Conservation of [(C2H4NH3)3N]2·(ZrF7)2·H2O layers during the topotactic dehydration of [(C2H4NH3)3N]2·(ZrF7)2·9H2O

Tren amine cations [(C₂H₄NH₃)₃N]³⁺ and zirconate or tantalate anions adopt a ternary symmetry in two hydrates, [H₃tren]₂·(ZrF₇)₂·9H₂O and [H₃tren]₆·(ZrF₇)₂·(TaOF₆)₄·3H₂O, which crystallise in R32 space group with a_H = 8.871 (2) Å, c_H = 38.16 (1) Å and a_H = 8.758 (2) Å, c_H = 30.112 (9) Å, respectively. Similar [H₃tren]₂·(MX₇)₂·H₂O (M = Zr, Ta; X = F, O) sheets are found in both structures; they are separated by a water layer (O_w(2)-O_w(3)) in [H₃tren]₂·(ZrF₇)₂·9H₂O. Dehydration of [H₃tren]₂·(ZrF₇)₂·9H₂O starts at room temperature and ends at 90 °C to give [H₃tren]₂·(ZrF₇)₂·H₂O. [H₃tren]₂·(ZrF₇)₂·H₂O layers remain probably unchanged during this dehydration and the existence of one intermediate [H₃tren]₂·(ZrF₇)₂·3H₂O hydrate is assumed. O_w(1) molecules are tightly hydrogen bonded with -NH₃⁺ groups and decomposition of [H₃tren]₂·(ZrF₇)₂·H₂O occurs from 210 °C to 500 °C to give successively [H₃tren]₂·(ZrF₆)·(Zr₂F₁₂) (285 °C), an intermediate unknown phase (320 °C) and ZrF₄.     

Comparison of one-, two-, and three-dimensional iron phosphates containing ethylenediamine

A new two-dimensional (2d) iron phosphate, (C₂N₂H₁₀)Fe₂O(PO₄)₂, has been synthesized under hydrothermal conditions in the system of FeCl₃-H₃PO₄-C₂N₂H₈-H₂O. The crystal data is: space group P2₁/c, a=10.670(1) Å, b=10.897(1) Å, c=9.918(1) Å, β=105.632(1)°, Z=4. The layered structure consists of double sheet layers, of composition Fe₂O(PO₄)₂, built from FeO₅ trigonal bipyramids and PO₄ tetrahedra. The amine holds the layers together via H-bonding. The study of the magnetic properties reveals two magnetic transitions at 160 and 30 K with spin-glass-like behavior below 160 K. By varying the hydrothermal conditions, three other iron phosphates were synthesized: the one-dimensional (1d) (C₂N₂H₁₀)Fe(HPO₄)₂(OH)·H₂O, the 2d (C₂N₂H₁₀)Fe₂(PO₄)₂(OH)₂, and the three-dimensional (3d) (C₂N₂H₁₀)₂Fe₄O(PO₄)₄·H₂O. The 1d compound can be used as the starting reagent in the synthesis of both the 2d compound and the 3d lipscombite Fe₃(PO₄)₂(OH)₂ due to the similar building blocks in their structures. In the 3d phosphate (C₂N₂H₁₀)₂Fe₄O(PO₄)₄·H₂O, manganese can substitute for half of the iron atoms. Magnetic study shows ordering transitions at about 30 K, however, manganese substitution depresses the magnetic ordering temperature.     

Thermal decomposition of Cu(NO3)2·3H2O at reduced pressures

Thermolysis of Cu(NO₃)₂·3H₂O is studied by means of XRD analysis in situ and mass spectral analysis of the gas phase at P=1/10 Pa at low heating rate. It is shown that stage I of the dehydration (40-80 °C) results in the consecutive appearance of crystalline Cu(NO₃)₂·2.5H₂O and Cu(NO₃)·H₂O. Anhydrous Cu(NO₃)₂ formed during further dehydration at 80-110 °C is moderately sublimed at 120-150 °C. Dehydration is accompanied by thermohydrolysis, leading to the appearance of Cu₂(OH)₃NO₃ and gaseous H₂O, HNO₃, NO₂, and H₂O. The higher pressure in the system, the larger amount of thermohydrolysis products is observed. The formation of the crystalline intermediate CuO_x(NO₃)_y was observed by diffraction methods. Final product of thermolysis (CuO) is formed at 200-250 °C.     

