WorldWideScience

Sample records for nhsubscript 4cl times

  1. ?????????? ?????, ?????????? ??????????? ?? ?????????? ?????????? ????? ? ?????? ???????? ZnCl2 +NH4Cl

    OpenAIRE

    Kuntyi, Orest; Zozulya, Galyna

    2010-01-01

    Zinc cementation by magnesium from ZnCl2 + NH4Cl aqueous solutions has been investigated. The amount of magnesium has been established as 0.8?2.0 g per 1 g of conditioned zinc to obtain recovery degree ? 99 %. At low concentrations of Zn2+ ions (0.025?0.1 M ZnCl2) dispersed deposit is formed with nanoparticles of reduced metal; at high concentrations (0.25?0.5 M) coarse-crystalline and fern-shaped deposit is formed. ?????????? ?????????? ????? ??????? ? ?????? ???????? ZnCl2 + NH4Cl. ????????...

  2. Reduction behaviors of Zr for LiCl-KCl-ZrCl4 and LiCl-KCl-ZrCl4-CdCl2

    International Nuclear Information System (INIS)

    Kim, Si Hyung; Yoon, Jongho; Kim, Gha Young; Kim, Tack Jin; Shim, Joon Bo; Kim, Kwang Rag; Jung, Jae Hoo; Ahn, Do Hee; Paek, Seungwoo

    2013-01-01

    The reduction potentials of most of the zirconium ions on the solid cathode are smaller (about 0.4V) than that of uranium, and thus zirconium can be recovered prior to uranium during the reduction stage. In the case of a liquid cadmium cathode, which is one of the major cathodes, the reduction potential can be changed because zirconium reacts with the liquid cadmium. Up to now, it has not been well known what the reduction potential of Zr was on the liquid Cd cathode. According to the Cd-Zr phase diagram, there are four intermetallic compounds between cadmium and zirconium. It is easier to use the solid cathode than the liquid cadmium cathode in LiCl-KCl-ZrCl 4 containing CdCl 2 to identify the formation of the Cd-Zr phase. In this study, the reduction behaviors of zirconium were compared in the LiCl-KCl-ZrCl 4 and LiCl-KCl-ZrCl 4 -CdCl 2 solutions when using a solid cathode. The reduction behavior of Zr at a solid W cathode and a Cd-coated W cathode was compared in a LiCl-KCl-ZrCl 4 solution at 500 .deg. C. It was observed from the results using a solid W cathode that Zr 4+ ions were gradually oxidized to Zr 2+ , Zr, and ZrCl during the reduction sweep, but the final oxidation peak of Zr 2+ to Zr 4+ seemed to be unclear during the oxidation sweep. In the case of the Cd-coated W electrode, only a Cd 2 Zr phase was formed at 500 .deg. C, which seemed to be related to the melting point of Cd-Zr intermetallics. Through additional studies at different temperatures, the formation behavior will be studied

  3. Molecular beam electric deflection of the tetrahalides CF4, CCl4, SiF4, SiCl4, GeCl4, TiF4, TiCl4, VF4, and VCl4

    International Nuclear Information System (INIS)

    Muenter, A.A.; Dyke, T.R.; Falconer, W.E.; Klemperer, W.

    1975-01-01

    Using molecular beam electric deflection, the temperature dependence of polar behavior has been studied for the molecules CF 4 , CCl 4 , SiF 4 , SiCl 4 , GeCl 4 , TiF 4 TiCl 4 , VF 4 , VF 4 , and VCl 4 . A number of these molecules show polar behavior consistent with a vibrationally induced dipole moment for states with one or both of the triply degenerate vibrations excited. In four of the tetrachloride species, the presence of a vibrationally induced dipole moment was confirmed by the change in polar behavior with isotopic substituion of the Cl atoms. The deflection behavior of the transition metal tetrahalides varied from nonpolar in VCl 4 to very polar in TiF 4

  4. Reactions UF{sub 4} - ClF, UF{sub 4} - ClF{sub 3}, UF{sub 5} - ClF, UF{sub 5} - ClF{sub 3}; Reactions UF{sub 4} - ClF, UF{sub 4} - ClF{sub 3}, UF{sub 5} - ClF, UF{sub 5} - ClF{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Luce, M; Benoit, R; Hartmanshenn, O [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1968-07-01

    The reaction between ClF{sub 3} and UF{sub 4} is partially explained by the study of the reactions of the three systems: UF{sub 4}-ClF, UF{sub 5}-ClF and UF{sub 5}-ClF{sub 3}. The analytical techniques used are: the micro-sublimation, the infra-red spectroscopy and the thermogravimetry. The origin of the by-products is indicated. (authors) [French] La reaction entre ClF{sub 3} et UF{sub 4} est partiellement expliquee grace a l'etude des reactions des trois systemes UF{sub 4}-ClF, UF{sub 5}-ClF et UF{sub 5}-ClF{sub 3}. Les techniques analytiques utilisees sont: la micro-sublimation, la spectroscopie infrarouge et la thermogravimetrie. L'origine des sous-produits est indiquee. (auteurs)

  5. Raman spectra of the system TeCl4-SbCl5

    International Nuclear Information System (INIS)

    Brockner, W.; Demiray, A.F.

