Investigation of phase equilibria in the Er2O3–Na2O–P2O5 system: the partial system ErPO4–NaPO3–Er(PO3)3

The partial system ErPO₄–NaPO₃–Er(PO₃)₃ of the Er₂O₃–Na₂O–P₂O₅ oxide system has been investigated by thermoanalytical methods and X-ray powder diffraction. On the basis of the obtained results the phase diagram of the partial system is proposed. The system is bounded by three subsystems: (i) ErPO₄–Er(PO₃)₃, (ii) Er(PO₃)₃–NaPO₃ and (iii) ErPO₄–NaPO₃. Their phase diagrams are proposed. In the Er(PO₃)₃–NaPO₃ subsystem an intermediate compound NaEr(PO₃)₄ occurs; it melts incongruently at 655 °C. It was found that ErPO₄ and NaEr(PO₃)₄ form a section which is a real system only in the subsolidus region (below 646 °C). Two ternary invariant points (one ternary peritectic and one ternary eutectic) occur in the investigated partial system ErPO₄–NaPO₃–Er(PO₃)₃.     

β-Fe2O3 nanomaterials from an iron(II) diketonate-diamine complex: a study from molecular precursor to growth process

Iron oxide is a key multi-functional material in many different fields of modern technology. The β-Fe(2)O(3) cubic phase, one of the least studied Fe-O systems, was obtained by Chemical Vapor Deposition (CVD) using for the first time a Fe(II) β-diketonate diamine complex, Fe(hfa)(2)·TMEDA, as the molecular source (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine). The strong visible light absorption of β-Fe(2)O(3) deposits highlights their possible functional application in photocatalytic hydrogen production under solar light. A comprehensive investigation on the Fe(ii) complex, performed by a joint experimental-theoretical approach, explains the molecular origin of its excellent thermal behaviour and reveals why this species is a successful precursor for the CVD of iron oxide nanostructures.     

Activity Coefficients for the System HCl +GaCl3 + H2O from 5 to 55°C

Activity coefficients for HCl in HCl + GaCl₃ + H₂O at eleven different temperatures from 5 to 55°C have been determined at total experimental ionic strengths from 0.01 to 3.0 mol-kg^–1 using a cell of the type: Pt; H₂(g, 1 atm)|HCl (m_A) + GaCl₃(m_B)|AgCl, Ag (A) The results for the 770 experimental emf data points have been used to determine the variation of the activity coefficients of HCl with the change in molality of GaCl₃ in the solution. It is found that the linear form of Harned's rule is not obeyed for this system.     

Study of ceramic pigments based on cobalt doped Y2O3–Al2O3 system

Ceramic pigments based on Y₂O₃–Al₂O₃ system doped by cobalt as a colourant agent were synthesized by solid-state reaction at temperatures up to 1,400 °C. The reactivity of initial mixtures of components was improved by the mineralizer LiF and the mechanical activation in a planetary ball mill. The temperature region of the product formation was followed by the method of thermal analysis. The effect of the synthetic method on the phase composition of the products was studied by X-ray diffraction analysis. Studied pigment-application properties of the product include the measurement of optical properties in the visible region of light and particle size distribution. The simple solid-state reaction led to the formation of turquoise samples that contain mainly blue CoAl₂O₄ spinel and next to it also YAlO₃ perovskite and Y₃Al₅O₁₂ garnet phases. The mineralizer LiF promotes the formation of yttrium aluminium double oxides of sandy-yellow to grey–brown colour hue, although the samples also contain small amount of blue CoAl spinel phase. Intensive milling process did not results in CoAl spinel phase and the samples contain yttrium aluminium perovskite and cobalt oxide. Evaluation of Kubelka–Munk absorption as a function of the pigment concentration was found that hiding is complete by adding of 5 mass% of pigment to the ceramic glaze. Resulting colour hue of all pigment applications into ceramic glaze is blue. The size of particles lies in the range of 7–26 μm.     

