presence of the antioxidants under study was used to obtain lead selenide films of stoichiometric composition with thicknesses of 230?670 nm. With the Na₂SO₃ + C₆H₈O₆, Na₂SO₃, C₆H₈O₆, and SnCl₂ antioxidants used to stabilize selenurea solutions, a tendency is observed toward a decrease in the lattice constants of PbSe films from 6.1531 ± 0.0003 to 6.1367 ± 0.0002 Å, an increase in the share of nanosize particles, and rise in the PbSe energy gap width from 0.78 to 1.0 e V.

     

(Liquid + liquid) equilibrium of (imidazolium ionic liquids + organic salts) aqueous two-phase systems at T = 298.15 K and the influence of salts and ionic liquids on the phase separation

(Liquid + liquid) equilibrium for the {1-ethyl-3-methylimidazolium tetrafluoroborate ([C₂mim]BF₄)/1-propyl-3-methylimidazolium tetrafluoroborate ([C₃mim]BF₄) + organic salt + H₂O} aqueous two-phase systems (ATPSs) have been experimentally ascertained at T = 298.15 K. Three empirical equations were used to correlate the binodal data. On the basis of the empirical equation of the binodal curve with the highest accuracy and lever rule, the (liquid + liquid) equilibrium data were calculated by MATLAB. The reliability of the tie line compositions was proved by the empirical correlation equations given by the Othmer–Tobias and Bancroft equations. The effective excluded volume (EEV) values obtained from the binodal model for these systems were determined. The EEV and the binodal curves plotted in molality both indicate that the salting-out abilities of the four salts follow the order: Na₃C₆H₅O₇ > (NH₄)₃C₆H₅O₇ > Na₂C₄H₄O₄ ≈ Na₂C₄H₄O₆, while the phase-separation abilities of the investigated ILs are in the order of [C₃mim]BF₄ > [C₂mim]BF₄. In the systems investigated, the effect of salts on the phase-forming capability was also evaluated in the shape of the salting-out coefficient obtained from fitting the tie-line data to a Setschenow-type equation. The phase-forming ability increases with the increase of salting-out coefficient.     

Mixed-ligand platinum(IV) complexes with amino acids and adenine

Complexing in platinum(IV)-adenine-amino acid (α-alanine (Ala), lysine (Lys), or histidine (His)) systems was studied by pH titration. The stability constants of 1: 1: 1 complexes were determined. The stability of these mixed-ligand complexes changes in the following order: Lys < Ala < His. Reactions between aqueous solutions of H₂PtCl₆ and amino acids produced the following coordination compounds: Pt(C₃H₆NO₂)(C₅H₅N₅)Cl₃ · 2H₂O, or Pt(Ala^?)(Ade)Cl₃ · 2H₂O (I); Pt(C₅H₅N₅)(C₆H₁₄N₂O₂)Cl₄ · 2H₂O, or Pt(Ade)(Lys)Cl₄ · 2H₂O (II); and Pt(C₅H₅N₅)(C₆H₉N₃O₂)Cl₄ · 3H₂O or Pt(Ade)(Hist)Cl₄ · 3H₂O (III). These complexes were characterized by ¹³C NMR, IR, and X-ray photoelectron spectroscopy. Alanine is complexed via both amino and carboxy groups; lysine, via α-amino group exclusively; and histidine, via the amino group and the N3 heterocyclic atom. Adenine in these complexes is monodentate due to the N7 heterocyclic atom. The adenine amino group is apparently H-bonded to a water oxygen atom.     

New hydrophobic L‐amino acid salts: maleates of L‐leucine,L‐isoleucine and L‐norvaline

Crystals of maleates of three amino acids with hydrophobic side chains [L‐leucenium hydrogen maleate, C₆H₁₄NO₂⁺·C₄H₃O₄⁻, (I), L‐isoleucenium hydrogen maleate hemihydrate, C₆H₁₄NO₂⁺·C₄H₃O₄⁻·0.5H₂O, (II), and L‐norvalinium hydrogen maleate–L‐norvaline (1/1), C₅H₁₁NO₂⁺·C₄H₃O₄⁻·C₅H₁₂NO₂, (III)], were obtained. The new structures contain C₂²(12) chains, or variants thereof, that are a common feature in the crystal structures of amino acid maleates. The L‐leucenium salt is remarkable due to a large number of symmetrically non‐equivalent units (Z′ = 3). The L‐isoleucenium salt is a hydrate despite the fact that L‐isoleucine is a nonpolar hydrophobic amino acid (previously known amino acid maleates formed hydrates only with lysine and histidine, which are polar and hydrophilic). The L‐norvalinium salt provides the first example where the dimeric cation L‐Nva...L‐NvaH⁺ was observed. All three compounds have layered noncentrosymmetric structures. Preliminary tests have shown the presence of the second harmonic generation (SGH) effect for all three compounds.     