Synthesis, structure and optical features of single adamantanoid Hg-SePh-X anionic clusters stabilized by octahedral complexes (Ph = phenyl; X = Cl, Br, I)

The ligand dppmo₂ [CH₂{P(O)Ph₂}₂] (Ph = phenyl), MgCl₂·6H₂O, MgBr₂, MgI₂, FeBr₂, CoBr₂, NiBr₂ and Hg(SePh)₂ react one at a time to give the complex salt of the general formula [M(dppmo₂)₃][Hg₄X₄(SePh)₆]·4dmf·H₂O (M = Mg²⁺, Fe²⁺, Co²⁺, Ni²⁺; X = Cl, Br, I; dmf = dimethylformamide). The cations [M(dppmo₂)₃]²⁺ are predominantly octahedral with axial angles from 175° to 178°. The adamantane like anions [Hg₄X₄(SePh)₆]²⁻ are examples of single adamantanoid species, since these compounds normally appear as polymers or fused cages. Adamantanoid cages are the preferential thermodynamic configuration for this atomic aggregate. They appear as single molecules or ions however only in a halogen rich reactions milieu.     

Synthesis and structure of [C6H14N2][(UO2)4(HPO4)2(PO4)2(H2O)]·H2O: An expanded open-framework amine-bearing uranyl phosphate

A new open-framework compound, [C₆H₁₄N₂][(UO₂)₄(HPO₄)₂(PO₄)₂(H₂O)]·H₂O, (DUP-1) has been synthesized under mild hydrothermal conditions. The resulting structure consists of diprotonated DABCOH₂²⁺ (C₆H₁₄N₂²⁺) cations and occluded water molecules occupying the channels of a complex uranyl phosphate three-dimensional framework. The anionic lattice contains uranophane-like sheets connected by hydrated pentagonal bipyramidal UO₇ units. [C₆H₁₄N₂][(UO₂)₄(HPO₄)₂(PO₄)₂(H₂O)]·H₂O possesses five crystallographically unique U centers. U(VI) is present here in both six- and seven-coordinate environments. The DABCOH₂²⁺ cations are held within the channels by hydrogen bonds to both two uranyl oxygen atoms and a μ₂-O atom. Crystallographic data (193 K, Mo Kα, λ=0.71073 Å): DUP-1, monoclinic, P2₁/n, a=7.017(1) Å, b=21.966(4) Å, c=17.619(3) Å, β=90.198(3)°, Z=4, R(F)=4.76% for 382 parameters with 6615 reflections with I>2σ(I).     

Two-dimensional composition diagram of the Al(OH)3-dien-HFaq.-ethanol system: Evidence of a new tetrahedral (Al4F18) polyanion

Six domains appear in the 2D composition diagram of the Al(OH)₃-dien-HF_aq.-ethanol system at 190 °C and [Al³⁺] = 1 mol L⁻¹ under microwave heating. Four organic-inorganic fluorides crystallise: [H₃dien]·(AlF₆) (P2₁/c, Z = 4), [H₃dien]₂·(AlF₅(H₂O))₃·2H₂O (P2₁/n, Z = 4), [H₃dien]·(AlF₆)·2H₂O, which was previously known, and [H₃dien]₂·(Al₄F₁₈) (C2/c, Z = 4). A new (Al₄F₁₈)⁶⁻ polyanion, which results from the tetrahedral association of four AlF₆ octahedra linked by corners, is evidenced in [H₃dien]₂·(Al₄F₁₈).     

New synthetic method and thermochemistry of szaibelyite

A new synthetic method of szaibelyite (2MgO·B₂O₃·H₂O) has been reported. The enthalpy of solution of 2MgO·B₂O₃·H₂O in 2.9842 mol dm⁻³ HCl (aq) was determined. From a combination of this result with measured enthalpies of solution of H₃BO₃ in 2.9842 mol dm⁻³ HCl (aq) and of MgO in (HCl+H₃BO₃) solution, together with the standard molar enthalpies of formation of MgO (s), H₃BO₃ (s), and H₂O (l), the standard molar enthalpy of formation of −(2884.36±1.82) kJ mol⁻¹ of 2MgO·B₂O₃·H₂O was obtained.     

