Phase equilibria in the liquid ternary system [Th(NO3)4(TBP)2]-[UO2(NO3)2(TBP)2]-Isooctane at different temperatures

The phase diagrams of the ternary systems [Th(NO₃)₄(TBP)₂]-[UO₂(NO₃)₂(TBP)₂]-isooctane in the temperature range 298.15–333.15 K were constructed. These diagrams contain the field of homogeneous solutions and the field of separation into two liquid phases (I, II). Phase I is enriched in [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂(TBP)₂], and phase II is enriched in isooctane. With increasing temperature from 298.25 to 333.15 K, the mutual solubility of Th(NO₃)₄(TBP)₂ and isooctane does not change noticeably, but the two-phase fields somewhat contract. In the two-phase systems [UO₂(NO₃)₂(TBP)₂] is preferentially distributed in phase I, although the binary system [UO₂(NO₃)₂(TBP)₂]-isooctane is single-phase over the entire temperature range examined. The preferential accumulation of [UO₂(NO₃)₂(TBP)₂] in phase I causes the redistribution of [Th(NO₃)₄(TBP)₂] and isooctane into phases II and I, respectively. The compositions of the ternary systems in the critical points at different temperatures were determined. The electronic absorption spectra of uranyl nitrate solvate with TBP in the homogeneous and two-phase systems were recorded and analyzed. Original Russian Text ? A.K. Pyartman, V.A. Keskinov, V.V. Lishchuk, Ya.A. Reshetko, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 5, pp. 420–422.     

Phase Separation in the Ternary Liquid System [Th(NO3)4(TBP)2]— [UO2(NO3)2(TBP)2]—Decane at Various Temperatures

The phase diagram of the ternary liquid system [Th(NO₃)₄(TBP)₂]— [UO₂(NO₃)₂(TBP)₂]—decane was studied within the 298.15–333.15 K range. The system has the area of homogeneous solutions and area of binary liquid subsystems (with separation); one phase (I) is enriched in [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂·(TBP)₂] and the other phase (II), in decane. The temperature does not substantially affect the area of phase separation. In two-phase systems, [UO₂(NO₃)₂(TBP)₂] is mainly concentrated in phase I, in spite of the fact that the binary system [UO₂(NO₃)₂(TBP)₂]—decane is single-phase in the entire temperature range studied. Concentration of [UO₂(NO₃)₂(TBP)₂] in phase I results in redistribution of [Th(NO₃)₄(TBP)₂] into phase II. The points of the critical composition of the ternary system are compositions with similar content of the solvates [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂(TBP)₂] at all the temperatures studied. __________ Translated from Radiokhimiya, Vol. 47, No. 6, 2005, pp. 520–522. Original Russian Text Copyright ? 2005 by Keskinov, Mishina, Pyartman.     

Phase Separation in the Ternary Liquid System [Nd(NO3)3(TBP)3]-[UO2(NO3)2(TBP)2]-Tetradecane at Different Temperatures

Phase diagram of the ternary liquid system [Nd(NO₃)₃(TBP)₃]-[UO₂(NO₃)₂(TBP)₂]-tetradecane at 288.15–345.15 K is studied. There are homogeneous and two-phase regions in the diagram. One of the phases (I) is enriched with [Nd(NO₃)₃(TBP)₃] and [UO₂(NO₃)₂(TBP)₂], and the second phase (II), with tetradecane. The two-phase region decreases with increasing temperature. The upper critical temperature of solution (mixing) of the binary and ternary systems is T _cr = 344.85±0.5 K. The critical compositions of the ternary liquid system depend on the temperature. The two-phase systems demonstrate preferential concentration of [UO₂(NO₃)₂(TBP)₂] in phase I, despite the fact that the binary system [UO₂(NO₃)₂(TBP)₂]-tetradecane is homogeneous over the entire temperature range studied. __________ Translated from Radiokhimiya, Vol. 47, No. 2, 2005, pp. 154–157. Original Russian Text Copyright ? 2005 by Pyartman, Keskinov, Mishina, Kudrova.     

Phase equilibria in the liquid ternary system [Y(NO3)3(TBP)3]-[UO2(NO3)2(TBP)2]-C14H30 at different temperatures

The phase diagrams of the ternary system [Y(NO₃)₃(TBP)₃]-[UO₂(NO₃)₂(TBP)₂]-tetradecane in the temperature range 298.15–333.15 K were constructed. These diagrams contain the field of homogeneous solutions and the field of separation into two liquid phases (I, II). Phase I is enriched in [Y(NO₃)₃(TBP)₃] and [UO₂(NO₃)₂(TBP)₂], and phase II is enriched in tetradecane. With increasing temperature, the two-phase fields contract. The critical points of the ternary liquid systems depend on temperature. In the two-phase systems, [UO₂(NO₃)₂(TBP)₂] is preferentially distributed in phase I, although the binary system [UO₂(NO₃)₂(TBP)₂] tetradecane is homogeneous over the entire temperature range. Original Russian Text ? V.A. Keskinov, V.V. Lishchuk, A.K. Pyartman, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 5, pp. 417–419.     

