Magnetic behavior of tetrahedral Cr4+ compounds: Sr2CrO4, Ba2CrO4, and Ba3CrO5

The preparation of the compounds Sr₂CrO₄, Ba₂CrO₄, and Ba₃CrO₅ is described. The characterization of these three Cr⁴⁺ compounds by X-ray and magnetic susceptibility experiments has been conducted. The magnetic moments for Sr₂CrO₄, Ba₂CrO₄, and Ba₃CrO₅ were determined to be in good agreement with the calculated value expected for a tetrahedral Cr⁴⁺ ion. Weak antiferromagnetic ordering for all three compounds is indicated from the small paramagnetic Weiss constants determined from the susceptibility data in the temperature region 80–300 K. Distortions of the tetrahedra from ideality, as determined from the structural features, further cause a reduction in the magnetic moments from the theoretical values.     

Ternary Systems LiBr–LiVO<Subscript>3</Subscript>–Li<Subscript>2</Subscript>CrO<Subscript>4</Subscript> and KBr–KVO<Subscript>3</Subscript>–K<Subscript>2</Subscript>CrO<Subscript>4</Subscript>

The binary system KVO₃–K₂CrO₄ and two ternary systems, LiBr–LiVO₃–Li₂CrO₄ and KBr–KVO₃–K₂CrO₄, were studied. In the ternary systems, the compositions and melting points of eutectic alloys were determined by differential thermal analysis: (49.0 mol % LiBr, 5.0 mol % LiVO₃, 46.0 mol % Li₂CrO₄, 400°C) and (17.0 mol % KBr, 78.0 mol % KVO₃, 5.0 mol % K₂CrO₄, 458°C), respectively.     

The chemistry of chromyl fluoride III. Reactions with inorganic systems

Reactions of CrO₂F₂ with MF or MF₂ gave the corresponding M₂CrO₂F₄ and MCrO₂F₄ fluorochromates. With the Lewis Acids (SO₃, TaF₅, SbF₅) and (CF₃CO)₂O known and new chromyl compounds [CrO₂(CF₃COO)₂, CrO₂(SO₃F)₂, CrO₂FTaF₆, CrO₂FSbF₆, CrO₂FSb₂F₁₁] were produced. Chromyl fluoride and inorganic salts (CF₃COONa and NaNO₃) produced the following complexes - Na₂CrO₂F₂(CF₃COO)₂ and Na₂CrO₂F₂(NO₃)₂. Unusual solid products were obtained with CrO₂F₂ and NO, NO₂, SO₂.A new method of preparing CrO₂F₂ is also presented.     

The phase diagram for the binary system K2CrO4CaCrO4

The phase diagram for the binary system K₂CrO₄CaCrO₄ has been determined for CaCrO₄ concentrations up to 60 mole%, using the techniques of differential thermal analysis, X-ray diffraction, and drop calorimetry. Essential features of the phase diagram are: the solid-solid phase transition for pure K₂CrO₄ at 670°C, β-K₂CrO₄ ? α-K₂CrO₄; a eutectoid reaction at 14 mole% CaCrO₄ and 548°C, β-K₂CrO₄ ? α-K₂CrO₄ + K₂CrO₄ · CaCrO₄; a peritectoid event at 50 mole% CaCrO₄ and 640°C, β-K₂CrO₄ + CaCrO₄ ? K₂CrO₄ · CaCrO₄; and a eutectic reaction at 51 mole% CaCrO₄ and 678°C, L ? β-K₂CrO₄ + CaCrO₄. X-ray diffraction studies lead to the determination of the unit cell dimensions for the K₂CrO₄ · CaCrO₄ double salt, a C-centered monoclinic form with a₀ = 7.615(6) Å, b₀ = 22.797(15) Å, c₀ = 9.777(9) Å, β = 115.45(5)°.     

Electrochemical reduction mechanism of silver chromate in lithium cells

A general mechanism is proposed to explain the charge—discharge features of the LiAg₂CrO₄ system.For a low discharge rate, the process leads to Ag and Li₂CrO₄ formation through a dissolution—precipitation, mechanism. Li₂ CrO₄ is reducible in two steps at lower potentials. For high discharge we show the formation of an intermediate compound, called Ag ₂, Li₂CrO₄ which evolves either to a mixture of metallic Ag and Li₂CrO₄ or is reduced with the formation of a Cr(V) compound at higher potential than Li₂CrO₄.This mechanism obtained with experimental electrodes is in excellent agreement with the behaviour of Ag₂CrO₄ commercial cells.     