    1980-01-01

    Raman spectra of the solid and molten TeCl 4 . SbCl 5 addition compound and of some TeCl 4 -SbCl 5 mixtures have been recorded. Two modifications of the crystalline TeCl 4 -SbCl 5 compound have been found. The structure of the melt can be described by the equilibrium TeCl 3 + + SbCl 6 - reversible TeCl 4 + SbCl 5 lying on the left side. Mixtures with other stoichiometry contain the 1:1 adduct only and excess TeCl 4 or SbCl 5 , respectively. Such melts are built up by the ionic species TeCl 3 + and SbCl 6 - also and TeCl 4 or SbCl 5 according to stoichiometry. (author)

  6. The crystal structure of TeCl3+AuCl4-

    International Nuclear Information System (INIS)

    Jones, P.G.; Jentsch, D.; Schwarzmann, E.

    1986-01-01

    TeCl 3 + AuCl 4 - crystallizes in the triclinic space group Panti 1 with a=7.564(2), b=7.720(3), c=8.964(3) A, α=78.26(3), β=88.84(3), γ=89.35(3) 0 , Z=2. The structure was refined to R 0.041 for 1380 reflections. The cation polyhedron, including secondary Te...Cl interactions, is a square pyramid with mean Te-Cl 2.294, Te...Cl 3.028 A. The secondary interactions link the ions to form centrosymmetric (TeCl 3 .AuCl 4 ) 2 dimers. (orig.)

  7. Quatenary Na//F, Cl, CO3, MoO4 system

    International Nuclear Information System (INIS)

    Kochkarov, Zh.A.; Lok''yaeva, S.M.; Shurdumov, G.K.; Gasanaliev, A.M.; Trunin, A.S.

    1999-01-01

    Perspective in applied respect quatenary system (NaF) 2 -(NaCl)-Na 2 CO 3 -Na 2 MoO 4 being element of narrowing of more complex six-membered mutual Na//F, Cl, CO 3 , MoO 4 (WO 4 ) system is investigated by differential thermal analysis with the use of projection-thermographic method for the first time. Crystallization tree of Na//F, Cl, CO 3 , MoO 4 system is established. It is shown that this system by tetrahedrating (NaF) 2 -Na 2 CO 3 -Na 3 ClMoO 4 section is triangulated on two stable system: (NaF) 2 -Na 3 ClMoO 4 -Na 2 CO 3 -(NaCl) 2 and (NaF) 2 -Na 3 ClMoO 4 -Na 2 CO 3 -Na 2 MoO 4 . Phase single units are determined too. Coordinates of desired quatenary nonvariant points are calculated on analytical models of surfaces by mutual crystallization of two phases and are refined by differential thermal analysis [ru

  8. Volatility of components of saturated vapours of UCl4-CsCl and UCl4-LiCl molten mixtures

    International Nuclear Information System (INIS)

    Smirnov, M.V.; Kudyakov, V.Ya.; Salyulev, A.B.; Komarov, V.E.; Posokhin, Yu.V.; Afonichkin, V.K.

    1979-01-01

    The flow method has been used for measuring the volatility of the components from UCl 4 -CsCl and UCl 4 -LiCl melted mixtures containing 2.0, 5.0, 12.0, 25.0, 33.0, 50.0, 67.0, and 83.0 mol.% of UCl 4 within the temperature ranges of 903-1188 K and 740-1200 K, respectively. The chemical composition of saturated vapours above the melted salts has been determined. The melted mixtures in question exhibit negative deviation from ideal behaviour. Made was the conclusion about the presence in a vapour phase, along with monomeric UCl 4 , LiCl, CsCl and Li 2 Cl 2 , Cs 2 Cl 2 dimers of double compounds of the MeUCl 5 most probable composition. Their absolute contribution into a total pressure above the UCl 4 -CsCl melted mixtures is considerably smaller than above the UCl 4 -LiCl mixtures

  9. Thermal gravimetric analysis of the CsCuCl3, Cs2CuCl4 and Cs2CuCl4x2H2O crystals

    International Nuclear Information System (INIS)

    Soboleva, L.V.; Vasil'eva, M.G.

