Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

Science.gov (United States)

Yu, Na; Klepov, Vladislav V.; Villa, Eric M.; Bosbach, Dirk; Suleimanov, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.; Alekseev, Evgeny V.

2014-07-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O (α-, β-RbUAs) and the anhydrous phase Rb[UO2(AsO3OH)(AsO2(OH)2)] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions.

The reaction of fluorine atoms with methanol: yield of CH3O/CH2OH and rate constant of the reactions CH3O + CH3O and CH3O + HO2.

Science.gov (United States)

Assaf, Emmanuel; Schoemaecker, Coralie; Vereecken, Luc; Fittschen, Christa

2018-04-25

Xenondifluoride, XeF2, has been photolysed in the presence of methanol, CH3OH. Two reaction pathways are possible: F + CH3OH → CH2OH + HF and F + CH3OH → CH3O + HF. Both products, CH2OH and CH3O, will be converted to HO2 in the presence of O2. The rate constants for the reaction of both radicals with O2 differ by more than 3 orders of magnitude, which allows an unequivocal distinction between the two reactions when measuring HO2 concentrations in the presence of different O2 concentrations. The following yields have then been determined from time-resolved HO2 profiles: φCH2OH = (0.497 ± 0.013) and φCH3O = (0.503 ± 0.013). Experiments under low O2 concentrations lead to reaction mixtures containing nearly equal amounts of HO2 (converted from the first reaction) and CH3O (from the second reaction). The subsequent HO2 decays are very sensitive to the rate constants of the reaction between these two radicals and the following rate constants have been obtained: k(CH3O + CH3O) = (7.0 ± 1.4) × 10-11 cm3 s-1 and k(CH3O + HO2) = (1.1 ± 0.2) × 10-10 cm3 s-1. The latter reaction has also been theoretically investigated on the CCSD(T)//M06-2X/aug-cc-pVTZ level of theory and CH3OH + O2 have been identified as the main products. Using μVTST, a virtually pressure independent rate constant of k(CH3O + HO2) = 4.7 × 10-11 cm3 s-1 has been obtained, in good agreement with the experiment.

Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution.

Science.gov (United States)

Korenev, Vladimir S; Floquet, Sébastien; Marrot, Jérôme; Haouas, Mohamed; Mbomekallé, Israël-Martyr; Taulelle, Francis; Sokolov, Maxim N; Fedin, Vladimir P; Cadot, Emmanuel

2012-02-20

Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

A New Open-framework Iron Borophosphate from Ionic Liquids: KFe[BP2O8(OH

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Guangmei Wang

2011-04-01

Full Text Available A new open-framework iron borophosphate, KFe[BP2O8(OH], has been obtained by ionothermal synthesis from KH2PO4, FeCl3∙4H2O, H3BO3 and [C4mpyr]Br (1-butyl-1-methylpyrrolidinium bromide. Single-crystal X-ray diffraction analysis shows that KFe[BP2O8(OH] (monoclinic, P21/c, a = 9.372(2 Å , b = 8.146(2Å , c = 9.587(2 Å, β = 101.18(3°, V = 718.0(2Å3 and Z = 4 has a three-dimensional (3-D framework structure composed by {Fe(IIIO5(OH} octahedra as well as {BO3(OH} and {PO4} tetrahedra. As anionic structural sub-unit, KFe[BP2O8(OH], contains an infinite open-branched {[BP2O8(OH]4-} chain which is formed by alternating {BO3(OH} and {PO4} tetrahedra. {Fe(IIIO5(OH} octahedra share common O corners with five phosphate tetrahedra and the OH corner links to the hydrogen borate group to give a 3D framework. The negative charges of the inorganic framework are balanced by K+ ions.

Synthesis, crystal structure refinement, and nonlinear-optical properties of CaB3O5(OH): Comparative crystal chemistry of calcium triborates

International Nuclear Information System (INIS)

Yamnova, N. A.; Aksenov, S. M.; Stefanovich, S. Yu.; Volkov, A. S.; Dimitrova, O. V.

2015-01-01

Calcium triborate CaB 3 O5(OH) obtained by hydrothermal synthesis in the Ca(OH) 2 –H 3 BO 3 –Na 2 CO 3 –KCl system is studied by single-crystal X-ray diffraction. The parameters of the orthorhombic unit cell are as follows: a = 13.490(1), b = 6.9576(3), and c = 4.3930(2) Å; V = 412.32(3) Å 3 and space group Pna2 1 . The structure is refined in the anisotropic approximation of the atomic displacement parameters to R = 4.28% using 972 vertical bar F vertical bar > 4σ(F). It is confirmed that the crystal structure of Ca triborate CaB 3 O 5 (OH) is identical to that described earlier. The hydrogen atom is localized. An SHG signal stronger than that of the quartz standard is registered. The phase transition of calcium triborate into calciborite is found on heating. The comparative crystal-chemical analysis of a series of borates with the general chemical formula 2CaO · 3B 2 O 3 · nH 2 O (n = 0–13) with the constant CaO: B 2 O 3 = 2: 3 ratio and variable content of water is performed

Determination of the rate constant for the OH(X2Π) + OH(X2Π) → H2O + O(3P) reaction over the temperature range 295 to 701 K.

Science.gov (United States)

Altinay, Gokhan; Macdonald, R Glen

2014-01-09

The rate constant for the radical-radical reaction OH(X(2)Π) + OH(X(2)Π) → H2O + O((3)P) has been measured over the temperature and pressure ranges 295-701 K and 2-12 Torr, respectively, in mixtures of CF4, N2O, and H2O. The OH radical was produced by the 193 nm laser photolysis of N2O. The resulting O((1)D) atoms reacted rapidly with H2O to produce the OH radical. The OH radical was detected by high-resolution time-resolved infrared absorption spectroscopy using a single Λ-doublet component of the OH(1,0) P1e/f(4.5) fundamental vibrational transition. A detailed kinetic model was used to determine the reaction rate constant as a function of temperature. These experiments were conducted in a new temperature controlled reaction chamber. The values of the measured rate constants are quite similar to the previous measurements from this laboratory of Bahng and Macdonald (J. Phys. Chem. A 2007 , 111 , 3850 - 3861); however, they cover a much larger temperature range. The results of the present work do not agree with recent measurements of Sangwan and Krasnoperov (J. Phys. Chem. A 2012 , 116 , 11817 - 11822). At 295 K the rate constant of the title reaction was found to be (2.52 ± 0.63) × 10(-12) cm(3) molecule(-1) s(-1), where the uncertainty includes both experimental scatter and an estimate of systematic errors at the 95% confidence limit. Over the temperature range of the experiments, the rate constant can be represented by k1a = 4.79 × 10(-18)T(1.79) exp(879.0/T) cm(3) molecule(-1) s(-1) with a uncertainty of ±24% at the 2σ level, including experimental scatter and systematic error.

Ilyukhinite (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 • 3H2O, a New Mineral of the Eudialyte Group

Science.gov (United States)

Chukanov, N. V.; Rastsvetaeva, R. K.; Rozenberg, K. A.; Aksenov, S. M.; Pekov, I. V.; Belakovsky, D. I.; Kristiansen, R.; Van, K. V.

2017-12-01

A new eudialyte-group mineral, ilyukhinite, ideally (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 · 3H2O, has been found in peralkaline pegmatite at Mt. Kukisvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. It occurs as brownish orange, with vitreous luster anhedral grains up to 1 mm across in hydrothermally altered peralkaline rock, in association with aegirine, murmanite, albite, microcline, rhabdophane-(Ce), fluorite, sphalerite and molybdenite. The Mohs hardness is 5; cleavage is not observed. D meas 2.67(2), D calc 2.703 g/cm3. Ilyukhinite is optically uniaxial (-): ω = 1.585(2), ɛ = 1.584(2). The IR spectrum is given. The average chemical composition of ilyukhinite (wt %; electron microprobe, ranges given in parentheses; H2O determined by gas chromatography) is as follows: 3.07 (3.63-4.43) Na2O, 0.32 (0.28-0.52) K2O, 10.63 (10.26-10.90) CaO, 3.06 (2.74-3.22) MnO, 1.15 (0.93-1.37) FeO, 0.79 (0.51-0.89) La2O3, 1.21 (0.97-1.44) Ce2O3, 0.41 (0.30-0.56) Nd2O3, 0.90 (0.77-1.12) TiO2, 10.94 (10.15-11.21) ZrO2, 1.40 (0.76-1.68) Nb2O5, 51.24 (49.98-52.28) SiO2, 1.14 (0.89-1.37) SO3, 0.27 (0.19—0.38) Cl, 10.9(5 )H2O,-0.06-O = C1, total is 98.27. The empirical formula is H36.04(Na3.82K0.20)(Ca5.65Ce0.22La0.14Nd0.07)(Mn1.285Fe0.48)(Zr2.645Ti0.34)Nb0.31Si25.41S0.42Cl0.23O86.82. The crystal structure has been solved ( R = 0.046). Ilyukhinite is trigonal, R3 m; a = 14.1695(6) Å, b = 31.026(1) Å, V = 5394.7(7) Å3, Z = 3. The strongest XRD reflections [ d, Å (I, %) ( hkl)] are 11.44 (82) (101), 7.09 (70) (110), 6.02 (44) (021), 4.371 (89) 205), 3.805 (47) (303, 033), 3.376 (41) (131), 2.985 (100) (315, 128), 2.852 (92) (404). Ilyukhinite was named in memory of Vladimir V. Ilyukhin (1934-1982), an outstanding Soviet crystallographer. The type specimen of ilyukhinite has been deposited in the collection of the Natural History Museum, University of Oslo, Norway.

Hydrothermal synthesis and crystal structures of new uranyl oxalate hydroxides: α- and β-[(UO2)2(C2O4)(OH)2(H2O)2] and [(UO2)2(C2O4)(OH)2(H2O)2].H2O

International Nuclear Information System (INIS)

Duvieubourg, Laurence; Nowogrocki, Guy; Abraham, Francis; Grandjean, Stephane

2005-01-01

Two modifications of the new uranyl oxalate hydroxide dihydrate [UO 2 ) 2 (C 2 O 4 )(OH) 2 (H 2 O) 2 ] (1 and 2) and one form of the new uranyl oxalate hydroxide trihydrate [(UO 2 ) 2 (C 2 O 4 )(OH) 2 (H 2 O) 2 ].H 2 O (3) were synthesized by hydrothermal methods and their structures determined from single-crystal X-ray diffraction data. The crystal structures were refined by full-matrix least-squares methods to agreement indices R(wR)=0.0372(0.0842) and 0.0267(0.0671) calculated for 1096 and 1167 unique observed reflections (I>2σ(I)), for α (1) and β (2) forms, respectively and to R(wR)=0.0301(0.0737) calculated for 2471 unique observed reflections (I>2σ(I)), for 3. The α-form of the dihydrate is triclinic, space group P1-bar , Z=1, a=6.097(2), b=5.548(2), c=7.806(3)A, α=89.353(5), β=94.387(5), γ=97.646(5) o , V=260.88(15)A 3 , β-form is monoclinic, space group C2/c, Z=4, a=12.180(3), b=8.223(2), c=10.777(3)A, β=95.817(4), V=1073.8(5)A 3 . The trihydrate is monoclinic, space group P2 1 /c, Z=4, a=5.5095(12), b=15.195(3), c=13.398(3)A, β=93.927(3), V=1119.0(4)A 3 . In the three structures, the coordination of uranium atom is a pentagonal bipyramid composed of dioxo UO 2 2+ cation perpendicular to five equatorial oxygen atoms belonging to one bidentate oxalate ion, one water molecule and two hydroxyl ions in trans configuration in 2 and in cis configuration in 1 and 3. The UO 7 polyhedra are linked through hydroxyl oxygen atoms to form different structural building units, dimers [U 2 O 10 ] obtained by edge-sharing in 1, chains [UO 6 ] ∼ and tetramers [U 4 O 26 ] built by corner-sharing in 2 and 3, respectively. These units are further connected by oxalate entities that act as bis-bidentate to form one-dimensional chains in 1 and bi-dimensional network in 2 and 3. These chains or layers are connected in frameworks by hydrogen-bond arrays

Tiberiobardiite, Cu9Al(SiO3OH2(OH12(H2O6(SO41.5·10H2O, a New Mineral Related to Chalcophyllite from the Cretaio Cu Prospect, Massa Marittima, Grosseto (Tuscany, Italy: Occurrence and Crystal Structure

Directory of Open Access Journals (Sweden)

Cristian Biagioni

2018-04-01

Full Text Available The new mineral species tiberiobardiite, ideally Cu9Al(SiO3OH2(OH12(H2O6(SO41.5·10H2O, has been discovered in the Cretaio Cu prospect, Massa Marittima, Grosseto, Tuscany, Italy, as very rare, light green, vitreous, tabular {0001}, pseudo-hexagonal crystals, up to 200 μm in size and 5 μm in thickness, associated with brochantite. Electron microprobe analysis gave (in wt %, average of 5 spot analyses: SO3 10.37, P2O5 3.41, As2O5 0.05, SiO2 8.13, Al2O3 5.54, Fe2O3 0.74, CuO 62.05, and ZnO 0.03, for a total of 90.32. Based on an idealized O content of 42 atoms per formula unit, assuming the presence of 16 H2O groups and 13.5 cations (without H, the empirical formula of tiberiobardiite is (Cu8.69Al0.21Fe0.10Σ9.00Al1.00(Si1.51P0.54Σ2.05S1.44O12.53(OH13.47·16H2O. The main diffraction lines, corresponding to multiple hkl indices, are [d in Å (relative visual intensity]: 9.4 (s, 4.67 (s, 2.576 (m, 2.330 (m, and 2.041 (mw. The crystal structure study revealed tiberiobardiite to be trigonal, space group R 3 ¯ , with unit-cell parameters a = 10.6860(4, c = 28.3239(10 Å, V = 2801.0(2 Å3, and Z = 3. The crystal structure was refined to a final R1 = 0.060 for 1747 reflections with Fo > 4σ (Fo and 99 refined parameters. Tiberiobardiite is the Si-analogue of chalcophyllite, with Si4+ replacing As5+ through the coupled substitution As5+ + O2− = Si4+ + (OH−. The name tiberiobardiite honors Tiberio Bardi (b. 1960 for his contribution to the study of the mineralogy of Tuscany.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})

Energy Technology Data Exchange (ETDEWEB)

Yu, Na; Klepov, Vladislav V. [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Villa, Eric M. [Department of Chemistry, Creighton University, 2500 California Plaza, Omaha NE 68178 (United States); Bosbach, Dirk [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Suleimanov, Evgeny V. [Department of Chemistry, Lobachevsky State University of Nizhny Novgorod, 603950 Nizhny Novgorod (Russian Federation); Depmeier, Wulf [Institut für Geowissenschaften, Universität zu Kiel, 24118 Kiel (Germany); Albrecht-Schmitt, Thomas E., E-mail: albrecht-schmitt@chem.fsu.edu [Department of Chemistry and Biochemistry, Florida State University, 102 Varsity Way, Tallahassee, FL 32306-4390 (United States); Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Institut für Kristallographie, RWTH Aachen University, 52066 Aachen (Germany)

2014-07-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.

Synthesis and crystal structure of the solid solution Co3(SeO3)3-x(PO3OH)x(H2O) involving crystallographic split positions of Se4+ and P5+.

Science.gov (United States)

Zimmermann, Iwan; Johnsson, Mats

2013-10-21

Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co3(SeO3)3-x(PO3OH)x(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se(4+) and P(5+) share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P(5+). The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 °C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) μB per Co atom was observed.

Fabrication and properties of highly luminescent materials from Tb(OH)3-SiO2 and Tb(OH)3-SiO2:Eu3+ nanotubes

International Nuclear Information System (INIS)

Tran Thu Huong; Tran Kim Anh; Le Quoc Minh

2009-01-01

Luminescent nanomaterials with one-dimensional (1D) structures have attracted much attention due to their unique properties and potential applications in nanophotonics and nanobiophotonics. In this paper, we report a synthesis of terbium - hydroxide - at - silica Tb(OH) 3 -SiO 2 and Tb(OH) 3 -SiO 2 :Eu 3+ nanotubes. Terbium - hydroxide tubes were synthesized by soft template method. The size of the tubes can be controlled precisely and have outer diameters ranging from 80 to 120 nm, wall thickness of about 30 nm, and lengths ranging from 300 to 800 nm. To fabricate core/shell materials, the seed growth method is used. FESEM, X-ray diffraction, Raman spectra of Tb(OH) 3 and Tb(OH) 3 -SiO 2 nanotubes were investigated. The photoluminescence (PL) spectrum of Tb(OH) 3 under 325 nm excitation consists of four main peaks at 488, 542, 582, and 618 nm. Furthermore, a preliminary suggestion for the mechanism of growth of the Tb(OH) 3 nanotubes using the soft - template synthesis technique has been proposed. The PL intensity from Tb(OH) 3 -SiO 2 or Tb(OH) 3 -SiO 2 :Eu 3+ nanotubes is much stronger than that of Tb(OH) 3 .

Investigation of the crystal structure of a basic bismuth(III) nitrate with the composition [Bi6O4(OH)(4)](0.54(1))[Bi6O5(OH)(3)](0.46(1))(NO3)(5.54(1))

DEFF Research Database (Denmark)

Christensen, Axel Norlund; Lebech, Bente

2012-01-01

A basic bismuth(III) nitrate with the composition [Bi6O4(OH)(4)](0.5)[Bi6O5(OH)(3)](0.5)(NO3)(5.5) formed in a slow crystal growth mode has an ordered crystal structure with the monoclinic space group P2(1) and lattice parameters a = 15.850(3), b = 14.986(3), c = 18.230(4) angstrom, beta = 107...... a trigonal R (3) over bar cell with a = 15.1865(1) and c = 15.8416(1) angstrom (hexagonal setting). In a Rietveld type structure model refinement with a total of 28 atom sites (4 Bi, 3 N, 15 O and 6 H), the composition of this sample is determined to be [Bi6O4(OH)(4)](0.54(1))[Bi6O5(OH)(3)](0.46(1))(NO3)(5.54(1))....

The borosulfates K{sub 4}[BS{sub 4}O{sub 15}(OH)], Ba[B{sub 2}S{sub 3}O{sub 13}], and Gd{sub 2}[B{sub 2}S{sub 6}O{sub 24}

Energy Technology Data Exchange (ETDEWEB)

Gross, Peter; Kirchhain, Arno; Hoeppe, Henning A. [Universitaet Augsburg, Institut fuer Physik (Germany)

2016-03-18

K{sub 4}[BS{sub 4}O{sub 15}(OH)], Ba[B{sub 2}S{sub 3}O{sub 13}], and Gd{sub 2}[B{sub 2}S{sub 6}O{sub 24}] were obtained by a new synthetic approach. The strategy involves initially synthesizing the complex acid H[B(HSO{sub 4}){sub 4}] which is subsequently reacted in an open system with anhydrous chlorides of K, Ba, and Gd to the respective borosulfates and a volatile molecule (HCl). Furthermore, protonated borosulfates should be accessible by appropriate stoichiometry of the starting materials, particularly in closed systems, which inhibit deprotonation of H[B(HSO{sub 4}){sub 4}] via condensation and dehydration. This approach led to the successful synthesis of the first divalent and trivalent metal borosulfates (Ba[B{sub 2}S{sub 3}O{sub 13}] with band-silicate topology and Gd{sub 2}[B{sub 2}S{sub 6}O{sub 24}] with cyclosilicate topology) and the first hydrogen borosulfate K{sub 4}[BS{sub 4}O{sub 15}(OH)]. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, crystal structure refinement, and nonlinear-optical properties of CaB{sub 3}O{sub 5}(OH): Comparative crystal chemistry of calcium triborates

Energy Technology Data Exchange (ETDEWEB)

Yamnova, N. A., E-mail: aks.crys@gmail.com; Aksenov, S. M. [Moscow State University, Faculty of Geology (Russian Federation); Stefanovich, S. Yu. [Moscow State University, Faculty of Chemistry (Russian Federation); Volkov, A. S.; Dimitrova, O. V. [Moscow State University, Faculty of Geology (Russian Federation)

2015-09-15

Calcium triborate CaB{sub 3}O5(OH) obtained by hydrothermal synthesis in the Ca(OH){sub 2}–H{sub 3}BO{sub 3}–Na{sub 2}CO{sub 3}–KCl system is studied by single-crystal X-ray diffraction. The parameters of the orthorhombic unit cell are as follows: a = 13.490(1), b = 6.9576(3), and c = 4.3930(2) Å; V = 412.32(3) Å{sup 3} and space group Pna2{sub 1}. The structure is refined in the anisotropic approximation of the atomic displacement parameters to R = 4.28% using 972 vertical bar F vertical bar > 4σ(F). It is confirmed that the crystal structure of Ca triborate CaB{sub 3}O{sub 5}(OH) is identical to that described earlier. The hydrogen atom is localized. An SHG signal stronger than that of the quartz standard is registered. The phase transition of calcium triborate into calciborite is found on heating. The comparative crystal-chemical analysis of a series of borates with the general chemical formula 2CaO · 3B{sub 2}O{sub 3} · nH{sub 2}O (n = 0–13) with the constant CaO: B{sub 2}O{sub 3}= 2: 3 ratio and variable content of water is performed.

Attikaite, Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O, a new mineral species

Science.gov (United States)

Chukanov, N. V.; Pekov, I. V.; Zadov, A. E.

2007-12-01

Attikaite, a new mineral species, has been found together with arsenocrandalite, arsenogoyazite, conichalcite, olivenite, philipsbornite, azurite, malachite, carminite, beudantite, goethite, quartz, and allophane at the Christina Mine No. 132, Kamareza, Lavrion District, Attiki Prefecture (Attika), Greece. The mineral is named after the type locality. It forms spheroidal segregations (up to 0.3 mm in diameter) consisting of thin flexible crystals up to 3 × 20 × 80 μm in size. Its color is light blue to greenish blue, with a pale blue streak. The Mohs’ hardness is 2 to 2.5. The cleavage is eminent mica-like parallel to {001}. The density is 3.2(2) g/cm3 (measured in heavy liquids) and 3.356 g/cm3 (calculated). The wave numbers of the absorption bands in the infrared spectrum of attikaite are (cm-1; sh is shoulder; w is a weak band): 3525 sh, 3425, 3180, 1642, 1120 w, 1070 w, 1035 w, 900 sh, 874, 833, 820, 690 w, 645 w, 600 sh, 555, 486, 458, and 397. Attikaite is optically biaxial, negative, α = 1.642(2), β = γ = 1.644(2) ( X = c) 2 V means = 10(8)°, and 2 V calc = 0°. The new mineral is microscopically colorless and nonpleochroic. The chemical composition (electron microprobe, average over 4 point analyses, wt %) is: 0.17 MgO, 17.48 CaO, 0.12 FeO, 16.28 CuO, 10.61 Al2O3, 0.89 P2O5, 45.45 As2O5, 1.39 SO3, and H2O (by difference) 7.61, where the total is 100.00. The empirical formula calculated on the basis of (O,OH,H2O)22 is: Ca2.94Cu{1.93/2+} Al1.97Mg0.04Fe{0.02/2+} [(As3.74S0.16P0.12)Σ4.02O16.08](OH)3.87 · 2.05H2 O. The simplified formula is Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O. Attikaite is orthorhombic, space group Pban, Pbam or Pba2; the unit-cell dimensions are a = 10.01(1), b = 8.199(5), c = 22.78(1) Å, V = 1870(3) Å3, and Z = 4. In the result of the ignition of attikaite for 30 to 35 min at 128 140°, the H2O bands in the IR spectrum disappear, while the OH-group band is not modified; the weight loss is 4.3%, which approximately corresponds to two H2O

Effect of B{sub 2}O{sub 3}/P{sub 2}O{sub 5} substitution on the properties and structure of tin boro-phosphate glasses

Energy Technology Data Exchange (ETDEWEB)

Saitoh, Akira, E-mail: asaito@ehime-u.ac.jp [Graduate School of Science and Engineering, Ehime University, Matsuyama, 3 Bunkyo-cho (Japan); Tricot, Grégory [LASIR UMR-CNRS 8516, Université de Lille 1, Villeneuve d' Ascq 59655 (France); UCCS UMR-CNRS 8181, Université de Lille 1, Villeneuve d' Ascq 59655 (France); Rajbhandari, Prashant [UCCS UMR-CNRS 8181, Université de Lille 1, Villeneuve d' Ascq 59655 (France); Anan, Shoji; Takebe, Hiromichi [Graduate School of Science and Engineering, Ehime University, Matsuyama, 3 Bunkyo-cho (Japan)

2015-01-15

Effect of B{sub 2}O{sub 3}/P{sub 2}O{sub 5} substitution on the properties and structure of the ternary 67SnO–(33–x)P{sub 2}O{sub 5}–xB{sub 2}O{sub 3} composition line (from x = 0–33 mol%) are examined in this contribution. We show that density and glass transition temperature increase while molar volume and thermal expansion coefficient decrease with increasing B{sub 2}O{sub 3} concentration. Density and thermal properties experience an original three-domain evolution with rapid (region I: 0 ≤ x < 5), substantial (II: 5 < x ≤ 15), and moderate (III: 15 < x ≤ 33) increase. In order to explain this unconventional behaviour, the glass structure has been investigated using high magnetic field 1 dimensional {sup 31}P and {sup 11}B MAS–NMR, micro-Raman and infrared spectroscopies. {sup 11}B MAS–NMR experiments allow to (i) monitor the 3- and 4-fold coordinated borate species proportion and (ii) highlight the presence of unreported 4-fold coordinated species in the region (III). Finally, it is shown that substitution of P{sub 2}O{sub 5} by B{sub 2}O{sub 3} induces an alteration of the dimeric phosphate network and formation of mixed anion structure that consists of Q{sup 0} phosphate units, 3- and 4-fold coordinated borate units and their combinations. - Highlights: • We examined B{sub 2}O{sub 3}/P{sub 2}O{sub 5} substitution effect on the ternary SnO–P{sub 2}O{sub 5}–B{sub 2}O{sub 3} glasses. • We show a three-domains evolution for density and thermal properties. • The structure was investigated by {sup 31}P and {sup 11}B NMR, Raman and IR spectroscopies. • 3 and 4-folded borate species and unreported 4-folded species are revealed. • Mixed anion structure consists of Q{sup 0} phosphate unit and 3- and 4-folded borate units.