Molar extinction coefficients in aqueous solutions of some amino acids

Mass attenuation coefficients of amino acids viz. glycine (C₂H₅NO₂), l-Serine (C₃H₇NO₃), l-Theronine (C₄H₉NO₃), l-Proline (C₅H₉NO₂), l-Valine (C₅H₁₁NO₂) and l-Phenylalanine (C₉H₁₁NO₂) in aqueous solutions have been determined at 81, 356, 511, 662, 1173 and 1332 keV by the gamma-ray transmission method in a narrow beam good geometry setup. Precisely measured densities of these solutions were used for the determination of these coefficients which varied systematically with the corresponding changes in the concentrations (g/cm³) of the solutions. Molar extinction coefficients of amino acids were then obtained at these energies and were found to be in good agreement with the theoretical results. In addition, total interaction cross sections of amino acids in aqueous solutions were also calculated.     

Die Polytherme des Quinären Systems Na+, K+, Mg2+/Cl−, SO//H2O im Bereich von +25° bis −10°C

Polythermal Curves of the Quinary System Na⁺, K⁺, Mg²⁺/Cl^?, SO//H₂O in Range between +25°C and ?10°C Proceeding from the 0°C, ?5°C and ?10°C isothermal curves of the quinary system Na⁺, K⁺, Mg²⁺/C1^?, SO//H₂O with saturation at NaCl, KCl, and carnallite, respectively, the polythermal curve is represented between 25°C and ?10°C. Within the new defined range of the polythermal curve the invariant five-salt-paragenesis NaCI, KCI, Glauber's salt (Na₂SO₄ · 10 H₂O), bitter salt (MgSO₄ · 7 H₂O), Schoenite (K₂SO₄ · MgSO₄ · 6 H₂O) can be found at ?7,2°C. It represents also the lowest temperature of formation of Schoenite in this system. It was necessary, moreover, to reconsider further univariant and invariant equilibrium solutions in the range between 25° and 0°C.     

Zeta Potential of Pyrophyllite in Aqueous Solutions of Alkaline and Alkaline Earth Metal Cations and Low‐Molecular‐Weight Organic Anions

Electrokinetic behavior of pyrophyllite in aqueous solutions of K⁺, Na⁺, Mg²⁺, and Ca²⁺ ions and effect of low‐molecular‐weight organic anions like acetate (C₂H₃O₂ ^?), oxalate (C₂O₄ ^2?), and citrate (C₆H₅O₇ ^3?) on the zeta potential was investigated. Pyrophyllite has higher negative zeta potential values in the presence of alkaline metal cations than in water, and it comes close to positive values in the presence of alkaline earth metal cations at low pH values. Results revealed that presence of low‐molecular‐weight organic anions led to a decrease in the zeta potential in the order of acetate>citrate>oxalate.     

Equilibrium phase behavior of aqueous two-phase systems containing 17R4/L64 and citrates

The cloud points (CPs) of the copolymers 17R4 and L64 were first measured, and then the effects of salts ((NH₄)₃C₆H₅O₇, K₃C₆H₅O₇) on 17R4 and L64 were researched. After finishing the work described above, the temperature (278.15, 283.15, and 288.15) K of aqueous two-phase systems was determined, which consist of 17R4-(NH₄)₃C₆H₅O₇, 17R4-K₃C₆H₅O₇, L64-(NH₄)₃C₆H₅O₇, and L64-K₃C₆H₅O₇. Finally, the liquid–liquid equilibrium (LLE) data of binodal curve and the tie line for 17R4-(NH₄)₃C₆H₅O₇ aqueous two- phase systems (ATPSs) 17R4-K₃C₆H₅O₇ ATPSs, L64-(NH₄)₃C₆H₅O₇ ATPSs, and L64-K₃C₆H₅O₇ ATPSs were obtained. Nonlinear fitting of the empirical equation was used for making the diagram. The results showed that the change in the size of the two-phase areas increases with the increase of temperature. The capacity of the salts to induce phase segregation follows the Hofmeister series, that is, K₃C₆H₅O₇?>?(NH₄)₃C₆H₅O₇. In addition, the findings also showed that the phase separation ability of 17R4 is better than that of L64.     

