LiCl-LiBr-LiVO3-Li2MoO4 quaternary system

The phase equilibrium in the LiCl-LiBr-LiVO₃-Li₂MoO₄ quaternary system was studied by differential thermal analysis. The composition corresponding to the minimum in the curve of monovariant equilibria of the quaternary system was determined to be 10.6 mol % LiCl, 38.0 mol % LiBr, 30.3 mol % LiVO₃, and 21.1 mol % Li₂MoO₄, with the melting point at 389°C.     

LiF-LiVO3-Li2SO4-Li2MoO4 four-component system

The LiF-LiVO₃-Li₂SO₄-Li₂MoO₄ four-component system was studied using differential thermal analysis. The eutectic composition was determined (mol %): LiF, 25.0; LiVO₃, 43.8; Li₂SO₄, 14.8; Li₂MoO₄, 16.5. The eutectic melting point is 428°C; the enthalpy of melting is 260 J/g.     

LiF-LiBr-LiVO3-Li2MoO4-Li2SO4 quinary system

Phase equilibria in the LiF-LiBr-LiVO₃-Li₂MoO₄-Li₂SO₄ quinary system were studied by differential thermal analysis. A eutectic composition was determined to be 4.0 mol % LiF, 38.4 mol % LiBr, 30.8 mol % LiVO₃, 19.2 mol % Li₂MoO₄, and 7.6 mol % Li₂SO₄ with a melting point of 372°C and an enthalpy of melting of 164 ± 7 kJ/kg.     

The LiF-LiCl-Li2SO4-Li2MoO4 quaternary system

Phase equilibria in the LiF-LiCl-Li₂SO₄-Li₂MoO₄ quaternary system have been investigated by differential thermal analysis. The eutectic composition (in mol %) has been determined as LiF, 16.2; LiCl, 51.5; Li₂SO₄, 16.2; and Li₂MoO₄, 16.2. The melting point of the eutectic is 402°C, and the enthalpy of melting is 291 J/g.     

Thermal Analysis of the System Li2WO4-Li4P2O7-WO3

The system Li₂WO₄-Li₄P₂O₇-WO₃ in the range of WO₃ contents of up to 60 mol % was studied by thermal analysis. In the examined range of the composition triangle, the crystallization fields of lithium tungstate and pyrophosphate, of congruently melting compound D (Li₂WO₄·WO₃), and of incongruently melting compound D ₂ (2Li₂WO₄·Li₄P₂O₇) were revealed, and the glass formation region was established. Low-melting compositions showing promise for synthesis of lithium-tungsten oxide bronzes were revealed.     

Zur Konstitution von Ba2WO3F4 und Ba2MoO3F4

On the Structure of Ba₂Wo₃F₄ and Ba₂MoO₃F₄ Ba₂[WO_2/2O₂F₂]F₂ has been prepared for the first time as colourless single crystals (from powder, Au-tube, 680°C, 90 d). It crystallizes in the monoclinic (C c) crystal system with a = 1151.1, b = 938.2, c = 718.8 pm, ß = 126.17°, Z = 4. d_x = 6.17, d_pyk = 6.13 g · cm^?3. (Fourcirclediffractometer PW 1100, Fa. Philips, MoKα-, ω-2Θ-scan, 1832 I₀(hkl) R = 8.3, R_w = 7.4%). Parameters see in the text. The isotypic Ba₂MoO₃F₄ has been prepared as powder (a = 1147.5, b = 937.0, c = 725.1 pm, ß = 126.42°). The structure shows chains of (WO_2/2O₂F₂) groups along [001]. To establish O^2? and F^? on the positions IR and Raman Spectra are employed. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Cs3LiZn2(WO4)4 and Rb3Li2Ga(MoO4)4: different filled derivatives of the cation‐deficient Cs6Zn5(MoO4)8 structure