Decomposition thermique et etude vibrationnelle de NiNa4(P3O9)2·6H2O

We have studied the dehydration and the calcination under atmospheric pressure of cyclotriphosphate tetrahydrate of nickel and sodium, NiNa₄(P₃O₉)₂·6H₂O, between 25 and 700°C by thermal analyses (TG, DTA) infrared spectrometry and X-ray diffraction. This study allows us the identification and the crystallographic characterization of a new phase, NiNa₄(PO₃)6, obtained between 350 and 450°C. NiNa₄(PO₃)₆ crystallizes in the triclinic system, P_–1, with the following unit cell parameters a=6.157(3) Å, b=6.820(6) Å, c=10.918(6) Å, =80.21(5)°, =97.80(9)°, =113.49(3)°, V=409.8 ų, Z=1, M(19)=25 and F(19)=48 (0.0095; 42). The calcination of NiNa₄(PO₃)₆, between 500 and 600°C, leads to a mixture of long-chain polyphosphates NiNa(PO₃)₃ and NaPO₃. The kinetic characteristics of the dehydration of NiNa₄(P₃O₉)₂·6H₂O were determined and discussed. The vibrational spectrum of the title compound, NiNa₄(P₃O₉)2·6H₂O, was interpreted in the domain of the stretching vibrations of the P₃O₉ rings, on the basis of its crystalline structure and in the light of the calculation of the normal IR frequencies of the P₃O₉ ring with D_3h symmetry.

This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis and magnetic properties of ZnFe2O4 obtained by mechanochemically assisted low-temperature annealing of mixtures of Zn and Fe oxalates

The mechanism of formation of zinc ferrite (ZnFe₂O₄) from ZnC₂O₄·1.8H₂O-2Fe^IIC₂O₄·2H₂O and ZnC₂O₄·1.8H₂O-Fe₂^III(C₂O₄)₃·6H₂O mixtures is investigated. By combination of TG and XRPD measurements it has been shown that microcrystalline ZnFe₂O₄ forms from physical mixtures after prolonged annealing at 1000 °C while nanocrystalline ZnFe₂O₄ powders are produced by mild annealing (1 h at 500 °C in air) of mechanically activated mixtures. The magnetic properties of ZnFe₂O₄ powders obtained from physical and from milled mixtures are compared.     

Kinetics of the anation reaction of pentaamineaquacobalt(III) by phosphorous acid/hydrogenphosphite

Summary The kinetics of the anation reaction of [Co(NH₃)₅H₂O]³⁺ by H₃PO₃/H₂PO ₃ ^– , to give [CoH₂PO₃(NH₃)₅]²⁺, have been studied at 60, 70 and 80°C, in the acidity range [H⁺](M)=1.5 · 10^–1 –2.0 · 10^–3. Only H₂PO₃ is found to be reactive. The rate data is consistent with an I_d mechanism. The mean value of outer sphere association of [Co(NH₃)H₂O]³⁺ with H₂PO ₃ ^– is 1.5 M^–1. Values of the interchange constants are: 10⁴4k_i(s^–1)= 0.29, 1.47, 5.13, at 60, 70 and 80 °C respectively (H= 1.4 · 10²KJmol^–1, S=8.3 · 10 JK^–1 mol^–1). The first acidity constant of H₃PO₃ at I=1.0 has also been determined: 10²K_a(M)=4.8, 5.2 and 5.5, at 25, 40 and 50 °C respectively.     

H2O + Fe(NO3)3 + Ni(NO3)2 ternary system isotherms at 0 °C and 30 °C

H₂O + Ni(NO₃)₂ binary system were investigated in the temperature range from −25 °C to 55 °C. The solid-liquid equilibria of the ternary system H₂O + Fe(NO₃)₃ + Ni(NO₃)₂ were studied using a synthetic method based on conductivity measurements. Tow isotherms were established at 0 °C and 30 °C, and the appearing stable solid phases are iron nitrate nonahydrate (Fe(NO₃)₃·9H₂O), iron nitrate hexahydrate (Fe(NO₃)₃·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) and nickel nitrate tetrahydrate (Ni(NO₃)₂·4H₂O).     

Partial exchange of the Li, Na and K alkaline cations in the HNi(PO4)·H2O layered compound