Gas hydrate formation in the system C2H6–H2–H2O at pressures up to 250 MPa

Decomposition curves of gas hydrates formed in the ethane–hydrogen–water system were studied in the pressure interval 2–250 MPa. Gas hydrates synthesized at low (up to 5 MPa) pressures were also studied with use of X-ray powder diffraction and Raman spectroscopy. It was shown that ethane–hydrogen mixtures with hydrogen contents 0–30 mol.% form cubic structure I gas hydrates. Higher hydrogen concentration most probably results in appearance of another hydrate phase. We speculate that the gas mixtures with the hydrogen content above 60 mol.% form cubic structure II double hydrate of hydrogen and ethane at temperatures below ≈280 K and pressures above 25 MPa.     

Palladium-catalyzed oxidative C–H bond coupling of indoles and benzaldehydes: a new approach to the synthesis of 3-benzoylindoles

A palladium-catalyzed dehydrogenative acylation of indoles using easily accessible aldehydes as the acyl source is described. This reaction provides a new approach for the synthesis of 3-acylindoles.     

Thermodynamics of the System HCl + SmCl3 + H2O from 5 to 55°C. Application of Harned's Rule and the Pitzer Formalism

A comprehensive array of electrochemical cell measurements for the system HCl +SmCl₃ + H₂O was made from 5 to 55°C using a cell without liquid junction ofthe type:Pt; H₂(g, 1 atm)|HCl (m _A) + SmCl₃ (m _B)|AgCl, Ag (A)The present study, unlike previous studies of trivalent ions, are not complicatedby hydrolysis reactions. Measurements of the emf were performed for solutionsat constant total ionic strengths of 0.025, 0.05, 0.1, 0.25, 0.5, 1.0, 1.5, 2.0, 2.5,and 3.0 mol-kg^–1. The mean activity coefficients of HCl (_HCl) in the mixtureswere calculated using the Nernst equation. All the experimental emf measurements(about 850) were first treated in terms of the simpler Harned's rule. Harnedinteraction coefficients (_AB and _AB) were calculated. The linear form of Harned'srule is valid for most ionic strengths, but quadratic terms are needed at I = 1.5and 3 mol-kg^–1. The Pitzer model was used to evaluate the activity coefficientsusing literature values, ⁽⁰⁾, ⁽¹⁾, and C , for HCl from 0 to 50°C and 25°C forSmCl₃. The effect of temperature on the parameters for SmCl₃ has been estimatedusing enthalpy and heat-capacity data. The mixing parameter _H,Sm wasdetermined at 25°C. The addition of the _H,Sm,Cl coefficient did not improve the fitsignificantly and no temperature dependence was found to be significant. Thevalue of _H,Sm = 0.2 ± 0.01 represented the values of _HCl with a standarddeviation of = 0.009 over the entire range of temperatures and ionic strength.The use of higher-order electrostatic effects (^E_H,Sm, ^E_H,Sm) was included as itgave a better fit of the activity coefficients of HCl.     

Synthesis and selected properties of a new solid solution in the Zn2FeV3O11–Mg2FeV3O11 system

The binary Zn₂FeV₃O₁₁?CMg₂FeV₃O₁₁ system has been studied by XRD, DTA, IR, and SEM methods. A new continuous substitution solid solution with the formula Zn_2?x Mg _x FeV₃O₁₁ has been obtained by high-temperature synthesis. The DTA investigations were used to choose the heating temperatures as well as for determination of thermal stability of the new triclinic phase. The influence of the degree of Mg²⁺ ion incorporation on the unit cell volume as well as on the position of the IR absorption bands of the solid solution have been determined. The morphology of crystals of the new phase is presented.     

Comparison of the impact of the addition of three alkaline earth metal oxides BaO,SrO and ZnO on sintering of glass–ceramic glazes from the SiO2–Al2O2–CaO–MgO–Na2O–K2O system

Journal of Thermal Analysis and Calorimetry - Glazes are the most important elements in the technology of producing the ceramic wares. They not only give aesthetic effects, like color and gloss,...     

Study of the solubility of components in the system Mg(ClO3)2-2NH2C2H4OH · H3C6H5O7-H2O

The solubility of components in the system Mg(ClO₃)₂-2NH₂C₂H₄OH · H₃C₆H₅O₇-H₂O was studied from the complete freezing temperature ?59.4°C to 20.0°C. A polythermal solubility diagram was constructed, in which the crystallization fields were determined for ice, Mg(ClO₃)₂ · 16H₂O, Mg(ClO₃)₂ · 12H₂O, Mg(ClO₃)₂ · 6H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇ · H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇, and two new compounds, [(HOC(CH₂COOH)₂COO)₂Mg · 2H₂O] and [HOC(CH₂COO)₂MgCOOH · 2H₂O], which were identified by chemical and physicochemical analysis methods.     

