Vol 90, No 5 (2016)
- Year: 2016
- Articles: 37
- URL: https://journals.rcsi.science/0036-0244/issue/view/10261
Chemical Thermodynamics and Thermochemistry
Thermodynamics of a third-generation poly(phenylene-pyridyl) dendron decorated with dodecyl groups in the range of T → 0 to 480 K
Abstract
The heat capacity of a glassy third-generation poly(phenylene-pyridyl) dendron decorated with dodecyl groups is studied for the first time via high-precision adiabatic vacuum and differential scanning calorimetry in the temperature range of 6 to 520 K. The standard thermodynamic functions (molar heat capacity Cp°, enthalpy H°(T), entropy S°(T), and Gibbs energy G°(T)-H°(0)) in the range of T → 0 to 480 K, and the entropy of formation at 298.15 K, are calculated on the basis of the obtained data. The thermodynamic properties of the dendron and the corresponding third-generation poly(phenylene-pyridyl) dendrimer studied earlier are compared.
Thermodynamic properties of alloys of the binary In–Yb system
Abstract
The thermochemical properties of melts of the binary In–Yb system were studied by the calorimetry method at 1160–1380 K over the whole concentration interval. It was shown that significant negative heat effects of mixing are characteristic features for these melts. Using the ideal associated solution (IAS) model, the activities of components, Gibbs energies and the entropies of mixing in the alloys, and the phase diagram of this system were calculated. They agree with the data from literature.
Thermochemical characteristics of chitosan–polylactide copolymers
Abstract
The energies of combustion of chitosan and its block-copolymers with different polylactide contents are determined in a static bomb calorimeter. Standard enthalpies of combustion and formation are calculated for these substances. The dependences of the thermochemical characteristics on block-copolymer composition are determined and discussed.
Epoxide composites with thermally reduced graphite oxide and their properties
Abstract
The properties of epoxide composites modified by thermal reduced graphite oxide are studied. The dielectric permittivities of epoxide composites with additives of up to 1.5 wt % of reduced graphite oxide are studied at a frequency of 9.8 GHz. It is shown that despite its low electrical conductivity, the large specific surface area of reduced graphite oxide allows us to create epoxide composites with high complex dielectric permittivities and dielectric loss tangents.
Heat capacity, entropy of Ln2(MoO4)3 (Ln = La, Sm, and Gd), and the high-temperature enthalpy of Ln2(MoO4)3 (Ln = Eu, Dy, and Ho)
Abstract
The low-temperature heat capacity of Ln2(MoO4)3 (Ln = La, Sm, and Gd) is investigated by means of adiabatic calorimetry within the range of 60–300 K. The temperature dependences of the heat capacity are found and the values of the standard entropy are calculated, based on extrapolations to 0 K. Characteristic temperatures for molybdates are determined from the results of IR spectroscopic studies. The high-temperature enthalpy of Ln2(MoO4)3 (Ln = Eu, Dy, and Ho) is measured via high-temperature microcalorimetry, and the temperature dependence of heat capacity is calculated in the range of 298–1000 K. Since samarium and gadolinium molybdates are of the same structural type as terbium molybdate, we can estimate the anomaly of the heat capacity in the low-temperature region using the data for terbium molybdate and find the entropy of samarium and gadolinium molybdates.
Chemical Kinetics and Catalysis
Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds
Abstract
The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.
Selective determination of rate constants of reactions of atomic hydrogen with various functional groups of a complex molecule
Abstract
The possibility of determining absolute values of the rate constants of reactions of active intermediate species with different functional groups of molecules is demonstrated by measuring macrokinetic combustion characteristics. The Arrhenius parameters of the rate constant of the reaction between atomic hydrogen with the methylene group of ethanol and molecular oxygen within the temperature range of 830–970 K are determined. The reasons for the differences between the rate constants of reactions with the methylene and methyl groups of an ethanol molecule are discussed using thermochemical data. It is found that the obtained values of activation energies and preexponential factors of rate constants are in good agreement with the literature data on the region of lower temperatures.
