Oxygen solubility in liquid nickel containing zirconium

The solubility of oxygen in liquid nickel containing zirconium at 1873 K has been experimentally studied for the first time. It has been shown that zirconium is a rather strong deoxidizing agent in liquid nickel. The equilibrium constant of the reaction of zirconium and oxygen dissolved in liquid nickel (logK_(1)(Ni) =–6.788), the interaction parameters characterizing these solutions (e_Zr(Ni)^O =–2.01; e_O(Ni)^Zr =–0.35; e_Zr(Ni)^Zr = 0.24), and the activity coefficient of zirconium in nickel at infinite dilution (γ_Zr(Ni)^o = 1.03 × 10^–8) have been determined. The zirconium content at the minimum of the oxygen solubility curve and the corresponding oxygen concentration have been determined.     

X-ray structural study of fluorinated β-diketonate complexes of zirconium(IV)

Three novel complexes of zirconium(IV) are prepared and characterized by single crystal X-ray diffraction: zirconium(IV) pivaloyltrifluoroacetonate Zr(ptac)₄, zirconium(IV) trifluoroacetylacetonate Zr(tfac)₄, and zirconium(IV) hexafluoroacetylacetonate Zr(hfac)₄. Crystal data for C₃₂H₄₀F₁₂ZrO₈: a = 19.9842(6) Å, b = 11.8417(3) Å, c = 16.4831(5) Å; β = 95.2880(10)°, monoclinic, space group Cc, Z = 4, d _calc = 1.491 g/cm³, R = 0.061. Crystal data for C₂₀H₁₆F₁₂ZrO₈: a = 21.5063(15) Å, b = 7.9511(5) Å, c = 16.0510(10) Å; β = 113.736(4)°, monoclinic, space group C2/c, Z = 4, d _calc = 1.860 g/cm³, R = 0.047. Crystal data for C₂₀H₄F₂₄ZrO₈: a = 15.3533(13) Å, b = 20.2613(15) Å, c = 19.6984(17) Å; β = 95.828(2)°, monoclinic, space group P2₁/c, Z = 2, d _calc = 2.004 g/cm³, R = 0.078. All the structures are molecular and include isolated mononuclear Zr(β-dik)₄ complex molecules. Coordination environment of zirconium atom is made by eight oxygen atoms of four β-diketonates; the coordination polyhedron is an almost regular square antiprism. The Zr-O distances fall within 2.14–2.23 Å. Complexes in the structures are joined by van der Waals interactions. Using the structural data, the van der Waals energies of crystal lattices of the studied compounds are calculated by the atom-atom potential method.     

Physicochemical properties and mixed electronic and ionic conduction of composite ceramics in the system ZrO<Subscript>2</Subscript>-Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

Composites ZrO₂-(Bi₂CuO₄+ 20 wt % Bi₂O₃) (50–80 vol % ZrO₂) are synthesized and their physicochemical properties are studied. It is demonstrated that the composites comprise triple-phase mixtures of ZrO₂ of a monoclinic modification, Bi₂CuO₄, and solid solution Bi_2?x Zr _x O_{3 + x/2} and retain their mechanical strength up to 800°C. Impedance spectroscopy is used to examine their electroconductivity at 700–800°C in the interval of partial oxygen pressures extending from 37 to 2.1 × 10⁴ Pa. Contributions made by electronic and ionic constituents to their overall conductivity are evaluated. The best specimens’ conductivity is ～0.01 S cm^?1, with the electronic and ionic transport numbers nearly equal. The composite consisting of 50 vol % ZrO₂ and 50 vol % (Bi₂CuO₄ + 20 wt % Bi₂CuO₄) is tested in the role of an oxygen-separating membrane. The selective flux of oxygen in the temperature interval 750–800°C amounts to (2.2–6.3) × 10^?8 mol cm^?2 s^?1, testifying that these materials may be used as gas-separating membranes.     