New nighttime retrievals of O(3P) and OH densities in the mesosphere/lower thermosphere using SABER/TIMED observations

Science.gov (United States)

Panka, P.; Kutepov, A. A.; Kalogerakis, K. S.; Janches, D.; Feofilov, A.; Rezac, L.; Marsh, D. R.; Yigit, E.

2017-12-01

We present first retrievals of O(3P) and OH densities in the mesosphere/lower thermosphere (MLT) using SABER/TIMED OH 2.0 and 1.6 μm limb emission observations. Recently, Kaufmann et al. [2014] reported that current SABER O(3P) densities are on average 30% higher compared to other observations. In this study we applied new detailed non-LTE model [Panka et al. 2017] of nighttime OH(v), which accounts for the new mechanism OH(v≥5)+O(3P)→O(1D)+OH(v-5) of energy transfer recently suggested by Sharma et al. [2015] and confirmed through laboratory studies by Kalogerakis et al. [2016]. Based on this model we developed a new self-consistent two channel retrieval approach for O(3P) and OH density. Using this approach, we retrieved O(3P) densities that are 10-40% lower than current SABER O(3P), as well as total OH density which is retrieved for the first time using SABER observations. We compare our retrieveals with the results of other observations and models. As it was recently shown by Panka et al. [2017], the new mechanism of OH quenching produces a significant pumping of CO2 4.3 µm emission. We discuss the effects these new O(3P) and OH retrievals have on the nighttime CO2 density retrievals from the SABER 4.3 µm channel.

Testing fast photochemical theory during TRACE-P based on measurements of OH, HO2, and CH2O

Science.gov (United States)

Olson, Jennifer R.; Crawford, J. H.; Chen, G.; Fried, A.; Evans, M. J.; Jordan, C. E.; Sandholm, S. T.; Davis, D. D.; Anderson, B. E.; Avery, M. A.; Barrick, J. D.; Blake, D. R.; Brune, W. H.; Eisele, F. L.; Flocke, F.; Harder, H.; Jacob, D. J.; Kondo, Y.; Lefer, B. L.; Martinez, M.; Mauldin, R. L.; Sachse, G. W.; Shetter, R. E.; Singh, H. B.; Talbot, R. W.; Tan, D.

2004-08-01

Measurements of several short-lived photochemical species (e.g., OH, HO2, and CH2O) were obtained from the DC-8 and P3-B aircraft during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) campaign. To assess fast photochemical theory over the east Asian coast and western Pacific, these measurements are compared to predictions using a photochemical time-dependent box model constrained by coincident measurements of long-lived tracers and physical parameters. Both OH and HO2 are generally overpredicted by the model throughout the troposphere, which is a different result from previous field campaigns. The calculated-to-observed ratio of OH shows an altitude trend, with OH overpredicted by 80% in the upper troposphere and by 40-60% in the middle troposphere. Boundary layer and lower tropospheric OH ratios decrease from middle tropospheric values to 1.07 for the DC-8 and to 0.70 for the P3-B. HO2 measured on the DC-8 is overpredicted by a median of 23% and shows no trend in the agreement with altitude. Three subsets of data which compose 12% of the HO2 measurements represent outliers with respect to calculated-to-observed ratios: stratospherically influenced air, upper tropospheric data with NO > 135 pptv, and data from within clouds. Pronounced underpredictions of both HO2 and OH were found for stratospherically influenced air, which is in contrast to previous studies showing good agreement of predicted and observed HOx in the stratosphere. Observational evidence of heterogeneous uptake of HO2 within low and middle tropospheric clouds is presented, though there is no indication of significant HO2 uptake within higher-altitude clouds. Model predictions of CH2O are in good agreement with observations in the median for background concentrations, but a large scatter exists. Factors contributing to this scatter are examined, including the limited availability of some important constraining measurements, particularly CH3OOH. Some high concentrations of CH2O

Vibrational spectroscopic study of poldervaartite CaCa[SiO3(OH)(OH)

Science.gov (United States)

Frost, Ray L.; López, Andrés; Scholz, Ricardo; Lima, Rosa Malena Fernandes

2015-02-01

We have studied the mineral poldervaartite CaCa[SiO3(OH)(OH)] which forms a series with its manganese analogue olmiite CaMn[SiO3(OH)](OH) using a range of techniques including scanning electron microscopy, thermogravimetric analysis, Raman and infrared spectroscopy. Chemical analysis shows the mineral is reasonably pure and contains only calcium and manganese with low amounts of Al and F. Thermogravimetric analysis proves the mineral decomposes at 485 °C with a mass loss of 7.6% compared with the theoretical mass loss of 7.7%. A strong Raman band at 852 cm-1 is assigned to the SiO stretching vibration of the SiO3(OH) units. Two Raman bands at 914 and 953 cm-1 are attributed to the antisymmetric vibrations. Intense prominent peaks observed at 3487, 3502, 3509, 3521 and 3547 cm-1 are assigned to the OH stretching vibration of the SiO3(OH) units. The observation of multiple OH bands supports the concept of the non-equivalence of the OH units. Vibrational spectroscopy enables a detailed assessment of the molecular structure of poldervaartite.

SMA OBSERVATIONS OF THE W3(OH) COMPLEX: PHYSICAL AND CHEMICAL DIFFERENTIATION BETWEEN W3(H{sub 2}O) AND W3(OH)

Energy Technology Data Exchange (ETDEWEB)

Qin, Sheng-Li [Department of Astronomy, Yunnan University, and Key Laboratory of Astroparticle Physics of Yunnan Province, Kunming, 650091 (China); Schilke, Peter; Sánchez-Monge, Álvaro [Physikalisches Institut, Universität zu Köln, Zülpicher Str. 77, D-50937 Köln (Germany); Wu, Jingwen [Department of Physics and Astronomy, University of California, Los Angeles, CA 90095 (United States); Wu, Yuefang [Department of Astronomy, Peking University, Beijing, 100871 (China); Liu, Tie [Korea Astronomy and Space Science Institute 776, Daedeokdaero, Yuseong-gu, Daejeon, Korea 305-348 (Korea, Republic of); Liu, Ying, E-mail: slqin@bao.ac.cn [Department of Physics and Hebei Advanced Thin Film Laboratory, Hebei Normal University, Shijiazhuang 050024 (China)

2015-04-10

We report on the Submillimeter Array (SMA) observations of molecular lines at 270 GHz toward the W3(OH) and W3(H{sub 2}O) complex. Although previous observations already resolved the W3(H{sub 2}O) into two or three sub-components, the physical and chemical properties of the two sources are not well constrained. Our SMA observations clearly resolved the W3(OH) and W3(H{sub 2}O) continuum cores. Taking advantage of the line fitting tool XCLASS, we identified and modeled a rich molecular spectrum in this complex, including multiple CH{sub 3}CN and CH{sub 3}OH transitions in both cores. HDO, C{sub 2}H{sub 5}CN, O{sup 13}CS, and vibrationally excited lines of HCN, CH{sub 3}CN, and CH{sub 3}OCHO were only detected in W3(H{sub 2}O). We calculate gas temperatures and column densities for both cores. The results show that W3(H{sub 2}O) has higher gas temperatures and larger column densities than W3(OH) as previously observed, suggesting physical and chemical differences between the two cores. We compare the molecular abundances in W3(H{sub 2}O) to those in the Sgr B2(N) hot core, the Orion KL hot core, and the Orion Compact Ridge, and discuss the chemical origin of specific species. An east–west velocity gradient is seen in W3(H{sub 2}O), and the extension is consistent with the bipolar outflow orientation traced by water masers and radio jets. A north–south velocity gradient across W3(OH) is also observed. However, with current observations we cannot be assured whether the velocity gradients are caused by rotation, outflow, or radial velocity differences of the sub-components of W3(OH)

40 CFR 721.10018 - Calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Calcium hydroxide oxide silicate (Ca6... New Uses for Specific Chemical Substances § 721.10018 Calcium hydroxide oxide silicate (Ca6(OH)2O2... substance identified as calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3) (PMN P-01-442; CAS No. 13169...

Band structure and optical properties of highly anisotropic LiBa2[B10O16(OH)3] decaborate crystal

International Nuclear Information System (INIS)

Smok, P.; Kityk, I.V.; Berdowski, J.

2003-01-01

The band structure (BS), charge density distribution and linear-optical properties of the anisotropic crystal LiBa 2 [B 10 O 16 (OH) 3 ] (LBBOH) are calculated using a self-consistent norm-conserving pseudopotential method within the framework of the local-density approximation theory. A high anisotropy of the band energy gap (4.22 eV for the E parallel b, 4.46 eV for the E parallel c) and giant birefringence (up to 0.20) are found. Comparison of the theoretically calculated and the experimentally measured polarised spectra of the imaginary part of the dielectric susceptibility ε 2 shows a good agreement. The anisotropy of the charge density distribution, BS dispersion and of the optical spectra originate from anisotropy between the 2p z B-2p z O and 2p y,x B-2p y,y O bonding orbitals. The observed anisotropy in the LBBOH is principally different from that of β-BaB 2 O 4 (BBO) single crystals. In the LBBOH single crystals the anisotropy of optical and charge density distribution is caused by different projection of the orbitals originating from particular borate clusters on the particular crystallographic axes, contrary to the BBO, where the anisotropy is caused prevailingly by a different local site symmetry of oxygen within the borate planes. The observed anisotropy is analysed in terms of the band energy dispersion and space charge density distribution

Crystal structure and magnetism of Fe2(OH)[B2O4(OH)

DEFF Research Database (Denmark)

Kurayoshi, Yotaro; Hara, Shigeo; Sato, Hirohiko

2014-01-01

The structure and magnetism of Fe2(OH)[B2O4(OH)] are reported. Powder x-ray diffraction reveals a characteristic structure containing two crystallographically independent zigzag-ladder chains of magnetic Fe2+ ions. Magnetization measurements reveal a phase transition at 85 K, below which a weak...... spontaneous magnetization (approximate to 0.15 μB/Fe) appears. Below 85 K, magnetization increases with decreasing temperature down to 70 K, below which it decreases and approaches a constant value at low temperature. The Mossbauer spectrum at room temperature is composed of two paramagnetic doublets...... corresponding to the two crystallographic Fe2+ sites. Below 85 K, each doublet undergoes further splitting because of the magnetic hyperfine fields. The temperature dependence of the hyperfine field is qualitatively different for the two distinguishable Fe2+ sites. This is responsible for the anomalous...

Kinetics of the Reactions of O((sup 3)P) and Cl((sup 2)P) with HBr and Br2

Science.gov (United States)

Nicovich, J. M.; Wine, P. H.

1997-01-01

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.

Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

Energy Technology Data Exchange (ETDEWEB)

Abdelbaky, Mohammed S.M. [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain); Amghouz, Zakariae, E-mail: amghouz.uo@uniovi.es [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain); Servicios Científico-Técnicos, University of Oviedo—CINN, Oviedo 33006 (Spain); Fernández-Zapico, Eva; García-Granda, Santiago; García, José R. [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain)

2015-09-15

Lanthanide–organic frameworks based on 2,5-pyridinedicaboxylate (25p) ligand, formulated as [Yb{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pYb), [Y{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pY-1) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] (25pY-2), have been obtained as single phases under hydrothermal conditions. 25pYb and 25pY-1 are isostructural, and crystallize in the triclinic space group, P-1, with a=8.6075(5) Å, b=14.8478(7) Å, c=15.9164(9) Å, α=86.277(4)°, β=80.196(5)°, γ=81.785(4)°, and a=8.7166(6) Å, b=14.966(1) Å, c=15.966(1) Å, α=86.260(6)°, β=80.036(6)°, γ=81.599(6)°, respectively. 25pY-2 crystallizes in the monoclinic space group, P2{sub 1}/c, with a=24.9117(17) Å, b=13.7340(8) Å, c=14.3385(10) Å, β=100.551(7)°. 25pYb and 25pY-2 have been structurally characterized by single-crystal X-ray diffraction. The 25pYb structure is based on tetranuclear cubane-like [Yb{sub 4}(OH){sub 4}]{sup 8+} clusters, which are interconnected to eight neighbouring clusters through teen surrounding 25p ligands leading to neutral 3D framework, while the structure of 25pY-2 is based on two independent cuban-like [Y{sub 4}(OH){sub 4}]{sup 8+} clusters, which are joined together through Y1 cation leading to the formation of hexanuclear [Y{sub 6}(OH){sub 8}]{sup 10+} clusters, which in turn are joined via Y2 cation resulting in infinite inorganic chain extending along c-axis, and each chain is interconnected to six adjacent chains through 25p ligands leading finally to 3D framework. The luminescence properties of Eu{sup 3+} and Tb{sup 3+} doped 25pY-1 and 25pY-2 compounds have also been investigated. All materials has been characterized by powder X-ray diffraction, thermal analyses (TG–SDTA–MS), FTIR spectroscopy, C–H–N elemental analysis, scanning electron microscopy (SEM-EDX), and powder X-ray thermodiffraction. - Graphical abstract: Nowadays, lanthanide–organic frameworks (LOFs) attract

THE INFLUENCES OF Fe(III ION and Fe(OH3 COLLOID ON THE PHOTODEGRADATION of p-CHLOROPHENOL CATALYZED BY TiO2

Directory of Open Access Journals (Sweden)

Endang Tri Wahyuni

2010-06-01

Full Text Available The influences of ionic Fe(III and colloidal Fe(OH3 on the effectiveness of p-chlorophenol photodegradation catalyzed by TiO2 has been studied. Photodegradation was carried out in a batch system by irradiating a suspension of TiO2, p-chlorophenol, and Fe(III as ionic or colloidal forms, using UV lamp for a period of time accompanied by magnetic stirring. Concentration of photodegraded p-chlorophenol was calculated by subtracting the initial concentration with that of undegraded p-chlorophenol. Concentration of undegraded p-chlorophenol was determined by gas chromatography. In this study, TiO2 mass and the photodegradation time were optimized. The influences of concentration of Fe(III solution, mass of Fe(OH3, and pH of the solution have also been systematically studied. The research results showed that the presence of Fe(III ions improved the effectiveness of photocatalytical degradation of p-chlorophenol, which was proportional to the concentrations of Fe(III ion. In contrast, the increasing mass of Fe(OH3 led to a decrease in the degree of p-chlorophenol photodegradation. Furthermore, it was observed that increasing pH of the solution resulted in a decrease in the photodegradation of p-chlorophenol. This phenomena may be due to the different species of TiO2 available at the surface of photocatalyst and of ionic Fe(III and colloidal Fe(OH3 in the solution resulted from the pH alteration. The highest photodegradation degree, ca. 80 % was obtained when 20 mg of TiO2 was applied in the photodegradation of 50 mL of 100 ppm p-chlorophenol solution in the presence of 100 ppm Fe3+ irradiated by UV-light for 25 hours.    Keywords: p-chlorophenol photodegradation, TiO2, Fe(III species

Carbon-14 immobilization via the CO2-Ba(OH)2 hydrate gas-solid reaction

International Nuclear Information System (INIS)

Haag, G.L.

1980-01-01

Although no restrictions have been placed on the release of carbon-14, it has been identified as a potential health hazard due to the ease in which it may be assimilated into the biosphere. The intent of the Carbon-14 Immobilization Program, funded through the Airborne Waste Program Management Office, is to develop and demonstrate a novel process for restricting off-gas releases of carbon-14 from various nuclear facilities. The process utilizes the CO 2 -Ba(OH) 2 hydrate gas-solid reaction to directly remove and immobilize carbon-14. The reaction product, BaCO 3 , possesses both the thermal and chemical stability desired for long-term waste disposal. The process is capable of providing decontamination factors in excess of 1000 and reactant utilization of greater than 99% in the treatment of high volumetric, airlike (330 ppM CO 2 ) gas streams. For the treatment of an air-based off-gas stream, the use of packed beds of Ba(OH) 2 .8H 2 O flakes to remove CO 2 has been demonstrated. However, the operating conditions must be maintained between certain upper and lower limits with respect to the partial pressure of water. If the water vapor pressure in the gas is less than the dissociation vapor pressure of Ba(OH) 2 .8H 2 O, the bed will deactivate. If the vapor pressure is considerably greater, pressure drop problems will increase with increasing humidity as the particles curl and degrade. Results have indicated that when operated in the proper regime, the bulk of the increase in pressure drop results from the conversion of Ba(OH) 2 .8H 2 O to BaCO 3 and not from the hydration of the commercial Ba(OH) 2 .8H 2 O (i.e. Ba(OH) 2 .7.50H 2 O) to Ba(OH) 2 .8H 2 O

Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, a new phosphate mineral from Këster tin deposit (Yakutia, Russia): occurrence and crystal structure

Science.gov (United States)

Yakovenchuk, Victor N.; Pakhomovsky, Yakov A.; Konopleva, Nataliya G.; Panikorovskii, Taras L.; Bazai, Ayya; Mikhailova, Julia A.; Bocharov, Vladimir N.; Ivanyuk, Gregory Yu.; Krivovichev, Sergey V.

2017-12-01

Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, is a new secondary phosphate mineral from the Këster deposit, Arga-Ynnykh-Khai massif, NE Yakutia, Russia. It is monoclinic, P21, a = 8.4264(4), b = 12.8309(6), c = 14.6928(9) Å, β = 98.514(6)o, V = 1571.05(15) Å3 and Z = 2 (from single-crystal X-ray diffraction data). Batagayite crystals are blades up to 2 mm long, flattened on {001} and elongated on [100]; blades often grow in radial aggregates. Associated minerals are arsenolite, native copper, epifanovite, fluorapatite, libethenite, Na-analogue of batagayite, pseudomalachite, quartz, sampleite, tobermorite, and Mg-analogue of hopeite. The streak is white and the luster is vitreous. The mineral is brittle and has a perfect cleavage on {001}, no parting was observed. The Mohs hardness is 3. Density, determined by the float-sink method in Clerici solution, is 2.90(3) g/cm3, and the calculated density is 3.02 g/cm3 (using the empirical formula and single-crystal unit-cell parameters). Batagayite is biaxial, optically negative, α = 1.566 ± 0.002, β = 1.572 ± 0.002, γ = 1.573 ± 0.002 at 589 nm. 2V meas. = 40(5)°, 2V calc = 44.3°. Optical orientation: Z is perpendicular to (001), further details unclear. No dispersion or pleochroism were observed. The mean chemical composition determined by electron microprobe is: Na2O 0.31, MgO 1.39, Al2O3 0.55, SiO2 0.48, P2O5 34.37, K2O 0.17, CaO 2.76, MnO 1.03, CuO 5.80, ZnO 35.62, CdO 0.24 wt%. The H2O content estimated from the crystal-structure refinement is 16.83 wt%, giving a total of 99.55 wt%. The empirical formula calculated on the basis of P + Si = 7 is (Zn6.22Cu1.04Ca0.70Mg0.49Mn0.21Al0.15Na0.14K0.05Cd0.03)Σ9.03(P6.89Si0.11)Σ7.00O24.91(OH)3.09·12.10H2O. The mineral easily dissolves in 10% room-temperature HCl. The eight diagnostic lines in the X-ray powder-diffraction pattern are (I-d[Å]-hkl): 100-14.59-001, 25-6.34-012, 11-6.02-111, 37-4.864-003, 13-4.766-112, 20-3.102-1 \\overline {2} \\overline {4} , 11-2.678-2

Canted antiferromagnetism in KNi3[PO3(F,OH)]2[PO2(OH)2]F2 with a stair-case Kagomé lattice

Science.gov (United States)

Liu, Li-Chen; Ren, Wei-Jian; Huang, Ya-Xi; Pan, Yuanming; Mi, Jin-Xiao

2017-10-01

A new nickel phosphate KNi3[PO3(F,OH)]2[PO2(OH)2]F2 has been synthesized using a modified hydrothermal method. Structural characterizations show that it adopts a 3D framework structure with 2D layers of Ni octahedra in a stair-case Kagomé lattice. The Ni2 octahedron at the inversion center shares two trans-faces with Ni1 octahedra to form a linear trimer (Ni3O8F6) as the basic structural unit. The Ni-trimers are linked between themselves by sharing F-corners and to [PO3(F,OH)] tetrahedral groups by sharing O-corners to form 2D stair-case Kagomé layers, which are parallel to the (100) plane and are stacked along the a-axis. Successive Kagomé layers are combined together by [PO2(OH)2] tetrahedral groups and interstice cations K+. Magnetic measurements reveal that KNi3[PO3(F,OH)]2[PO2(OH)2]F2 exhibits a canted antiferromagnetic ordering with a ferromagnetic component at low temperatures.

Infrared and Raman spectroscopic characterization of the silicate mineral olmiite CaMn2+[SiO3(OH)](OH) - implications for the molecular structure

Science.gov (United States)

Frost, Ray L.; Scholz, Ricardo; López, Andrés; Xi, Yunfei; Granja, Amanda; Žigovečki Gobac, Željka; Lima, Rosa Malena Fernandes

2013-12-01

We have studied the mineral olmiite CaMn[SiO3(OH)](OH) which forms a series with its calcium analogue poldervaartite CaCa[SiO3(OH)](OH) using a range of techniques including scanning electron microscopy, thermogravimetric analysis, Raman and infrared spectroscopy. Chemical analysis shows the mineral is pure and contains only calcium and manganese in the formula. Thermogravimetric analysis proves the mineral decomposes at 502 °C with a mass loss of 8.8% compared with the theoretical mass loss of 8.737%. A strong Raman band at 853 cm-1 is assigned to the SiO stretching vibration of the SiO3(OH) units. Two Raman bands at 914 and 953 cm-1 are attributed to the antisymmetric vibrations. Two intense Raman bands observed at 3511 and 3550 cm-1 are assigned to the OH stretching vibration of the SiO3(OH) units. The observation of multiple OH bands supports the concept of the non-equivalence of the OH units. Vibrational spectroscopy enables a detailed assessment of the molecular structure of olmiite.

Effect of B2O3 and P2O5 on fluorosilicic mica glass-ceramic sintering process

Directory of Open Access Journals (Sweden)

Wu S.

2010-01-01

Full Text Available To study the effect of B2O3 and P2O5 on fluorosilicic mica glass-ceramic sintering process, six sets of K2O-MgO-SiO2-F glasses were prepared by using B2O3 and P2O5 as sintering aid, respectively. Green bodies of the glass powder were formed by gel casting and sintered at 800, 850, 900, 950, 1000oC for 6 hours, resectively. The sintering and crystallization behavior were studied by thermal shrinkage , X-ray diffraction and SEM. The results showed that the shrinkage rate of the glass with 2wt% B2O3 and P2O5 was highest, while the rate of the glass with 5wt% P2O5 was lowest. An additional crystal other than fluorosilicic mica was precipitated in the glass ceramics generated by sintering of glass powder. The present results confirmed that the glass powder of pure K2O-MgO-SiO2-Fsystem had poor sinterability, while glass powder with minor addition of P2O5 and/or B2O3 showed good sinterability. This result was also verified by SEM.

A Mixed-Valent Molybdenum Monophosphate with a Layer Structure: KMo 3P 2O 14

Science.gov (United States)

Guesdon, A.; Borel, M. M.; Leclaire, A.; Grandin, A.; Raveau, B.

1994-03-01

A new mixed-valent molybdenum monophosphate with a layer structure KMo 3P 2O 14 has been isolated. It crystallizes in the space group P2 1/ m with a = 8.599(2) Å, b = 6.392(2) Å, c = 10.602(1) Å, and β = 111.65(2)°. The layers [Mo 3P 2O 14] ∞ are parallel to (100) and consist of [MoPO 8] ∞ chains running along limitb→ , in which one MoO 6 octahedron alternates with one PO 4 tetrahedron. In fact, four [MoPO 8] ∞ chains share the corners of their polyhedra and the edges of their octahedra, forming [Mo 4P 4O 24] ∞ columns which are linked through MoO 5 bipyramids along limitc→. The K + ions interleaved between these layers are surrounded by eight oxygens, forming bicapped trigonal prisms KO 8. Besides the unusual trigonal bipyramids MoO 5, this structure is also characterized by a tendency to the localization of the electrons, since one octahedral site is occupied by Mo(V), whereas the other octahedral site and the trigonal bipyramid are occupied by Mo(VI). The similarity of this structure with pure octahedral layer structures suggests the possibility of generating various derivatives, and of ion exchange properties.