Two new compounds, namely cubic tricaesium lithium dizinc tetrakis(tetraoxotungstate), Cs₃LiZn₂(WO₄)₄, and tetragonal trirubidium dilithium gallium tetrakis(tetraoxomolybdate), Rb₃Li₂Ga(MoO₄)₄, belong to the structural family of Cs₆Zn₅(MoO₄)₈ (space group I 3d , Z = 4), with a partially incomplete (Zn_5/6□_1/6) position. In Cs₃LiZn₂(WO₄)₄, this position is fully statistically occupied by (Zn_2/3Li_1/3), and in Rb₃Li₂Ga(MoO₄)₄, the 2Li + Ga atoms are completely ordered in two distinct sites of the space group I 2d (Z = 4). In the same way, the crystallographically equivalent A ⁺ cations (A = Cs, Rb) in Cs₆Zn₅(MoO₄)₈, Cs₃LiZn₂(WO₄)₄ and isostructural A ₃LiZn₂(MoO₄)₄ and Cs₃LiCo₂(MoO₄)₄ are divided into two sites in Rb₃Li₂Ga(MoO₄)₄, as in other isostructural A ₃Li₂R (MoO₄)₄ compounds (AR = TlAl, RbAl, CsAl, CsGa, CsFe). In the title structures, the WO₄ and (Zn,Li)O₄ or LiO₄, GaO₄ and MoO₄ tetrahedra share corners to form open three‐dimensional frameworks with the caesium or rubidium ions occupying cuboctahedral cavities. The tetrahedral frameworks are related to that of mayenite 12CaO·7Al₂O₃ and isotypic compounds. Comparison of isostructural Cs₃M Zn₂(MoO₄)₄ (M = Li, Na, Ag) and Cs₆Zn₅(MoO₄)₈ shows a decrease of the cubic lattice parameter and an increase in thermal stability with the filling of the vacancies by Li⁺ in the Zn position of the Cs₆Zn₅(MoO₄)₈ structure, while filling of the cation vacancies by larger Na⁺ or Ag⁺ ions plays a destabilizing role. The series A ₃Li₂R (MoO₄)₄ shows second harmonic generation effects compatible with that of β′‐Gd₂(MoO₄)₃ and may be considered as nonlinear optical materials with a modest nonlinearity.     

Complex compounds of tetracycline with WO 4 2− and MoO 4 2− ions. Investigation by pH-metric and conductometric methods

By using pH-metric and conductometric methods it has been found that tetracycline (H₃TC) forms with WO ₄ ^2– and MoO ₄ ^2– ions the following complex compounds: [WO₃HTC]^2–, [WO₃(H₂TC)₂]^2– and [MoO₃(H₂TC)₂]^2–. Stability constants log/gb ₁ ^k =7.86 and log ₁ ^k =7.80 for [WO₃HTC]^2– and [MoO₃HTC]^2–, respectively, have been calculated from pH-metric measurements.     

Electronic structure and one-electron properties of the MoO2Cl2 molecule. Electronic spectra of the MoO2Cl2, MoO2Br2 and WO2Br2 molecules

The SCF-X -SW method in an overlapping atomic spheres approximation has been used to calculate the electronic structure, ionization potentials, energies and oscillator strengths of the allowed optical transitions and also some of the one-electron properties of the MoO₂Cl₂ molecule. The electronic absorption spectra of vapours over molybdenum and tungsten dioxodibromides have been measured. Interpretation of the experimental electronic absorption spectra of the MoO₂Cl₂, MoO₂Br₂ and WO₂Br₂ molecules is discussed.     

Three-component systems LiBr-LiVO<Subscript>3</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript> and LiBr-Li<Subscript>2</Subscript>SO<Subscript>4</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>

Phase equilibria in the three-component systems LiBr-LiVO₃-Li₂MoO₄ and LiBr-Li₂SO₄-Li₂MoO₄ have been studied using differential thermal analysis (DTA). Eutectic compositions have been determined (mol %): in the system LiBr-LiVO₃-Li₂MoO₄, 56.0 LiBr, 22.0 LiVO₃, and 22.0 Li₂MoO₄ with a melting temperature of 413°C; and in the system LiBr-Li₂SO₄-Li₂MoO₄, 65.0 LiBr, 14.0 Li₂SO₄, and 21.0 Li₂MoO₄ with a melting temperature of 421°C. Phase fields have been demarcated.     

Tune color of single-phase LiGd(MoO4)2-X(WO4)X: Sm3+, Tb3+ via adjusting the proportion of matrix and energy transfer to create white-light phosphor

A series of LiGd(MO₄)₂: Sm³⁺, Tb³⁺ (M = Mo, W) phosphors was prepared by a conventional solid state reaction method. Powder X-Ray diffraction (XRD) analysis reveals that the compounds are of the same structure type. Their luminescent properties have been studied. The optimal doping concentrations are 8% for Sm³⁺ and 18% for Tb³⁺ in the LiGd(MoO₄)₂ host. Sm³⁺ and Tb³⁺ have different sensitivity to the Mo/W ratio. For LiGd(MoO₄)_2-X(WO₄)_X: Sm³⁺ (X = 0, 0.4, 0.8, 1.2, 1.6, 2.0), the strongest emission intensity is 1.766 times than that of the weakest, while 171 times for LiGd(MoO₄)_2-X(WO₄)_X: Tb³⁺. The experimental results show that Mo/W ratio strong influences on the properties of LiGd(MoO₄)_2-X(WO₄)_X: Tb³⁺. With the increasing of WO₄²⁻ groups concentration, the shape of characteristic excitation peaks of Tb³⁺ is almost the same and the excitation intensity gradually increase. Moreover, the energy transfer from Tb³⁺ to Sm³⁺ has been realized in the co-doped phosphors. The experimental analysis and theoretical calculations reveal that the quadrupole–quadrupole interaction is the dominant mechanism for the Tb³⁺→Sm³⁺ energy transfer. Therefore, luminous intensity can be adjusted by different sensitivities to matrix composition and energy transfer from Tb³⁺→Sm³⁺. By this tuning color method, white-light-emitting phosphor has been prepared. The excitation wavelength is 378 nm, and this indicates that the white-light-emitting phosphor could be pumped by near-UV light.     