Synthesis,crystal structure,and kinetics of thermal decomposition of the Zn(II) complex with vanillin

A complex [Zn(C₈H₇O₃)₂(H₂O)₂] (C₈H₈O₃ is vanillin) has been synthesized and characterized by IR, elemental analysis, and X-ray diffraction single-crystal analysis. The crystals are monoclinic, space group C2/c, a = 22.236(8) Å, b = 10.594(2) Å, c = 7.8190(16) Å, α = 89.90(3)°, β = 106.87(4)°, γ = 89.99(3)°, V = 1762.6(8) ų, Z = 4, F(000) = 832, S = 1.079, ρ _c = 1.521g cm^?3, R = 0.0221, R _w = 0.0604, μ = 1.433 mm^?1. The Zn²⁺ ion is six-coordinated with a distorted octahedron geometry. The complex forms a three-dimensional network through intermolecular hydrogen bonds. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal conditions by the TG and DTG methods. The kinetic equation can be expressed as dα/dt = Ae^?E/RT 2(1 ? α)[1 ? ln(1 ? α)]^1/2. The kinetic parameters (E, A), activation entropy ΔS ^≠, and activation free-energy ΔG ^≠ were also gained.     

Synthesis and crystal structure of hydrogen strontium paratungstate Sr<Subscript>4.5</Subscript>H[W<Subscript>12</Subscript>O<Subscript>40</Subscript>(OH)<Subscript>2</Subscript>] · 30H<Subscript>2</Subscript>O

The conditions for formation of individual isopolytungstates in solutions of the Sr(NO₃)₂-Na₂WO₄-HNO₃-H₂O system acidified to Z = ν(H⁺)/ν(WO ₄ ^2? ) = 1.29 were studied. The conditions of formation of strontium paratungstate B, strontium hydroheptatungstate, and hydrogen strontium paratungstate were determined. An X-ray diffraction study of single crystals of Sr_4.5H[W₁₂O₄₀(OH)₂] · 30H₂O was carried out. Selected crystallographic data for H₆₃O₇₂Sr_4.50W₁₂ are: M _r = 3815.99, monoclinic, space group P2₁/c, a = 11.41270(10) Å, b = 23.7575(3) Å, c = 12.4392(2) Å, β = 110.476(2)°, V = 3159.64(7) ų at T = 293 K, Z = 2, ρ = 4.011 g/cm³, F₀₀₀ = 3396, μ(MoK _α) = 25.635 mm^?1, ?14 ≤ h ≤ 14, ?30 ≤ k ≤ 30, ?16 ≤ l ≤ 16, R _F = 0.0430, wR ² = 0.1067 (R _F = 0.0506, wR ² = 0.1129), and S = 1.043.     

Crystal structures of two one-dimensional coordination polymers constructed from Mn<Superscript>2+</Superscript> ions,chelating hexafluoro-acetylacetonate anions,and flexible bipyridyl bridging ligands

The syntheses and crystal structures of two one-dimensional coordination polymers, [Mn(C₅HO₂F₆)₂(C₁₆H₂₀N₂)] _n (1) and [Mn(C₅HO₂F₆)₂(C₂₀H₂₀N₂)] _n (2), are described, where C₅HO₂F₆ ^? is the hexafluoro acetylacetonate anion, C₁₆H₂₀N₂ is 1,6-bis(4-pyridyl)-hexane, and C₂₀H₂₀N₂ is 1,4-bis[2-(3-pyridyl)ethyl]-benzene. In both phases, the metal ion lies on a crystallographic twofold axis and is coordinated by two chelating C₅HO₂F₆ ^? anions and two bridging bipyridyl ligands to generate a cis-MnN₂O₄ octahedron. The bridging ligands, which are completed by crystallographic inversion symmetry in both compounds, connect the metal nodes into zigzag [20 1 ] chains in 1 and contorted [001] chains in 2. Intrachain C–H???O interactions occur in 1 but not in 2, which may be correlated with the relative orientations of the ligands. Crystal data: 1, C₂₆H₂₂F₁₂MnN₂O₄, M _r = 709.40, monoclinic, C2/c (No. 15), a = 9.3475(2) Å, b = 16.6547(3) Å, c = 18.3649(4) Å, β = 91.1135(8)°, V = 2858.50(10) ų, Z = 4, R(F) = 0.030, w R(F ²) = 0.075. 2, C₃₀H₂₂F₁₂MnN₂O₄, M _r = 757.44, monoclinic, C2/c (No. 15), a = 19.9198(2) Å, b = 10.6459(2) Å, c = 16.8185(3) Å, β = 119.8344(8)°, V = 3093.91(9) Å3, Z = 4, R(F) = 0.032, w R(F ²) = 0.078.     