Li2CrO4 · 2H2O: Ungewöhnliche Wasserstoffbrückenbindung und Koordination der O-Liganden des Anions CrO42−

Li₂CrO₄ · 2H₂O: Unusual Hydrogen Bridge Bonding and Coordination for Oxygen of the Anions CrO₄^2? The crystal structure of Li₂CrO₄ · 2H₂O was solved including the positions of hydrogen by X-ray methods. Li₂CrO₄ · 2H₂O: P2₁2₁2₁, Z = 4, a = 5.503(1) Å, b = 7.733(2) Å, c = 11.987(2) Å, Z(F_o) with (F_o)² ? 3σ(F_o)² = 2284, Z (parameter) = 99, R/R_w = 0.025/0.029 LiCrO₄ · 2H₂O contains a locally bordered hydrogen bridge bonding system between water molecules as donors and two O of CrO₄^2? as acceptors. This system connects anions in the direction [010]. It is noticeable that oxygen ligands of the anion CrO₄^2? have strongly differing coordination.     

Ternary Systems NaHal–NaVO<Subscript>3</Subscript>–Na<Subscript>2</Subscript>CrO<Subscript>4</Subscript> (Hal = Cl,Br)

Phase equilibria in the ternary systems NaHal–NaVO₃–Na₂CrO₄ (Hal = Cl, Br) were studied. By differential thermal analysis, eutectic alloys were found at points with coordinates (14.0 mol % NaCl, 66.5 mol % NaVO3, 19.5 mol % Na₂CrO₄, 530°C) and (27.0 mol % NaBr, 47.5 mol % NaVO₃, 25.5 mol % Na₂CrO₄, 499°C). By differential scanning calorimetry, the specific enthalpies of melting of the eutectics were determined. X-ray powder diffraction analysis of the eutectic alloy in the system NaBr–NaVO₃–Na₂CrO₄ was made.     

Reactivity in The Solid State Between Ag2S and Ag2CrO4

Reactivity, in the solid state between Ag₂S and Ag₂CrO₄, was investigated by DTA, XRD and IR methods. It was found that, according to a composition of an initial Ag₂S/Ag₂CrO₄ mixture, the products of a reaction of Ag₂S with Ag₂ CrO₄ can be: solid solution with Ag₂CrO₄ structure (Ag₂Cr_1–xS_xO₄) and AgCrO₂; or solid solution Ag₂Cr_1–xS_xO₄, Ag₂SO₄, AgCrO₂ and metallic silver; or Ag₂S, β-Ag₈S₄O₄, Ag, AgCrO₂, Ag₂SO₄ and Ag₂Cr_1–xS_xO₄ solid solution. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kryometrische Untersuchungen. IV. Lösungen von oxidischen Mo6+- und Cr6+-Verbindungen in geschmolzenem K2Cr2O7 und KNO3

The depression of freezing point of molten K₂Cr₂O₇ and KNO₃ as solvents was measured after addition of small concentrations of the following compounds: to K₂Cr₂O₇: MoO₃, CrO₃, (NH₄)₂CrO₄, K₂MoO₄, Na₂MoO₄, Li₂MoO₄, and Na₂Mo₂O₇, respectively; to KNO₃: CrO₃, (NH₄)₂Cr₂O₇ K₂Cr₂O₇, K₂CrO₄ and MoO₃, (NH₄)₆(Mo₇O₂₄) · 4 H₂O, K₂Mo₂O₇, K₂MoO₄, Na₂MoO₄ and Li₂MoO₄, respectively. It could be concluded from the measured values of the freezing point depression if a reaction between solvent and solute took place.     

Phase equilibria in the stable tetrahedron LiF–LiBr–Li<Subscript>2</Subscript>CrO<Subscript>4</Subscript>–KBr of the quaternary reciprocal system Li,KǁF,Br,CrO<Subscript>4</Subscript>

Phase equilibria in the stable tetrahedron LiF–LiBr–Li₂CrO₄–KBr of the quaternary reciprocal system Li,K∥F,Br,CrO₄ were studied by differential thermal analysis. The composition (equiv %) and melting point of a quaternary eutectic were found as (2% LiF, 60% LiBr, 3% Li₂CrO₄, 35% KBr, 315°C).     