Catalytic hydrogenation of carbon monoxide over nanostructured perovskite-like gadolinium and strontium ferrites
Abstract
The catalytic properties of perovskite-like ferrites (An + 1BnO3n + 1, where n = 1, 2, 3, …, ∞; A = Gd, Sr; and B = Fe) synthesized via ceramic and sol-gel technology in the hydrogenation of carbon monoxide are studied. The interrelation between catalytic activity, selectivity to olefins and synthetic methods for complex oxide preparation, the number of perovskite layers, crystallite size, composition, and the valence state of iron is established.
Selective hydrogenation of dienic and acetylenic compounds on metal-containing catalysts
Abstract
Studies on selective hydrogenation of dienic and acetylenic hydrocarbons and their derivatives on metal-containing catalysts are reviewed. The review covers publications over a wide period of time and concentrates on the fundamental principles of catalyst operation. The catalysts modified in the surface layer were shown to be promising for selective hydrogenation.
Kinetics of synthesis of monomeric betaines in aqueous solutions
Abstract
In the nucleophilic addition of N-(3-dimethylaminopropyl)methacrylamide to acrylic acid (1 : 1) in aqueous solutions, forming monomeric β-propiobetaine, the dependence of the initial rate on the starting reagent concentration was found to have a pronounced maximum (whose position does not depend on the temperature at 30–70°С). In the case of the addition of N,N-dimethylaminoethyl methacrylate, the dependence was exponential. The dependences of equilibrium conversions on the starting reagent concentrations were of the same type and had a maximum for both systems. The detected concentration effects are related to the peculiarities of the pre-reaction association of the reagents.
Photocatalytic activity of ZNO with different morphologies synthesized by a sonochemical method
Abstract
Different morphologies of ZnO structures were successfully synthesized in precursor solutions with the pH of 8, 9, 10, 11, and 12 by a sonochemical method at room temperature. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopy. The photocatalytic activities of ZnO samples with different morphologies were evaluated via the degradation of methylene blue (C16H18ClN3S). In this research, the flower-like ZnO sample of densely assembled nanoplates exhibited the highest photodegradation of 64% under UV light irradiation within 300 min.
Oxidation kinetics of crystal violet by potassium permanganate in acidic medium
Abstract
The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298–318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy (Ea), enthalpy change (ΔH*), free energy change (ΔG*), and entropy change (ΔS*) have also been evaluated.
Physical Chemistry of Solutions
Properties of solvate shells and the mobility of ions, according to molecular dynamics data
Abstract
The solvate shells of an ion, its velocity autocorrelation function, and diffusion coefficient D are found, and the interrelations between them are analyzed. A single ion in the system of atoms of a liquid is considered a model system. The interaction between the ion and atoms of the liquid is described by polarization potential U(r); the interaction between atoms of the liquid alone is described by the Lennard–Jones potential. A classical molecular dynamics method is used. Five solvate shells around the ion are found, and the lifetimes of atoms on each shell are calculated. It is found that the velocity autocorrelation function is of a vibrating nature. The spectrum of the autocorrelator and the frequency of cluster vibrations in a linear approximation are compared. Dependences D on parameters of potential U(r) are found. No dependence D on the ion mass is found; this is explained by solvation. The Einstein–Stokes formula and the HSK approximation are used in discussing the results. It is shown that at small radii of the ion, dependence D on parameters U(r) is described by such a model. When the ion radius is increased, the deviation from this dependence and an increase in D are observed. The results are compared to experimental mobilities of O2- and Ar2+ ions in liquid argon.
Thermodynamics of the dissolution of crystalline L-methionine in water
Abstract
The enthalpies of dissolution of crystalline L-methionine in water and aqueous solutions of potasium hydroxide at 298.15 K are measured by means of direct calorimetry. The standard enthalpies of formation are calculated for L-methionine and products of its dissociation in aqueous solution.
Enthalpies of glycylglycinate ion transfer from water to a water–ethanol solvent
Abstract
The heat effects of mixing a sodium glycylglycinate water solution with a solvent containing from 0.0 to 0.8 mole fraction of ethanol are measured by means of calorimetry at 298.15 K. The enthalpies of sodium glycylglycinate and glycylglycinate ion transfer from water to water–ethanol solutions of different compositions are calculated. The increase of the concentration of nonaqueous component in solution leads to higher endothermicity of glycylglycinate ion transfer, resulting in weaker solvation. The contribution from the enthalpy of glycylglycinate ion resolvation to the heat effects of its complexation reactions with transition metal ions is assessed.