Calculation of the thermodynamic characteristics of ions in vapor over sodium fluoride

The geometric parameters, normal vibration frequencies, and thermochemical characteristics of the ions present in vapor over sodium fluoride, Na₂F⁺, Na₃F ₂ ⁺ , NaF ₂ ^? , and Na₂F ₃ ^? , were calculated ab initio by the Hartree-Fock method and taking into account electron correlation. The main equilibrium configuration of all ions was found to be the linear configuration of D _∞h symmetry. Pentaatomic ions could also exist as two isomers, planar cyclic of C _2v symmetry and bipyramidal of D _3h symmetry. Their energies were higher than that of the D _∞h isomers, and their contents in vapor were negligibly low. The energies and enthalpies of dissociation of the ions with the elimination of the NaF molecule were calculated. The enthalpies of formation of the ions were obtained.     

Volatile zirconium complexes with sterically hindered β-diketonates: Structure and thermal properties

The structure and thermal properties of a novel zirconium(IV) complex with a methoxy substituted β-diketonate ligand tetrakis-(2-methoxy-2,6,6-trimethylheptane-3,5-dionato)zirconium are described. The complex sublimes without decomposition under low pressure (10^–2 Torr) at 200 °C. The crystal structure of the complex is molecular and is composed of two structural Zr(zis)₄ isomers in a 1:1 ratio. The crystallographic data are as follows: C₈₈H₁₅₂F₂₄O₂₄Zr₂, P-1, a = 12.1350(7) Å, b = 19.7733(10) Å, c = 21.0526(12) Å, α = 83.338(2)°, β = 89.571(2)°, γ = 73.515(2)°, V = 4809.5(5) ų, Z = 2, d = 1.227 g/cm³. The coordination environment of the zirconium atom consists of eight oxygen atoms from four β-diketonate ligands; the coordination polyhedron is a square antiprism. The Zr–O distances are in a range 2.127-2.202 Å. The thermal properties of the complex are studied by TG–DTA. The effect of the crystal structure (molecular packing) on the volatility and thermal properties is compared for the new complex and two other analogous zirconium complexes with β-diketonate ligands containing bulky terminal substituents. The results of the mass spectrometric study of thermal behavior of the complexes on programmed heating of vapor under the conditions similar to those in a hot wall CVD reactor under low pressure, including the decomposition in the presence of oxygen, are discussed.     

The synthesis and thermodynamic properties of strontium fluoromanganite Sr<Subscript>2.5</Subscript>Mn<Subscript>6</Subscript>O<Subscript>12.5 − δ</Subscript>F<Subscript>2</Subscript>

The existence of the [SrF_0.8O_0.1]_2.5[Mn₆O₁₂] = Sr_2.5Mn₆O_{12.5 ? δ}F₂ compound was established in the SrO-Mn₂O₃-SrF₂ system at 900°C and p(O₂) = 1 atm. The crystal structure of strontium fluoromanganite was determined from the X-ray powder diffraction data, electron diffraction, and high-resolution electron microscopy. It can be described in the monoclynic system with four Miller hklm indices: hklm: H = h a* + k b* + l c ₁ ^* + m q ₁, q ₁, q ₁ = c ₂ ^* = γc ₁ ^* , γ ≈ 0.632, a ≈ a ≈ 9.72 Å, b ≈ 9.55 Å, c ₁ ≈ 2.84 Å, c ₂ ≈ 4.49 Å, monoclinic angle γ ≈ 95.6°. The electromotive force method with a solid fluorine ion electrolyte was used to refine the composition of fluoromanganite and determine the thermodynamic functions of its formation from phases neighboring in the phase diagram (SrMn₃O₆, Mn₂O₃, SrF₂, and oxygen), ΔG°, kJ/mol = ?(111.7 ± 1.9) + (89.5 ± 1.5) × 10^?3 T.     