(Sr6N)[CoN2][CN2]2: The first low-valency nitridometalate carbodiimide

The first nitridocobaltate carbodiimide (Sr₆N)[CoN₂][CN₂]₂ has been synthesized from the elements Sr, Co, and graphite powder and NaN₃ (as a nitrogen source). The crystal structure was determined from X-ray single-crystal diffraction data as orthorhombic (space group P2₁2₁2, No. 18, a=9.8807(6) Å, b=14.6474(9) Å, c=3.8569(3) Å, V=558.2 Å³, Z=2, R₁=0.0265, wR₂=0.0383). (Sr₆N)[CoN₂][CN₂]₂ is the first low-valency 3d-transition nitridometalate containing additional [CN₂]²⁻ groups. The crystal structure can be described as an array of rocksalt-like columns of Sr and N linked via common corners and connected by [NCN]²⁻ and [Co^IN₂]⁵⁻ units located within structural channels running along [0 0 1]. The magnetic susceptibility follows the Curie-Weiss law with an effective moment of 3.26 μ_B consistent with two unpaired spins (d⁸, Co^I). The compound is a bad metallic conductor with a resistivity of order 1 mΩ cm at 300 K. Vibrational spectroscopic data support the existence of carbodiimide [NCN]²⁻ species. The Co K-edge X-ray absorption spectra (XAS) of Ca₅[CoN₂]₂ and (Sr₆N)[CoN₂][CN₂]₂ confirm the presence of Co^I within the complex anions.     

Synthesis and spectral properties of Ce[Ag(CN)2]3

Cerium ion luminescence in crystalline hosts forms the basis of many blue phosphor and scintillator technologies. We report the synthesis of luminescent single crystals of cerium dicyanoargentate. The luminescence properties are characterized using both steady-state and time-resolved spectroscopy. The broad, overlapping dicyanoargentate and Ce³⁺ emissions are decomposed into three Gaussians, revealing the characteristic dicyanoargentate emission at 350 nm while the Ce³⁺ 5d–4f transitions are observed at 359 nm and 391 nm. Excitation measurements show that the 4f–5d Ce³⁺ absorption overlaps the 320 nm emission of the dicyanoargentate ions, leading to a strong coupling between the dicyanoargentate energy donors and Ce³⁺ acceptors. We conclude that the cerium is excited through an energy transfer process from the dicyanoargentate species, resulting in strong room temperature luminescence.     

New arsenates (V) NaKAl2O[AsO4]2 and Na2KAl3[AsO4]4

The title compounds have been synthesized by a solid state reaction route using a salt flux. Their crystal structures were determined from single crystal X-ray data. NaKAl₂O[AsO₄]₂ crystallizes with the orthorhombic K₂Fe₂O[AsO₄]₂-type, Pnma, a = 8.2368(6) Å, b = 5.5228(3) Å, c = 17.0160(13) Å and Z = 4, whereas Na₂KAl₃[AsO₄]₄ crystallizes with the orthorhombic K₃Fe₃[AsO₄]₄-type, Cmce, a = 10.5049(9), b = 20.482(2), c = 6.3574(6) Å and Z = 4. The NaKAl₂O[AsO₄]₂ structure is built up of [Al₂As₂O₉]²⁻ layers perpendicular to the c-axis which are separated by A⁺ alkali layers. The [Al₂As₂O₉]²⁻ layers consist of ribbons of edge-sharing AlO₆ octahedra, running along the a direction and which are connected through AsO₄ tetrahedra by sharing corners. The Na₂KAl₃[AsO₄]₄ structure contains [Al₃As₄O₁₆]³⁻ layers perpendicular to the b-axis separated by A⁺ alkali layers. The [Al₃As₄O₁₆]³⁻ layer consists of a layer of corner-sharing AlO₆ octahedra which are also connected to the AsO₄ tetrahedra by sharing corners.     