Cluster self-organization of germanate systems: suprapolyhedral precursor clusters and self-assembly of K2Nd4Ge4O13(OH)4, K2YbGe4O10(OH), K2Sc2Ge2O7(OH)2, and KScGe2O6(PYR)

International Nuclear Information System (INIS)

Ilyushin, G.D.; Dem'yanets, L.N.

2008-01-01

One performed the computerized (the TOPOS 4.0 software package) geometric and topological analyses of all known types of K, TR-germanates (TR = La-Lu, Y, Sc, In). The skeleton structure are shown as three-dimensional 3D, K, TR, Ge-patterns (graphs) with remote oxygen atoms. TR 4 3 3 4 3 3 + T 4 3 4 3, K 2 YbGe 4 O 14 (OH) pattern, TR 6 6 3 6 + T1 6 8 6 + T2 3 6 8, K 2 Sc 2 Ge 2 O 7 (OH) 2 , TR 6 4 6 4 + T 6 4 6 and KScGe 2 O 6 - TR 6 6 3 6 3 4 + T1 6 3 6 + T2 6 4 3 patterns served as crystal-forming 2D TR,Ge-patterns for K 2 Nd 4 Ge 4 O 13 (OH) 4 . One performed the 3D-simulation of the mechanism of self-arrangement of the crystalline structures: cluster-precursor - parent chain - microlayer - microskeleton (super-precursor). Within K 2 Nd 4 Ge 4 O 13 (OH) 4 , K 2 Sc 2 Ge 2 O 7 (OH) 2 and KScGe 2 O 6 one identified the invariant type of the cyclic hexapolyhedral cluster-precursor consisting of TR-octahedrons linked by diorthogroups stabilized by K atoms. For K 2 Nd 4 Ge 4 O 13 (OH) 4 one determined the type of the cyclic tetrapolyhedral cluster-precursor consisting of TR-octavertices linked by tetrahedrons. The cluster CN within the layer just for KScGe 2 O 6 water-free germanate (the PYR pyroxene analog) is equal to 6 (the maximum possible value), while in the rest OH-containing germanates it constitutes 4. One studied the formation mechanism of Ge-radicals in the form of Ge 2 O 7 and Ge 4 O 13 groupings, GeO 3 chain and the tubular structure consisting of Ge 8 O 20 fixed cyclic groupings [ru

A neodymium(III)-ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)].H2O.

Science.gov (United States)

Trombe, Jean-Christian; Galy, Jean; Enjalbert, Renée

2002-10-01

The title compound, diammonium aqua-mu-carbonato-tri-mu-oxalato-dineodymium(III) hydrate, (NH(4))(2)[Nd(2)(CO(3))(C(2)O(4))(3)(H(2)O)].H(2)O, involving the two ligands oxalate and carbonate, has been prepared hydrothermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (1/2, 1/2, 1/2). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three-dimensional network. The carbonate group acts as a bis-chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis-chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.

Integrated nanophotonic hubs based on ZnO-Tb(OH3/SiO2 nanocomposites

Directory of Open Access Journals (Sweden)

Lin Yu

2011-01-01

Full Text Available Abstract Optical integration is essential for practical application, but it remains unexplored for nanoscale devices. A newly designed nanocomposite based on ZnO semiconductor nanowires and Tb(OH3/SiO2 core/shell nanospheres has been synthesized and studied. The unique sea urchin-type morphology, bright and sharply visible emission bands of lanthanide, and large aspect ratio of ZnO crystalline nanotips make this novel composite an excellent signal receiver, waveguide, and emitter. The multifunctional composite of ZnO nanotips and Tb(OH3/SiO2 nanoparticles therefore can serve as an integrated nanophotonics hub. Moreover, the composite of ZnO nanotips deposited on a Tb(OH3/SiO2 photonic crystal can act as a directional light fountain, in which the confined radiation from Tb ions inside the photonic crystal can be well guided and escape through the ZnO nanotips. Therefore, the output emission arising from Tb ions is truly directional, and its intensity can be greatly enhanced. With highly enhanced lasing emissions in ZnO-Tb(OH3/SiO2 as well as SnO2-Tb(OH3/SiO2 nanocomposites, we demonstrate that our approach is extremely beneficial for the creation of low threshold and high-power nanolaser.

Antimicrobial activity study of a μ3-oxo bridged [Fe3O(PhCO2)6(MeOH)3](NO3)(MeOH)2] cluster

Science.gov (United States)

Pathak, Sayantan; Jana, Barun; Mandal, Manab; Mandal, Vivekananda; Ghorai, Tanmay K.

2017-11-01

Synthesis, characterization and antimicrobial activity of a tri-nuclear μ3-Oxobridged Fe(III) cluster [Fe3O(PhCO2)6(MeOH)3](NO3)(MeOH)2(1) is reported. Cluster 1 is synthesized in a single pot reaction among Fe(NO3)3·9H2O, C6H5COOH, NaN3 (1:4:1) in MeOH. Single crystal X-ray diffraction studies of the isolated crystals show that it is μ3-Oxo bridged trimeric assembly of three Fe atoms via bridging benzoate anions. Furthermore, BVS calculations show that all three Fe atoms in complex 1 are in +3 oxidation state and are surrounded by benzoate anions and methanol in octahedral environment. The oxidation state of iron is also confirmed from the cyclic voltamogram. FT-IR spectroscopy and CHN analysis of the isolated crystals further supports the functional group attached to the periphery of the complex. The nanomolecular size of complex 1 is 1.29 nm. The antimicrobial efficiency studies of the complex 1 show significant inhibition of the growth of the organisms, viz. B. cereus MTCC 1272, S. epidermidis MTCC 3086 and S. typhimurium MTCC 98 and produced 23 ± 1.93 mm, 16 ± 1.77 mm and 12 ± 2.42 mm inhibition zones respectively. However, it shows zero inhibition to the strain of E. coli MTCC 723.

Enhanced electrochemical performance of Ti substituted P2-Na2/3Ni1/4Mn3/4O2 cathode material for sodium ion batteries

International Nuclear Information System (INIS)

Zhao, Wenwen; Tanaka, Akinobu; Momosaki, Kyoko; Yamamoto, Shinji; Zhang, Fabi; Guo, Qixin; Noguchi, Hideyuki

2015-01-01

Highlights: • Ti substituted P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 cathode was synthesized. • Structural and electrochemical properties of Na 2/3 Ni 1/4 Ti x Mn 3/4-x O 2 were studied. • Ti substituted cathodes exhibit enhanced cycleability and rate performance. • Ti substitution has impact on stabilizing the P2 structure during cycling. -- Abstract: Ti substituted P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 cathode material with the composition of Na 2/3 Ni 1/4 Ti x Mn 3/4-x O 2 has been synthesized by solid state method. The influence of Ti substitution for Mn on the structure, morphology and electrochemical performances of P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 has been investigated. X-ray diffraction (XRD) results of Ti substituted sample show that they exhibit same diffraction patterns as those of pristine P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 . Progressive change in the lattice parameters of Ti substituted samples suggests that Mn was successfully substituted by Ti. In contrast to P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 which shows step-type voltage profiles, Ti substituted samples show sloping voltage profiles. Drastic capacity fade occurred for P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 cathode, while Ti substituted cathodes still show high capacity retention over 92% after 25 cycles at the voltage range of 2.0-4.3 V. Even cycled at high upper cut-off voltage of 4.5 V, Ti=0.20 sample can deliver a reversible capacity of 140 mAhg −1 with the capacity retention over 92% after 25 cycles. Furthermore, Ti substituted cathodes exhibit enhanced rate capability over pristine P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 cathode. Comparison of the Ex-situ XRD results of the cycled P2-Na 2/3 Ni 1/4 Mn 3/4 O 2 and its substituted samples provides evidence that the improved electrochemical performance of Ti substituted cathodes would be attributed to the stabilization of the structure with Ti substitution

The molecular structure of the borate mineral inderite Mg(H4B3O7)(OH) · 5H2O--a vibrational spectroscopic study.

Science.gov (United States)

Frost, Ray L; López, Andrés; Xi, Yunfei; Lima, Rosa Malena Fernandes; Scholz, Ricardo; Granja, Amanda

2013-12-01

We have undertaken a study of the mineral inderite Mg(H4B3O7)(OH) · 5H2O a hydrated hydroxy borate mineral of magnesium using scanning electron microscopy, thermogravimetry and vibrational spectroscopic techniques. The structure consists of [Formula: see text] soroborate groups and Mg(OH)2(H2O)4 octahedra interconnected into discrete molecules by the sharing of two OH groups. Thermogravimetry shows a mass loss of 47.2% at 137.5 °C, proving the mineral is thermally unstable. Raman bands at 954, 1047 and 1116 cm(-1) are assigned to the trigonal symmetric stretching mode. The two bands at 880 and 916 cm(-1) are attributed to the symmetric stretching mode of the tetrahedral boron. Both the Raman and infrared spectra of inderite show complexity. Raman bands are observed at 3052, 3233, 3330, 3392 attributed to water stretching vibrations and 3459 cm(-1) with sharper bands at 3459, 3530 and 3562 cm(-1) assigned to OH stretching vibrations. Vibrational spectroscopy is used to assess the molecular structure of inderite. Copyright © 2013 Elsevier B.V. All rights reserved.

Crystal structures of Th(OH)PO4, U(OH)PO4 and Th2O(PO4)2. Condensation mechanism of M(IV)(OH)PO4 (M= Th, U) into M2O(PO4)2

International Nuclear Information System (INIS)

Dacheux, N.; Clavier, N.; Wallez, G.; Quarton, M.

2007-01-01

Three new crystal structures, isotypic with β-Zr 2 O(PO 4 ) 2 , have been resolved by the Rietveld method. All crystallize with an orthorhombic cell (S.G.: Cmca) with a = 7.1393(2) Angstroms, b = 9.2641(2) Angstroms, c 12.5262(4) Angstroms, V = 828.46(4) (Angstroms) 3 and Z = 8 for Th(OH)PO 4 ; a = 7.0100(2) Angstroms, b = 9.1200(2) Angstroms, c = 12.3665(3) Angstroms, V 790.60(4) (Angstroms) 3 and Z = 8 for U(OH)PO 4 ; a 7.1691(3) Angstroms, b 9.2388(4) Angstroms, c = 12.8204(7) Angstroms, V 849.15(7) (Angstroms) 3 and Z = 4 for Th 2 O(PO 4 ) 2 . By heating, the M(OH)PO 4 (M Th, U) compounds condense topotactically into M 2 O(PO 4 ) 2 , with a change of the environment of the tetravalent cation that lowers from 8 to 7 oxygen atoms. The lower stability of Th 2 O(PO 4 ) 2 compared to that of U 2 O(PO 4 ) 2 seems to result from this unusual environment for tetravalent thorium. (authors)

Thermal transformation of synthetic borax, Na2[B4O5(OH)4]x8H2O

International Nuclear Information System (INIS)

Abdullaev, G.K.

1981-01-01

Using the methods of high temperature roentgenography and derivatography thermal transformation of synthetic borax is studied. It is established that borax dehydration proceeds in four stages (50-80, 80-100, 100-150 and 150-500 deg C) with the formation of three intermediate crystalline hydrate forms (one stable and two unstable) and one final stable crystalline phase. The stable crystalline phases correspond to synthetic tincalconite Na 2 [B 4 O 5 (OH) 4 ]x3H 2 O and sodium tetraborate Na 2 B 4 O 7 . Thermal transformation of borax into tincalconite and sodium tetraborate is explained on the basis of their crystal structures [ru

Magnetostructural correlations in the antiferromagnetic Co2-x Cux(OH)AsO4 (x=0 and 0.3) phases

International Nuclear Information System (INIS)

Pedro, I. de; Rojo, J.M.; Pizarro, J.L.; Rodriguez Fernandez, J.; Arriortua, M.I.; Rojo, T.

2011-01-01

The Co 2-x Cu x (OH)AsO 4 (x=0 and 0.3) compounds have been synthesized under mild hydrothermal conditions and characterized by X-ray single-crystal diffraction and spectroscopic data. The hydroxi-arsenate phases crystallize in the Pnnm orthorhombic space group with Z=4 and the unit-cell parameters are a=8.277(2) A, b=8.559(2) A, c=6.039(1) A and a=8.316(1) A, b=8.523(2) A, c=6.047(1) A for x=0 and 0.3, respectively. The crystal structure consists of a three-dimensional framework in which M(1)O 5 -trigonal bipyramid dimers and M(2)O 6 -octahedral chains (M=Co and Cu) are present. Co 2 (OH)AsO 4 shows an anomalous three-dimensional antiferromagnetic ordering influenced by the magnetic field below 21 K within the presence of a ferromagnetic component below the ordering temperature. When Co 2+ is partially substituted by Cu 2+ ions, Co 1.7 Cu 0.3 (OH)AsO 4 , the ferromagnetic component observed in Co 2 (OH)AsO 4 disappears and the antiferromagnetic order is maintained in the entire temperature range. Heat capacity measurements show an unusual magnetic field dependence of the antiferromagnetic transitions. This λ-type anomaly associated to the three-dimensional antiferromagnetic ordering grows with the magnetic field and becomes better defined as observed in the non-substituted phase. These results are attributed to the presence of the unpaired electron in the dx 2 -y 2 orbital and the absence of overlap between neighbour ions. - Graphical abstract: Schematic drawing of the Co 2-x Cu x (OH)AsO 4 (x=0 and 0.3) crystal structure view along the |0 1 0| direction. Polyhedra are occupied by the M(II) ions (M=Co and Cu) and the AsO 4 groups are represented by tetrahedra. Open circles correspond to the oxygen atoms, and small circles show the hydrogen atoms. Highlights: → Synthesis of a new adamite-type compound, Co 1.7 Cu 0.3 (OH)AsO 4 . → Single crystal structure, spectroscopic characterization and magnetic properties. → Unusual dependence on the magnetic field for

Carbon-14 immobilization via the Ba(OH)28H2O process

International Nuclear Information System (INIS)

Haag, G.L.; Nehls, J.W. Jr.; Young, G.C.

1982-01-01

The airborne release of 14 C from various nuclear facilities has been identified as a potential biohazard due to the long half-life of 14 C (5730 yrs) and the ease in which it may be assimilated into the biosphere. At Oak Ridge National Laboratory, technology is under development, as part of the Airborne Waste Management Program, for the removal and immobilization of this radionuclide. Prior studies have indicated that the 14 C will likely exist in the oxidized form as CO 2 and will contribute slightly to the bulk CO 2 concentration of the gas stream, which is airlike in nature (approx. 330 ppMv CO 2 ). The technology under development utilizes the CO 2 - Ba(OH) 2 8H 2 O gas-solid reaction with the mode of gas-solid contacting being a fixed bed. The product, BaCO 3 , possessing excellent thermal and chemical stability, prerequisites for the long-term disposal of nuclear wastes. For optimal process operation, studies have indicated that an operating window of adequate size does exist. When operating within the window, high CO 2 removal efficiency (effluent concentrations 99%), and an acceptable pressure drop across the bed (3 kPa/m at 13 cm/s superficial velocity) are possible. This paper will address three areas of experimental investigation. These areas are (1) micro-scale studies on 150-mg samples to provide information concerning surface properties, kinetics, and equilibrium vapor pressures, (2) macro-scale studies on large fixed beds (4.2 kg reactant) to determine the effects of humidity, temperature, and gas flow-rate upon bed pressure drop and CO 2 breakthrough, and (3) the design, construction, and initial operation of a pilot unit capable of continuously processing a 34 m 3 /h (20 ft 3 /min) air-based gas stream

Carbon-14 immobilization via the Ba(OH)2.8H2O process

International Nuclear Information System (INIS)

Haag, G.L.; Nehls, J.W. Jr.; Young, G.C.

1983-03-01

The airborne release of 4 C from varous nuclear facilities has been identified as a potential biohazard due to the long half-life of 14 C (5730 y) and the ease with which it may be assimilated into the biosphere. At ORNL, technology has been developed for the removal and immobilization of this radionuclide. Prior studies have indicated that 14 C will likely exist in the oxidized form as CO 2 and will contribute slightly to the bulk CO 2 concentration of the gas stream, which is airlike in nature (approx. 330 ppmv CO 2 ). The technology that has been developed utilizes the CO 2 -Ba(OH) 2 .8H 2 O gas-solid reaction with the mode of gas-solid contacting being a fixed bed. The product, BaCO 3 , possesses excellent thermal and chemical stability, prerequisites for the long-term disposal of nuclear wastes. For optimal process operation, studies have indicated that an operating window of adequate size does exist. When operating within the window, high CO 2 removal efficiency (effluent concentrations 99%), and an acceptable pressure drop across the bed (3 kPa/m at a superficial velocity of 13 cm/s) are possible. This paper addresses three areas of experimental investigation: (1) microscale studies on 150-mg samples to provide information concerning surface properties, kinetics, and equilibrium vapor pressures; (2) macroscale studies on large fixed beds (4.2 kg of reactant) to determine the effects of humidity, temperature, and gas flow rate upon bed pressure drop and CO 2 breakthrough; and (3) design, construction, and initial operation of a pilot unit capable of continuously processing a 34-m 3 /h (20-ft 3 /min) air-based gas stream

Atom-radical reaction dynamics of O(3P)+C3H5→C3H4+OH: Nascent rovibrational state distributions of product OH

Science.gov (United States)

Park, Jong-Ho; Lee, Hohjai; Kwon, Han-Cheol; Kim, Hee-Kyung; Choi, Young-Sang; Choi, Jong-Ho

2002-08-01

The reaction dynamics of ground-state atomic oxygen [O(3P)] with allyl radicals (C3H5) has been investigated by applying a combination of crossed beams and laser induced fluorescence techniques. The reactants O(3P) and C3H5 were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of precursor allyl iodide, respectively. A new exothermic channel of O(3P)+C3H5→C3H4+OH was observed and the nascent internal state distributions of the product OH (X 2Π:υ″=0,1) showed substantial bimodal internal excitations of the low- and high-N″ components without Λ-doublet and spin-orbit propensities in the ground and first excited vibrational states. With the aid of the CBS-QB3 level of ab initio theory and Rice-Ramsperger-Kassel-Marcus calculations, it is predicted that on the lowest doublet potential energy surface the major reaction channel of O(3P) with C3H5 is the formation of acrolein (CH2CHCHO)+H, which is consistent with the previous bulk kinetic experiments performed by Gutman et al. [J. Phys. Chem. 94, 3652 (1990)]. The counterpart C3H4 of the probed OH product in the title reaction is calculated to be allene after taking into account the factors of reaction enthalpy, barrier height and the number of intermediates involved along the reaction pathway. On the basis of population analyses and comparison with prior calculations, the statistical picture is not suitable to describe the reactive atom-radical scattering processes, and the dynamics of the title reaction is believed to proceed through two competing dynamical pathways. The major low N″-components with significant vibrational excitation may be described by the direct abstraction process, while the minor but extraordinarily hot rotational distribution of high N″-components implies that some fraction of reactants is sampled to proceed through the indirect short-lived addition-complex forming process.

Synthesis and characterization of the lead borate Pb{sub 6}B{sub 12}O{sub 21}(OH){sub 6}

Energy Technology Data Exchange (ETDEWEB)

Schoenegger, Sandra; Ortner, Teresa S.; Wurst, Klaus; Heymann, Gunter; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

2016-11-01

A lead borate with the composition Pb{sub 6}B{sub 12}O{sub 21}(OH){sub 6} was synthesized through a hydrothermal synthesis, using lead metaborate in combination with sodium nitrate and potassium nitrate. The compound crystallizes in the trigonal, non-centrosymmetric space group P3{sub 2} (no. 145) with the lattice parameters a = 1176.0(4), c = 1333.0(4) pm, and V = 0.1596(2) nm{sup 3}. Interestingly, the data of Pb{sub 6}B{sub 12}O{sub 21}(OH){sub 6} correct the structure of a literature known lead borate with the composition ''Pb{sub 6}B{sub 11}O{sub 18}(OH){sub 9}''. For the latter compound, nearly identical lattice parameters of a = 1176.91(7) and c = 1333.62(12) pm were reported, possessing a crystal structure, in which the localization and refinement of one boron atom was obviously overlooked. The structure of Pb{sub 6}B{sub 12}O{sub 21}(OH){sub 6} is built up from trigonal planar BO{sub 3} and tetrahedral BO{sub 4} groups forming complex chains. The Pb{sup 2+} cations are located between neighboring polyborate chains. The here reported compound Pb{sub 6}B{sub 12}O{sub 21}(OH){sub 6} and ''Pb{sub 6}B{sub 11}O{sub 18}(OH){sub 9}'' were, however, produced under different synthesis conditions. While ''Pb{sub 6}B{sub 11}O{sub 18}(OH){sub 9}'' was synthesized via a hydrothermal synthesis including ethylenediamine and acetic acid, the here reported lead borate Pb{sub 6}B{sub 12}O{sub 21}(OH){sub 6} could be obtained under moderate hydrothermal conditions (240 C) without the addition of organic reagents.

Variable dimensionality and new uranium oxide topologies in the alkaline-earth metal uranyl selenites AE[UO2)(SeO3)2] (AE=Ca, Ba) and Sr[UO2)(SeO3)2] · 2H2O

International Nuclear Information System (INIS)

Almond, Philip M.; Peper, Shane M.; Bakker, Eric; Albrecht-Schmitt, Thomas E.

2002-01-01

Three new alkaline-earth metal uranyl selenites, Ca[UO 2 )(SeO 3 ) 2 ] (1), Sr[UO 2 )(SeO 3 ) 2 ] · 2H 2 O (2), and Ba[UO 2 )(SeO 3 ) 2 ] (3), have been prepared from the reactions of CaCO 3 and Ca(OH) 2 , SrCl 2 and Sr(OH) 2 , or BaCl 2 and Ba(OH) 2 with UO 3 and SeO 2 under mild hydrothermal conditions. Single-crystal X-ray diffraction experiments reveal that the structures of 1-3 differ in both connectivity and dimensionality even though all contain the same fundamental building unit, namely [UO 2 (SeO 3 ) 4 ]. This polyhedron consists of a linear uranyl unit that is bound by one chelating and three bridging selenite anions creating a pentagonal bipyramidal environment around the U(VI) center. The crystal structure of 1 contains one-dimensional ribbons where the edges are terminated by monodentate selenite anions. The interior of the ribbons are constructed from edge-sharing pentagonal bipyramidal UO 7 units. The structure of 2 is also one-dimensional; however, here there are chains of edge-sharing pentagonal bipyramidal UO 7 dimers that are connected by bridging selenite anions. Ba[(UO 2 )(SeO 3 ) 2 ] (3) is two-dimensional, and the highly ruffled anionic sheets present in this structure are formed from both bridging and chelating/bridging selenite anions bound to uranyl moieties. The anionic substructures in 1-3 are separated by Ca 2+ , Sr 2+ , or Ba 2+ cations. Crystallographic data (193 K, MoKα, λ=0.71073): 1, triclinic, space group P1-bar, a=5.5502(6) A, b=6.6415(7) A, c=11.013(1) A, α=104.055(2) deg., β=93.342(2) deg., γ=110.589(2) deg. , Z=2, R(F)=4.56% for 100 parameters with 1530 reflections with I>2σ(I); 2, triclinic, space group P1-bar, a=7.0545(5) A, b=7.4656(5) A, c=10.0484(6) A, α=106.995(1) deg., β=108.028(1) deg., γ=98.875(1) deg., Z=2, R(F)= 2.43% for 128 parameters with 2187 reflections with I>2σ(I); 3, monoclinic, space group P2 1 /c, a=7.3067(6) A, b=8.1239(7) A, c=13.651(1) A, β=100.375(2) deg., Z=4, R(F)=4.31% for 105 parameters

Treatment with 1,25(OH){sub 2}D{sub 3}induced HDAC2 expression and reduced NF-κB p65 expression in a rat model of OVA-induced asthma

Energy Technology Data Exchange (ETDEWEB)

Zhou, Y.; Wang, G.F.; Yang, L.; Liu, F.; Kang, J.Q.; Wang, R.L.; Gu, W.; Wang, C.Y. [Department of Gerontology Medicine, Xinhua Hospital, Shanghai Jiatong University School of Medicine, Shanghai (China)

2015-04-28

Recent evidence indicates that a deficiency of 1,25-dihydroxyvitamin D{sub 3} (1,25[OH]{sub 2}D{sub 3}) may influence asthma pathogenesis; however, its roles in regulating specific molecular transcription mechanisms remain unclear. We aimed to investigate the effect of 1,25(OH){sub 2}D{sub 3} on the expression and enzyme activity of histone deacetylase 2 (HDAC2) and its synergistic effects with dexamethasone (Dx) in the inhibition of inflammatory cytokine secretion in a rat asthma model. Healthy Wistar rats were randomly divided into 6 groups: control, asthma, 1,25(OH){sub 2}D{sub 3} pretreatment, 1,25(OH){sub 2}D{sub 3} treatment, Dx treatment, and Dx and 1,25(OH){sub 2}D{sub 3} treatment. Pulmonary inflammation was induced by ovalbumin (OVA) sensitization and challenge (OVA/OVA). Inflammatory cells and cytokines in the bronchoalveolar lavage (BAL) fluid and histological changes in lung tissue were examined. Nuclear factor kappa B (NF-κB) p65 and HDAC2 expression levels were assessed with Western blot analyses and quantitative reverse-transcriptase polymerase chain reaction (qRT-PCR). Enzyme activity measurements and immunohistochemical detection of HDAC2 were also performed. Our data demonstrated that 1,25(OH){sub 2}D{sub 3} reduced the airway inflammatory response and the level of inflammatory cytokines in BAL. Although NF-κB p65 expression was attenuated in the pretreatment and treatment groups, the expression and enzyme activity of HDAC2 were increased. In addition, 1,25(OH){sub 2}D{sub 3} and Dx had synergistic effects on the suppression of total cell infusion, cytokine release, and NF-κB p65 expression, and they also increased HDAC2 expression and activity in OVA/OVA rats. Collectively, our results indicated that 1,25(OH){sub 2}D{sub 3}might be useful as a novel HDAC2 activator in the treatment of asthma.