Synthesis and Luminescence of Europium-Containing Compositions Based on Yttrium Oxide and Oxyfluorides

By heating the products isolated from an ethyl acetate medium, luminescent europium-containing compositions based on yttrium oxyfluorides and oxide have been synthesized. The concentration of Eu³⁺ ions in the compositions was from 0.10 to 10 at % of the yttrium content. It has been shown that the (Eu_хY_1–х)_nO_n–1F_{n + 2}, (Eu_хY_1–х)OF, (Eu_хY_1–х)₂O₃, and (Eu_хY_1–х)5O₄F₇ phases are formed during the synthesis. The luminescence of the compositions is related to the ⁵D₀ → ⁷F_j electron transitions of Eu³⁺ ions. It depends on the synthesis conditions, the type of matrix, the position of the Eu³⁺ ions in the crystal lattice, the excitation wavelength, and other factors.     

Apparent Molar Volumes of Aqueous Solutions of Magnesium Tetraborate from 283.15 to 363.15 K and 0.1 MPa

Densities for aqueous solutions of magnesium tetraborate MgB₄O₇(aq) at the molalities of (0.00556–0.03341) mol·kg^?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V _? ) of MgB₄O₇(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB₄O₇(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a₀?+?a₁?×?T?+?a₂?×?T ²?+?a₃/T?+?a₄?×?ln(T)?+?a₅?×?T ³ (where T is temperature in Kelvin, a _i are model parameters) for MgB₄O₇ were obtained for the first time.     

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>, Ni<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript>) and the 3-amino 4-methyl benzoate ion

The syntheses and crystal structures of the layered coordination polymers M(C₈H₈NO₂)₂ [M = Mn (1), Co (2), Ni (3) and Zn (4)] are described. These isostructural compounds contain centrosymmetric trans-MN₂O₄ octahedra as parts of infinite sheets; the ligand bonds to three adjacent metal ions in μ³-N,O,O′ mode from both its carboxylate O atoms and its amine N atom. In each case, weak intra-sheet N–H?O and C–H?O hydrogen bonds may help to consolidate the structure. Crystal data: 1, C₁₆H₁₆MnN₂O₄, M _r = 355.25, monoclinic, P2₁/c (No. 14), a = 10.6534(2) Å, b = 4.3990(1) Å, c = 15.5733(5) Å, β = 95.1827(10)°, V = 726.85(3) ų, Z = 2, R(F) = 0.026, wR(F ²) = 0.067. 2, C₁₆H₁₆CoN₂O₄, M _r = 359.24, monoclinic, P2₁/c (No. 14), a = 10.6131(10) Å, b = 4.3374(4) Å, c = 15.3556(17) Å, β = 95.473(4)°, V = 703.65(12) ų, Z = 2, R(F) = 0.041, wR(F ²) = 0.091. 3, C₁₆H₁₆N₂NiO₄, M _r = 359.02, monoclinic, P2₁/c (No. 14), a = 10.6374(4) Å, b = 4.2964(2) Å, c = 15.2827(8) Å, β = 95.9744(14)°, V = 694.66(6) ų, Z = 2, R(F) = 0.028, wR(F ²) = 0.070. 4, C₁₆H₁₆N₂O₄Zn, M _r = 365.68, monoclinic, P2₁/c (No. 14), a = 10.6385(5) Å, b = 4.2967(3) Å, c = 15.2844(8) Å, β = 95.941(3)°, V = 694.89(7) ų, Z = 2, R(F) = 0.038, wR(F ²) = 0.107.     

Paramagnetic centers related to Al,Sc, In,and Nb impurities in KTiOAsO<Subscript>4</Subscript>crystals

Electron paramagnetic resonance (EPR) is applied to study Al-, Sc-, In-, and Nb-doped KTiOAsO₄ (KTA) crystals. Paramagnetic hole centers O^? are observed after ionizing irradiation of KTA crystals. These centers are, as a rule, unstable at room temperature and are slowly annealed for about two weeks. Oxygen ions are bridging two cations in KTA. Near the impurity, two p-orbitals of oxygen atoms participate in covalent bonding with cations, whereas the third p-orbital remains free and under the radiation effect captures the hole thus forming the paramagnetic center of M ⁿ⁺-O^?-M^(n?1)+ (here M ⁿ⁺ is the lattice cation and M^(n?1)+ is the impurity cation of Al, In, Sc, or Nb). In the centers investigated the specific principal direction of the g-factor g ～ 2 is normal to the M ⁿ⁺-O^?-M^(n?1)+ plane, and the main value of g _max falls in this plane. The direction of the O^?-M^(n?1)+ bond is close to the selected direction of the hyperfine interaction with the impurity ion. The models of six hole centers and the found parameters of EPR spectra are discussed.     