The exchange of the Li⁺(1), Na⁺(2) and K⁺(3) alkaline cations in the layered HNi(PO₄)·H₂O was carried out starting from a methanolic solution containing the Li(OH)·H₂O hydroxide for (1) and the M(OH) (M=Na and K) hydroxides together with the (C₆H₁₃NH₂)_0.75HNiPO₄·H₂O phases for (2) and (3). The compounds are stable until, approximately, 280 °C for (1) and 400 °C for phases (2) and (3), respectively. The IR spectra show the bands belonging to the water molecule and the (PO₄)³⁻ oxoanion. The diffuse reflectance spectra indicate the existence of Ni(II), d⁸, cations in slightly distorted octahedral geometry. The calculated Dq and Racah (B and C) parameters have a mean value of Dq=765, B=905 and , respectively, in accordance with the values obtained habitually for this octahedral Ni(II) cation. The study of the exchange process performed by X-ray powder diffraction indicates that the exchange of the Li⁺ cation in the lamellar HNi(PO₄)·H₂O phase is the minor rapid reaction, whereas the exchange of the Na⁺ and K⁺ cations needs the presence of the intermediate (C₆H₁₃NH₂)_0.75HNiPO₄·H₂O intercalate in order to obtain the required product with the sodium and potassium ions. The Scanning electronic microscopy (SEM) images show a mean size of particle of 5 μm. The Li⁺ exchanged compound exhibits small ionic conductivity (Ω cm⁻¹ is in the 10⁻⁸-10⁻⁹ range) probably restrained by the methanol solvent. Magnetic measurements carried out from 5 K to room temperature indicate antiferromagnetic coupling as the major interaction in the three phases. Notwithstanding the Li and K phases show a weak ferromagnetism at low temperatures.     

The hydrothermal decomposition of calcium monosulfoaluminate 14-hydrate to katoite hydrogarnet and β-anhydrite: An in-situ synchrotron X-ray diffraction study

We apply in-situ synchrotron X-ray diffraction to study the transformation of calcium monosulfoaluminate 14-hydrate Ca₄Al₂O₆(SO₄)·14H₂O [monosulfate-14] to hydrogarnet Ca₃Al₂(OH)₁₂ on the saturated water vapor pressure curve up to 250 °C. We use an aqueous slurry of synthetic ettringite Ca₆Al₂(SO₄)₃(OH)₁₂·26H₂O as the starting material; on heating, this decomposes at about 115 °C to form monosulfate-14 and bassanite CaSO₄·0.5H₂O. Above 170 °C monosulfate-14 diffraction peaks slowly diminish in intensity, perhaps as a result of loss of crystallinity and the formation of an X-ray amorphous meta-monosulfate. Hydrogarnet nucleates only at temperatures above 210 °C. Bassanite transforms to β-anhydrite (insoluble anhydrite) at about 230 °C and this transformation is accompanied by a second burst of hydrogarnet growth. The transformation pathway is more complex than previously thought. The mapping of the transformation pathway shows the value of rapid in-situ time-resolved synchrotron diffraction.     

Infrared evolved gas analysis during thermal investigation of lanthanum, europium and samarium carbonates

The characterisation of rare earth elements carbonates (REECs) was performed by thermal analysis (TG-DTG) combined with simultaneous infrared evolved gas analysis-Fourier transform infrared (EGA-FTIR) spectroscopy. The TG-DTG curves were obtained using the Perkin-Elmer PC series TGA-7 thermogravimetric analyser in the temperature range 25-800 °C both in dynamic air and nitrogen atmosphere.La₂(CO₃)₃·nH₂O, Eu₂(CO₃)₃·nH₂O and Sm₂(CO₃)₃·nH₂O were analysed, the dehydration and decarbonation steps were investigated and the water content was calculated. The trace rare earth elements in lanthanum, europium and samarium carbonates were determined by Philips PU 7000 inductively coupled plasma atomic emission spectrometry (ICP-AES) and the concentration of REE ranged from 6.2×10⁻⁵ to 4.2×10⁻⁴% (w/w).     

Influence of silicic acid and glauconite on thermal dehydration of Ca(H2PO4)2 · H2O

The thermal dehydration of mixtures of Ca(H₂PO₄)₂·H₂O with silicic acid and glauconite was studied by thermal (under dynamic and quasi-isothermal-quasi-isobaric conditions), X-ray and Chromatographic analyses.It was found that the dehydration of Ca(H₂PO₄)₂·H₂O is accelerated in the mixtures. SiO₂·nH₂O and glauconite react with the intermediates of dehydration of Ca(H₂PO₄)₂·H₂O, and silicophosphates and Al, K, Fe-phosphates are formed, respectively. The total degree of polymerization of calcium polyphosphates is lower in the mixtures than in Ca(PO₃)₂ itself.