Parameters of Li2O2 · H2O crystallization from the LiOH-H2O2-H2O ternary system

The decomposition kinetics of peroxide products contained in the liquid phase of the LiOH-H₂O₂-H₂O ternary system were studied, and the applicability of the solubility method to studying this system was demonstrated for hydrogen peroxide concentrations in the liquid phase from 2 to 6 wt % and temperatures of 21–33°C. The stabilizing influence of solid Li₂O₂ · H₂O on hydrogen peroxide decomposition was demonstrated. The temperature and concentration boundaries of existence were determined for the Li₂O₂ · H₂O phase, whose identity was verified by chemical analysis and qualitative X-ray powder diffraction analysis.     

Activity Coefficients of HCl + GdCl3 + H2O System from 5 to 55°C. Application of Pitzer Formalism

The emf of the cell

Thermodynamic properties of the system NH4NO3–KNO3–H2O at 298.15 K

The water activity and osmotic coefficients of the system {y NH₄NO₃+(1-y) KNO₃}(aq) has been measured at total molalities from 0.2 mol kg⁻¹ to about saturation of one of the solutes for different ionic-strength fractions y of NH₄NO₃ with y=0.2, 0.5 and 0.8 at the temperature 298.15 K using the hygrometric method. The obtained data allow the deduction of the thermodynamic parameters. From these measurements, new Pitzer ionic mixing parameters are determined and used to predict the solute activity coefficients in the mixture. The results obtained are used to calculate the excess Gibbs energy at total molalities for different ionic-strength fractions of NH₄NO₃.     

Transport numbers of H+ and O2- in the electrochemical system (H2 + H2O),Me/BaCe0.9Nd0.1O3-α/Me,(H2 + H2O)

In the temperature range 873–1123 K, transport numbers of oxygen ions and protons are determined in the system (H₂ + H₂O), Me/BaCe_0.9Nd_0.1O_3-α/Me,(H₂ + H₂O), where Me = Ag, Au, Pt, Ni, by the emf and current methods. The determined transport numbers are independent of the determination method, the electrode material, the current direction (anodic and cathodic polarization of the electrode), polarizability of electrodes, and the partial water (hydrogen) pressure in the gas phase. This unambiguously suggests that the transport numbers refer to the solid electrolyte, and not the electrochemical system as a whole. It also follows that partial currents of the hydrogen ionization and the oxygen ion discharge are determined by the transport numbers of protons and oxygen ions in the electrolyte. At a constant temperature, their ratio is affected by neither the electrode potential nor the gas phase composition, i.e., both electrode reactions have a common limiting step (or steps). Deceased.     

Phases in the subsolidus area of the system CuO–V2O5–Fe2O3

The phase equilibria in the solid state in the system FeVO₄?CCu₃V₂O₈ and FeVO₄?CCuO have been determined. Based on the obtained DTA and XRD analysis results and some additional research, a phase diagram in the whole subsolidus area of the system CuO?CV₂O₅?CFe₂O₃ has been worked out. Eighteen subsidiary subsystems can be distinguished in this ternary system. Basic properties of the obtained phases with howardevansite- and lyonsite-type structure have been investigated by DTA, IR, and SEM methods.     

The System HCl + NdCl3 + H2O from 5 to 55 ∘C: A Study of Harned's Rule

The activity coefficients of HCl (γ_A) in aqueous mixtures of HCl and NdCl₃ were determined by the electromotive-force (emf) measurement of cells without liquid junctions of the type:

DTA–TGA and XRD study of the formation of LISICON-type Li1+xCrxZr2−x(PO4)3 ceramic using ZrOCl2·8H2O as precursor

Journal of Thermal Analysis and Calorimetry - This contribution is devoted to thermoanalytical investigation of the mechanism of the formation of solid solutions of Li1+xCrxZr2?x(PO4)3. The...