Effects of dipotassium-trioxohydroxytetrafluorotriborate, K2[B3O3F4OH], on cell viability and gene expression of common human cancer drug targets in a melanoma cell line.

Science.gov (United States)

Pojskic, Lejla; Haveric, Sanin; Lojo-Kadric, Naida; Hadzic, Maida; Haveric, Anja; Galic, Zoran; Galic, Borivoj; Vullo, Daniela; Supuran, Claudiu T; Milos, Mladen

2016-12-01

Recently it was found that dipotassium-trioxohydroxytetrafluorotriborate, K2(B3O3F4OH), is a potent and highly specific inhibitor of precancerous cell processes. We conducted gene expression profiling of human melanoma cells before and after treatment with two concentrations (0.1 and 1 mM) of this boron inorganic derivative in order to assess its effects on deregulation of genes associated with tumor pathways. Parallel trypan blue exclusion assay was performed to assess the cytotoxicity effects of this chemical. Treatment with K2(B3O3F4OH) induced a significant decrease of cell viability in melanoma cellline at both tested concentrations. Furthermore, these treatments caused deregulation of more than 30 genes known as common anti-tumor drug targets. IGF-1 and hTERT were found to be significantly downregulated and this result may imply potential use of K2(B3O3F4OH) as an inhibitor or human telomerase and insulin-like growth factor 1, both of which are associated with various tumor pathways.

Side-by-Side In(OH3 and In2O3 Nanotubes: Synthesis and Optical Properties

Directory of Open Access Journals (Sweden)

Tao Xiaojun

2009-01-01

Full Text Available Abstract A simple and mild wet-chemical approach was developed for the synthesis of one-dimensional (1D In(OH3 nanostructures. By calcining the 1D In(OH3 nanocrystals in air at 250 °C, 1D In2O3 nanocrystals with the same morphology were obtained. TEM results show that both 1D In(OH3 and 1D In2O3 are composed of uniform nanotube bundles. SAED and XRD patterns indicate that 1D In(OH3 and 1D In2O3 nanostructures are single crystalline and possess the same bcc crystalline structure as the bulk In(OH3 and In2O3, respectively. TGA/DTA analyses of the precursor In(OH3 and the final product In2O3 confirm the existence of CTAB molecules, and its content is about 6%. The optical absorption band edge of 1D In2O3 exhibits an evident blueshift with respect to that of the commercial In2O3 powders, which is caused by the increasing energy gap resulted from decreasing the grain size. A relatively strong and broad purple-blue emission band centered at 440 nm was observed in the room temperature PL spectrum of 1D In2O3 nanotube bundles, which was mainly attributed to the existence of the oxygen vacancies.

The Vaporization of B2O3(l) to B2O3(g) and B2O2(g)

Science.gov (United States)

Jacobson, Nathan S.; Myers, Dwight L.

2011-01-01

The vaporization of B2O3 in a reducing environment leads to formation of both B2O3(g) and B2O2(g). While formation of B2O3(g) is well understood, many questions about the formation of B2O2(g) remain. Previous studies using B(s) + B2O3(l) have led to inconsistent thermodynamic data. In this study, it was found that after heating, B(s) and B2O3(l) appear to separate and variations in contact area likely led to the inconsistent vapor pressures of B2O2(g). To circumvent this problem, an activity of boron is fixed with a two-phase mixture of FeB and Fe2B. Both second and third law enthalpies of formation were measured for B2O2(g) and B2O3(g). From these the enthalpies of formation at 298.15 K are calculated to be -479.9 +/- 41.5 kJ/mol for B2O2(g) and -833.4 +/- 13.1 kJ/mol for B2O3(g). Ab initio calculations to determine the enthalpies of formation of B2O2(g) and B2O3(g) were conducted using the W1BD composite method and show good agreement with the experimental values.

Synthesis and structural characterization of (H4APPIP)[V3(C2O4)2(HPO4)3(PO4)(H2O)]·6H2O (APPIP=1,4-bis(3-aminopropyl)piperazine), a layered vanadium oxalatophosphate containing double 6-ring units

International Nuclear Information System (INIS)

Tang, M.-F.; Lii, K.-H.

2004-01-01

A new vanadium(III) oxalatophosphate has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction and thermogravimetric analysis. It crystallizes in the triclinic space group P1-bar with a=11.604(2) A, b=12.391(2) A, c=15.220(3) A, α=71.090(3) deg., β=82.630(3) deg., γ=62.979(3) deg., V=1843.8(5) A 3 and Z=2. The structure consists of V 6 (HPO 4 ) 6 double 6-ring (D6R) units connected by coordinating C 2 O 4 2- and PO 4 3- anions to form anionic sheets in the ab plane with charge-compensating quadruply protonated 1,4-bis(3-aminopropyl)piperazinium cations and water molecules between the sheets. It is one of the few compounds with 2D layer structures and the second example containing D6R units in the system of metal oxalatophosphates. The iron analogue was also synthesized

Synthesis and investigation of aluminium uranium-containing compounds of Al[B5UO6]2[OH]·nH2O (B5=P, As) composition

International Nuclear Information System (INIS)

Chernorukov, N.G.; Sulejmanov, E.V.; Barch, S.V.

2001-01-01

The technique of synthesis of hydroxyuranophosphate and hydroxyuranoarsenate of aluminium is developed. Hydroxyuranophosphates and hydroxyuranoarsenates of aluminium are prepared by reaction of interaction of aqueous solutions of orthophosphoric (orthoarsenic) acid (0.05 mol/l), uranyl nitrate (0.05 mol/l) and aluminium nitrate (0.1 mol/l) at 20 Deg C. Peculiarities of the structure and thermal degradation reactions are studied by the methods of x-ray diffraction, IR spectroscopy, thermography. It is shown that in dependence on outer conditions in the systems Al[PUO 6 ] 2 ·[OH]·nH 2 O and Al[AsUO 6 ] 2 ·[OH]·nH 2 O crystal hydrates with hydrate numbers n=3-11(13) and anhydrous compounds form. The compounds have laminated type of lattice. Two-dimensional layers of [P(As)UO 6 ] ∞ n- are the basis of anion sublattice of these compounds. Aluminium in coordination surrounding of hydroxy groups and water molecules forms cationic sublattice [ru

Electrical mobility of silver ion in Ag2O-B2O3-P2O5-TeO2 glasses.

Science.gov (United States)

Sklepić, Kristina; Vorokhta, Maryna; Mošner, Petr; Koudelka, Ladislav; Moguš-Milanković, Andrea

2014-10-16

The effect of adding TeO(2) into (100 - x)[0.5Ag(2)O - 0.1B(2)O(3) - 0.4P(2)O(5)] - xTeO(2), with 0-80 mol % TeO(2) glass, on the structural changes and electrical properties has been investigated. DSC and thermodilatomery were used to study their thermal behavior, structure was studied by Raman spectroscopy, and electrical properties have been studied by impedance spectroscopy over a wide temperature and frequency range. The introduction of TeO(2) as a third glass former to the glass network causes the structural transformation from TeO(3) (tp) to TeO(4) (tbp) which contributes to the changes in conductivity. The glasses with low TeO(2) content show only a slow decrease in dc conductivity with addition of TeO(2) due to the increase of the number of nonbridging oxygens, which increases the mobility of Ag(+) ions. The steep decrease in conductivity for glasses containing more than 40 mol % TeO(2) is a result of decrease of the Ag(2)O content and stronger cross-linkage in glass network through the formation of more Te-(eq)O(ax)-Te bonds in TeO(4) tbp units. The glasses obey ac conductivity scaling with respect to temperature, implying that the dynamic process is not temperature dependent. On the other hand, the scaling of the spectra for different glass compositions showed the deviations from the Summerfield scaling because of the local structural disorder which occurs as a result of the structural modifications in the tellurite glass network.

Raman spectroscopic study of structure and crystallisation behaviour of MoO3-La2O3-B2O3 and MoO3-ZnO-B2O3 glasses

Science.gov (United States)

Aleksandrov, L.; Komatsu, T.; Nagamine, K.; Oishi, K.

2011-03-01

In this study, we focus on the structure and crystallization behavior of MoO3-La2O3-B2O3 and MoO3-ZnO-B2O3 glasses. Glasses of both systems were prepared by a melt-quenching method. The thermal stability of the glasses was examined using differential thermal anaysis (DTA) measurements, and the crystalline phases formed by heat treatments were identified by X-ray diffraction (XRD) analysis. Raman scattering spectra at room temperature for the glasses and crystallized samples were measured with a laser microscope operated with an Ar+ (wavelength: 488 nm) laser. DTA measurements indicated that the thermal stability against crystallization of the glasses decreases drastically with increasing MoO3 content. XRD analysis confirmed that crystallization at 600°C for 3 h of glass with the nominal composition of 50MoO3-25La2O3-25B2O3 resulted in the formation of monoclinic LaMoBO6. Crystallization of 50ZnO-xMoO3-(50-x)B2O3 glasses formed triclinic α-ZnMoO4 as an initial crystalline phase. Moreover, for 30 mol% MoO3 glass, transmission electron microscopy observations showed the formation of α-ZnMoO4 nanocrystals with a diameter of ~ 5 nm. Raman bands at 860, 930 and 950 cm-1 suggested that the coordination state of Mo6+ ions in the glasses were mainly (MoO4)2- tetrahedral units. Therefore, MoO3-containing glasses have good potential for optical applications.

Structural aspects of B2O3-substituted (PbO)0.5(SiO2)0.5 glasses

International Nuclear Information System (INIS)

Sudarsan, V.; Kulshreshtha, S.K.; Shrikhande, V.K.; Kothiyal, G.P.

2002-01-01

Lead borosilicate glasses having general formulae (PbO) 0.5-x (SiO 2 ) 0.5 (B 2 O 3 ) x with 0.0≤x≤0.4 and (PbO) 0.5 (SiO 2 ) 0.5-y (B 2 O 3 ) y with 0.0≤y≤0.5 have been prepared by a conventional melt-quench method and characterized by 29 Si, 11 B magic angle spinning (MAS) NMR techniques and infrared spectroscopy, as regards their structural features. From 29 Si NMR results, it has been inferred that with increasing concentration of boron oxide, (PbO) 0.5-x (SiO 2 ) 0.5 (B 2 O 3 )x glasses exhibit a systematic increase in the number of Q 4 structural units of Si at the expense of Q 2 structural units, along with the formation of Si-O-B linkages. On the other hand, for (PbO) 0.5 (SiO 2 ) 0.5-y (B 2 O 3 ) y glasses, there is no direct interaction between SiO 2 and B 2 O 3 in the glass network, as revealed by the 29 Si MAS NMR studies. Boron exists in both trigonal and tetrahedral configurations for these two series of glasses and for the (PbO) 0.5 (SiO 2 ) 0.5-y (B 2 O 3 ) y series of glasses; the relative concentration of these two structural units remains almost constant with increasing B 2 O 3 concentration. In contrast, for (PbO) 0.5-x (SiO 2 ) 0.5 (B 2 O 3 ) x glasses, there is a slight increase in the number of BO 3 structural units above x = 0.2, as there is a competition between SiO 2 and B 2 O 3 for interaction with Pb 2+ , thereby leading to the formation of BO 3 structural units. For both series of glasses, the thermal expansion coefficient is found to decrease with increasing B 2 O 3 concentration, the effect being more pronounced for the (PbO) 0.5-x (SiO 2 ) 0.5 (B 2 O 3 ) x series of glasses due to the increased concentration of Q 4 structural units of silicon and better cross-linking as a result of the formation of Si-O-B-type linkages. (author)

Determination of the hydrogen positions in the novel barium boroarsenate Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] by combined single crystal X-ray and powder neutron investigations

Energy Technology Data Exchange (ETDEWEB)

Lieb, Alexandra [School of Chemistry, University of Southampton (United Kingdom); Fakultaet fuer Verfahrens- und Systemtechnik, Lehrstuhl fuer Technische Chemie, Otto-von-Guericke-Universitaet, Magdeburg (Germany); Weller, Mark T. [School of Chemistry, University of Southampton (United Kingdom); Department of Chemistry, University of Bath (United Kingdom)

2017-11-17

The boroarsenate Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was obtained by the reaction of NH{sub 4}H{sub 2}AsO{sub 4}, B(OH){sub 3} and BaBr{sub 2}.2H{sub 2}O in the melt. Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was obtained as thin colorless needles, together with spherical crystals of BAsO{sub 4} as by-product, grown on a pellet of Ba[BAsO{sub 5}]. The products could be separated mechanically. For neutron scattering experiments a sample was prepared with {sup 11}B(OH){sub 3} as a starting material. The crystal structure of Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was determined by single-crystal X-ray diffraction and exhibits a layer structure with an unprecedented layer topology. The exact positions of the hydrogen atoms were determined using combined single-crystal X-ray and powder neutron diffraction investigations. Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was further characterized by IR spectroscopy and EDX analysis. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Carbonate hydrates of the heavy alkali metals: preparation and structure of Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O und Cs{sub 2}CO{sub 3} . 3 H{sub 2}O; Carbonat-Hydrate der schweren Alkalimetalle: Darstellung und Struktur von Rb{sub 2}CO{sub 3} . 1,5 H{sub 2}O und Cs{sub 2}CO{sub 3} . 3 H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Cirpus, V.; Wittrock, J.; Adam, A. [Koeln Univ. (Germany). Inst. fuer Anorganische Chemie

2001-03-01

Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O and Cs{sub 2}CO{sub 3} . 3 H{sub 2}O were prepared from aqueous solution and by means of the reaction of dialkylcarbonates with RbOH and CsOH resp. in hydrous alcoholes. Based on four-circle diffractometer data, the crystal structures were determined (Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O: C2/c (no. 15), Z = 8, a = 1237.7(2) pm, b = 1385.94(7) pm, c = 747.7(4) pm, {beta} = 120.133(8) , V{sub EZ} = 1109.3(6) . 10{sup 6} pm{sup 3}; Cs{sub 2}CO{sub 3} . 3 H{sub 2}O: P2/c (no. 13), Z = 2, a = 654.5(2) pm, b = 679.06(6) pm, c = 886.4(2) pm, {beta} = 90.708(14) , V{sub EZ} = 393.9(2) . 10{sup 6} pm{sup 3}). Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O is isostructural with K{sub 2}CO{sub 3} . 1.5 H{sub 2}O. In case of Cs{sub 2}CO{sub 3} . 3 H{sub 2}O no comparable structure is known. Both structures show {sub {infinity}}{sup 1}[(CO{sub 3}{sup 2-})(H{sub 2}O)]-chains, being connected via additional H{sub 2}O forming columns (Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O) and layers (Cs{sub 2}CO{sub 3} . 3 H{sub 2}O), respectively. (orig.)

Selective synthesis of clinoatacamite Cu2(OH)3Cl and tenorite CuO nanoparticles by pH control

DEFF Research Database (Denmark)

Engelbrekt, Christian; Malcho, Phillip; Andersen, Jonas

2014-01-01

, it directed the growth of Cu2(OH)3Cl to provide pure clinoatacamite without the presence of related poly- morphs. The products were characterized by transmission electron microscopy, infrared spectroscopy, ultraviolet–visible light spectroscopy, X-ray powder diffraction (XRD), scanning transmission X......-ray microscopy and atomic force microscopy. Infrared spectroscopy was essential for characterization of closely related polymorphs of Cu2(OH)3Cl indistinguishable by XRD. A plausible mechanism has been proposed and discussed for the formation of the CuO and Cu2(OH)3Cl nanostructures....

EPR Structural Investigations on Ag2O-B2O3-CaO-P2O5 Vitreous System

Directory of Open Access Journals (Sweden)

Razvan Stefan

2011-10-01

Full Text Available Glass samples from vitreous system 1.5Ag2O98.5%[0.47B2O3(0.53-xCaOxP2O5] with 0  x  0.08 have been obtained by undercooled method. The magnetic species existing in glass powders have been highlighting by mean of electronic paramagnetic resonance (EPR. The resonance linewidth analysis reveal the interactions between magnetic ions.

Theoretical study of H3AXH3 and H3AYH2 (A = B, Al, Ga; X = N, P, As and Y = O, S, and Se), electrostatic and hyperconjugative interactions roles

International Nuclear Information System (INIS)

El Guerraze, Abdelaali; El-Nahas, Ahmed M.; Jarid, Abdellah; Serrar, Chafiq; Anane, Hafid; Esseffar, M'hamed

2005-01-01

H 3 AXH n (A = B, Al, and Ga; XH n = NH 3 , PH 3 , AsH 3 , H 2 O, SH 2 and SeH 2 ) donor-acceptor complexes are studied from conformational and coordination-mode points of view at B3LYP/6-311+G(3df,2p) and CCSD(T)/6-311+G(3df,2p) levels of theory. The metallic character of gallium atom is responsible of the irregular structural and coordination mode trends in free and complexed gallane (GaH 3 ). The intuitive staggered conformation is not adopted by all compounds because there is, in some cases, competition between H(donor)-H(acceptor) electrostatic interaction and hyperconjugative electronic delocalisation. All H 3 AXH 3 (X = N, P, and As) complexes are staggered. In accordance with Pophristic-Goodman's study (V. Pophristic, L. Goodman, Nature 411 (2001) 565), hyperconjugation is behind this geometrical preference. For the H 3 AYH 2 series, the H 3 BOH 2 staggered conformation is also favoured by this interaction. Nevertheless, H 3 AlOH 2 and H 3 GaOH 2 are curiously eclipsed and not favoured by the hyperconjugation. This paradox is clarified by both electrostatic and energetic delocalisation interactions analysis. The coordination mode is horizontally and vertically discussed in N and O groups of the periodic table within these complex sets

Li2Sr4B12O23: A new alkali and alkaline-earth metal mixed borate with [B10O18]6− network and isolated [B2O5]4− unit

International Nuclear Information System (INIS)

Zhang Min; Pan Shilie; Han Jian; Yang Zhihua; Su Xin; Zhao Wenwu

2012-01-01

A novel ternary lithium strontium borate Li 2 Sr 4 B 12 O 23 crystal with size up to 20 mm×10 mm×4 mm has been grown via the top-seeded solution growth method below 730 °C. Single-crystal XRD analyses showed that Li 2 Sr 4 B 12 O 23 crystallizes in the monoclinic space group P2 1 /c with a=6.4664(4) Å, b=8.4878(4) Å, c=15.3337(8) Å, β=102.02(3)°, Z=2. The crystal structure is composed of [B 10 O 18 ] 6− network and isolated [B 2 O 5 ] 4− unit. The IR spectrum further confirmed the presence of both BO 3 and BO 4 groups. TG-DSC and Transmission spectrum were reported. Band structures and density of states were calculated. - Graphical abstract: A new phase, Li 2 Sr 4 B 12 O 23 , has been discovered in the ternary M 2 O–M′O–B 2 O 3 (M=alkali-metal, M′=alkalineearth metal) system. The crystal structure consists of [B 10 O 18 ] 6− network and isolated [B 2 O 5 ] 4− unit. Highlights: ► Li 2 Sr 4 B 12 O 23 is a a novel borate discovered in the M 2 O–M′O–B 2 O 3 (M=alkali-metal, M′=alkaline-earth metal) system. ► Li 2 Sr 4 B 12 O 23 crystal structure has a three-dimensional crystal structure with [B 10 O 18 ] 6− network and isolated [B 2 O 5 ] 4− unit. ► Sr 1 and Sr 2 are located in two different channels constructed by 3 ∞ [B 10 O 18 ] network.

Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

Science.gov (United States)

Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

2016-11-17

The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

Gauthierite, KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}].8H{sub 2}O, a new uranyl-oxide hydroxy-hydrate mineral from Shinkolobwe with a novel uranyl-anion sheet-topology

Energy Technology Data Exchange (ETDEWEB)

Olds, Travis A. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Kampf, Anthony R. [Natural History Museum of Los Angeles County, Los Angeles, CA (United States). Mineral Sciences Dept.; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Burns, Peter C. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Notre Dame Univ., IN (United States). Dept. of Chemistry and Biochemistry,; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

2017-03-15

Gauthierite, KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}].8H{sub 2}O, is a new uranyl-oxide hydroxy-hydrate mineral from the Shinkolobwe Mine, Democratic Republic of Congo, Africa. It occurs on a matrix of uraninite-bearing quartz gangue associated with soddyite and a minor metazeunerite.metatorbernite series mineral. It is a product of oxidation.hydration weathering of uraninite. Gauthierite is monoclinic, P2{sub 1}/c, with a = 29.844(2) Aa, b = 14.5368(8) Aa, c = 14.0406(7) Aa, β = 103.708(6) , V = 5917.8(6)Aa{sup 3} and Z = 8. Prismatic crystals have pronounced lengthwise striations and reach about 1mm in length. Gauthierite is yellowish orange with a light orange streak and vitreous lustre. The Mohs hardness is ∝ 3 to 4. It is brittle with an uneven fracture and perfect cleavage on {0 1 0}. The calculated density based on the empirical formula is 5.437 g/cm{sup 3}. Optically, gauthierite is biaxial (-), with α = 1.780(5), β = 1.815(5), γ = 1.825(5) (white light), 2V{sub meas.} = 58(1) ; dispersion is extreme (r>>v). The optical orientation is X = b, Y∼a{sup *}, Z∼c (or X = b, Y and a=14 in obtuse β); it is pleochroic with X very pale yellow, Y and Z orange-yellow; X<2}O 1.29, PbO 7.17, UO{sub 3} 82.10, H{sub 2}O 8.78 (structure), total 99.34 wt.%. The empirical formula (based on 34 O a.p.f.u.) is: K{sub 0.67}Pb{sub 0.78}U{sub 7}O{sub 34}H{sub 23.77}. The ideal formula is KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}](H{sub 2}O){sub 8}, which requires K{sub 2}O 1.90, PbO 9.00, UO{sub 3} 80.74, H{sub 2}O 8.35, total 100 wt.%. Raman and infrared spectral data confirm the presence of UO{sub 2}{sup 2+}, OH{sup -} and molecular H{sub 2}O. The eight strongest powder X-ray diffraction lines are [d{sub obs} in Aa (hkl) I{sub rel}]: 7.28 (020,400) 49, 3.566 (040, -802, -204) 67, 3.192 (622, -224) 100, 2.541 (-842,-244) 18, 2.043 (406) 14, 2.001 (662,-264, 14.2.0) 23, 1.962 (426,-146) 14, and 1

The first study of antiferromagnetic eosphorite-childrenite series (Mn{sub 1−x}Fe{sub x})AlP(OH){sub 2}H{sub 2}O (x=0.5)

Energy Technology Data Exchange (ETDEWEB)

Behal, D. [Sektion Kristallographie, Department für Geo- und Umweltwissenschaften, Ludwig-Maximilians-Universität München (LMU), Theresienstrasse 41, D-80333 Munich (Germany); Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München (TUM), Lichtenbergstrasse 1, D-85748 Garching (Germany); Röska, B. [Sektion Kristallographie, Department für Geo- und Umweltwissenschaften, Ludwig-Maximilians-Universität München (LMU), Theresienstrasse 41, D-80333 Munich (Germany); Park, S.-H., E-mail: sohyun.park@lmu.de [Sektion Kristallographie, Department für Geo- und Umweltwissenschaften, Ludwig-Maximilians-Universität München (LMU), Theresienstrasse 41, D-80333 Munich (Germany); Pedersen, B. [Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München (TUM), Lichtenbergstrasse 1, D-85748 Garching (Germany); Benka, G.; Pfleiderer, Ch. [Chair E21, Physik-Department, Technische Universität München (TUM), James-Franck-Strasse 1, D-85748 Garching (Germany); Wakabayashi, Y.; Kimura, T. [Division of Materials Physics, Graduate School of Engineering Science, Osaka University, Toyonaka 560-8531 (Japan)

2017-04-15

This study presents for the first time the antiferromagnetic structure of the eosphorite-childrenite series (Mn{sub 1-x}Fe{sub x})AlPO{sub 4}(OH){sub 2}H{sub 2}O (x=0.5), based on neutron single crystal diffraction at 3 K in combination with group theoretical representation analysis. The new magnetic structure is described in the magnetic space group P{sub C}mnb, maintaining the atomistic unit cell size (a×b×c) with a ~6.9 Å, b ~10.4 Å, c ~13.4 Å. Mn-rich and Fe-rich zones within solid solution crystals are expanded up to several hundred micrometers, as seen in electron microprobe and polarisation microscopy. Magnetic susceptibility and specific heat measurements on two different eosphorite-childrenite crystals show the magnetic transition temperature between 6.5 K and 6.8 K as the Mn{sup 2+}/Fe{sup 2+} ratio varies over single compositional zones. Below the Néel temperature, a magnetic field between 1.5 T and 2 T parallel to the a-axis causes a 180° spin-flip, reaching the saturation (5.25 μ{sub B} pfu) toward high magnetic fields. - Highlights: • New magnetic structure of (Mn{sub 1-x}Fe{sub x})AlPO{sub 4}(OH){sub 2}H{sub 2}O (x=0.5). • Magnetic phase transition at 6.5–6.6 K. • Magnetic interaction anisotropy in (Mn{sub 0.5}Fe{sub 0.5})AlPO{sub 4}(OH){sub 2}H{sub 2}O. • Compositional zones in the eosphorite-childrenite series.