    1977-01-01

    The thermal characteristics of crystals of Cs 2 CuCl 4 , Cs 2 CuCl 4 x2H 2 O, and CsCuCl 3 were investigated thermogravimetrically. The derivatogram of the Cs 2 CuCl 4 crystal is characterized by the presence of a single endothermal effect at 505 deg C. The derivatogram of the Cs 2 CuCl 4 x2H 2 O crystal contains three endothermal effects: at 40, 135, and 480 deg C. The derivatogram of the CsCuCl 3 crystal shows the presence of two endothermal effects at 142 and 455 deg C. The thermogravimetric data on Cs 2 CuCl 4 and CsCuCl 3 crystals reveal crystal decomposition on melting; hence, these crystals cannot be grown from melts

  10. Heat capacity of Sr10(PO4)6Cl2 and Ca10(PO4)6Cl2 by DSC

    International Nuclear Information System (INIS)

    Venkata Krishnan, R.; Jena, Hrudananda; Govindan Kutty, K.V.; Nagarajan, K.

    2008-01-01

    Strontium and calcium chloroapatites were synthesized by wet chemical method, characterized by X-ray diffraction and are found to be phase pure materials. The measured room temperature lattice parameter of Ca 10 (PO 4 ) 6 Cl 2 is a = 9.523 A, c = 6.855 A and for Sr 10 (PO 4 ) 6 Cl 2 is a = 9.876 A, c = 7.188 A. Heat capacity measurements were carried out on Ca 10 (PO 4 ) 6 Cl 2 and Sr 10 (PO 4 ) 6 Cl 2 by DSC in the temperature range 298-800 K. The heat capacity values of Sr 10 (PO 4 ) 6 Cl 2 is higher at all temperatures than Ca 10 (PO 4 ) 6 Cl 2 . Enthalpy and entropy increments were computed. Heat capacity values of Ca 10 (PO 4 ) 6 Cl 2 and Sr 10 (PO 4 ) 6 Cl 2 at 298 K are 758 and 868 J K -1 mol -1 , respectively

  11. ZnCl 2- and NH 4Cl-hydroponics gel electrolytes for zinc-carbon batteries

    Science.gov (United States)

    Khalid, N. H.; Ismail, Y. M. Baba; Mohamad, A. A.

    Absorbency testing is used to determine the percentage of ZnCl 2 or NH 4Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl 2 or NH 4Cl solution decreases with increasing solution concentration. The conductivity of ZnCl 2- and NH 4Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm -1 at 3 M ZnCl 2 and 7 M NH 4Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 Ω, a maximum power density of 12.7 and 12.2 mW cm -2, and a short-circuit current density of 29.1 and 33.9 mA cm -2 for ZnCl 2- and NH 4Cl-HPG electrolytes, respectively.

  12. Reactions UF4 - ClO2F and UF5 - ClO2F

    International Nuclear Information System (INIS)

    Benoit, Raymond; Besnard, Ginette; Hartmanshenn, Olivier; Luce, Michel; Mougin, Jacques; Pelissie, Jean

    1970-02-01

    The study of the reaction UF 4 - ClO 2 F between 0 deg. and 100 deg. C, by various techniques (micro-sublimation, isopiestic method, IR and UV spectrography, thermogravimetry and X-ray diffraction) shows that intermediate steps are possible before the production of UF 5 . The whole reaction may be schematised by two equations: (1) n UF 4 + ClO 2 F → n UF x + ClO 2 (4 4 + ClO 2 F → UF x + 1/2 Cl 2 + O 2 . The more the temperature rises, the more the second equation becomes experimentally verified. The reaction at 0 deg. C between UF 5 and ClO 2 F may be represented by: UF 5 + ClO 2 F → UF 6 ClO 2 . The reactions: UF 5 + ClO 2 F → UF 6 + ClO 2 , UF 5 + ClO 2 F → UF 6 + 1/2 Cl 2 + O 2 are verified, the first and the second at 25 deg. C., the second from 50 deg. to 150 deg. C. From the results of AGRON it is possible to predict the residual solids before complete volatilization as UF 6 . The IR spectra of ClO 2 F adsorbed on UF 4 and UF x at 60 deg. C have been compared with those of gaseous ClO 2 F and UF 6 adsorbed on UF 4 . (authors) [fr

  13. Volatility of components of saturated vapours of UCl/sub 4/-CsCl and UCl/sub 4/-LiCl molten mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, M V; Kudyakov, V Ya; Salyulev, A B; Komarov, V E; Posokhin, Yu V; Afonichkin, V K