[NH3(CH2)2NH3][Co(SO4)2(H2O)4]: Chemical preparation, crystal structure, thermal decomposition and magnetic properties

Cobalt ethylenediammonium bis(sulfate) tetrahydrate, [NH₃(CH₂)₂NH₃][Co(SO₄)₂(H₂O)₄], has been synthesised by slow evaporation at room temperature. It crystallises in the triclinic system, space group , with the unit cell parameters: a = 6.8033(2), b = 7.0705(2), c = 7.2192(3) Å, α = 74.909(2)°, β = 72.291(2)°, γ = 79.167(2)°, Z = 1 and V = 317.16(2) Å³. The Co(II) atom is octahedrally coordinated by four water molecules and two sulfate tetrahedra leading to trimeric units [Co(SO₄)₂(H₂O)₄]. These units are linked to each other and to the ethylenediammonium cations through OW-H…O and N-H…O hydrogen bonds, respectively. The zero-dimensional structure is described as an alternation between cationic and anionic layers along the crystallographic b-axis. The dehydration of the precursor proceeds through three stages leading to crystalline intermediary hydrate phases and an anhydrous compound. The magnetic measurements show that the title compound is predominantly paramagnetic with weak antiferromagnetic interactions.     

Evidence for the non-existence of a bragg reflection superlattice in K2Pt(CN)4Br0.3·3H2O and K2Pt(CN)4Cl0.3·3H2O

An extensive and careful search for superlattice reflections in K₂Pt(CN)₄Br_0.3·3H₂O and K₂Pt(CN)₄Cl_0.3·3H₂O has yielded no evidence for an enlarged cell. Six individual crystals obtained via different preparative methods, from solutions at several pH values from 2 to 10, and subjected to a variety of conditions of temperature and humidity have been examined. All samples gave identical cells and nearly identical diffraction patterns. Two samples gave a single weak non-integral 00l neutron reflection which is not explainable by order contamination or double diffraction.     

The preparation and growth of pure single crystals of K2Pt(CN)4Br0.3·3H2O and K2Pt(CN)4Cl0.3·3H2O

The preparation of pure single crystals of K₂Pt(CN)₄Br_0.3·3H₂O and K₂Pt(CN)₄Cl_0.3·3H₂O has been investigated. Crystals with reproducible d.c. conductivity and dielectric constants were obtained only when the mixed valence platinum salt contained one halide. The bromide complex was particularly susceptible to contamination by chloride, and a preparation scheme is presented which excludes the unwanted halide. The best quality crystals were grown by slow evaporation of solutions which were 1 molar in urea and 0.1 molar in the appropriate potassium halide.     

Crystal structure of KCP (K2[Pt (CN)4]Br0.3 · 3 H2O) at 90 K

We have investigated the crystal structure of KCP at 90 K using single crystal methods. The Pt-Pt distances within a chain are equal only within the limits of three standard deviations, but show a strongly anisotropic thermal vibration with a preferred motion parallel to the c-axis. The center of the KCP structure is fully occupied, either by Br or by water.     

Microemulsion-assisted solvothermal synthesis of Nd2(CO3)3·8H2O microstructures

Microstructures of Nd₂(CO₃)₃·8H₂O with various morphological structures and sizes were successfully synthesized using the microemulsion-assisted solvothermal method. The obtained products were characterized by X-ray diffraction (XRD), differential scanning calorimetry and thermal gravimetric analysis (DSC-TGA), scanning electron microscope (SEM), transmission electron microscope (TEM) and electron diffraction (ED). The results showed that pyramid-like and spherical Nd₂(CO₃)₃·8H₂O microstructures were synthesized depending on the reaction time and reaction temperature. Moreover, the reaction time and temperature also played important roles in controlling the morphologies and sizes of the resulting Nd₂(CO₃)₃·8H₂O microstructures.     

On the water distribution in K2[Pt(CN)4]Br0.3 · 3D2O a single crystal neutron diffraction structure analysis

A single crystal neutron diffraction analysis of the linear conductor K₂[Pt(CN)₄]Br_0.3 · 3D₂O is reported. Complementary to former X-ray investigations the distribution of the water molecules was studied and three different types of D₂O could be located. Besides the full and reduced occupied two- and four-fold D₂O-positions, a third site nearby the Br^?-position was clearly identified giving the picture of a filled center of the unit cell occupied partially by Br^? and D₂O. There is no argument left for a crystallographically different second Br^?-site.     

Size and morphology-controlled Ni2[Fe(CN)6]·xH2O Prussian Blue analogue fabricated via a hydrothermal route

Nanocrystalline Prussian Blue analogue Ni₂[Fe(CN)₆]·xH₂O was synthesized through hydrothermal process at 180 °C for 24 h with NiSO₄·6H₂O and K₄[Fe(CN)₆]·3H₂O as precursors. The effects of reactant concentration and protective matrix (Polyethylene glycol 400, PEG-400) on the size and morphology of nanoparticles were investigated. The as-synthesized products were identified as face-centered cubic structure by powder X-ray diffraction. Field-emission scanning electron microscopy and transmission electron microscopy images showed that well dispersed nanoparticles with fairly narrow size distribution were successfully prepared.     