Carbon–carbon bond fission on oxidation of primary alcohols to carboxylic acids

α-Carbon–carbon bond cleavage is shown to be a general side reaction accompanying the oxidation of unbranched primary alcohols to the corresponding carboxylic acids using HNO₃, CrO₃/H₂SO₄/H₂O/acetone, CrO₃/CH₃COOH, PDC/DMF, H₅IO₆/CrO₃, KMnO₄/H⁺, KMnO₄/HO^?, NiCl₂/NaClO, TEMPO/PhI(OAc)₂. Therefore, the product formed is always contaminated with a carboxylic acid containing one carbon atom less. Systems such as PhI(OAc)₂/TEMPO or H₅IO₆/CrO₃/CH₃CN reduce to a minimum the content of this impurity. Temperature, the order of reagent addition, and additives such as oxalic acid or cerium salts produce a profound effect on the formation of the undesirable impurity during the Jones oxidation of primary alcohols.     

Hydrogen peroxide oxidation of hydrocarbons catalyzed by Cr(VI) oxo compounds

>CrO₃, (NBu₄)₂CrO₄, (NBu₄)₂Cr₂O₇, and (NBu₄)Cr₄O₁₃ catalyze the hydrogen peroxide oxidation of cyclohexane, ethylbenzene, and styrene in acetonitrile. The active species is apparently a Cr(VI) peroxo complex.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 210–211, January, 1990.     

3DOM InVO4-supported chromia with good performance for the visible-light-driven photodegradation of rhodamine B

Three-dimensionally ordered macroporous (3DOM) monoclinic InVO₄ and its supported chromia (yCrO_x/3DOM InVO₄, y denotes as the weight percentage of Cr₂O₃, y = 5, 10, 15, and 20 wt%) photocatalysts were fabricated using the ascorbic acid-assisted polymethyl methacrylate-templating and incipient wetness impregnation methods, respectively. Physicochemical properties of the materials were characterized by means of a number of analytical techniques. Photocatalytic activities of the samples were evaluated for the degradation of rhodamine B (RhB) in the presence of H₂O₂ under visible-light illumination. Compared to 3DOM InVO₄ and 15CrO_x/bulk InVO₄, yCrO_x/3DOM InVO₄ showed much better visible-light-driven photocatalytic performance for RhB degradation, with the 15CrO_x/3DOM InVO₄ sample performing the best. It is concluded that the CrO_x loading, higher surface area and surface oxygen vacancy density and lower bandgap energy as well as the better quality of 3DOM structure were responsible for the good photocatalytic performance of 15CrO_x/3DOM InVO₄ for the degradation of RhB.     

Schwingungsspektren und Kraftkonstanten von Chrom(VI)-Sauerstoff-Verbindungen

The infrared and RAMAN spectra of Cr₃O, CrO₄O and CrO₃ have been measured and assigned. The force constant of a modified valence force field have been calculated and compared with the force constants of CrO, Cr₂O, CrO₃F^?, CrO₃Cl^?, CrO₂F₂ and CrO₂Cl₂. The valence force constant f_CrO depends almost linearly on the distance d(CrO). The bending frequency δ(CrOCr) has to be reassigned. The unit cell parameters of α- and β-Cs₂Cr₃O₁₀ and Cs₂Cr₄O₁₃ have been determined by means of Guinier X-ray powder techniques.     

Functionalization at C-12 in labdanic diterpenes: synthesis of the natural diterpenic lactones isolated from cistus ladaniferus L.

Oxidative cyclization of Labdanediol (XII) and methyl Labdanolate (Ib) with Pb(OAc)₄, and subsequent oxidation with reagents as RuO₄, O₃, CrO₃, or (Bu^t)₂ CrO₄ affords, in excellent yield, the natural diterpenic lactones II, III, VII, VIII, XI and XIII, isolated from $\text{Cistus ladaniferus L.}$     

Crystal Structures of the Europium and Yttrium Hydroxychromates Eu(OH)(CrO4) and Y(OH)(CrO4); Structural Evolution as a Function of the Ln3+ Ionic Radius