    1979-01-01

    The flow method has been used for measuring the volatility of the components from UCl/sub 4/-CsCl and UCl/sub 4/-LiCl melted mixtures containing 2.0, 5.0, 12.0, 25.0, 33.0, 50.0, 67.0, and 83.0 mol.% of UCl/sub 4/ within the temperature ranges of 903-1188 K and 740-1200 K, respectively. The chemical composition of saturated vapours above the melted salts has been determined. The melted mixtures in question exhibit negative deviation from ideal behaviour. Made was the conclusion about the presence in a vapour phase, along with monomeric UCl/sub 4/, LiCl, CsCl and Li/sub 2/Cl/sub 2/, Cs/sub 2/Cl/sub 2/ dimers of double compounds of the MeUCl/sub 5/ most probable composition. Their absolute contribution into a total pressure above the UCl/sub 4/-CsCl melted mixtures is considerably smaller than above the UCl/sub 4/ -LiCl mixtures.

  14. Interaction of cis-[Ru(DMSO)4Cl2] with acetate-ion in solutions

    International Nuclear Information System (INIS)

    Buslaeva, T.M.; Rudnitskaya, O.V.; Kabanova, A.G.; Fedorova, G.A.

    2000-01-01

    Solutions of cis-[Ru(DMSO) 4 Cl 2 ] in water and alcohols in the presence of CH 3 COONa in dependence on concentration and relation of reagents are studied. It is shown that introduction of acetate-ion in solution of cis-[Ru(DMSO) 4 Cl 2 ] in methanol directs to formation of fac-[Ru(DMSO) 3 Cl 3 ] - which can be separated as sodium salt insoluble in methanol. It is necessary to mention that spectrum of solution of cis-[Ru(DMSO) 4 Cl 2 ] in methanol varies in time but these changes are insignificant in comparison with changes taking place in the presence of CH 3 COONa. Compound Na[Ru(DMSO) 3 (CH 3 COO) 2 Cl] is prepared and characterized spectrally for the first time [ru

  15. Determination of the equilibrium constant of FeZrCl6 formation from FeCl3 and ZrCl4

    International Nuclear Information System (INIS)

    Berdonosov, S.S.; Kharisov, B.I.; Nikitin, M.I.

    1992-01-01

    Equilibrium pressures of chlorine formed in the course of reaction FeCl 3 +ZrCl 4 ↔ FeZrCl 6 +0.5 Cl 2 were determined at the temperatures of 250-325 deg C. The values of equilibrium constant K p of the reaction mentioned at the temperatures of 250, 275, 300 and 325 deg were calculated, taking into consideration the determined values of p Cl2 and literature data on equilibrium pressures of ZrCl 4 and FeCl 3 vapours

  16. Quaternary reciprocal system Na,K//Cl,Co3,MoO4

    International Nuclear Information System (INIS)

    Kochkarov, Zh.A.; Gasanaliev, A.M.

    2004-01-01

    Quaternary reciprocal system Na,K//Cl,Co 3 ,MoO 4 has been investigated for the first time by differential thermal analysis using the methods of projective and differential geometry. A stable (KCl) 2 -Na 2 CO 3 -K 2 CO 3 -K 2 MoO 4 tetrahedron and (NaCl) 2 -(KCl) 2 -Na 2 CO 3 -K 2 MoO 4 -Na 2 MoO 4 pentatope have been revealed in the system. It has been found that four quadruple invariant points are realized in the Na,K//Cl,Co 3 ,MoO 4 system, including one eutectic and three peritectic points [ru

  17. The oxidation of ReCl_5 with oleum: synthesis and crystal structure of Re_2O_4Cl_4(SO_4)

    International Nuclear Information System (INIS)

    Betke, Ulf; Wickleder, Mathias S.

    2012-01-01

    The reaction of ReCl_5 and fuming sulfuric acid (25 % SO_3) in a sealed glass tube at 200 C led to red, needle shaped single crystals of Re_2O_4Cl_4(SO_4) (monoclinic, C2/c, a = 1501.8(2) pm, b = 1545.9(2) pm, c = 945.18(8) pm, β = 98.761(9) , Z = 8). In the crystal structure the [ReO_2] moieties are linked by [SO_4]"2"- tetrahedra to chains along the [101] direction. Each sulfate ion connects four rhenium atoms, additional two chloride ions complete the octahedral coordination sphere of each rhenium atom according to "1_∞[ReO_2_/_1Cl_2_/_1(SO_4)_2_/_4]. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Thermodynamics of HfCl4-KCl molten mixtures containing HfCl4 up to 33.3 mol. per cent

    International Nuclear Information System (INIS)

    Smirnov, M.V.; Salyulev, A.B.; Kudyakov, V.Ya.