Synthesis and crystal structure of a 1D coordination polymer [Cd(NITpPy)<Subscript>2</Subscript>(N(CN)<Subscript>2</Subscript>)<Subscript>2</Subscript>)]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A novel one-dimensional chain complex [Cd(NITpPy)₂(N(CN)₂)₂)] _n (NITpPy = 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and characterized structurally. It crystallizes in the triclinic space group P \(\bar 1\) with a = 7.1742(13), b = 9.4913(17), c = 13.208(2) Å, α = 71.020(2)°, β=87.308(2)°, γ = 70.503(2)°, V = 799.8(3) ų, C₂₈H₃₂CdN₁₂O₄, Mr = 713.06, Z = 1, ρ _c = 1.48 g/cm³, μ(MoK _α) = 0.736 mm^?1, F(000) = 364, R = 0.0275 and wR = 0.0605 for 2702 observed reflections with I > 2σ(I). The crystal structure consists of infinite chains of [Cd(NITpPy)₂(N(CN)₂)₂)] units linked by dicyanamide anions [N(CN)₂]^?. Each Cd²⁺ ion is six-coordinated with the geometry of a distorted octahedron.     

Investigation of the α-BiO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>F<Subscript>3 − 2<Emphasis Type="Italic">y</Emphasis></Subscript>-based tysonite-type solid solutions by X-ray diffraction and impedance spectroscopy

Tysonite solid solutions Bi_{1 ? x} M _x (O, F)_{3 ? d} (M = Na, Sr, or Nd) based on α-BiO _y F_{3 ? 2y} were prepared by solid-state synthesis at 873 K with subsequent quenching to ice-cold water. Aliovalent substitutions in both the cation and anion sublattices (M ⁿ⁺ → Bi³⁺ and O^2? → F^?) made it possible to vary the anion-vacancy density. The solid solutions were characterized by X-ray diffraction and impedance spectroscopy. The homogeneity regions for the tysonite solid solution were determined; triangulation schemes at 873 K were suggested for the systems BiF₃-BiOF-NaBiF₄ and BiF₃-BiOF-SrF₂, and a scheme of the subsolidus phase diagram for the system BiO_0.1F_2.8-NdF₃ was suggested. In the system BiO_0.1F_2.8-NdF₃, the transition temperature from the low-symmetry tysonite phase (phase II, space group P \(\overline 3 \) c1, Z = 6) to the high-symmetry one (phase I, space group P6₃/mmc, Z = 2) decreases with increasing anion-vacancy density. Conductivity measurements were performed in the temperature range 300–523 K and the frequency range from 5 to 1 × 10⁶ Hz. The conductivity of samples in the system BiO_0.1F_2.8-NdF₃ increases with increasing bismuth-ion and anion-vacancy concentrations.     

Dissolution kinetics of silver metal nanoparticles in their reaction with nitric acid in an reverse micelle solution of AOT

The dissolution of silver nanoparticles in their reaction with aqueous HNO₃ solubilized to an reverse micelle solution of sodium bis(2-ethylhexyl)sulfosuccinate in decane is studied spectrophotometrically. A physicochemical model is advanced for quantifying the process kinetics on th basis of the following autocatalytic scheme: Ag⁰ + H⁺ + NO ₃ ^? → Ag⁺ + products (k ₁), and Ag⁰ + Ag⁺ + NO ₃ ^? → 2Ag⁺ + products (k ₂). The effective rate constant k ₂ decreases with decreasing solubilization capacity V _S/V _O (where V _S is the volume of the solubilized dispersed aqueous phase and V _O is the volume of the micelle solution); the solubilization capacity determines the size of the micelle cavities in which the reaction between Ag⁰ and HNO₃ occurs: k ₂ = 74 (V _S/V _O) · 100% ≈ 3.8%), 41 (2.9), and 35 (2.0) L/(mol s). The effective constant k ₁ is determined with a high uncertainty; the effect of V _S/V _O on k ₁ has the opposite tendency.     