Binary molybdates K4M2+(MoO4)3 (M2+=Mg, Mn, Co) and crystal structure of K4Mn(MoO4)3

Binary molybdates K₄M²⁺ (MoO₄)₃ (M²⁺=Mg, Mn, Co) isostructural to triclinic \ga-K₄Zn(WO₄)₃ were synthesized, and optimal conditions for their spontaneous crystallization were found. It was established by XRPA and DTA that at 530°C the structure of the compound with cobalt undergoes a transition to the orthorhombic structure of K₄Zn(MoO₄)₃. The structure of K₄Mn(MoO₄)₃ was determined from single crystal diffraction data (a=7.613, b=9.955, c=10.156 Å,α=92.28,β=106.66,γ=105.58°, Z=2, space group $P\bar 1$ , R=0.030). In this compound, Mn has a higher coordination number (CN=5+1) than that of Zn inα-K₄Zn(WO₄)₃ (CN=4+1). The main structural feature is pairs of MnO₆ octahedra linked by the bridging MoO₄ tetrahedra into ribbons stretching along the a axis. The structure is compared with related structures of binary molybdates and other members of the alluaudite family.     

Phase equilibria in the Tl2MoO4-Nd2(MoO4)3-Hf(MoO4)2 system and the crystal structure of double molybdate TlNd(MoO4)2

The Tl₂MoO₄-Nd₂(MoO₄)₃-Hf(MoO₄)₂ system was studied in the subsolidus region using X-ray powder diffraction. New triple molybdates were found to exist in this system: Tl₅NdHf(MoO₄)₆ (5: 1: 2), TlNdHf_0.5(MoO₄)₃ (1: 1: 1), and Tl₂NdHf₂(MoO₄)_6.5 (2: 1: 4). The first TlNd(MoO₄)₂ single crystals were grown from melt solutions with spontaneous nucleation. Their crystal structure was refined from X-ray diffraction data (Bruker X8 Apex automated diffractometer, MoK _α radiation, 386 F(hkl), R = 0.0136). The tetragonal unit cell parameters are as follows: a = 6.3000(2) Å, c = 9.5188(5) Å, V = 377.80(3) ų, Z = 2, ρ_calcd = 5.876 g/cm³, space group P4/nnc. The structure is a framework built of NdO₈ and TlO₈ tetragonal antiprisms linked via shared lateral edges and alternating in the checkerboard order. Layers share oxygen vertices with MoO₄ interlayer tetrahedra and are linked into the framework.     

LiFe(MoO4)2, LiGa(MoO4)2 and Li3Ga(MoO4)3

The structures of lithium iron dimolybdate, LiFe(MoO₄)₂, and lithium gallium dimolybdate, LiGa(MoO₄)₂, are shown to be isomorphous with each other. Their structures consist of segregated layers of LiO₆ bicapped trigonal bipyramids and Fe(Ga)O₆ octahedra separated and linked by layers of isolated MoO₄ tetrahedra. The redetermined structure of trilithium gallium trimolybdate, Li₃Ga(MoO₄)₃, shows substitional disorder on the Li/Ga site and consists of perpendicular chains of LiO₆ trigonal prisms and two types of differently linked Li/GaO₆ octahedra.     

Beiträge zur Chemie der Oxidhalogenide von Molybdän und Wolfram. IV. Der Transport von MoO2 mit J2 und die Existenz von MoO2J2

The possibility to transport MoO₂ with J₂ in a temperature gradient T₂/T₁ suggests the existence of MoO₂J₂. Starting from the reaction MoO₂ + J₂ ? MoO₂J₂ in the consideration of the function of temperature for the rates of chemical transport, the values ΔH^O_R ? 28.8 (±2) kcal/mole and ΔS^O_R ? 9.0 (±2) cl are deduced. From this the values ΔH^O(MoO₂J₂, g, 298) ? ?99.5 (±3.5) kcal/mole and S^O(MoO₂J₂, g, 298) ? 86 (±3) cl are derived. The comparison of the thermodynamic data for MoO₂X₂ and WO₂X₂ (X = Cl, Br, J) leads to the conclusion, that the existence of MoO₂J₂ in the vapour phase is very probable indeed.     