Phase diagrams of ionic liquids-based aqueous biphasic systems as a platform for extraction processes

In the past few years, ionic liquid-based aqueous biphasic systems have become the subject of considerable interest as a promising technique for the extraction and purification of several macro/biomolecules. Aiming at developing guidelines for more benign and efficient extraction processes, phase diagrams for aqueous biphasic systems composed of ionic liquids and inorganic/organic salts are here reported. Several combinations of ionic liquid families (imidazolium, pyridinium, phosphonium, quaternary ammonium and cholinium) and salts [potassium phosphate buffer (KH₂PO₄/K₂HPO₄ at pH 7), potassium citrate buffer (C₆H₅K₃O₇/C₆H₈O₇ at pH 5, 6, 7 and 8) and potassium carbonate (K₂CO₃ at pH ∼13)] were evaluated to highlight the influence of the ionic liquid structure (cation core, anion and alkyl chain length), the pH and the salt nature on the formation of aqueous biphasic systems. The binodal curves and respective tie-lines reported for these systems were experimentally determined at (298 ± 1) K. In general, the ability to promote the aqueous biphasic systems formation increases with the pH and alkyl chain length. While the influence of the cation core and anion nature of the ionic liquids on their ability to form aqueous biphasic systems closely correlates with ionic liquids capacity to be hydrated by water, the effect of the different salts depends of the ionic liquid nature and salt valency.     

Application of aqueous mixtures of polypropylene glycol or polyethylene glycol with salts in proteomic analysis

Partitioning of Bovine serum albumin (BSA), β-lactoglobulin (β-LG) and zein as model proteins in aqueous two-phase systems (S) containing polypropylene glycol (PPG425) or polyethylene glycol (PEG 6000) and salts (MgSO₄, (NH₄)₂SO₄, Na₂SO₄) is presented in this paper. The effects of different factors such as tie-line length, salt type and polymer type on the partition coefficient and recovery percent of proteins were analysed. The model proteins were separated by these systems (S) and directly used for gel electrophoresis without separating the target proteins from phase-forming reagents. The results revealed that the S, studied in this work could be used as a novel prefractionation method in proteomic analysis and could separate proteomic proteins in multigroup by one step extraction.     

Hexa­aqua­magnesium(II) bis­[N‐(6‐amino‐3,4‐di­hydro‐3‐methyl‐5‐nitro­so‐4‐oxopyrimidin‐2‐yl)­glycinate] dihydrate

The analysis of the title compound, [Mg(H₂O)₆](C₇H₈N₅O₄)₂·2H₂O, continues our study of the reactivity of metal ions with N‐protected amino acids. The Mg ion lies on an inversion centre with Mg—O 2.0437 (10)‐2.0952 (10) Å. The [Mg(H₂O)₆]²⁺cations, anions and water mol­ecules are linked by an extensive hydrogen‐bond network.     

Preparation of double pyrophosphates in aqueous systems chromium(III) salt−sodium pyrophosphate

The specifics of preparation of chromium double pyrophosphates in systems Cr(NO₃)₃–Na₄P₂O₇–H₂O, CrCl₃–Na₄P₂O₇–C₂O, and KCr(SO₄)₂–Na₄P₂O₇–H₂O are discussed. Changes in pH of the mentioned systems have been studied depending of the component ratio. The effects of the deposition duration and sodium pyrophosphate concentration on pH have been studied for system Cr(NO₃)₃–Na₄P₂O₇–H₂O. Phase composition has been determined for compounds prepared in systems Cr(NO₃)₃–Na₄P₂O₇–H₂O and KCr(SO₄)₂–Na₄P₂O₇–H₂O. It has been found that the acid residue anions do not substantially affect the formation of a continuous series of compounds consisting of hydroxy and hydro combinations of chromium ions and pyrophosphate ion, whereas cations can have an effect. System KCr(SO₄)₂–Na₄P₂O₇–C₂O is less sensitive to reaction conditions than systems in which normal salts Cr(NO₃)₃ and CrCl₃ act as a source of Cr³⁺ cation. A product stable over time can be prepared in system KCr(SO₄)₂–Na₄P₂O₇–C₂O; after heat treatment at 900°C, it is a mixture of KCrP₂O₇ and a-CrPO₄ phases.