Phase diagram of the Pr–Mn–O system in composition–temperature–oxygen pressure coordinates
Abstract
The phase relations in the Pr–Mn–O system were studied by the static method at lowered oxygen pressure in combination with thermal analysis and high-temperature X-ray diffraction. The equilibrium oxygen pressure in dissociation of PrMn2O5 and PrMnO3 was measured, and the thermodynamic characteristics of formation of these compounds from elements were calculated. The Р–Т–х phase diagram of the Pr–Mn–O system was constructed in the “composition–oxygen pressure–temperature” coordinates.
Intermolecular interactions in rifabutin–2-hydroxypropyl-β-cyclodextrin–water solutions, according to solubility data
Abstract
The formulations of rifabutin (RB) and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD), obtained using different preparation techniques, are studied by means of differential scanning calorimetry and molecular spectroscopy (FTIR, NMR, Raman scattering, and photon correlation light scattering). It is established that molecules of RB do not form inclusion complexes with the molecules of HP-β-CD, and an increase in the solubility of RB determined earlier is caused by the formation of weak intermolecular associates.
Temperature dependences of saturated vapor pressure and the enthalpy of vaporization of n-pentyl esters of dicarboxylic acids
Abstract
The saturated vapor pressures and enthalpies of vaporization of n-pentyl esters of linear С2–С6 dicarboxylic acids are determined by the transpiration method in the temperature range of 309.2–361.2 K. The dependences of enthalpies of vaporization on the number of carbon atoms in the molecule and on the retention indices have been determined. The predictive capabilities of the existing calculation schemes for estimation of enthalpy of vaporization of the studied compounds have been analyzed.
Effect of the chemical modification of a macrocycle and the acidity of a medium on the spectral properties and basicity of tetraphenylporphyrin in HCl–N,N-dimethylformamide system at 298 K
Abstract
Spectrophotometric titration is used to study the basicity of tetraphenylporphine and its derivatives with electron-donor and electron-acceptor substituents in the 4-positions of meso-aryl fragments (5,10,15,20-tetra(4-R-phenyl)porphine, R:–OH,–NH2,–COOH,–Cl) in a system НСl–N,N-dimethylformamide at 298 K. An equation for calculating the dependence of the Hammett constant (Н0) on the НСl concentration in a НСl–N,N-dimethylformamide system at 298 K is proposed. It is found that protonation of the intracycle nitrogen atoms of tetrapyrrole macrocycles of the indicated compounds occurs in two stages in this system. The corresponding ionization constants and concentration ranges of the existence of mono- and doubly-protonated dication forms of the indicated compounds are determined. It is found that both the introduction of strong substituents into the macrocycle of porphyrin and the properties of the medium facilitate the formation of mono- and doubly-protonated forms of porphyrins in solutions.
On the structures of ethylene glycol, monoethanolamine, and ethylenediamine in the liquid phase
Abstract
Characteristics of instant (I) and frozen (F) structures of ethylene glycol (EG), monoethanolamine (MEA), and ethylenediamine (ED) are determined by means of molecular dynamics in the temperature range of 268–443 K. Radial distribution functions are obtained and compared for the I- and F-structures of fluids. Coordination numbers of molecules are calculated and the energies of intermolecular hydrogen bonds are estimated for the studied compounds. The greatest difference between the I- and F-structures is observed in ED, and the least difference is observed in EG. The F-structures are compared to the crystal structures of the studied compounds.