The compounds Eu(OH)(CrO₄) and Y(OH)(CrO₄) were obtained under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analysis. They are isostructural and crystallize in the monoclinic system, space group P2₁/n (no. 14) with lattice parameters a = 8.278(1) Å, b = 11.400(2) Å, c = 8.393(1) Å, β = 93.76(2)°, V = 790.3(2) Å³, Z = 4, d = 4.79 g · cm^–3 for Eu(OH)(CrO₄) and a = 8.151(1) Å, b = 11.362(2) Å, c = 8.285(1) Å, β = 94.23(1)°, V = 765.2(2) Å³, Z = 4, d = 3.85 g · cm^–3 for Y(OH)(CrO₄). The [EuO₈] polyhedra form infinite double chains along the a direction, which are connected by common edges and corners. These double chains are related together in the two other directions by the [CrO₄]^2– tetrahedra to form a three‐dimensional network in which channels appear parallel to the [100] direction. We examine the structural evolution, as a function of the Ln³⁺ ionic radius, in the series Ln(OH)(CrO₄) compounds (with Ln = Nd, Eu, Gd, Tb, Er, Yb) and Y(OH)(CrO₄). To determine the best coordination number of each lanthanide and yttrium ions, different calculations of bond valence sum were realized.     

Paper chromatographie studies on periodic precipitation

Summary An investigation of the nature of the rhythmic patterns obtained by diffusing the reactant solution on the circular filter papers impregnated with precipitating agents and a protective colloid (2% agar agar) has been made. The systems: AgNO₃–K₂CrO₄, Pb(NO₃)₂–K₂CrO₄, Ba(NO₃)₂–K₂CrO₄, Co(NO₃)₂–K₄Fe(CN)₆, and Co(NO₃)₂–K₃Fe(CN)₆ have been studied. An attempt has been made to explain the radial and ring rhythmicity on filter papers on the basis of coagulation theory ofDhar andChatterji.     

The crystallographic and magnetic characteristics of Sr2CrO4 (K2NiF4-type) and Sr10(CrO4)6F2 (apatite-type)

Solid-state reaction between SrCO₃, Cr₂O₃ and SrF₂ has produced the apatite phase Sr₁₀(CrO₄)₆F₂ and Sr₂CrO₄ which adopts the K₂NiF₄-type structure. The reaction outcome was very sensitive to the heating rate with rapid rise times favouring the formation of Sr₂CrO₄, which has been synthesised at ambient pressure for the first time. Powder X-ray diffraction and electron diffraction confirmed that Sr₂CrO₄ adopts a body centred tetragonal cell (space group I4/mmm) with lattice parameters a=3.8357(1) Å and c=12.7169(1) Å, while a combination of neutron and X-ray diffraction verified Sr₁₀(CrO₄)₆F₂ is hexagonal (space group P6₃/m) with lattice parameters a=9.9570(1) Å and c=7.4292(1) Å. X-ray photoelectron spectroscopy and magnetic measurements were used to characterise the oxidation states of chromium contained within these phases.     

Preparation and crystal structure of a new bismuth chromate: Bi8(CrO4)O11

Single crystals of a new bismuth chromate, Bi₈(CrO₄)O₁₁, were prepared by hydrothermal reaction of NaBiO₃·nH₂O in K₂CrO₄ solution. The bismuth chromate crystallizes in the monoclinic space group P2₁/m with a=9.657(3), b=11.934(3), c=13.868(2)Å and β=104.14(1)°, Z=4 and the final R factors are R=0.038 and R_w=0.041 for 3541 unique reflections. The crystal structure has a slab built up by (CrO₄)²⁻ tetrahedra and distorted bismuth polyhedra which are five-fold pyramids, six-fold trigonal prisms and octahedra. The distance of lone pair from nucleus for bismuth atoms ranges from 0.29 to 1.12 Å, depending on the coordination environment. Bi₈(CrO₄)O₁₁ decomposes to Bi₁₄CrO₂₄ and a small amount of an unknown phase at 796 °C.     

Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)]

Two novel isopropylamine‐templated uranyl chromates, [(CH₃)₂CHNH₃]₃[(UO₂)₃(CrO₄)₂O(OH)₃] ( 1 ) and [(CH₃)₂CHNH₃]₂[(UO₂)₂(CrO₄)₃(H₂O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X‐ray diffraction crystal structure analysis [ 1 : trigonal, P31m, a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) ų; 2 : monoclinic, P2₁/c, a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) ų]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO₄ tetrahedra to form [(UO₂)₃(CrO₄)₂O(OH)₃]^3– layers, whereas, in the structure of 2 , UO₇ and UO₆(H₂O) pentagonal bipyramids are linked through CrO₄ tetrahedra into the [(UO₂)₂(CrO₄)₃(H₂O)]^2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.