Atmospheric Chemistry of cis-CF3CH=CHF: Kinetics of reactions with OH radicals and O3 and products of OH radical initiated oxidation

DEFF Research Database (Denmark)

Nilsson, Elna Johanna Kristina; Nielsen, Ole John; Johnson, Matthew Stanley

2009-01-01

Long path length FTIR-smog chamber techniques were used to measure k(OH + cis-CF3CH@CHF) = (1.20 ± 0.14) 1012 and k(O3 + cis-CF3CH@CHF) = (1.65 ± 0.16) 1021 cm3 molecule 1 s1 in 700 Torr of N2/O2 diluent at 296 K. The OH initiated oxidation of cis-CF3CH@CHF gives CF3CHO and HCOF in molar yields w...

Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.

Science.gov (United States)

Yan, Chao; Kocevska, Stefani; Krasnoperov, Lev N

2016-08-11

Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.

Studies of Eu2O3 - Bi2O3 - B2O3 glasses using Raman and IR spectroscopy

International Nuclear Information System (INIS)

Pop, Lidia; Culea, Eugen N.; Bratu, I.

2004-01-01

The bismuth borate (3Bi 2 O 3 ·B 2 O 3 ) glasses were prepared with different concentrations of Eu 3+ . The structure of these systems were investigated by Raman and IR spectroscopy. The structural study reveals that the glasses contain BiO 3 , BiO 6 , BO 3 , BO 4 and Eu-O structural units. For the samples with a higher content of Eu 2 O 3 , the spectra became very large indicating a more disordered structure. The hygroscopic character of the 3Bi 2 O 3 ·B 2 O 3 glass matrix and the progressive decrease of this behaviour with increasing the Eu 2 O 3 content was observed. Therefore, we conclude that the europium oxide acts as a network modifier in these glasses. (authors)

Topotactic synthesis of Co3O4 nanoboxes from Co(OH)2 nanoflakes

International Nuclear Information System (INIS)

Tian Li; Huang Kelong; Liu Younian; Liu Suqin

2011-01-01

Hollow nanocubes of spinel Co 3 O 4 with the dimension of 20 nm were successfully prepared via a facile and reproducible solvothermal route. The structure and morphology of Co 3 O 4 nanoboxes were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscope (HRTEM) techniques. And a possible growth mechanism of Co 3 O 4 nanoboxes were suggested that solid Co 3 O 4 nanocubes nucleate in-situ and grow epitaxially from hexagonal β-Co(OH) 2 precursors with the structural matching relationship of [0 0 1] β-Co(OH) 2 //[1 1 1] Co 3 O 4 , and then solid Co 3 O 4 nanocubes gradually hollow and convert to single-crystal nanoboxes owing to Ostwald ripening. - Graphical abstract: The formation mechanism of Co 3 O 4 nanoboxes can be expressed as epitaxial growth of Co 3 O 4 nanocubes from β-Co(OH) 2 nanoflakes due to a topotactic transformation and hollowing process owing to Ostwald ripening. Highlights: → Co 3 O 4 nanoboxes were prepared by a convenient, economical and controllable hydrothermal route. → Morphology and structure of Co 3 O 4 nanoboxes were characterized by XRD, SEM, and TEM techniques. → Co 3 O 4 nanoboxes grow epitaxially from Co(OH) 2 by topotactic transformation was suggested.

OH yields from the CH3CO+O-2 reaction using an internal standard\\ud

OpenAIRE

Carr, S.A.; Baeza-Romero, M.T.; Blitz, M.A.; Pilling, M.J.; Heard, D.E.; Seakins, P.W.

2007-01-01

Laser flash photolysis of CH3C(O)OH at 248 nm was used to create equal zero time yields of CH3CO and OH. The absolute OH yield from the CH3CO + O2 (+M) reaction was determined by following the OH temporal profile using the zero time\\ud OH concentration as an internal standard. The OH yield from CH3CO + O2 (+M) was observed to decrease with increasing pressure with an extrapolated zero pressure yield\\ud close to unity (1.1 ± 0.2, quoted uncertainties correspond to 95% confidence limits). The r...

Effects of Sm3+/Yb3+ co-doping and temperature on the Raman, IR spectra and structure of [TeO2-GeO2-K2O-Sm2O3/Yb2O3] glasses

International Nuclear Information System (INIS)

Shaltout, I.; Badr, Y.

2006-01-01

Effects of Sm 3+ /Yb 3+ co-doping on Raman scattering, IR absorption, temperature dependence of the Raman spectra up to 210 o C and the structure of two glass systems of the composition (80TeO 2 -10GeO 2 -8K 2 O-2Sm 2 O 3 /Yb 2 O 3 ) is discussed. It was found that the addition of Yb 3+ to the glass very strongly enhances the intensities of the antistokes' Raman bands at 155, 375, 557 and 828 cm -1 and quenches both the intensities of the stokes' vibration modes of the TeO 4 units in the range of 120-770 cm -1 and the intensities of the OH - stretching vibration modes in the range of 2600-3300 cm -1 . Sm 2 O 3 /Yb 2 O 3 rare earth co-doping has a great influence on removing and/or changing the nature of the OH - groups. The appearance and splitting of the stretching vibration modes of the OH - groups at lower frequencies (2770, 2970 cm -1 ) for the Sm +3 singly doped glass sample, compared to the band at ∼3200 cm -1 for the Sm 3+ /Yb 3+ co-doped glass sample, suggested that the OH - groups are more strongly bonded and incorporated with the glass matrix for the singly doped glass. Heating the sample up continuously weakens the hydrogen bonding of the OH - groups to the glass matrix leading to creation of NBO and breakdown of the connectivity of the OH - groups to the TeO 4 , TeO 3+1 and TeO 3 structural units. Raman bands at 286, 477, 666 and 769 cm -1 were assigned to its respective vibrations of Te 2 O 7 , TeO 4 -4 species, the (Te-O-Te) bending vibrations of the TeO 4 triagonal bipyramids (tbps), the axial symmetric stretching vibration modes (Te ax -O) s with bridging oxygen BO atoms and to the (Te-O) nbo non-bridging stretching vibration modes of the TeO 3+1 and/or TeO 3 pyramids

Ge 3P 6Si 2O 25: A cage structure closely related to the intersecting tunnel structure KMo 3P 6Si 2O 25

Science.gov (United States)

Leclaire, A.; Raveau, B.

1988-08-01

A germanosilicophosphate Ge 3P 6Si 2O 25 has been isolated. Its structure was solved from a single-crystal study in the space group P overline31c . Its cell parameters are a = b = 7.994(1) Å, c = 16.513(2) Å, Z = 2. The refinement by full-matrix least-squares calculations leads to R = 0.043 with 686 independent reflections. The structure of this oxide is built up from corner-sharing PO 4 and SiO 4 tetrahedra and GeO 6 octahedra. One observes a feature common to several silicophosphates: the presence of the structural unit P 6Si 2O 25 built up from a disilicate group sharing its corners with six PO 4 tetrahedra. The structural relationships between this oxide and the silicophosphates AMo 3P 6Si 2O 25 and Si 3P 6Si 2O 25 (or Ge 3P 6 Ge 2O 25) are described.

Syntheses, crystal structures and solid-state properties of the lanthanoid-containing nanoclusters [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-}

Energy Technology Data Exchange (ETDEWEB)

Gupta, Rakesh; Saini, Mukesh Kumar; Hussain, Firasat [Department of Chemistry, University of Delhi (India)

2014-12-15

A series of lanthanoid-substituted polyoxometalates have been synthesized by a self-assembly process in potassium chloride solution by the reaction of dilacunary [P{sub 2}W{sub 19}O{sub 69}(H{sub 2}O)]{sup 14-} with mid- and late-lanthanoid Ln(NO{sub 3}){sub 3}.nH{sub 2}O salts leading to the formation of the tetrameric tungstophosphates [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-} [Ln = Y{sup 3+} (1), Sm{sup 3+} (2), Eu{sup 3+} (3), Gd{sup 3+} (4), Tb{sup 3+} (5), Dy{sup 3+} (6), Ho{sup 3+} (7), Er{sup 3+} (8), Tm{sup 3+} (9), Yb{sup 3+} (10)]. The polyanions were isolated as potassium or mixed-alkali salts. Most of the compounds were characterized by single-crystal X-ray diffraction and various analytical techniques, such as FTIR, UV/Vis, {sup 31}P NMR and photoluminescence spectroscopy, magnetism, as well as thermogravimetric analysis. The FTIR spectra suggest that all the compounds are isomorphous. The crystal structures of these complexes consist of four A-[α-PW{sub 10}O{sub 36}]{sup 7-} units, each incorporating two Ln{sup III} ions to create four Keggin-like anions that further assemble with three additional tungstate units to form a tetramer species with C{sub 2} symmetry. The photoluminescent properties of 3a and 6a were investigated following photoexcitation at room temperature. The magnetic properties of 3a, 4a, 5a and 6a were investigated at room temperature, the complexes exhibiting paramagnetic behaviour. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Electron excitation cross sections for the 2s(2)2p(3)4S(O) -- 2s(2)2p(3)2D(O) (forbidden) and 4S(O) -- 2s2p(4) 4P (resonance) transitions in O II

Science.gov (United States)

Zuo, M.; Smith, Steven J.; Chutjian, A.; Williams, I. D.; Tayal, S. S.; Mclaughlin, Brendan M.

1995-01-01

Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.

Zero photoelastic and water durable ZnO-SnO-P2O5-B2O3 glasses

Science.gov (United States)

Saitoh, Akira; Nakata, Kohei; Tricot, Grégory; Chen, Yuanyuan; Yamamoto, Naoki; Takebe, Hiromichi

2015-04-01

We report properties of zero birefringent xZnO-(67-x)SnO-(33-y)P2O5-y B2O3 glasses, within 18.5 ≤ x ≤ 22 and y = 0, 3, and 10 mol. %. These compositions of boro-phosphate glasses provide both zero photoelastic constant (PEC) and improved water durability. x = 19 and y = 3 compositions show minimum PEC of -0.002 × 10-12 Pa-1, which can contribute to candidate material for fiber current sensor devise without lead. The structures of zero photoelastic glasses were investigated by Raman scattering and nuclear magnetic resonance spectroscopies. Compositions of zero PEC glasses are explained by the empirical model proposed by Zwanziger et al. [Chem. Mater. 19, 286-290 (2007)].

Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn2II(OH2)2(HPO3)2(C2O4)

International Nuclear Information System (INIS)

Ramaswamy, Padmini; Mandal, Sukhendu; Natarajan, Srinivasan

2009-01-01

A novel manganese phosphite-oxalate, [C 2 N 2 H 10 ][Mn 2 II (OH 2 ) 2 (HPO 3 ) 2 (C 2 O 4 )] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO 3 )] ∞ , formed by MnO 6 octahedra and HPO 3 units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one-dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn 2+ ions. - Abstract: A new antiferromagnetic three-dimensional inorganic-organic hybrid compound, [C 2 N 2 H 10 ][Mn 2 II (OH 2 ) 2 (HPO 3 ) 2 (C 2 O 4 )] has been prepared hydrothermally. The compound has neutral manganese layers pillared by oxalate units. The neutral manganese layers are shown here. Display Omitted

Pb4(OH)4(BrO3)3(NO3): An Example of SHG Crystal in Metal Bromates Containing π-Conjugated Planar Triangle.

Science.gov (United States)

Kong, Fang; Hu, Chun-Li; Liang, Ming-Li; Mao, Jiang-Gao

2016-01-19

The first example of SHG crystal in the metal bromates containing π-conjugated planar triangle systems, namely, Pb4(OH)4(BrO3)3(NO3), was successfully synthesized via the hydrothermal method. Furthermore, a single crystal of centrosymmetric Pb8O(OH)6(BrO3)6(NO3)2·H2O was also obtained. Both compounds contain similar [Pb4(OH)4] cubane-like tetranuclear clusters, but they display different one-dimensional (1D) chain structures. Pb4(OH)4(BrO3)3(NO3) features a zigzag [Pb4(OH)4(BrO3)3](+) 1D chain, while Pb8O(OH)6(BrO3)6(NO3)2·H2O is composed of two different orthogonal chains: the linear [Pb4(OH)4(BrO3)2](2+) 1D chain along the b-axis and the zigzag [Pb4O2(OH)2(BrO3)4](2-) 1D chain along the a-axis. The NO3 planar triangles of the compounds are all isolated and located in the spaces of the structures. Pb4(OH)4(BrO3)3(NO3) exhibits the first example of SHG crystal in the metal bromates with π-conjugated planar triangle. The second-harmonic generation (SHG) efficiency of Pb4(OH)4(BrO3)3(NO3) is approximately equal to that of KDP and it is phase-matchable. Dipole moment and theory calculations indicate that BrO3, NO3, and PbO4 groups are the origin of its SHG efficiency, although some of the contributions cancel each other out.

Synthesis, crystal structure, and nonlinear optical properties of Bi2Cu5B4O14

International Nuclear Information System (INIS)

Pan Shilie; Smit, Jared P.; Marvel, Michael R.; Stampler, Evan S.; Haag, Jacob M.; Baek, Jaewook; Halasyamani, P. Shiv; Poeppelmeier, Kenneth R.

2008-01-01

Bi 2 Cu 5 B 4 O 14 crystallizes in the noncentrosymmetric triclinic space group P1 (No. 1) with cell parameters a=10.1381(11) A, b=9.3917(11) A, c=3.4566(4) A, α=105.570(2) o , β=92.275(2) o , γ=107.783(2) o , Z=1 and R 1 =0.0401 and wR 2 =0.0980. It is a layered structure that is built up from sheets of rectangular CuO 4 and trigonal BO 3 groups. The sheets are connected by infinite chains of edge shared BiO 6 polyhedra that intersect the bc plane at an angle slightly greater than 90 o . The second-harmonic generation efficiency of Bi 2 Cu 5 B 4 O 14 , using 1064 nm radiation, is about one half times that of KH 2 PO 4 . - Graphical abstract: The figure shows a layered structure that is built up from sheets of distorted rectangular CuO 4 and trigonal BO 3 groups. The sheets are connected by infinite chains of edge shared BiO 6 polyhedra that intersect the bc plane. These distortions lead to the second-harmonic generation efficiency of Bi 2 Cu 5 B 4 O 14 about one half times that of KH 2 PO 4 Display Omitted

A Novel Ruthenium-Decorating Polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH2]·24H2O: An Active Heterogeneous Oxidation Catalyst for Alcohols

Directory of Open Access Journals (Sweden)

Rong Wan

2018-01-01

Full Text Available The first example of wholly inorganic ruthenium-containing polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH2]·24H2O (1 was isolated and systematically characterized by element analysis, infrared spectroscopy (IR, thermogravimetric analyses (TGA, X-ray photoelectron spectroscopy (XPS, energy dispersive X-ray spectroscopy (EDX and single-crystal X-ray diffraction. Compound 1 is composed of an unprecedented {Mo14}-type isopolymolybdate with a di-ruthenium core precisely encapsulated in its center, exhibiting a three-tiered ladder-like structure. The title compound can act as an efficient heterogeneous catalyst in the transformation of 1-phenylethanol to acetophenone. This catalyst is also capable of being recycled and reused for at least ten cycles with its activity being retained under the optimal conditions.

Atmospheric chemistry of CF3CH2CH2OH

DEFF Research Database (Denmark)

Hurley, Michael D.; Misner, Jessica A.; Ball, James C.

2005-01-01

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF3CH2C(O)H and CF3CH2CH2OH in 700 Torr of N-2 or air diluent at 296 2 K. The rate constants determined were k(Cl+CF3CH2C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF3CH2C(O)H) = (2.57 +/- 0.44...

Crystal structure of a new polar borate Na{sub 2}Ce{sub 2}[BO{sub 2}(OH)][BO{sub 3}]{sub 2} · H{sub 2}O with isolated boron triangles

Energy Technology Data Exchange (ETDEWEB)

Topnikova, A. P.; Belokoneva, E. L., E-mail: elbel@geol.msu.ru; Dimitrova, O. V.; Volkov, A. S. [Moscow State University, Faculty of Geology (Russian Federation)

2016-11-15

Crystals of a new polar borate Na{sub 2}Ce{sub 2}[BO{sub 2}(OH)][BO{sub 3}]{sub 2} · H{sub 2}O were prepared by hydrothermal synthesis. The crystals are orthorhombic, a = 7.2295(7) Å, b = 11.2523(8) Å, c = 5.1285(6) Å, Z = 2, sp. gr. C2mm (Amm2), R = 0.0253. The formula of the compound was derived from the structure determination. The Ce and Na atoms are coordinated by nine and six O atoms, respectively. The Ce position is split, and a small amount of Ce is incorporated into the Na1 site with the isomorphous substitution for Na. The anionic moieties exist as isolated BO{sub 3} and BO{sub 2}(OH) triangles. The planes of the BO{sub 2}(OH) triangles with mm2 symmetry are parallel to the ab plane. The planes of the BO{sub 3} triangles with m symmetry are perpendicular to the ab plane and are rotated in a diagonal way. The splitting of the Ce positions and the polar arrangement of the BO{sub 2}(OH) triangles, water molecules, and Na atoms are observed along the polar a axis. The new structure is most similar to the new borate NaCa{sub 4}[BO{sub 3}]{sub 3} (sp. gr. Ama2), in which triangles of one type are arranged in a polar fashion along the c axis. Weak nonlinear-optical properties of both polar borates are attributed to the quenching of the second-harmonic generation due to the mutually opposite orientation of two-thirds of B triangles in the unit cell.

Ba(OH)2.8H2O process for the removal and immobilization of carbon-14. Final report

International Nuclear Information System (INIS)

Haag, G.L.; Holladay, D.W.; Pitt, W.W. Jr.; Young, G.C.

1986-01-01

The airborne release of 14 C from various nuclear facilities has been identified as a potential biohazard due to the long half-life of 14 C (5730 years) and the ease with which it may be assimilated into the biosphere. At ORNL, technology has been developed for the removal and immobilization of this radionuclide. Prior studies have indicated that 14 C will likely exist in the oxidized form as CO 2 and will contribute slightly to the bulk CO 2 concentration of the gas stream, which is air-like in nature (approx.300 ppM/sub v/ CO 2 ). The technology that has been developed utilizes the CO 2 -Ba(OH) 2 .8H 2 O gas-solid reaction with the mode of gas-solid contacting being a fixed bed. The product, BaCO 3 , possesses excellent thermal and chemical stability, prerequisites for the long-term disposal of nuclear wastes. For optimal process operation, studies have indicated that an operating window of adequate size does exist. When operating within the window, high CO 2 removal efficiency (effluent concentrations 99%), and an acceptable pressure drop across the bed (3 kPa/m at a superficial velocity of 13 cm/s) are possible. Three areas of experimental investigation are reported: (1) microscale studies on 150-mg samples to provide information concerning surface properties, kinetics, and equilibrium vapor pressures; (2) macroscale studies on large fixed beds (4.2 kg of reactant) to determine the effects of humidity, temperature, and gas flow rate upon bed pressure drop and CO 2 breakthrough; and (3) design, construction, and operation of a pilot unit capable of continuously processing a 34-m 3 /h (20-ft 3 /min) air-based gas stream

Kamarizaite, Fe{3/3+}(AsO4)2(OH)3 · 3H2O, a new mineral species, arsenate analogue of tinticite

Science.gov (United States)

Chukanov, N. V.; Pekov, I. V.; Möckel, S.; Mukhanova, A. A.; Belakovsky, D. I.; Levitskaya, L. A.; Bekenova, G. K.

2010-12-01

Kamarizaite, a new mineral species, has been identified in the dump of the Kamariza Mine, Lavrion mining district, Attica Region, Greece, in association with goethite, scorodite, and jarosite. It was named after type locality. Kamarizaite occurs as fine-grained monomineralic aggregates (up to 3 cm across) composed of platy crystals up to 1 μm in size and submicron kidney-shaped segregations. The new mineral is yellow to beige, with light yellow streak. The Mohs hardness is about 3. No cleavage is observed. The density measured by hydrostatic weighing is 3.16(1) g/cm3, and the calculated density is 3.12 g/cm3. The wavenumbers of absorption bands in the IR spectrum of kamarizaite are (cm-1; s is strong band, w is weak band): 3552, 3315s, 3115, 1650w, 1620w, 1089, 911s, 888s, 870, 835s, 808s, 614w, 540, 500, 478, 429. According to TG and IR data, complete dehydration and dehydroxylation in vacuum (with a weight loss of 15.3(1)%) occurs in the temperature range 110-420°C. Mössbauer data indicate that all iron in kamarizaite is octahedrally coordinated Fe3+. Kamarizaite is optically biaxial, positive: n min = 1.825, n max = 1.835, n mean = 1.83(1) (for a fine-grained aggregate). The chemical composition of kamarizaite (electron microprobe, average of four point analyses) is as follows, wt %: 0.35 CaO, 41.78 Fe2O3, 39.89 As2O5, 1.49 SO3, 15.3 H2O (from TG data); the total is 98.81. The empirical formula calculated on the basis of (AsO4,SO4)2 is Ca0.03Fe{2.86/3+} (AsO4)1.90(SO4)0.10(OH)2.74 · 3.27H2O. The idealized formula is Fe{3/3+}(AsO4)2(OH)3 · 3H2O. Kamarizaite is an arsenate analogue of orthorhombic tinticite, space group Pccm, Pcc2, Pcmm, Pcm21, or Pc2 m; a = 21.32(1), b = 13.666(6), c =15.80(1) Å, V= 4603.29(5) Å3, Z= 16. The strongest reflections of the X-ray powder diffraction pattern [ bar d , Å ( I, %) ( hkl)] are: 6.61 (37) (112, 120), 5.85 (52) (311), 3.947 (100) (004, 032, 511), 3.396 (37) (133, 431), 3.332 (60) (314), 3.085 (58) (621, 414, 324

Copper(II) perrhenate Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}: Synthesis from isopropanol and CuReO{sub 4}, structure and properties

Energy Technology Data Exchange (ETDEWEB)

Mikhailova, D., E-mail: d.mikhailova@ifw-dresden.de [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, D-76434 Eggenstein-Leopoldshafen (Germany); Institute for Complex Materials, IFW Dresden, Helmholtzstrasse 20, D-01069 Dresden (Germany); Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden (Germany); Engel, J.M. [Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 2, D-64287 Darmstadt (Germany); Schmidt, M. [Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden (Germany); Tsirlin, A.A. [National Institute of Chemical Physics and Biophysics, Akadeemia tee 23, 12618 Tallinn (Estonia); Ehrenberg, H. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, D-76434 Eggenstein-Leopoldshafen (Germany); Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 2, D-64287 Darmstadt (Germany)

2015-12-15

The crystal structure of Cu{sup +}Re{sup 7+}O{sub 4} is capable of a quasi-reversible incorporation of C{sub 3}H{sub 7}OH molecules. A room-temperature reaction between CuReO{sub 4} and C{sub 3}H{sub 7}OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu{sup 2+}(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}. Upon heating under reducing conditions, this compound transforms back into CuReO{sub 4}, albeit with ReO{sub 2} and metallic Cu as by-products. The crystal structure of Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO{sub 6}-octahedra and ReO{sub 4}-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} is paramagnetic down to 4 K because the spatial arrangement of the Cu{sup 2+} half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μ{sub B} is slightly above the spin-only value and typical for Cu{sup 2+} ions. - Highlights: • Novel Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} compound has a sequence of inorganic and organic layers. • Hydrogen bonds provide an additional bonding Isopropanol molecules serve as a reducing agent during decomposition. • No direct Cu-O-Re-O-Cu connections via d{sub x2-y2} orbital of Cu{sup 2+} explain paramagnetism. • Hydrogen bonds provide an additional bonding. • Isopropanol molecules serve as a reducing agent during decomposition.