Molecular interactions in binary mixtures of methyl formate with 1-butanol, 1-pentanol, and 1-hexanol by using ultrasonic data at 303 K
Abstract
Density (ρ), viscosity (η), and ultrasonic velocity (U) have been measured for binary mixtures of methyl formate with 1-butanol, 1-pentanol and 1-hexanol at 303 K. From the experimental results, adiabatic compressibility (β), acoustic impedance (Z), viscous relaxation time (τ), free length (Lf), free volume (Vf), internal pressure (πi), and Gibbs free energy (ΔG) have been determined. Excess values of various parameters have also been calculated and interoperated in terms of molecular interactions. The deviations in the parameters show that strength of intermolecular interactions between methyl formate with selected 1-alcohols have been observed in the order of 1-butanol < 1-pentanol < 1-hexanol.
Thermodynamic and kinetic properties of cis-diammineglycolatoplatinum in different water solvents
Abstract
The dissolution behavior of cis-diammineglycolatoplatinum (nedaplatin) in saline, water and glucose were studied by a microcalorimetric method. The integral heats and differential heats of the dissolution were measured to establish the equation for the solute and the heats. The corresponding half-life, kinetic and thermodynamic properties of the nedaplatin solutions were determined. The results show that hydrogen bonds could be generated and the dissolution entropy of nedaplatin in different solvents is negative during the dissolution process, so as to enhance the drug stability, but there is an obvious difference in stability in different solvents.
Structure of Matter and Quantum Chemistry
Computer simulation of the hydration of a chloride anion in a nanopore with hydrophilic walls
Abstract
The hydration of a single-charged chloride anion Cl- in a model plane nanopore with structureless hydrophilic walls in water vapor at room temperature is simulated using the Monte Carlo method. It is established that the adsorption of a fraction of associate molecules Cl-(H2O)N on the walls enhances its thermodynamic stability and simulates the hydration of the ion at low vapor pressures. It is shown that a second stability crisis forms on the curve of the hydration work function in the mode of weak wall hydrophilicity.
Physicochemical properties of precursors of Al2O3–ZrO2 oxide ceramics prepared by electrochemical method
Abstract
Scanning electron microscopy, X-ray, and thermal analysis are used to examine the structure and properties of dispersive systems based on aluminum and zirconium oxides prepared electrochemically. The effect the conditions of synthesis have on the structure and morphology of Al2O3–ZrO2 particles is studied. It is shown that the effect of an electric field on the reaction medium allows us to adjust the physicоchemical properties and morphology.
Insights into the cycloaddition reaction mechanism between ketenimine and unsaturated hydrocarbon: A theoretical study
Abstract
The cycloaddition reaction mechanisms between interstellar molecule ketenimine and unsaturated hydrocarbon (ethyne and ethylene) have been systematically investigated employing the second-order Møller-Plesset perturbation theory (MP2) method. Geometry optimizations and vibrational analyses have been performed for the stationary points on the potential energy surfaces of the system. The calculated results show that it can be produced the five-membered cyclic carbene intermediates through pericyclic reaction processes between ketenimine and ethyne (or ethylene). For the reaction between ketenimine and ethyne, through the following H-transferred processes, carbene intermediate can be isomerized to the pyrrole compounds. For the reaction between ketenimine and ethylene, carbene intermediate can be isomerized to the pyrroline compounds. The present study is helpful to understand the reactivity of nitrogenous cumulene ketenimine and the formation of prebiotic species in interstellar space.
Physical Chemistry of Nanoclusters and Nanomaterials
Photon correlation spectroscopic and spectrophotometric studies of the formation of cadmium sulfide nanoparticles in ammonia–thiourea solutions
Abstract
Nucleation of CdS in an aqueous ammonia solution of thiourea and cadmium chloride was studied by photon correlation spectroscopy (PCS), static light scattering, and spectrophotometry. The hydrodynamic diameter of nanoparticles, light scattering intensity, and optical density of the solutions increased with temperature and synthesis time. The processes of formation, growth, and coagulation of nanoparticles can be transferred from solution to the filter surface by continuously filtering the reaction mixture through a 200-nm filter.
Microemulsion synthesis of hydroxyapatite nanomaterials and their adsorption behaviors for Cr3+ ions
Abstract
Hydroxyapatite (HAP) nanoparticles with different morphologies, such as nanorods, nanospheres, and their mixtures were successfully synthesized by microemulsion method with soluble additive. Their adsorption capacity for Cr3+ ion was investigated. Most of the Cr3+ were absorbed by HAP within 60 min. The adsorption capacity of the HAP nanospheres was the best, and the maximum Cr3+ removal ratio was 96.4%, revealing that the metal ions adsorption by HAP is dependent on the morphology of its particles.