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Zusammenfassung Mittels röntgenographischer, chromatographischer und thermischer (unter dynamischen und quasi-isothermen-quasi-isobaren Bedingungen) Analyse wurde die thermische Dehydratation eines Gemisches aus Ca(H₂PO₄)₂·H₂O, KieselsÄure und Glaukonit untersucht.Es wurde festgestellt, da\ die Dehydratation von Ca(H₂PO₄)₂·H₂O im Gemisch beschleunigt ablÄuft. SiO₂·nH₂O und Glaukonit reagieren mit den Zwischenprodukten der Dehydratation von Ca(H₂PO₄)₂·H₂O und formen Silikophosphate und Al,K,Fe-Phosphate. Der totale Polymerisationsgrad von Calciumpolyphosphat ist im Gemisch geringer als in Ca(PO₃)₂ selbst.

     

Hydrothermal synthesis and morphology variation of cadmium hydroxyapatite

Cadmium hydroxyapatite (Cd-Hap) crystals were synthesized by hydrothermal method at 200 °C using the solutions of Cd(NO₃)₂·4H₂O and (NH₄)₂HPO₄. Influences of pH values and reaction time on the crystalline phases and morphology of the products were investigated. In low pH reaction media, Cd₅H₂(PO₄)₄·4H₂O was formed and a relatively high pH reaction media was necessary to obtain Cd-Hap. Morphology of the Cd-Hap crystals changed from stubby hexagonal prismatic to rod-like in shape with the increase in the pH value. This morphological change was explained by the difference in growth mechanism through intermediate phases, Cd₅H₂(PO₄)₄·4H₂O in the low pH reaction media and Cd₂P₂O₇·5H₂O in the high pH reaction media.     

Integrated X-ray crystallography, optical and computational methods in studies of structure and luminescence of new synthesized complexes of lanthanides with ligands derived from 2,6-diformylpyridine

The reaction of 2,6-diformylpyridine-bis(benzoylhydrazone) [dfpbbh] and 2,6-diformylpyridine-bis(4-phenylsemicarbazone) [dfpbpsc] with lanthanides salts yielded the new chelates complexes [Eu(dfpbpsc-H⁺)₂]NO₃ (1), [Dy(fbhmp)₂][Dy(dfpbbh-2H⁺)₂]·2EtOH·2H₂O (fbhmp = 2-formylbenzoylhydrazone-6-methoxide-pyridine; Ph = phenyl; Py = pyridine; Et = ethyl) and [Er₂(dfpbbh-2H⁺)₂(μ-NO₃)(H₂O)₂(OH)]·H₂O.X-ray diffraction analysis was employed for the structural characterization of the three chelate complexes. In the case of complex 1, optical, synthetic and computational methods were also exploited for ground state structure determinations and triplet energy level of the ligand and HOMO-LUMO calculations, as well as for a detailed study of its luminescence properties.     

Calorimetric study and thermal analysis of [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O (Gly: glycin)

Two solid-state coordination compounds of rare earth metals with glycin, [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O and [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 342.90 K, while [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol⁻¹ and 53.9 J K⁻¹ mol⁻¹ for [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, 1.82 kJ mol⁻¹ and 5.5 J K⁻¹ mol⁻¹ for [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.     

Untersuchungen zur Reaktion von konzentrierter Phosphors?ure mit reinen und korrodierten Stahloberfl?chen

Zusammenfassung Mittels Mößbauerspektroskopie wurde gefunden, daß sich aus Rostkomponenten neben den normalen Eisen (III)- und Eisen (II)-phosphaten auch ein saures Eisen (III)-phosphat bilden kann, wenn sie mit konzentrierter Phosphorsäure behandelt werden. Voraussetzung hierfür ist, daß die Ausgangsphase eine reine Fe³⁺-Verbindung ist. Das saure Eisen(III)-phosphat, wahrscheinlich FeH₃(PO₄)₂ · 2,5 H₂O, enthält Fe³⁺ in nahezu kubischer Umgebung, die Kristallstruktur hat jedoch niedrigere Symmetrie. Unterhalb von 28 K setzt eine magnetische Ordnung ein. Es sind zwei Fälle mit verschiedener Spinstruktur und Verkantungen zu unterscheiden.

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Studies of the reaction of concentrated phosphoric acid with clean and corroded steel surfaces

Summary It was found by Mössbauer spectroscopy that an acid ferric phosphate in addition to the normal phosphates is formed by treatment of rust components with concentrated phosphoric acid, provided the initial phase is a pure Fe³⁺ compound. The acid ferric phosphate, probably FeH₃(PO₄)₂ x 2.5 H₂O, contains Fe³⁺ at an approximately cubic lattice site, although the crystal structure is of lower symmetry. Below 28 K, the substance shows magnetic ordering. Two different cases with canted spin structures were found.