Thermal and electrical properties of 60V2O5–5P2O5–(35− x) B2O3 ...

Indian Academy of Sciences (India)

The samples of composition 60V2O5–5P2O5–(35−)B2O3–CeO2, = 1, 2, 3, 4 and 5 mol% were prepared by the melt-quench method. The prepared samples were characterized by X-ray diffraction, thermogravimetric-differential thermal analysis and impedance spectroscopy. The activation energies were evaluated ...

Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

Science.gov (United States)

Knutsen, Karen; Dyer, Mark J.; Copeland, Richard A.

1996-01-01

Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

Structure of the demesmaekerite, Pb/sub 2/Cu/sub 5/(SeO/sub 3/)/sub 6/(UO/sub 2/)/sub 2/(OH)/sub 6/. 2H/sub 2/O

Energy Technology Data Exchange (ETDEWEB)

Ginderow, D [Laboratoire de Mineralogie-Cristallographie, Universite Pierre et Marie Curie, Paris, France; Cesbron, F [Bureau de Recherches Geologiques et Minieres (BRGM), 45 - Orleans (France)

1938-07-15

Msub(r) = 2172, triclinic, P1-bar, a = 11.955(5), b = 10.039(4), c = 5.639(2) A, ..cap alpha.. = 89.78(4), ..beta.. = 100.36(4), ..gamma.. = 91.34(4)/sup 0/, Z = 1, V = 666 A/sup 3/, Dsub(x) = 5.42(5), Dsub(m) = 5.28(4) Mg m/sup -3/, ..mu..(Mo K..cap alpha..) = 36.57 mm/sup -1/, F(000) = 1217, T = 295 K. The final R value is 0.060 for 3329 observed reflexions. The crystal structure consists of layers of (Cu(O,OH,H/sub 2/O)/sub 6/) octahedra parallel to (010) and linked to each other by oblique chains which are formed by oxygen bridges linking uranyl and selenium ions.

Chemical and Electrochemical Asymmetric Dihydroxylation of Olefins in I(2)-K(2)CO(3)-K(2)OsO(2)(OH)(4) and I(2)-K(3)PO(4)/K(2)HPO(4)-K(2)OsO(2)(OH)(4) Systems with Sharpless' Ligand.

Science.gov (United States)

Torii, Sigeru; Liu, Ping; Bhuvaneswari, Narayanaswamy; Amatore, Christian; Jutand, Anny

1996-05-03

Iodine-assisted chemical and electrochemical asymmetric dihydroxylation of various olefins in I(2)-K(2)CO(3)-K(2)OsO(2)(OH)(4) and I(2)-K(3)PO(4)/K(2)HPO(4)-K(2)OsO(2)(OH)(4) systems with Sharpless' ligand provided the optically active glycols in excellent isolated yields and high enantiomeric excesses. Iodine (I(2)) was used stoichiometrically for the chemical dihydroxylation, and good results were obtained with nonconjugated olefins in contrast to the case of potassium ferricyanide as a co-oxidant. The potentiality of I(2) as a co-oxidant under stoichiometric conditions has been proven to be effective as an oxidizing mediator in electrolysis systems. Iodine-assisted asymmetric electro-dihydroxylation of olefins in either a t-BuOH/H(2)O(1/1)-K(2)CO(3)/(DHQD)(2)PHAL-(Pt) or t-BuOH/H(2)O(1/1)-K(3)PO(4)/K(2)HPO(4)/(DHQD)(2)PHAL-(Pt) system in the presence of potassium osmate in an undivided cell was investigated in detail. Irrespective of the substitution pattern, all the olefins afforded the diols in high yields and excellent enantiomeric excesses. A plausible mechanism is discussed on the basis of cyclic voltammograms as well as experimental observations.

OH+ Formation in the Low-temperature O+(4S) + H2 Reaction

Science.gov (United States)

Kovalenko, Artem; Dung Tran, Thuy; Rednyk, Serhiy; Roučka, Štěpán; Dohnal, Petr; Plašil, Radek; Gerlich, Dieter; Glosík, Juraj

2018-04-01

Formation of OH+ in collisions of ground-state O+(4S) ions with normal H2 has been studied using a variable temperature 22-pole RF ion trap. From 300 to 30 K the measured reaction rate coefficient is temperature-independent, with a small decrease toward 15 K. The recent wave packet calculation predicts a slightly steeper temperature dependence. The rate coefficients at 300 and 15 K are almost the same, (1.4 ± 0.3) × 10‑9 cm3 s‑1 and (1.3 ± 0.3) × 10‑9 cm3 s‑1, respectively. The influence of traces of the two metastable ions, O+(2D) and O+(2P), has been examined by monitoring the H+ products of their reactions with H2, as well as by chemically probing them with N2 reactant gas.

Poly[[μ2-2,2′-diethyl-1,1′-(butane-1,4-diyldiimidazole-κ2N3:N3′](μ2-5-hydroxyisophthalato-κ2O1:O3zinc

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Ying-Ying Liu

2011-11-01

Full Text Available In the title coordination polymer, [Zn(C8H4O5(C14H22N4]n, the ZnII cation is coordinated by an O2N2 donor set in a distorted tetrahedral geometry. The ZnII ions are linked by μ2-OH-bdc (OH-H2bdc = 5-hydroxyisophthalic acid and bbie ligands [bbie = 2,2′-diethyl-1,1′-(butane-1,4-diyldiimidazole], forming a two-dimensional layer parallel to the ab plane. The layers are further connected through intermolecular C—H...O and O—H...O hydrogen bonds, forming a three-dimensional supramolecular structure. In the bbie ligand, the two C atoms in the ethyl group are each disordered over two positions with a site-occupancy ratio of 0.69:0.31.

Calcioferrite with composition (Ca3.94Sr0.06Mg1.01(Fe2.93Al1.07(PO46(OH4·12H2O

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Barbara Lafuente

2014-03-01

Full Text Available Calcioferrite, ideally Ca4MgFe3+4(PO46(OH4·12H2O (tetracalcium magnesium tetrairon(III hexakis-phosphate tetrahydroxide dodecahydrate, is a member of the calcioferrite group of hydrated calcium phosphate minerals with the general formula Ca4AB4(PO46(OH4·12H2O, where A = Mg, Fe2+, Mn2+ and B = Al, Fe3+. Calcioferrite and the other three known members of the group, montgomeryite (A = Mg, B = Al, kingsmountite (A = Fe2+, B = Al, and zodacite (A = Mn2+, B = Fe3+, usually occur as very small crystals, making their structure refinements by conventional single-crystal X-ray diffraction challenging. This study presents the first structure determination of calcioferrite with composition (Ca3.94Sr0.06Mg1.01(Fe2.93Al1.07(PO46(OH4·12H2O based on single-crystal X-ray diffraction data collected from a natural sample from the Moculta quarry in Angaston, Australia. Calcioferrite is isostructural with montgomeryite, the only member of the group with a reported structure. The calcioferrite structure is characterized by (Fe/AlO6 octahedra (site symmetries 2 and -1 sharing corners (OH to form chains running parallel to [101]. These chains are linked together by PO4 tetrahedra (site symmetries 2 and 1, forming [(Fe/Al3(PO43(OH2] layers stacking along [010], which are connected by (Ca/Sr2+ cations (site symmetry 2 and Mg2+ cations (site symmetry 2; half-occupation. Hydrogen-bonding interactions involving the water molecules (one of which is equally disordered over two positions and OH function are also present between these layers. The relatively weaker bonds between the layers account for the cleavage of the mineral parallel to (010.

Crystal structure, equation of state, and elasticity of hydrous aluminosilicate phase, topaz-OH (Al2SiO4(OH)2) at high pressures

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Mookherjee, Mainak; Tsuchiya, Jun; Hariharan, Anant

2016-02-01

We examined the equation of state and high-pressure elasticity of the hydrous aluminosilicate mineral topaz-OH (Al2SiO4(OH)2) using first principles simulation. Topaz-OH is a hydrous phase in the Al2O3-SiO2-H2O (ASH) ternary system, which is relevant for the mineral phase relations in the hydrated sedimentary layer of subducting slabs. Based on recent neutron diffraction experiments, it is known that the protons in the topaz-OH exhibit positional disorder with half occupancy over two distinct crystallographic sites. In order to adequately depict the proton environment in the topaz-OH, we examined five crystal structure models with distinct configuration for the protons in topaz-OH. Upon full geometry optimization we find two distinct space group, an orthorhombic Pbnm and a monoclinic P21/c for topaz-OH. The topaz-OH with the monoclinic P21/c space group has a lower energy compared to the orthorhombic Pbmn space group symmetry. The pressure-volume results for the monoclinic topaz-OH is well represented by a third order Birch-Murnaghan formulation, with V0mon = 348.63 (±0.04) Å3, K0mon = 164.7 (±0.04) GPa, and K0mon = 4.24 (±0.05). The pressure-volume results for the orthorhombic topaz-OH is well represented by a third order Birch-Murnaghan formulation, with V0orth = 352.47 (±0.04) Å3, K0orth = 166.4 (±0.06) GPa, and K0orth = 4.03 (±0.04). While the bulk moduli are very similar for both the monoclinic and orthorhombic topaz-OH, the shear elastic constants and the shear moduli are very sensitive to the position of the proton, orientation of the O-H dipole, and the space group symmetry. The S-wave anisotropy for the orthorhombic and monoclinic topaz-OH are also quite distinct. In the hydrated sedimentary layer of subducting slabs, transformation of a mineral assemblage consisting of coesite (SiO2) and diaspore (AlOOH) to topaz-OH (Al2SiO4(OH)2) is likely to be accompanied by an increase in density, compressional velocity, and shear wave velocity. However

Hilarionite, Fe{2/3+}(SO4)(AsO4)(OH) · 6H2O, a new supergene mineral from Lavrion, Greece

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Pekov, I. V.; Chukanov, N. V.; Yapaskurt, V. O.; Rusakov, V. S.; Belakovsky, D. I.; Turchkova, A. G.; Voudouris, P.; Magganas, A.; Katerinopoulos, A.

2014-12-01

A new mineral, hilarionite, ideally Fe{2/3+} (SO4)(AsO4)(OH) · 6H2O, has been found in the Hilarion Mine, Agios Konstantinos, Kamariza, Lavrion district, Attiki Prefecture, Greece. It was formed in the oxidation zone of a sulfide-rich orebody in association with goethite, gypsum, bukovskyite, jarosite, melanterite, chalcanthite, allophane, and azurite. Hilarionite occurs as light green (typically with an olive or grayish tint) to light yellowish green spherulites (up to 1 mm in size) and bunches of prismatic to acicular "individuals" up to 0.5 mm long that are in fact near-parallel or divergent aggregates of very thin, curved fibers up to 0.3 mm long and usually lesser than 2 μm thick. The luster is silky to vitreous. The Mohs' hardness is ca. 2. Hilarionite is ductile, its "individuals" are flexible and inelastic; fracture is uneven or splintery. D(meas) = 2.40(5), D(calc) = 2.486 g/cm3. IR spectrum shows the presence of arsenate and sulfate groups and H2O molecules in significant amounts. The Mössbauer spectrum indicates the presence of Fe3+ at two six-fold coordinated sites and the absence of Fe2+. Hilarionite is optically biaxial (+), α = 1.575(2), γ = 1.64(2), 2 V is large. The chemical composition (electron microprobe, average of 7 point analyses; H2O determined by modified Penfield method) is as follows, wt %: 0.03 MnO, 0.18 CuO, 0.17 ZnO, 33.83 Fe2O3, 0.22 P2O5, 18.92 As2O5, 22.19 SO3, 26.3 H2O, total is 101.82%. The empirical formula calculated on the basis of 15 O is: (Fe{1.90/3+}Cu0.01Zn0.01)Σ1.92[(SO4)1.24(AsO4)0.74(PO4)0.01]Σ1.99(OH)1.01 · 6.03H2O. The X-ray powder diffraction data show close structural relationship of hilarionite and kaňkite, Fe{2/3+}(AsO4)2 · 7H2O. Hilarionite is monoclinic, space group C2/ m, Cm or C2, a = 18.53(4), b = 17.43(3), c = 7.56(1) Å, β = 94.06(15)°, V = 2436(3) Å3, Z = 8. The strongest reflections in the X-ray powder diffraction pattern ( d, Å- I[ hkl]) are: 12.66-100[110], , 5.00-10[22l], , 4

H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds

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Ibon Alkorta

2016-02-01

Full Text Available A search of the Cambridge Structural Database (CSD was carried out for phosphine-water and arsine-water complexes in which water is either the proton donor in hydrogen-bonded complexes, or the electron-pair donor in pnicogen-bonded complexes. The range of experimental P-O distances in the phosphine complexes is consistent with the results of ab initio MP2/aug’-cc-pVTZ calculations carried out on complexes H2XP:OH2, for X = NC, F, Cl, CN, OH, CCH, H, and CH3. Only hydrogen-bonded complexes are found on the H2(CH3P:HOH and H3P:HOH potential surfaces, while only pnicogen-bonded complexes exist on H2(NCP:OH2, H2FP:OH2, H2(CNP:OH2, and H2(OHP:OH2 surfaces. Both hydrogen-bonded and pnicogen-bonded complexes are found on the H2ClP:OH2 and H2(CCHP:OH2 surfaces, with the pnicogen-bonded complexes more stable than the corresponding hydrogen-bonded complexes. The more electronegative substituents prefer to form pnicogen-bonded complexes, while the more electropositive substituents form hydrogen-bonded complexes. The H2XP:OH2 complexes are characterized in terms of their structures, binding energies, charge-transfer energies, and spin-spin coupling constants 2hJ(O-P, 1hJ(H-P, and 1J(O-H across hydrogen bonds, and 1pJ(P-O across pnicogen bonds.

Morphology Controlled Synthesis of α-GaO(OH Nanoparticles: Thermal Conversion to Ga2O3 and Photocatalytic Properties

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Ayse Dulda

2016-01-01

Full Text Available Morphology controlled α-GaO(OH particles have been synthesized via precipitation method which allows the tuning of relative growth rates of crystal facets. The effects of alkali addition rate and the type of alkali on the growth rates of the crystal facets during hydrolysis were also investigated. XRD and TG analysis confirmed that there was a phase transition from GaO(OH to Ga2O3 when precursor sample was calcined to 750°C. The single phase α-Ga2O3 was obtained after thermal treatment of NaOH precipitated precursor, while β-Ga2O3 was formed when the urea or NH4OH precipitated precursor was calcinated. Furthermore, the thermal, spectral, and photocatalytic properties connected to the crystal structure and morphology were discussed.

Glass formation and properties of glasses in V/sub 2/O/sub 5/-B/sub 2/O/sub 3/-P/sub 2/O/sub 5/ system

Energy Technology Data Exchange (ETDEWEB)

Sedmale, G P; Vajvad, Ya A; Arkhipova, S E; Laukmanis, L A

1987-01-01

The glass formation in the system V/sub 2/O/sub 5/-B/sub 2/O/sub 3/-P/sub 2/O/sub 5/ and the properties of the obtained glasses have been studied by methods including that of the mathematical design and the treatment of the obtained data on ECM. The glass formation region is limited by the molar content of V/sub 2/O/sub 5/ 30-80%, B/sub 2/O/sub 3/ 0-45%, P/sub 2/O/sub 5/ 20-65%. The chemical stability data show that at the molar content of V/sub 2/O/sub 5/ 45-50% the transfer of vanadium from the state of the modificator to the glass-forming agent takes place. For the studied glasses the electron mechanism of conductivity is the dominating one.

The phenomenon of phase separated in Na2O-B2O3-SiO2, Na2O-SiO2-P2O5 glasses

International Nuclear Information System (INIS)

Procyk, B.; Bieniarz, P.; Plichta, E.; Pudelek, B.; Kucinski, G.; Staniewicz-Brudnik, B.

1997-01-01

During the thermal treatment, the phenomenon of phase separation has been observed in the some glasses. The glass has became opaque, due to the opalescence of phase separated. Investigations of the phenomenon of phase separation were conducted using the basic systems: Na 2 O-B 2 O 3 -SiO 2 , Na 2 O-SiO 2 -P 2 O 5 and theirs modifications. The occurrence of binodal and spinodal phase decomposition was observed by TEM. The phase separation inhomogeneities have drop-like character and with higher concentration shows a tendency for coalescence. The influence of the chemical composition, temperature and time on the phenomenon of phase separation in the investigated glasses has been defined. (author)

Structural and physical properties of a novel misfit-layered cobalt oxide (CaOH)1.14CoO2

International Nuclear Information System (INIS)

Isobe, Masaaki; Shizuya, Mitsuyuki; Takayama-Muromachi, Eiji

2007-01-01

We have studied crystal structure and physical properties of a new layered cobalt oxide (CaOH) 1.14 CoO 2 . The compound is a composite crystal which consists of two interpenetrating subsystems of the CdI 2 -type CoO 2 layer and the rock-salt-type double CaOH atomic layer. The two subsystems have incommensurate periodicity along the a-axis, resulting in modulated crystal structure due to the inter-subsystem interaction. We found that the observed physical properties originate in the electronic state with a 'low-carrier-density limit' in the cobalt t 2g band

Urchin-Like Ni1/3Co2/3(CO3)1/2(OH)·0.11H2O for Ultrahigh-Rate Electrochemical Supercapacitors: Structural Evolution from Solid to Hollow.

Science.gov (United States)

Wei, Wutao; Cui, Shizhong; Ding, Luoyi; Mi, Liwei; Chen, Weihua; Hu, Xianluo

2017-11-22

Portable electronics and electric or hybrid electric vehicles are developing in the trend of fast charge and long electric mileage, which ask us to design a novel electrode with sufficient electronic and ionic transport channels at the same time. Herein, we fabricate a uniform hollow-urchin-like Ni 1/3 Co 2/3 (CO 3 ) 1/2 (OH)·0.11H 2 O electrode material through an easy self-generated and resacrificial template method. The one-dimensional chain-like crystal structure unit containing the metallic bonding and the intercalated OH - and H 2 O endow this electrode material with abundant electronic and ionic transport channels. The hollow-urchin-like structure built by nanorods contributes to the large electrode-electrolyte contact area ensuring the supply of ions at high current. CNTs are employed to transport electrons between electrode material and current collector. The as-assembled NC-CNT-2//AC supercapacitor device exhibits a high specific capacitance of 108.3 F g -1 at 20 A g -1 , a capacitance retention ratio of 96.2% from 0.2 to 20 A g -1 , and long cycle life. Comprehensive investigations unambiguously highlight that the unique hollow-urchin-like Ni 1/3 Co 2/3 (CO 3 ) 1/2 (OH)·0.11H 2 O electrode material would be the right candidate for advanced next-generation supercapacitors.

Structural change of NaO1/2-WO3-NbO5/2-LaO3/2-PO5/2 glass induced by electrochemical substitution of sodium ions with protons.

Science.gov (United States)

Ishiyama, Tomohiro; Yamaguchi, Takuya; Nishii, Junji; Yamashita, Toshiharu; Kawazoe, Hiroshi; Kuwata, Naoaki; Kawamura, Junichi; Omata, Takahisa

2015-05-28

Structural changes of 35NaO1/2-1WO3-8NbO5/2-5LaO3/2-51PO5/2 glass (1W-glass) before and after the electrochemical substitution of sodium ions with protons by alkali-proton substitution (APS) are studied by Raman and (31)P magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopies. The glass before APS consists of (PO3(-))8.6(P2O7(4-)) chains on average and the terminal Q(1) units (-O-PO3(3-)) are bound to MO6 octahedra (M denotes niobium or tungsten) through P-O-M bonds. Some non-bridging oxygens (NBOs) in the MO6 octahedra are present in addition to the bridging oxygens (BOs) in P-O-M bonds. APS induces fragmentation of the phosphate chains because the average chain length decreases to (PO3(-))3.7(P2O7(4-)) after APS, despite the total number of modifier cations of sodium and lanthanum ions and protons being unaffected by APS. This fragmentation is induced by some of the NBOs in the MO6 octahedra before APS, changing to BOs of the newly formed M-O-P bonds after APS, because of the preferential formation of P-OH bonds over M-OH ones in the present glass. We show that APS under the conditions used here is not a simple substitution of sodium ions with protons, but it is accompanied by the structural relaxation of the glass to stabilize the injected protons.

Syntheses and structural characterization of vanado-tellurites and vanadyl-selenites: SrVTeO{sub 5}(OH), Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}, Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O and Ba{sub 2}VSe{sub 3}O{sub 10}

Energy Technology Data Exchange (ETDEWEB)

Konatham, Satish; Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in

2017-05-15

Four new quaternary vanado-tellurites and vanadyl-selenites, namely, SrVTeO{sub 5}(OH)(1), Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}(2), Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O(3) and Ba{sub 2}VSe{sub 3}O{sub 10}(4) have been synthesized and structurally characterized by single crystal X-ray diffraction. The oxidation state of vanadium is +5 in tellurites 1 and 2 and +4 in selenites 3 and 4. The structures of SrVTeO{sub 5}(OH)(1) and Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}(2) compounds consist of (VTeO{sub 5}(OH)){sup 2-} and (V{sub 2}Te{sub 2}O{sub 11}){sup 4-}anionic chains respectively, which are built from tetrahedral VO{sub 4} and disphenoidal TeO{sub 4} moieties. Similarly the structures of Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O(3) and Ba{sub 2}VSe{sub 3}O{sub 10}(4) respectively contain (VSe{sub 2}O{sub 7}){sup 2-} and (VSe{sub 3}O{sub 10}){sup 4-} anionic chains, which are made up of octahedral VO{sub 6} and pyramidal SeO{sub 3} units. Compounds 1 and 3 have been characterized by thermogravimetric and infrared spectroscopic methods. Compounds 1 and 2 are wide band gap semiconductors. - Graphical abstract: Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O and Ba{sub 2}VSe{sub 3}O{sub 10} compounds contain (VSe{sub 2}O{sub 7}){sup 2-} and (VSe{sub 3}O{sub 10}){sup 4-} chains. - Highlights: • Four new vanado-tellurites and vanadyl-selenites are synthesized. • Their structural features are different. • The vanado-tellurites are wide band gap semiconductors.

Highly Depleted Ethane and Slightly Depleted Methanol in Comet 21P/Giacobini-Zinner: Application of Empirical g-Factors for CH3OH Near 50K

Science.gov (United States)

DiSanti, Michael A.; Bonev, Boncho P.; Mumma, Michael J.; Villanueva, Geronimo L.

2010-01-01

We report high resolution (lambda/delta lambda approximately 24,000) observations of Comet 21 P/Giacobini-Zinner (21P) between approximately 2.85 -- 3.54 micrometers, obtained with NIRSPEC at Keck 2 on UT 2005 June 03 (R(sub h) = 1.12 AU, delta = 1.45 AU). These simultaneously sampled multiple emissions from the v7 band of C2H6 and the v2 and v3 bands of CH3OH, together with several hot bands of H2O, permitting a direct measure of parent volatile abundances in 21P. Our spectra reveal highly depleted C2H6 (0.13-0.14 percent relative to H2O) and CH3OH/C2H6 approximately 10, consistent with previously published abundances from observations in the IR [1,2] and millimeter sub-mm (reporting CH3OH/H2O [3]) during its previous apparition in 1998. We observed similarly high CH3OH/C2H6, and also similar rotational temperature to that measured for 21 P, in Comet 8P/Tuttle [4,5]. We used our (higher signal-to-noise) NIRSPEC observations of 8P to produce effective (empirical) CH3OH g-factors for several lines in the v2 band. These will be presented together with interpretation of our results, including constraints on the spin temperature of water. We acknowledge support from the NASA Planetary Atmospheres, Planetary Astronomy, and Astrobiology Programs and from the NSF Astronomy and Astrophysics Research Grants Program.