Phase relations in the systems M2MoO4-Cr2(MoO4)3-Zr(MoO4)2 (M = Li, Na, or Rb)

Phase equilibria in the systems M₂MoO₄-Cr₂(MoO₄)₃-Zr(MoO₄)₂ (M = Li, Na, or Rb) were investigated by X-ray powder diffraction analysis, DTA, and IR spectroscopy. The subsolidus structure of the phase diagrams of the systems under study was established. Two phases are formed in the Rb₂MoO₄-Cr₂(MoO₄)₃-Zr(MoO₄)₂ system with the molar ratios of the starting components equal to 5: 1: 1 (S ₂) and 1: 1: 1 (S ₁). Proceeding from that the isostructurality of Rb₅FeHf(MoO₄)₆ and S ₂ the unit cell, parameters are determined for S ₂.     

Investigation par analyse thermique differentielle du systeme Gd2(MoO4)3-Bi2(MoO4)3

The phase diagram of the system Gd₂(MoO₄)₃-Bi(MoO₄)₃ has been studied by differential thermal analysis (DTA). Sealed platinum tubes were used as sample holders, in order to prevent the loss of Bi₂O₃ and MoO₃ through volatilization at high temperature. Various solid solutions and new phases are reported: α-Gd_2-x-Bi_x(MoO₄)₃, β -Gd_2-x-Bi_x(MoO₄)₃, α-Bi_2-xGd_x(MoO₄)₃, 3Gd₂(MoO₄)₃·2Bi₂(MoO₄)₃, etc.     

Phase equilibria in the Tl2MoO4-Fe2(MoO4)3-Hf(MoO4)2 system and the crystal structure of ternary molybdate Tl(FeHf0.5)(MoO4)3

The subsolidus region of the ternary salt system Tl₂MoO₄-Fe₂(MoO₄)₃-Hf(MoO₄)₂ was studied by X-ray powder diffraction. New compounds Tl₅FeHf(MoO₄)₆ (5: 1: 2) and Tl(Fe,Hf_0.5)(MoO₄)₃ (1: 1: 1). were found to be formed in this system. Crystals of new ternary molybdate of the composition Tl(FeHf_0.5)(MoO₄)₃ were grown by spontaneous flux crystallization. Its composition and crystal structure were refined based on X-ray diffraction data. The mixed three-dimensional framework of the crystal structure is composed of Mo tetrahedra sharing O vertices with (Fe,Hf)O₆ octahedra. The thallium atoms occupy wide channels in the framework.     

Temperature-dependent Raman spectroscopy studies of phase transformations in the K2WO4 and the MgMoO4 crystals

Temperature-dependent Raman spectroscopy studies of K₂WO₄ and MgMoO₄ polycrystals were performed in order to obtain information about vibrational and structural changes in these materials as a function of temperature. The stability of the monoclinic phase for both K₂WO₄ and MgMoO₄ samples was assessed and our results indicated that this phase is stable in the 295–723 K and 300–770 K ranges for K₂WO₄ and MgMoO₄, respectively. It was observed that both samples underwent two phase transformations above room temperature. The first phase transformations which occur at about 633 K and 640 K for K₂WO₄ and MgMoO₄, respectively, is most likely connected with weak tilting and/or rotations of WO₄/MoO₄ tetrahedral units that lead to a disorder in the oxygen sublattice. Raman spectroscopy data also indicated that K₂WO₄ and MgMoO₄ exhibited a first-order phase transition at around 723 K and 770 K, respectively, changing from monoclinic to hexagonal symmetry.     

Systems Tl2MoO4-E(MoO4)2, where E = Zr or Hf, and the crystal structure of Tl8Hf(MoO4)6

Systems Tl₂MoO₄-E(MoO₄)₂ (E = Zr, Hf) are studied using X-ray powder diffraction, DTA, and IR spectroscopy. Compounds Tl₈E(MoO₄)₆ and Tl₂E(MoO₄)₂ are found in these systems. T-x diagrams for the Tl₂MoO₄-Zr(MoO₄)₂ system are designed. Single crystals are grown and structure is solved for Tl₈Hf(MoO₄)₆. The compound crystallizes in a monoclinic structure with the unit cell parameters a = 9.9688(6) Å, b = 18.830(1) Å, c = 7.8488(5) Å, β = 108.538(1)°, Z = 2, space group C2/m. The main structural fragment is a [HfMo₆O₂₄]^8? isle group. Three crystallographically independent types of Tl polyhedra uniformly fill spaces between [HfMo₆O₂₄]^8? fragments to form a three-dimensional framework.