Synthesis of New Crystalline Pu(V) Compounds from Solutions: V. Crystal Structure of [Co(NH3)6][PuO2(C2O4)2] · 3H2O

The compound [Co(NH₃)₆][PuO₂(C₂O₄)₂] · 3H₂O was studied by single crystal X-ray diffraction. The structure contains dimeric complex anions [PuO₂(C₂O₄)₂] ₂ ⁶⁻ in which the coordination polyhedra of the Pu atoms are distorted pentagonal bipyramids sharing a common equatorial edge. In going from [Co(NH₃)₆] · [NpO₂(C₂O₄)₂] · 3H₂O to [Co(NH₃)₆][PuO₂(C₂O₄)₂] · 3H₂O, the An-O distances, both axial (in the actinyl group) and equatorial, decrease virtually isotropically. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 419–422. Original Russian Text Copyright ? 2005 by Grigor'ev, Antipin, Krot, Bessonov.     

Low temperature synthesis and optical properties of CaTiO3 nanoparticles from Ca(NO3)2·4H2O and TiO2 nanocrystals

Choosing low-melting-point Ca(NO₃)₂·4H₂O and high-reactive-activity TiO₂ nanocrystals as the raw materials, a simple and cost-effective route was developed for the synthesis of CaTiO₃ nanoparticles at 600 °C, which is much lower than that (about 1350 °C) used in the conventional solid state reaction methods. X-ray diffraction, energy dispersive X-ray spectroscopy and field emission scanning electron microscopy revealed the formation of orthorhombic phase CaTiO₃ nanoparticles with oxygen-deficiency at the surface. UV-vis absorption spectrum of the as-obtained CaTiO₃ nanoparticles displayed an absorption peak centered at around 325 nm (3.8 eV), together with a tail at lower energy side. Room temperature photoluminescence spectrum of the as-obtained CaTiO₃ nanoparticles upon laser excitation at 325 nm demonstrated a strong and broad visible light emission ranging from about 527 to 568 nm, which may be originated from the surface states and defect levels.     

Synthesis and characterization of a new organic dihydrogenomonophosphate [3,5-(CH3O)2C6H3NH3]2(H2PO4)2

Chemical preparation, crystal structure, calorimetric studies and spectroscopic investigation are given for a new organic cation dihydrogenomonophosphate [3,5-(CH₃O)₂C₆H₃NH₃]₂(H₂PO₄)₂. This compound is triclinic with the following unit cell parameters: a=9.030(6) Å, b=16.124(5) Å, c=8.868(3) Å, α=75.04(3)°, β=110.71(4)°, γ=104.61(1)°, Z=4, V=1148.0(1) Å³, Z=2 and ρ_cal.=1.454 g cm⁻³. Crystal structure was solved and refined to R=0.04, 2752 independent reflections. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions parallel to planes, between which are located the organic groups. Solid-state and MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of the phosphorous and carbon signals to the independent crystallographic sites and to the various atoms of the organic groups.     

Preparation of Sb2S3 nanostructures by the [BMIM][BF4] ionic liquid assisted low power sonochemical method

Sb₂S₃ nanorods were successfully synthesized by the ionic liquid assisted sonochemical method (ILASM). The starting reagents were Sb₂Cl₃, Thioacetamide, absolute ethanol (ETA) and the selected ionic liquid (IL) was 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]). The synthesized materials were subjected to 200 °C annealing treatment under controlled vacuum conditions. X-ray powder diffraction analysis showed that ultrasound irradiation played a key role on the crystallization degree of Sb₂S₃, whilst Scanning Electron Microscopy analysis showed that the addition of IL was fundamental for the formation of 1-D Sb₂S₃ nanostructures. XPS confirmed the formation of Sb₂S₃.The optical properties (band gap) were similar to previously reported for bulk Sb₂S₃.     

Electronic conduction in SiO2:N thin films grown by thermal oxidation of silicon in N2O

Silicon oxynitride [SiO₂:N] thin films have been grown by oxidizing silicon in N₂O at 900, 1000 and 1100 °C and at 760 and 1520 torr. It is shown that the dominant electrical conduction mechanism, for high electric fields, is the field assisted thermionic emission from the traps (Poole-Frenkel effect), and is not direct or Fowler-Nordheim tunneling, as typically occurs in thermal silicon oxide with similar thickness. Electrical conduction in these films occurs by field assisted electron emission from donor traps with energy levels varying in the range from 0.5 to 1 eV from the conduction band. The results shown here indicate that the best quality films are those grown at low temperature and pressure, since they give films with a higher critical electric field, a higher energy barrier depth at the traps and less donors compensated by acceptors than those grown at high temperatures and pressures.