Structural role of large cations in sulfides with Cs<Superscript>+</Superscript> and Tl<Superscript>+</Superscript>

The results of a crystallographic analysis of the structures of CsFe₂S₃, Tl₂PbZrS₄, and Tl₂PbGeS₄ with a 1:1 cation–anion ratio are used to identify a joint F sublattice for Cs and S in the first compound and two separate F sublattices for cations and anions in the second compound (the PbS structural type). The substitution of the small Ge⁴⁺ (with its tetrahedral coordination by sulfur) for Zr⁴⁺ in the composition results in an increase in the unit cell volume, i.e., a decrease in the packing density for both cations and anions in the structure of the third compound. In the absence of regular F sublattices, there are “two-dimensional” orderings, typical of the PbS type, for the atomic positions in the projections of this structure.     

<Emphasis Type="Italic">cis</Emphasis>-Dioxomolybdenum(VI) complexes of sterically encumbered phenol-based tetradentate N<Subscript>2</Subscript>O<Subscript>2</Subscript> ligands: Structural,spectroscopic, and electrochemical studies

Two cis-dioxomolybdenum(VI) complexes [MoO₂L] (L: L ¹, 2 and L: L ², 3) in a phenol-based sterically encumbered N₂O₂ ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P2₁/a with unit cell dimensions as a=16.2407(17) Å, b=7.2857(8) Å, c=18.400(2) Å, β=98.002(9)°, Z=4, and d _cal=1.486 g cm^?3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) Å, b=12.637(3) Å, c=34.673(5) Å, Z=4, and d _cal=1.187 g cm^?3. The structures were refined by a full-matrix least-squares procedure on F ² to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N₂O₄ donor set, which features a cis-Mo(–O)₂ and a trans-Mo(OPh)₂ arrangement. Compound 2 undergoes a quasireversible one-electron reduction at ?1.3 V vs Ag/AgCl reference due to Mo^VIO₂/Mo^VO₂ electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.     

Synthesis,structure, and thermal expansion of sodium zirconium arsenate phosphates

Sodium zirconium arsenate phosphates NaZr₂(AsO₄) _x (PO₄)_3?x were synthesized by precipitation technique and studied by X-ray diffraction and IR spectroscopy. In the series of NaZr₂(AsO₄) _x (PO₄)_3?x , continuous substitution solid solutions are formed (0 ≤ x ≤ 3) with the mineral kosnarite structure. The crystal structure of NaZr₂(AsO₄)_1.5(PO₄)_1.5 was refined by full-profile analysis: space group R \(\bar 3\) c, a = 8.9600(4)Å, c = 22.9770(9) Å, V = 1597.5(1) ų, R _wp = 4.55. The thermal expansion of the arsenate-phosphate NaZr₂(AsO₄)_1.5(PO₄)_1.5 and the arsenate NaZr₂(AsO₄)₃ was studied by thermal X-ray diffraction in the temperature range of 20–800°C. The average linear thermal expansion coefficients (α_av = 2.45 × 10^?6 and 3.91 × 10^?6 K^?1, respectively) indicate that these salts are medium expansion compounds.     

Crystal structure of nickel paratungstate B Ni<Subscript>5</Subscript>[W<Subscript>12</Subscript>O<Subscript>40</Subscript>(OH)<Subscript>2</Subscript>]·37H<Subscript>2</Subscript>O

From the solution of the system Na₂WO₄-HNO₃-Ni(NO₃)₂-H₂O acidified to Z = ν(H⁺)/ν(WO ₄ ^2? ) = 1.29, the green crystals of nickel paratungstate B Ni₅[W₁₂O₄₀(OH)₂]·37H₂O are isolated. By FTIR spectroscopy the isopoly anion is shown to belong to the structural type of paratungstate B. Using single crystal X-ray analysis, the structure of Ni₅[W₁₂O₄₀(OH)₂]·37H₂O is solved (M _r = 3840.36, monoclinic, P2₁/c space group, a = 21.9061(6) Å, b = 14.9297(4) Å, c = 22.1391(6) Å, β = 107.609(3)°, V = 6901.4(3)ų at T = 293 K, Z = 4, d_x = 3.696 g/cm³, F ₀₀₀ = 6944, μ = 21.368 mm^?1, ?33 ≤ h ≤ 33, ?22 ≤ k ≤ 22, ?33 ≤ l ≤33; the final uncertainty values for the observed reflections are R _F = 0.0532, wR ² = 0.0831 (R _F = 0.1088, wR ² = 0.0894 over all independent reflections), S = 0.978; CSD-421468).