Enhancement of photocatalytic H2 evolution over TiO2 nano-sheet films by surface loading NiS nanoparticles
Abstract
NiS/TiO2 nano-sheet films (NiS/TiO2 NSFs) photocatalysts were prepared by loading NiS nanoparticles as noble metal-free cocatalysts on the surface of TiO2 films through a solvothermal method. The prepared samples were characterized by XRD, SEM, EDS, UV–Vis absorption spectra and XPS analysis. The photocatalytic H2 evolution and photoluminescence spectroscopy (PL) experiments indicated that the NiS cocatalysts could efficiently promote the separation of photogenerated charge carriers in TiO2 and consequently enhance the H2 evolution activity. The hydrogen yield obtained from the optimal sample reached 4.31 μmol cm–2 at 3.0 h and the corresponding energy efficiency was about 0.26%, which was 21 times higher than that of pure TiO2 NSF. A possible photocatalytic mechanism of NiS cocatalyst on the improvement of the photocatalytic performance of TiO2 NSF was also proposed.
Synthesis and characterization of N-doped zinc oxide nanotetrapods
Abstract
Nitrogen-doped (N-doped) self-assembled nanotetrapods ZnO were synthesized via chemical vapor deposition process using N2O as a dopant source via vapor-solid (VS) growth. The decomposition of N2O gas giving NO and NO2 during the synthesis provided successful N-doping of the sample. All samples (N-doped and undoped) were characterized by XRD, SEM, TEM, EDX, photoluminescence (PL), Fourier transform infrared (FT-IR), and diffuse reflection spectra. After nitrogen-doping process, N-doped ZnO samples show the change in structural and optical properties. The detailed structure and the growth mechanism of individual ZnO tetrapod is characterized by TEM and SEM investigations. The TEM study gives the direct assumption about the formation of zincblende (sphalerite) structure on the initial stage of growth of N-doped tetrapods. Besides, SEM observation indicated that tetrapods have perfect tetrahedral symmetry. N-Doped ZnO samples exhibit a broad orange-red PL emission band, peaking near 2.1 eV, in good agreement with the deep-acceptor model for the nitrogen impurity. An IR absorption peak at 3146 cm–1 at room temperature was observed for N-doped sample. This peak has been unambiguously assigned to N–H complex.
Analysis of Van der Waals interactions between nanoparticles with different geometries, with accounting for three-particle contributions to the total energy
Abstract
The Axilrod–Teller–Muto method with corrections for triple interactions is used to calculate the energies of Van der Waals interaction for nanosystems containing particles with different geometries. Results are presented for symmetric systems with identical cubic particles of different sizes, for film and cubic particle systems, and for the systems with differently oriented nanorods. Boundary and particle arrangement effects are studied. The fundamental importance of allowing for nonadditive contributions to obtain a reliable quantitative description of interaction processes inside nanosystems is demonstrated. The results are compared to ones obtained using analytical macroscopic methods and the limits of the applicability of macroscopic approximations are estimated.
Physical Chemistry of Surface Phenomena
Multifractal parametrization for the volume of space forms on surfaces of ZnxCd1–xTe–Si(111) heterocompositions and estimating the energy of a surface with fractal structure
Abstract
Multifractal (MF) analysis is used to describe the volume of space forms on the surfaces of structures in the solid solution of a ZnxCd1–xTe–Si(111) substrate. AFM images of film surfaces have been are used for MF analysis. The parameters of MF spectra are determined for the distribution of volume of surface nanoforms. Based on the formal approach and data on the parameters of the fractal state for the volume and surfaces of nanoforms, an equation is proposed that considers the contribution from the fractal structure of the surface to its surface energy. The behavior of the system’s surface energy, depending on fractal parameters that describe states of the volume and surfaces of nanoforms is discussed.