Facile fabrication of flower like self-assembled mesoporous hierarchical microarchitectures of In(OH){sub 3} and In{sub 2}O{sub 3}: In(OH){sub 3} micro flowers with electron beam sensitive thin petals

Energy Technology Data Exchange (ETDEWEB)

Arul Prakasam, Balasubramaniam, E-mail: arul7777@yahoo.com [Laboratory of Green Chemistry, School of Engineering Science, Lappeenranta University of Technology, Sammonkatu 12, FI-50130, Mikkeli (Finland); Lahtinen, Manu; Peuronen, Anssi [Department of Chemistry, Laboratories of Inorganic and Analytical Chemistry, P.O. Box 35, FI-40014, University of Jyväskylä (Finland); Muruganandham, Manickavachagam [Department of Civil and Environmental Engineering, Temple University, Philadelphia, PA, 19122 (United States); Sillanpää, Mika [Laboratory of Green Chemistry, School of Engineering Science, Lappeenranta University of Technology, Sammonkatu 12, FI-50130, Mikkeli (Finland)

2016-12-01

A template and capping-reagent free facile fabrication method for mesoporous hierarchical microarchitectures of flower-like In(OH){sub 3} particles under benign hydrothermal conditions is reported. Calcination of In(OH){sub 3} to In{sub 2}O{sub 3} with the retention of morphology is also described. Both In(OH){sub 3} and In{sub 2}O{sub 3} microstructures were analyzed with SEM, EDX, TEM and powder X-ray diffraction. The crystal sizes for In(OH){sub 3} and In{sub 2}O{sub 3} were calculated using the Scherrer equation. In In(OH){sub 3} the thin flakes at the periphery of micro flowers were electron beam sensitive. The mechanism of self-assembly process was analyzed as well. - Highlights: • Hydrothermal fabrication In(OH){sub 3} self-assembled porous hierarchical architectures. • Induced dehydration in beam sensitive In(OH){sub 3} micro flowers. • Calcination of In(OH){sub 3} to In{sub 2}O{sub 3} with the retention of flower like morphology. • Phase pure synthesis of In{sub 2}O{sub 3} with the average crystal size of ∼37 nm.

CFA-2 and CFA-3 (Coordination Framework Augsburg University-2 and -3); novel MOFs assembled from trinuclear Cu(I)/Ag(I) secondary building units and 3,3',5,5'-tetraphenyl-bipyrazolate ligands.

Science.gov (United States)

Grzywa, Maciej; Geßner, Christof; Denysenko, Dmytro; Bredenkötter, Björn; Gschwind, Fabienne; Fromm, Katharina M; Nitek, Wojciech; Klemm, Elias; Volkmer, Dirk

2013-05-21

The syntheses of H2-phbpz, [Cu2(phbpz)]·2DEF·MeOH (CFA-2) and [Ag2(phbpz)] (CFA-3) (H2-phbpz = 3,3',5,5'-tetraphenyl-1H,1'H-4,4'-bipyrazole) compounds and their crystal structures are described. The Cu(I) containing metal-organic framework CFA-2 crystallizes in the tetragonal crystal system, within space group I4(1)/a (no. 88) and the following unit cell parameters: a = 30.835(14), c = 29.306(7) Å, V = 27 865(19) Å(3). CFA-2 features a flexible 3-D three-connected two-fold interpenetrated porous structure constructed of triangular Cu(I) subunits. Upon exposure to different kinds of liquids (MeOH, EtOH, DMF, DEF) CFA-2 shows pronounced breathing effects. CFA-3 crystallizes in the monoclinic crystal system, within space group P2(1)/c (no. 14) and the following unit cell parameters: a = 16.3399(3), b = 32.7506(4), c = 16.2624(3) Å, β = 107.382(2)°, V = 8305.3(2) Å(3). In contrast to the former compound, CFA-3 features a layered 2-D three-connected structure constructed from triangular Ag(i) subunits. Both compounds are characterized by elemental and thermogravimetric analyses, single crystal structure analysis and X-ray powder diffraction, FTIR- and fluorescence spectroscopy. Preliminary results on oxygen activation in CFA-2 are presented and potential improvements in terms of framework robustness and catalytic efficiency are discussed.

Peptide Fraction pOh2 Exerts Antiadipogenic Activity through Inhibition of C/EBP-α and PPAR-γ Expression in 3T3-L1 Adipocytes

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Thi Tuyet Nhung Nguyen

2017-01-01

Full Text Available Many studies have comprehensively examined the venom of Ophiophagus hannah snake. Its venom comprises different compounds exhibiting a wide range of pharmacological activities. In this investigation, four peptide fractions (PFs, ranging from 3 kDa to 10 kDa, isolated from the Vietnamese snake venom of O. hannah were separated by HPLC and investigated for their inhibitory activity on adipogenesis in 3T3-L1 adipocytes. The most effective PF was then further purified, generating two peptides, pOh1 and pOh2. Upon investigation of these two peptides on 3T3-L1 adipocytes, it was revealed that, at 10 μg/mL, pOh2 was able to inhibit the lipid accumulation in 3T3-L1 adipocytes by up to 56%, without affecting cell viability. Furthermore, the pOh2 downregulated the gene expression of important transcription factors C/EBP-α and PPAR-γ. In addition, aP2 and GPDH adipocyte-specific markers were also significantly reduced compared to untreated differentiated cells. Taken together, pOh2 inhibited the expression of key transcription factors C/EBP-α and PPAR-γ and their target genes, aP2 and GPDH, thereby blocking the adipocyte differentiation. In conclusion, this novel class of peptide might have potential for in vivo antiobesity effects.

Hydrothermal synthesis, structures and optical properties of A2Zn3(SeO3)4·XH2O (A=Li, Na, K; X=2 or 0)

Science.gov (United States)

Liu, Yunsheng; Mei, Dajiang; Xu, Jingli; Wu, Yuandong

2015-12-01

New alkali metal zinc selenites, A2Zn3(SeO3)4·XH2O (A=Li, Na, K; X=2 or 0) were prepared through hydrothermal reactions. Li2Zn3(SeO3)4·2H2O (1) crystallizes in the monoclinic space group P21/c with lattice parameters a=8.123(4), b=9.139(4), c=7.938(3) Å, β=112.838(9)°. Na2Zn3(SeO3)4·2H2O (2) crystallizes in the monoclinic space group C2/c with lattice parameters a=15.7940(18), b=6.5744(8), c=14.6787(17) Å, β=107.396(3)°. K2Zn3(SeO3)4 (3) crystallizes in the monoclinic space group C2/c with lattice parameters a=11.3584(12), b=8.6091(9), c=13.6816(14) Å, β=93.456(2)°. The anionic structures are composed of [Zn3O12]18- sheets, chains, and "isolated" units in compound 1, 2, 3, respectively, and trigonal pyramids SeO32-. The compounds were characterized by the solid state UV-vis-NIR diffuse reflectance spectroscopy, infrared spectra and thermogravimetric analysis.

o-Iminobenzosemiquinonate and o-imino-p-methylbenzosemiquinonate anion radicals coupled VO2+ stabilization.

Science.gov (United States)

Roy, Amit Saha; Saha, Pinaki; Adhikary, Nirmal Das; Ghosh, Prasanta

2011-03-21

The diamagnetic VO(2+)-iminobenzosemiquinonate anion radical (L(R)(IS)(•-), R = H, Me) complexes, (L(-))(VO(2+))(L(R)(IS)(•-)): (L(1)(-))(VO(2+))(L(H)(IS)(•-))•3/2MeOH (1•3/2MeOH), (L(2)(-))(VO(2+))(L(H)(IS)(•-)) (2), and (L(2)(-))(VO(2+))(L(Me)(IS)(•-))•1/2 L(Me)(AP) (3•1/2 L(Me)(AP)), incorporating tridentate monoanionic NNO-donor ligands {L = L(1)(-) or L(2)(-), L(1)H = (2-[(phenylpyridin-2-yl-methylene)amino]phenol; L(2)H = 1-(2-pyridylazo)-2-naphthol; L(H)(IS)(•-) = o-iminobenzosemiquinonate anion radical; L(Me)(IS)(•-) = o-imino-p-methylbenzosemiquinonate anion radical; and L(Me)(AP) = o-amino-p-methylphenol} have been isolated and characterized by elemental analyses, IR, mass, NMR, and UV-vis spectra, including the single-crystal X-ray structure determinations of 1•3/2MeOH and 3•1/2 L(Me)(AP). Complexes 1•3/2MeOH, 2, and 3•1/2 L(Me)(AP) absorb strongly in the visible region because of intraligand (IL) and ligand-to-metal charge transfers (LMCT). 1•3/2MeOH is luminescent (λ(ext), 333 nm; λ(em), 522, 553 nm) in frozen dichloromethane-toluene glass at 77 K due to π(diimine→)π(diimine)* transition. The V-O(phenolato) (cis to the V═O) lengths, 1.940(2) and 1.984(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP) are consistent with the VO(2+) description. The V-O(iminosemiquinonate) (trans to the V═O) lengths, 2.1324(19) in 1•3/2MeOH and 2.083(2) Å in 3•1/2 L(Me)(AP), are expectedly ∼0.20 Å longer due to the trans influence of the V═O bond. Because of the stronger affinity of the paramagnetic VO(2+) ion to the L(H)(IS)(•-) or L(Me)(IS)(•-), the V-N(iminosemiquinonate) lengths, 1.908(2) and 1.921(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP), are unexpectedly shorter. Density functional theory (DFT) calculations using B3LYP, B3PW91, and PBE1PBE functionals on 1 and 2 have established that the closed shell singlet (CSS) solutions (VO(3+)-amidophenolato (L(R)(AP)(2-)) coordination) of these

A theoretical study of the H-abstraction reactions from HOI by moist air radiolytic products (H, OH, and O (3P)) and iodine atoms (2P(3/2)).

Science.gov (United States)

Hammaecher, Catherine; Canneaux, Sébastien; Louis, Florent; Cantrel, Laurent

2011-06-23

The rate constants of the reactions of HOI molecules with H, OH, O ((3)P), and I ((2)P(3/2)) atoms have been estimated over the temperature range 300-2500 K using four different levels of theory. Geometry optimizations and vibrational frequency calculations are performed using MP2 methods combined with two basis sets (cc-pVTZ and 6-311G(d,p)). Single-point energy calculations are performed with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (pertubatively) electron excitations CCSD(T) using the cc-pVTZ, cc-pVQZ, 6-311+G(3df,2p), and 6-311++G(3df,3pd) basis sets. Reaction enthalpies at 0 K were calculated at the CCSD(T)/cc-pVnZ//MP2/cc-pVTZ (n = T and Q), CCSD(T)/6-311+G(3df,2p)//MP2/6-311G(d,p), and CCSD(T)/6-311++G(3df,3pd)//MP2/6-311G(d,p) levels of theory and compared to the experimental values taken from the literature. Canonical transition-state theory with an Eckart tunneling correction is used to predict the rate constants as a function of temperature. The computational procedure has been used to predict rate constants for H-abstraction elementary reactions because there are actually no literature data to which the calculated rate constants can be directly compared. The final objective is to implement kinetics of gaseous reactions in the ASTEC (accident source term evaluation code) program to improve speciation of fission products, which can be transported along the reactor coolant system (RCS) of a pressurized water reactor (PWR) in the case of a severe accident.

An open-framework three-dimensional indium oxalate: [In(OH)(C2O4)(H2O)]3.H2O

International Nuclear Information System (INIS)

Yang Sihai; Li Guobao; Tian Shujian; Liao Fuhui; Lin Jianhua

2005-01-01

By hydrothermal reaction of In 2 O 3 with H 2 C 2 O 4 .2H 2 O in the presence of H 3 BO 3 at 155 deg. C, an open-framework three-dimensional indium oxalate of formula [In(OH)(C 2 O 4 )(H 2 O)] 3 .H 2 O (1) has been obtained. The compound crystallizes in the trigonal system, space group R3c with a=18.668(3)A, c=7.953(2)A, V=2400.3(7)A 3 , Z=6, R 1 =0.0352 at 298K. The small pores in 1 are filled with water molecules. It loses its filled water at about 180 deg. C without the change of structure, then the bounded water at 260 deg. C, and completely decompounds at 324 deg. C. The residue is confirmed to be In 2 O 3

Carbon-14 immobilization via the CO2-Ba(OH)2 hydrate gas-solid reaction

International Nuclear Information System (INIS)

Haag, G.L.

1981-08-01

For the treatment of an air-based off-gas stream, the use of packed beds of Ba(OH) 2 .8H 2 O flakes to remove CO 2 has been demonstrated. However, the operating conditions must be maintained between certain upper and lower limits with respect to the partial pressure of water. If the water vapor pressure in the gas is less than the dissociation vapor pressure of Ba(OH) 2 .8H 2 O, the bed will deactivate. If the vapor pressure is considerably greater, pressure drop problems will increase with increaseing humidity as the particles curl and degrade. Results have indicted that when operated in the proper regime, the bulk of the increase in pressure drop results from the conversion of Ba(OH) 2 .8H 2 O to BaCO 3 and not from the hydration of the commercial Ba(OH) 2 .8H 2 O (i.e., Ba(OH) 2 .7.50H 2 O) to Ba(OH) 2 .8H 2 O

CaK2(AsO3OH)(H2O)2 cell length a | forthcoming | boms | Volumes ...

Indian Academy of Sciences (India)

Home; public; Volumes; boms; forthcoming; CaK2(AsO3OH)(H2O)2 cell length a. 404! error. The page your are looking for can not be found! Please check the link or use the navigation bar at the top. YouTube; Twitter; Facebook; Blog. Academy News. IAS Logo. 29th Mid-year meeting. Posted on 19 January 2018. The 29th ...

Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H{sub 2}O and OH(D{sub 2}O){sub n} (n = 1-3)

Energy Technology Data Exchange (ETDEWEB)

Hernandez, Federico J. [Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States); INFIQC, Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Centro Láser de Ciencias Moleculares, Universidad Nacional de Córdoba, Ciudad Universitaria, Pabellón, X5000HUA Córdoba (Argentina); Brice, Joseph T.; Leavitt, Christopher M.; Liang, Tao; Douberly, Gary E., E-mail: douberly@uga.edu [Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States); Raston, Paul L. [Department of Chemistry and Biochemistry, James Madison University, Harrisonburg, Virginia 22807 (United States); Pino, Gustavo A. [INFIQC, Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Centro Láser de Ciencias Moleculares, Universidad Nacional de Córdoba, Ciudad Universitaria, Pabellón, X5000HUA Córdoba (Argentina)

2015-10-28

Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H{sub 2}O and OH(D{sub 2}O){sub n} clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H{sub 2}O and OH–D{sub 2}O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D{sub 2}O){sub 2}, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D{sub 2}O molecules are observed shifted approximately 300 cm{sup −1} to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D{sub 2}O){sub 3}.

Modelling of the solid state electrochromic system WO/sub 3//HSbO/sub 3/ x 2H/sub 2/O/Ni(OH)/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Lagzdons, J L; Bajars, G E; Lusis, A R [AN Litovskoj SSR, Vilnyus. Inst. Fiziki Poluprovodnikov

1984-08-16

The problem of compatibility of electrochromic materials (ECM) with the solid electrolyte and the selection of solid electrolytes has been studied by means of modelling. The model electrochromic system (ECS) containing cathodically coloring ECM (WO/sub 3/), anodically coloring ECM (Ni(OH)/sub 2/), and a solid proton electrolyte (HSbO/sub 3/ x 2H/sub 2/O), as well as ECS containing H/sub x/WO/sub 3/ as counterelectrode has been investigated by the aid of cyclic voltammograms. Results show the compatibility of both the cathodic (WO/sub 3/) and anodic (Ni(OH)/sub 2/) ECM with solid proton electrolyte. Effective electrochromic devices can be worked out on their basis.

Structure and crystallization kinetics of Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses

Energy Technology Data Exchange (ETDEWEB)

Cheng Yin [College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082 (China); Xiao Hanning [College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082 (China)]. E-mail: zjbcy@126.com; Guo Wenming [College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082 (China); Guo Weiming [College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082 (China)

2006-05-15

The experimental IR (infrared spectra) and differential scanning calorimetry (DSC) curves of Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses, containing 30-60 mol% Bi{sub 2}O{sub 3}, have been investigated in the article. The composition dependence of IR absorption suggests that addition of Bi{sub 2}O{sub 3} results in a change in the short-range order structure of the borate matrix. The increase of Bi{sub 2}O{sub 3} content causes a progressive conversion of [BO{sub 3}] to [BO{sub 4}] units. Bi{sub 2}O{sub 3}, in the form of [BiO{sub 6}] octahedral units, plays the role of glass former. The crystallization kinetics of Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses were described by thermal stability indexes (k {sub gl}, {delta}T), activation energy (E) for crystallization and numerical factors(n, m) depending on the nucleation process and growth morphology, which were calculated by Satava method and the modified Ozawa-Chen method. When Bi{sub 2}O{sub 3} {<=} 45 mol%, the increase of Bi{sub 2}O{sub 3} tends to improve the thermal stabilities of the glasses. In this case, k {sub gl} may be more suitable for estimating the glass thermal stability in above composition range than {delta}T. A further increase of Bi{sub 2}O{sub 3} content will increase the crystallization trends of investigated glasses. Two possible kinds of growth mechanisms were involved in Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses: one-dimensional growth and two-dimensional growth. Moreover, structures of crystallized glasses were observed by X-ray diffraction (XRD). BiBO{sub 3} crystal with special non-linear optical properties can be obtained when Bi{sub 2}O{sub 3} {>=} 50 mol%.

Cross sections for Scattering and Mobility of OH- and H3 O+ ions in H2 O

Science.gov (United States)

Petrovic, Zoran; Stojanovic, Vladimir; Maric, Dragana; Jovanovic, Jasmina

2016-05-01

Modelling of plasmas in liquids and in biological and medical applications requires data for scattering of all charged and energetic particles in water vapour. We present swarm parameters for OH- and H3 O+, as representatives of principal negative and positive ions at low pressures in an attempt to provide the data that are not yet available. We applied Denpoh-Nanbu procedure to calculate cross section sets for collisions of OH- and H3 O+ ions with H2 O molecule. Swarm parameters for OH- and H3 O+ ions in H2 O are calculated by using a well tested Monte Carlo code for a range of E / N(E -electric field, N-gas density) at temperature T = 295 K, in the low pressure limit. Non-conservative processes were shown to strongly influence the transport properties even for OH- ions above the average energy of 0.2 eV(E / N >200 Td). The data are valid for low pressure water vapour or small amounts in mixtures. They will provide a basis for calculating properties of ion-water molecule clusters that are most commonly found at higher pressures and for modelling of discharges in liquids. Acknowledgment to Ministry of Education, Science and Technology of Serbia.

Pharmacokinetics of 1,25(OH)(2)D(3) and 1alpha(OH)D(3) in normal and uraemic men

DEFF Research Database (Denmark)

Brandi, Lisbet; Egfjord, Martin; Olgaard, Klaus

2002-01-01

,25(OH)(2)D(3) (n=6) protocol. RESULTS: After oral administration of 1,25(OH)(2)D(3) the bioavailability of 1,25(OH)(2)D(3) was 70.6+/-5.8/72.2+/-4.8% in healthy volunteers/uraemic patients (n.s.). After i.v. administration the volume of distribution of 1,25(OH)(2)D(3) was similar, 0.49+/-0.14 vs 0...

Pulse radiolytic study of the reaction OH + O3 in aqueous medium

International Nuclear Information System (INIS)

Sehested, K.; Holcman, J.; Bjergbakke, E.; Hart, E.J.

1984-01-01

In slightly alkaline solution the ozonide radical ion, O 3 - , forms as a product of the hydroxyl radical reaction with ozone. For each O 3 - formed, two O 3 molecules are consumed. In acid solution the product of this reaction is the perhydroxyl radical, HO 2 , formed from one O 3 molecule. Our results are consistent with the gas-phase reaction where the products are HO 2 and O 2 . A rate constant of (1.1 +/- 0.2) x 10 8 dm 3 mol -1 s -1 is found for the reaction OH + O 3 → HO 2 + O 2 . This rate constant was obtained by three systems, by buildup of O 3 - in basic solutions, by competition of the OH radical with the carbonate ion, and directly by O 3 consumption in acid solution. The rate constant for the reaction of HO 2 with O 3 is very low, 4 dm 3 mol -1 s -1 . At pH greater than or equal to 1, HO 2 reacts with O 3 preferentially in its dissociated form, O 2 - . No spectroscopic evidence has been found for the HO 3 and HO 4 free-radical intermediates. 24 references, 4 figures, 2 tables

B2O3/SiO2 substitution effect on structure and properties of Na2O-CaO-SrO-P2O5-SiO2 bioactive glasses from molecular dynamics simulations.

Science.gov (United States)

Ren, Mengguo; Lu, Xiaonan; Deng, Lu; Kuo, Po-Hsuen; Du, Jincheng

2018-05-23

The effect of B2O3/SiO2 substitution in SrO-containing 55S4.3 bioactive glasses on glass structure and properties, such as ionic diffusion and glass transition temperature, was investigated by combining experiments and molecular dynamics simulations with newly developed potentials. Both short-range (such as bond length and bond angle) and medium-range (such as polyhedral connection and ring size distribution) structures were determined as a function of glass composition. The simulation results were used to explain the experimental results for glass properties such as glass transition temperature and bioactivity. The fraction of bridging oxygen increased linearly with increasing B2O3 content, resulting in an increase in overall glass network connectivity. Ion diffusion behavior was found to be sensitive to changes in glass composition and the trend of the change with the level of substitution is also temperature dependent. The differential scanning calorimetry (DSC) results show a decrease in glass transition temperature (Tg) with increasing B2O3 content. This is explained by the increase in ion diffusion coefficient and decrease in ion diffusion energy barrier in glass melts, as suggested by high-temperature range (above Tg) ion diffusion calculations as B2O3/SiO2 substitution increases. In the low-temperature range (below Tg), the Ea for modifier ions increased with B2O3/SiO2 substitution, which can be explained by the increase in glass network connectivity. Vibrational density of states (VDOS) were calculated and show spectral feature changes as a result of the substitution. The change in bioactivity with B2O3/SiO2 substitution is discussed with the change in pH value and release of boric acid into the solution.

In(OH){sub 3} and In{sub 2}O{sub 3} nanorice and microflowers: morphology transformation and optical properties

Energy Technology Data Exchange (ETDEWEB)

Ren Weian; Liu Ying; Mei Zongwei; Wen Xiaogang, E-mail: wenxg2001@163.com [Sichuan University, School of Materials Science and Engineering (China); Wang Suhua [Chinese Academy of Sciences, Institute of Intelligent Machines (China)

2013-02-15

In this work, In(OH){sub 3} and In{sub 2}O{sub 3} nanostructures with controllable complex morphologies were successfully synthesized through a simple hydrothermal process followed by annealing. The In(OH){sub 3} nanostructures were synthesized using urea as the alkaline source at a relatively low temperature without any templates or surfactants. The morphology transformation of In(OH){sub 3} from nanorice to microflowers was observed. The In(OH){sub 3} nanorice are 180 nm in diameter and 550 nm in length, the microflowers are about 3 {mu}m in diameter and composed of thin nanoflakes with 4-nm thickness. In{sub 2}O{sub 3} with similar morphology was formed by annealing In(OH){sub 3} precursors. The nanostructures were characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Our results suggest that a new nucleation-growth-etching-regrowth mechanism can explain the morphology transformation from nanorice to flower-like frameworks. Raman spectrum and photoluminescence (PL) properties of In{sub 2}O{sub 3} were also measured, and a 3-nm blue-shift of PL spectrum was observed due to the thinness of the nanostructures.

Structure, spectra and thermal, mechanical, Faraday rotation properties of novel diamagnetic SeO2-PbO-Bi2O3-B2O3 glasses

Science.gov (United States)

Chen, Qiuling; Su, Kai; Li, Yantao; Zhao, Zhiwei

2018-06-01

Faraday rotation diamagnetic glass has attracted research attentions in photonics, sensing and magneto optical devices due to their high refractive index, wide transmittance in UV and Fourier transform infrared (FT-IR) range and temperature independent Faraday rotation. Selenite modified heavy metal oxides glasses with composition of xSeO2-(10-x) B2O3-45PbO-45Bi2O3 (x = 0, 1, 5 and 10mol%) and 15%SeO2-40%PbO-45%Bi2O3 have been fabricated by melt-quenching method in present study. The influence of SeO2 on glass forming ability, thermal, mechanical properties and Faraday rotation were evaluated through X-ray Diffraction (XRD), Fourier transforms infrared spectra (FT-IR), Raman, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), Vicker's hardness and Verdet constant measurements. XRD spectra reveal that the good vitrification was achieved for glass with SeO2 amounts ≤10% even without B2O3. FT-IR, Raman and XPS spectra ascertain the existence of characteristic vibration of SeO4, SeO3, PbO4, BiO3 and BO3 units. The incorporation of SeO2 increases the connectivity of glassy network by increasing the Tg, thermal stability and mechanical hardness. The small band gap, high polarizable Se4+ ions and isolated SeO3 units contribute to Faraday rotation improvement.

40 CFR 721.9662 - Thieno[3,4-b]-1,4-dioxin, 2,3-dihydro- (9CI).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Thieno[3,4-b]-1,4-dioxin, 2,3-dihydro... Specific Chemical Substances § 721.9662 Thieno[3,4-b]-1,4-dioxin, 2,3-dihydro- (9CI). (a) Chemical...-b]-1,4-dioxin, 2,3-dihydro- (9CI) (PMN P-95-1825; CAS No. 126213-50-1) is subject to reporting under...

Interaction of actinide ions with [NaP5W30O110]14- and [P2W18O62]6-

International Nuclear Information System (INIS)

Choppin, G.R.; Wall, D.E.