Electric and adhesion properties of an interface between Sn1 − xMnxTe single crystals and Bi–Sn alloys
Abstract
The adhesion and electric properties of an interface between Sn1 − xMnxTe single crystals and a 57 wt % Bi and 43 wt % Sn alloy in a temperature range of ∼77–300 K are studied. It is shown that the Bi–Sn alloy and the above single crystals form an ohmic contact that exhibits fairly high work of adhesion and strength of adhesion, along with low contact resistance. The deposition of the Bi–Sn alloy on the end faces of the crystals results in the formation of such intermediate phases as Bi2Te3 and SnTe at the interface, the doping of the near-contact region of the crystal, and the filling of vacancies in the tin sublattice in this region with diffusing atoms of the contact alloy components.
Physical Chemistry of Separation Processes. Chromatography
Anomalous temperature dependence of gas chromatographic retention indices of polar compounds on nonpolar phases
Abstract
The character of the temperature dependences of the retention indices RI(Т) of polar sorbates on nonpolar stationary phases was found to depend on the dosed amounts of sorbates, but not on column overloading. A physicochemical model was suggested to explain the observed anomalies in RI(Т).
Colloid Chemistry and Electrochemistry
Formation of alloys upon the simultaneous electrochemical deposition of gold and tin from ethylene glycol and aqueous electrolytes
Abstract
An ethylene glycol (EG) solution containing Au(III) and Sn(IV) compounds, and conditions for the electrochemical deposition of Au–Sn alloy based on AuSn and Au5Sn intermetallics with total tin content of 30–55 at % are proposed. Fundamental difficulties of the deposition of alloys with high tin content, (including eutectic Au–Sn alloy) from aqueous electrolytes are revealed. It is determined via voltammetry that the simultaneous deposition of gold and tin from aqueous and EG electrolytes proceeds with the depolarization effect of both Au(III) and Sn(IV) as a result of the formation of the alloy, the increase in the rate of tin cathodic reduction being more noticeable in case of EG solution. Formation of SnCl2EG(H2O)2+ complex upon the dissolution of SnCl4 · 5H2O in glycol, the stability of the composition of tetracyanoaurate ions upon the dissolution of K[Au(CN)4], and the weakening of intermolecular interactions in EG with small amounts of water were revealed via IR spectroscopy. It is suggested that the depolarization effect is due not only to alloy formation, but also to the formation of SnCl2EG(H2O)2+ cations, their association with Au(CN)4- anions, and a change in the mechanism of Au(III) and Sn(IV) reduction.
Photochemistry and Magnetochemistry
Photogalvanic and photovoltaic effects in systems based on metal complexes of Schiff bases
Abstract
The nature of the processes that occur when electrodes modified with complexes [M(Schiff)] (M = Ni, Pd, Pt; Schiff denotes four-dentate Schiff base ligands) are irradiated with visible light for the potential use of these electrodes in photoelectrochemical energy conversion devices is considered. The factors responsible for shifts in the electrode potential upon photoexcitation, i.e., the nature of the metal site, the nature of the substituents in the sensitizer, and the oxygen concentration are discussed. Tentative mechanisms of the photovoltaic effects observed for conventional and semiconductor electrodes modified with [M(Schiff)] complexes are determined.
Short Communications
Phase diagrams of a condensed decane–eicosane–cyclododecane system
Abstract
An n-eicosane–cyclododecane–n-decane system related to eutectic-type systems is investigated by means of differential thermal analysis. The eutectic alloy with melting point of–33.8°C contains 2.8 wt % of n-eicosane, 89.2 wt % of n-decane, and 8.0 wt % of cyclododecane.
Features of the complexation of octadecane-2,4-dione and lanthanide ions in Langmuir monolayers
Abstract
Monolayers of octadecane-2,4-dione on the surfaces of EuCl3 and TbCl3 solutions in the concentration range of 1 × 10–4 to 5 × 10–3 M at pH 5.8 are studied. It is found that the limiting area of octadecane-2,4-dione molecule in a monolayer dependence on Eu3+ and Tb3+ concentration is of extreme nature. The formation of complex compounds in the ligand monolayer is postulated, and structures are proposed for these compounds at different concentrations of metal ions.