2003-01-01

Stability constants (log β 101 ) of Th 4+ , UO 2 2+ , NpO 2 + and Am 3+ with [NaP 5 W 30 O 110 ] 14- were determined by solvent extraction (μ = 0.1M NaCl) and found to be 6.18 ± 0.07, 3.80 ± 0.06, 2.98 ± 0.04, and 5.85 ± 0.05, respectively. The order of stability constants: Th 4+ > Am 3+ > UO 2 2+ > NpO 2 + is due to electrostatic repulsion between the actinyl oxygens and oxygens on the polyoxometalate surface. The order of stability constants for metal complexes with [P 2 W 18 O 62 ] 6- is Th 4+ > UO 2 2+ > Eu 3+ >NpO 2 + because the steric repulsion between actinyl oxygens and oxygens on polyoxometalate are less important. Enthalpies of complexation were measured by calorimetric titration of Th 4+ , UO 2 2+ , Nd 3+ with [NaP 5 W 30 O 110 ] 14- and [P 2 W 18 O 62 ] 6- . The results indicate that the conformation and charge distribution of the microscopic surface structures are important factors in the formation of pseudocolloids. (author)

Effect of Solids-To-Liquids, Na2SiO3-To-NaOH and Curing Temperature on the Palm Oil Boiler Ash (Si + Ca) Geopolymerisation System

Science.gov (United States)

Yahya, Zarina; Abdullah, Mohd Mustafa Al Bakri; Hussin, Kamarudin; Ismail, Khairul Nizar; Abd Razak, Rafiza; Sandu, Andrei Victor

2015-01-01

This paper investigates the effect of the solids-to-liquids (S/L) and Na2SiO3/NaOH ratios on the production of palm oil boiler ash (POBA) based geopolymer. Sodium silicate and sodium hydroxide (NaOH) solution were used as alkaline activator with a NaOH concentration of 14 M. The geopolymer samples were prepared with different S/L ratios (0.5, 1.0, 1.25, 1.5, and 1.75) and Na2SiO3/NaOH ratios (0.5, 1.0, 1.5, 2.0, 2.5, and 3.0). The main evaluation techniques in this study were compressive strength, X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscope (SEM). The results showed that the maximum compressive strength (11.9 MPa) was obtained at a S/L ratio and Na2SiO3/NaOH ratio of 1.5 and 2.5 at seven days of testing.

Structure and properties of CdO-B2O3 and CdO-MnO-B2O3 glasses; Criteria of getting the fraction of four coordinated boron atoms from infrared spectra

Science.gov (United States)

Doweidar, H.; El-Damrawi, G.; El-Stohy, Sh.

2017-11-01

IR spectra of CdO-B2O3 and xCdO·(50 - x)MnO·50B2O3 glasses (0 ≤ x ≤ 50 mol%) have been analyzed. The fraction N4 of four coordinated boron atoms obtained from the integrated area under the IR spectra of CdO-B2O3 glasses is markedly higher than the reported NMR values. In both cases, N4 does not change with CdO content. The difference between N4 values of both techniques has been correlated with the relative absorption coefficient of BO4 unit with respect to BO3 unit, as suggested by Chryssikos et al. N4 data of xCdO·(50 - x)MnO·50B2O3 glasses could be used to calculate the fraction of modifier and former CdO and MnO in the borate matrix, as a function of composition. There is a linear increase in both the density and molar volume with increasing CdO content. The change has been correlated with the contribution of CdO and MnO. Electric conduction is assumed to take place via hopping of small polarons. There is a decrease in conductivity with increasing CdO concentration, which suggests that the electrons related to Cd sites are more localized than those at Mn sites.

Structural, morphological and optical investigations on electron-beam irradiated PbF2-TeO2-B2O3-Eu2O3 glasses

Science.gov (United States)

Wagh, Akshatha; Petwal, Vikash; Dwivedi, Jishnu; Upadhyaya, V.; Raviprakash, Y.; Kamath, Sudha D.

2016-09-01

Combined structural, optical and morphological studies were carried out on Eu2O3 doped PbF2-TeO2-B2O3 glass samples, before and after being subjected to electron beam of energy 7.5 MeV. XRD confirmed the amorphous nature of the glasses even after 150 kGy electron beam irradiation. Densities of the irradiated samples showed slightly greater values when compared to their respective values before irradiation, which proved the increase in the compaction of the network. The intensities of the three prominent bands; B-O-B linkages, BO4 units and BO3 units of FT-IR spectra, of the titled glasses, showed slight decrease after electron beam irradiation. The decrement in the values of energy band gap and shift in cut-off wavelength towards red edge, proved the formation of color centers in the glass network after irradiation. The change in Hunter L values, through color measurement was a proof for the Farbe/color/absorption centers created in the glass sites after irradiation.

Syntheses and luminescence study for La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O (0≤x≤0.40) and the dehydrated products β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} (0≤x≤0.15)

Energy Technology Data Exchange (ETDEWEB)

Sun, Xiaorui; Zhou, Zhengyang; Yang, Haixia; Gao, Wenliang; Cong, Rihong, E-mail: congrihong@cqu.edu.cn; Yang, Tao, E-mail: taoyang@cqu.edu.cn

2016-05-15

La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O with the Eu{sup 3+}-doping upper limit of 40 atom% were synthesized hydrothermally. Thereafter, thermal treatments at 710 °C were applied to obtain β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9}. The solid solution range is even narrower, i.e. 0≤x≤0.15, due to the mismatch between La{sup 3+} and Eu{sup 3+}. The host borate system shows a typical concentration quenching effect at x=0.20 under CT excitation, and this is postponed to x=0.30 under the f−f excitation. β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} shows a very intense absorption of charge transfer, and gives strong red emissions at 615 nm with large R/O ratios (1.9–2.4). The saturation effect appears at x=0.11, which is probably due to the lattice distortion. Eu{sup 3+} luminescence was applied as the structural probe to study the local coordination environment change during the dehydration and re-crystallization processes of La{sub 0.93}Eu{sub 0.07}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O. - Highlights: • La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O (0≤x≤0.40) were prepared by hydrothermal method. • The Eu{sup 3+}-doping limit in β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} is 15 atom% proved by powder XRD. • La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O show relatively weaker red emissions. • β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} shows an intense CT absorption together with strong red emissions. • Eu{sup 3+} luminescence was studied when annealing La{sub 0.93}Eu{sub 0.07}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O.

Quenching of I(2P1/2) by O3 and O(3P).

Science.gov (United States)

Azyazov, Valeriy N; Antonov, Ivan O; Heaven, Michael C

2007-04-26

Oxygen-iodine lasers that utilize electrical or microwave discharges to produce singlet oxygen are currently being developed. The discharge generators differ from conventional chemical singlet oxygen generators in that they produce significant amounts of atomic oxygen. Post-discharge chemistry includes channels that lead to the formation of ozone. Consequently, removal of I(2P1/2) by O atoms and O3 may impact the efficiency of discharge driven iodine lasers. In the present study, we have measured the rate constants for quenching of I(2P1/2) by O(3P) atoms and O3 using pulsed laser photolysis techniques. The rate constant for quenching by O3, (1.8 +/- 0.4) x 10(-12) cm3 s-1, was found to be a factor of 5 smaller than the literature value. The rate constant for quenching by O(3P) was (1.2 +/- 0.2) x 10(-11) cm3 s-1.

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO_2(CH_3SO_3)_2, UO_2(CH_3SO_3)_2, ReO_3(CH_3SO_3), VO(CH_3SO_3)_2, and V_2O_3(CH_3SO_3)_4 and their thermal decomposition under N_2 and O_2 atmosphere

International Nuclear Information System (INIS)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S.

2011-01-01

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO_3, UO_2(CH_3COO)_2.2 H_2O, Re_2O_7(H_2O)_2, and V_2O_5 with CH_3SO_3H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO_2(CH_3SO_3)_2 (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm"3, Z=8) contains [MoO_2] moieties connected by [CH_3SO_3] ions to form layers parallel to (100). UO_2(CH_3SO_3)_2 (P2_1/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) "c"i"r"c"l"e, V=1.8937(3) nm"3, Z=8) consists of linear UO_2"2"+ ions coordinated by five [CH_3SO_3] ions, forming a layer structure. VO(CH_3SO_3)_2 (P2_1/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) "c"i"r"c"l"e, V=0.8290(2) nm"3, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO_3(CH_3SO_3) (P anti 1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2) "c"i"r"c"l"e, V=1.1523(4) nm"3, Z=8) a chain structure exhibiting infinite O-[ReO_2]-O-[ReO_2]-O chains is formed. Each [ReO_2]-O-[ReO_2] unit is coordinated by two bidentate [CH_3SO_3] ions. V_2O_3(CH_3SO_3)_4 (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm"3, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH_3SO_3] ligands. Additional methanesulfonate ions connect the [V_2O_3] groups along [001]. Thermal decomposition of the compounds was monitored under N_2 and O_2 atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N_2 the decomposition proceeds with reduction of the metal leading to the oxides MoO_2, U_3O_7, V_4O_7, and VO_2; for MoO_2(CH_3SO_3)_2, a small amount of MoS_2 is formed. If the thermal decomposition is carried out in a atmosphere of O_2 the oxides MoO_3 and V_2O_5 are formed. (Copyright copyright 2011 WILEY-VCH Verlag

Synthesis and crystal structure of Bi6.4Pb0.6P2O15.2

International Nuclear Information System (INIS)

Arumugam, N.; Lynch, V.; Steinfink, H.

2007-01-01

Bi 6.4 Pb 0.6 P 2 O 15.2 is a polymorph of structures with the general stoichiometry Bi 6+x M 1-x P 2 O 15+y . However, unlike previously published structures that consist of layers formed by edge sharing OBi 4 tetrahedra bridged by PO 4 and TO 6 (T=transition metal) tetrahedra and octahedra the title compound's structure is more complex. It is monoclinic, C2, a=19.4698(4) A, b=11.3692(3) A, c=16.3809(5) A, β=101.167(1) o , Z=10. Single-crystal X-ray diffraction data were refined by least squares on F 2 converging to R 1 =0.0387, wR 2 =0.0836 for 7023 intensities. The crystal twins by mirror reflection across (001) as the twin plane and twin component 1 equals 0.74(1). Oxygen ions are in tetrahedral coordination to four metal ions and the O(BiPb) 4 units share corners to form layers that are part of the three-dimensional framework. Eight oxygen ions form a cube around the two crystallographically independent Pb ions. Pb-O bond lengths vary from 2.265(14) to 2.869(14) A. Pairs of such cubes share an edge to form a Pb 3 O 20 unit. The two oxygen ions from the unshared edges are part of irregular Bi polyhedra. Other oxygen ions of Bi polyhedra are part only of O(BiPb) 4 units, and some oxygen ions of the polyhedra are also part of PO 4 tetrahedra. One, two, three and or four PO 4 moieties are connected to the Bi polyhedra. Bi-O bond lengths ≤3.1 A vary from 2.090(12) to 3.07(3) A. The articulations of Pb cubes, Bi polyhedra and PO 4 tetrahedra link into the three-dimensional structure. - Graphical abstract: View of the structure of Bi 6.4 Pb 0.6 P 2 O 15.2 parallel to the b-axis

pO2 and pCO2 increment in post-dialyzer blood: the role of dialysate.

Science.gov (United States)

Sombolos, Kostas I; Bamichas, Gerasimos I; Christidou, Fotini N; Gionanlis, Lazaros D; Karagianni, Anna C; Anagnostopoulos, Theodoros C; Natse, Taïsir A

2005-11-01

Blood returning from a dialyzer during hemodialysis has a higher pO2 and pCO2 content than blood entering the dialyzer, and this has been attributed to the dialysate. The present study investigates this phenomenon. Acid-base and blood-gas parameters (pH, pO2, pCO2 and HCO3) were measured in three groups of stable chronic hemodialysis patients (A, B, and C) undergoing high-flux hemodialysis. In group A (n = 15), "arterial" (a) and "venous" (v) samples were withdrawn simultaneously before dialysis (samples A0), 5 min after circulation of the blood with the dialysate in the by-pass mode (samples A5), and 5 min after high-flux hemodialysis at a zero ultrafiltration rate (samples A10). In group B (n = 11) (a) and (v) samples were withdrawn simultaneously before dialysis (samples B0), 5 min after isolated-ultrafiltration with closed dialysate ports ("isolated-closed" ultrafiltration) (samples B5), and 5 min after high-flux hemodialysis at a zero ultrafiltration rate (samples B10). In group C (n = 14), after an initial arterial blood sample withdrawal before hemodialysis (sample C0), high-flux hemodialysis at a zero ultrafiltration rate was initiated. Five minutes later, blood and dialysate samples were withdrawn simultaneously from the hemodialysis lines (samples C5). In all cases blood and dialysate (bicarbonate) flow rates were set at 0.300 and 0.700 L/min, respectively. FLX-18 hemodialyzers (membrane PEPA 1.8 m2) were used in this study. Analysis of variance revealed significant changes only in venous samples. A comparison of arterial and venous samples revealed no differences between groups A and B before the initiation of dialysis (A0a vs. A0v and B0a vs. B0v, P = NS). The pO2 content was higher in A5v samples than in A5a samples (83.5 +/- 11.2 vs. 88.8 +/- 14.0 mm Hg, P pO2, pCO2, and HCO3 in comparison to A10v samples (P pO2 and pCO2 values in A5v and A10v samples increased by 6.3% and 12.1% and by 1.29% and 52% in comparison to corresponding values of A5a and A10

Preparation of Zr(Mo,W)2O8 with a larger negative thermal expansion by controlling the thermal decomposition of Zr(Mo,W)2(OH,Cl)2∙2H2O.

Science.gov (United States)

Petrushina, Mariya Yu; Dedova, Elena S; Filatov, Eugeny Yu; Plyusnin, Pavel E; Korenev, Sergei V; Kulkov, Sergei N; Derevyannikova, Elizaveta A; Sharafutdinov, Marat R; Gubanov, Alexander I

2018-03-28

Solid solutions of Zr(Mo,W) 2 O 7 (OH,Cl) 2 ∙2H 2 O with a preset ratio of components were prepared by a hydrothermal method. The chemical composition of the solutions was determined by energy dispersive X-ray spectroscopy (EDX). For all the samples of ZrMo x W 2-x O 7 (OH,Cl) 2 ∙2H 2 O (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, and 2.0), TGA and in situ powder X-ray diffraction (PXRD) studies (300-1100 K) were conducted. For each case, the boundaries of the transformations were determined: Zr(Mo,W) 2 O 7 (OH,Cl) 2 ∙2H 2 O → orthorhombic-ZrMo x W 2-x O 8 (425-525 K), orthorhombic-ZrMo x W 2-x O 8  → cubic-ZrMo x W 2-x O 8 (700-850 K), cubic-ZrMo x W 2-x O 8  → trigonal-ZrMo x W 2-x O 8 (800-1050 K for x > 1) and cubic-ZrMo x W 2-x O 8  → oxides (1000-1075 K for x ≤ 1). The cell parameters of the disordered cubic-ZrMo x W 2-x O 8 (space group Pa-3) were measured within 300-900 K, and the thermal expansion coefficients were calculated: -3.5∙10 -6  - -4.5∙10 -6  K -1 . For the ordered ZrMo 1.8 W 0.2 O 8 (space group P2 1 3), a negative thermal expansion (NTE) coefficient -9.6∙10 -6  K -1 (300-400 K) was calculated. Orthorhombic-ZrW2O 8 is formed upon the decomposition of ZrW 2 O 7 (OH,Cl) 2 ∙2H 2 O within 500-800 K.

Physical limit of stability in supercooled D2O and D2O+H2O mixtures

Science.gov (United States)

Kiselev, S. B.; Ely, J. F.

2003-01-01

The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O+H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water-high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull's expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS, which lies below the homogeneous nucleation temperature, TH. We show that CP2 always lies inside in the so-called "nonthermodynamic habitat" and physically does not exist. However, the concept of a second "virtual" critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O+H2O mixtures. As an example, we consider here an equimolar D2O+H2O mixture in normal and supercooled states at atmospheric pressure, P=0.1 MPa.

Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, p-xylene + OH reaction.

Science.gov (United States)

Noda, Jun; Volkamer, Rainer; Molina, Mario J

2009-09-03

The OH-radical initiated oxidation of a series of monocyclic aromatic hydrocarbons (benzene, toluene, o-, m-, and p-xylene) in the presence of oxygen and NO(x) was investigated in a flowtube coupled with a chemical ionization mass spectrometer (CIMS). OH-radical addition to the aromatic ring--the major reaction pathway--has previously been shown to have a particular sensitivity to experimental conditions. This is the first flowtube study that demonstrates the atmospheric relevance of product yields from the OH-addition channel on the millisecond time scale (35-75 ms); the phenol yield from benzene and cresol yields from toluene are found to be 51.0 +/- 4.3% and 17.7 +/- 2.1%, in excellent agreement with previous studies under close to atmospheric conditions. We further report unambiguous experimental evidence that dealkylation is a novel and significant pathway for toluene and o-, m-, and p-xylene oxidation. At 150 Torr of O2 partial pressure, toluene is found to dealkylate with a yield of 5.4 +/- 1.2% phenol; similarly, m-, o-, and p-xylene dealkylate with yields of 11.2 +/- 3.8%, 4.5 +/- 3.2%, and 4.3 +/- 3.1% cresol, respectively. A dealkylation mechanism via OH-addition in the ipso position is feasible (DeltaH = -9 kcal/mol for phenol formation from toluene) but does not lend itself easily to explain the significant isomer effect observed among xylenes; instead an alternative mechanism is presented that can explain this isomer effect and forms phenol and likely epoxide type products with identical m/z (indistinguishable in our CIMS analysis) via a carbene-type intermediate. Dealkylation adds to the atmospheric production of phenol- and likely epoxide-type products, with aldehydes as expected co-products, and helps improve the carbon balance in the initial stages of aromatic oxidation.

Siudaite, Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O: a new eudialyte-group mineral from the Khibiny alkaline massif, Kola Peninsula

Science.gov (United States)

Chukanov, Nikita V.; Rastsvetaeva, Ramiza K.; Kruszewski, Łukasz; Aksenov, Sergey M.; Rusakov, Vyacheslav S.; Britvin, Sergey N.; Vozchikova, Svetlana A.

2018-03-01

The new eudialyte-group mineral siudaite, ideally Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O, was discovered in a peralkaline pegmatite situated at the Eveslogchorr Mt., Khibiny alkaline massif, Kola Peninsula, Russia. The associated minerals are aegirine, albite, microcline, nepheline, astrophyllite, and loparite-(Ce). Siudaite forms yellow to brownish-yellow equant anhedral grains up to 1.5 cm across. Its lustre is vitreous, and the streak is white. Cleavage is none observed. The Mohs' hardness is 4½. Density measured by hydrostatic weighing is 2.96(1) g/cm3. Density calculated using the empirical formula is equal to 2.973 g/cm3. Siudaite is nonpleochroic, optically uniaxial, negative, with ω = 1.635(1) and ɛ = 1.626(1) (λ = 589 nm). The IR spectrum is given. The chemical composition of siudaite is (wt%; electron microprobe, H2O determined by HCN analysis): Na2O 8.40, K2O 0.62, CaO 9.81, La2O3 1.03, Ce2O3 1.62, Pr2O3 0.21, Nd2O3 0.29, MnO 6.45, Fe2O3 4.51. TiO2 0.54, ZrO2 11.67, HfO2 0.29, Nb2O5 2.76, SiO2 47.20, Cl 0.54, H2O 3.5, -O = Cl - 0.12, total 99.32. According to Mössbauer spectroscopy data, all iron is trivalent. The empirical formula (based on 24.5 Si atoms pfu, in accordance with structural data) is [Na7.57(H2O)1.43]Σ9(Mn1.11Na0.88Ce0.31La0.20Nd0.05Pr0.04K0.41)Σ3(H2O)1.8(Ca5.46Mn0.54)Σ6(Fe3+ 1.76Mn2+ 1.19)Σ2.95Nb0.65(Ti0.20Si0.50)Σ0.71(Zr2.95Hf0.04Ti0.01)Σ3Si24.00Cl0.47O70(OH)2Cl0.47·1.82H2O. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is trigonal, space group R3m, with a = 14.1885(26) Å, c = 29.831(7) Å, V = 5200.8(23) Å3 and Z = 3. Siudaite is chemically related to georgbarsanovite and is its analogue with Fe3+-dominant M2 site. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.38 (60) (-114), 4.29 (55) (-225), 3.389 (47) (131), 3.191 (63) (-228). 2.963 (100) (4-15), 2.843 (99) (-444), 2.577 (49) (3-39). Siudaite is named after the Polish

Investigation on pseudosymmetry, twinning and disorder in crystal structure determinations: Ba(H2O)M2III[PO3(OH)]4 (M=Fe, V) as examples

International Nuclear Information System (INIS)

Sun Wei; Huang Yaxi; Pan Yuanming; Mi Jinxiao

2012-01-01

Twinning commonly occurs in monoclinic crystals with dimensionally similar a and c axes and results in pseudo-orthorhombic symmetries with overlapping diffractions. For example, twinning in the new synthetic compound Ba(H 2 O)Fe 2 [PO 3 (OH)] 4 , which varies in space group from P2 1 to P2 1 /c with approximately equal a and c axial lengths, gives rise to a pseudosymmetry of C222 1 . Similarly, the related compound Ba(H 2 O)V 2 [PO 3 (OH)] 4 is commonly twinned and varies in space groups as well, arising from ordered to disordered distributions of the barium cations and water molecules in the cavities. Moreover, analyses of these and other twinned structures show that the small average standard uncertainty of bond distances is a sensitive criterion for structure determinations, especially for those involving crystal twinning as well as order–disorder. A proper structure determination leads to small standard uncertainties of the atomic displacement parameters, which further result in the small standard uncertainties of bond distances. - Graphical abstract: Ba(H 2 O)M 2 III [PO 3 (OH)] 4 (M=Fe, V) varies in space group from P2 1 to P2 1 /c, arising from ordered to disordered distributions of Ba 2+ and H 2 O in the cavities. Highlights: ► Twinning commonly occurs in monoclinic crystals with a≈c. ► Overlapping diffractions from twin domains hamper with the determination of real space groups. ► Conventional criteria for evaluating the real space groups are not effective in this case. ► Small standard uncertainty of bond distances is proposed as a sensitive criterion. ► Using this criterion we determined the order–disorder structures of Ba(H 2 O)M 2 III [PO 3 (OH)] 4 (M=Fe, V) from twinned crystals.

Effect of B2O3 on luminescence of erbium doped tellurite glasses.

Science.gov (United States)

Shen, Xiang; Nie, Qiuhua; Xu, Tiefeng; Dai, Shixun; Wang, Xunsi

2007-02-01

The B2O3 was introduced into the Er3+ doped TeO2-ZnO-Na2O glass to increase the phonon energy of the host. The effect of B2O3 on the non-radiative rate of the 4I11/2-->4I13/2 transition of Er3+, the lifetime of the 4I11/2 and 4I13/2 levels, the green and red upconversion emissions intensity, and the 4I13/2-->4I15/2 emission intensity was discussed. The results show that the phonon energy of boro-tellurite glass is close to that of germanate glass and is quite smaller than that of borate glass. The lifetime of 4I11/2 level and the upconversion emissions decrease with increasing B2O3 concentration. The higher OH group concentration presented in the boro-tellurite glass may shorten the lifetime of 4I13/2 level and also reduce the quantum efficiency of 4I13/2-->4I15/2 emission. The future dehydrating procedures are suggested to enhance the efficiency of amplification at 1.5 microm band.

Hydrothermal crystallization of Na2Ti6O13, Na2Ti3O7, and Na16Ti10O28 in the NaOH-TiO2-H2O system at a temperature of 500 deg. C and a pressure of 0.1 GPa: The structural mechanism of self-assembly of titanates from suprapolyhedral clusters

International Nuclear Information System (INIS)

Hyushin, G. D.

2006-01-01

An increase in the NaOH concentration in the NaOH-TiO 2 (rutile)-H 2 O system at a temperature of 500 deg. C and a pressure of 0.1 GPa leads to the crystallization R-TiO 2 + Na 2 Ti 6 O 13 → Na 2 Ti 3 O 7 → Na 16 Ti 10 O 28 . Crystals of the Na 2 Ti 6 O 13 titanate (space group C2/m) have the three-dimensional framework structure Ti 6 O 13 . The structure of the Na 2 Ti 3 O 7 titanate (space group P2 1 /m) contains the two-dimensional layers Ti 3 O 7 . The structure of the Na 16 Ti 10 O 28 titanate (space group P-1) is composed of the isolated ten-polyhedron cluster precursors Ti 10 O 28 . In all the structures, the titanium atoms have an octahedral coordination (MTiO 6 ). The matrix self-assembly of the Na 2 Ti 6 O 13 and Na 2 Ti 3 O 7 (Na 4 Ti 6 O 14 ) crystal structures from Na 4 M 12 invariant precursors is modeled. These precursors are clusters consisting of twelve M polyhedra linked through the edges. It is demonstrated that the structurally rigid precursors Na 4 M 12 control all processes of the subsequent evolution of the crystal-forming titanate clusters. The specific features of the self-assembly of the Na 2 Ti 3 O 7 structure that result from the additional incorporation of twice the number of sodium atoms into the composition of the high-level clusters are considered