    1980-01-01

    Based on measurements of saturated vapour pressure in components of melted mixtures of HfCl 4 -KCl, depending on temperature and concentration, calculated are the results of changes in activity coefficients of hafnium tetrachloride and potassium chloride on transition from diluted solutions, where the Henry law is met, to those concentrated where the law is disobeyed. Growth in the activity coefficient of HfCl 4 is due to dissociation of complex groups of HfCl 6 2- into complexes with a lesser number of ligands and decreasing relative binding energy of Hf 4+ -Cl - there. In this case, marked changes take place in partial enthalpy and entropy of hafnium tetrachloride mixing. Similar dependences are observed for potassium chloride, but they are expressed considerably weaker. Evaporation enthalpy and entropy are calculated for HfCl 4 and KCl monomers from their melted mixtures of various concentrations

  19. Electric conductivity of PCl5-ZrCl4, PCl5-TaCl5, and PCl5-MoCl5 molten mixtures

    International Nuclear Information System (INIS)

    Salyulev, A.B.; Red'kin, A.A.; Moskalenko, N.I.

    1997-01-01

    When mixing individual molecular melts of PCl 5 with ZrCl 4 , TaCl 5 or with MoCl 5 , an essential (by several orders) increase in electric conductivity (up to 0.02-0.1 Ohm -1 ·cm -1 ), which stems, in all probability, from the appearance of complex ions PCl 4 + , ZrCl 5 - , ZrCl 6 2- , TaCl 5 - and MoCl 6 - in the molten mixtures as a result of chemical interaction

  20. ZnCl{sub 2}- and NH{sub 4}Cl-hydroponics gel electrolytes for zinc-carbon batteries

    Energy Technology Data Exchange (ETDEWEB)

    Khalid, N.H.; Ismail, Y.M. Baba; Mohamad, A.A. [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia)

    2008-01-21

    Absorbency testing is used to determine the percentage of ZnCl{sub 2} or NH{sub 4}Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl{sub 2} or NH{sub 4}Cl solution decreases with increasing solution concentration. The conductivity of ZnCl{sub 2}- and NH{sub 4}Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm{sup -1} at 3 M ZnCl{sub 2} and 7 M NH{sub 4}Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 {omega}, a maximum power density of 12.7 and 12.2 mW cm{sup -2}, and a short-circuit current density of 29.1 and 33.9 mA cm{sup -2} for ZnCl{sub 2}- and NH{sub 4}Cl-HPG electrolytes, respectively. (author)

  1. Maximum on the electrical conductivity polytherm of molten TeCl4

    International Nuclear Information System (INIS)

    Salyulev, Alexander B.; Potapov, Alexei M.

    2017-01-01

    The electrical conductivity of molten TeCl 4 was measured up to 761 K, i.e. 106 degrees above the normal boiling point of the salt. For the first time it was found that TeCl 4 electrical conductivity polytherm has a maximum. It was recorded at 705 K (Κ max =0.245 Sm/cm), whereupon the conductivity decreases as the temperature rises. The activation energy of electrical conductivity was calculated.

  2. Studies of the effects of TiCl3 in LiBH4/CaH2/TiCl3 reversible hydrogen storage system

    International Nuclear Information System (INIS)

    Liu Dongan; Yang Jun; Ni Jun; Drews, Andy

    2012-01-01

    nano-composite a fully reversible hydrogen storage material. These four states of LiCl in LiBH 4 /CaH 2 /TiCl 3 system, i.e. “formed-solid solution-molten solution-precipitation”, are reported for the first time and the detailed study of this system is beneficial to further improve hydrogen storage property of complex hydrides.

  3. Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

    Science.gov (United States)

    Gonçalves, Norberto S.; Noda, Lúcia. K.

    2017-10-01

    In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

  4. Chemical effects of (n, γ) nuclear reaction on (Mo6Cl8)Cl4

    International Nuclear Information System (INIS)

    Fucugauchi, L.A.; Millan, S.; Mondragon, A.; Solache-Rios, M.

    1994-01-01

    The chemical effects of 98 Mo(n, γ) 99 Mo reaction on molybdenum(II) chloride [(Mo 6 Cl 8 )Cl 4 ] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical applications in the enrichment of 99 Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo 6 Cl 8 )Cl 4 ] appears to offer good prospects. (author) 14 refs.; 2 figs

  5. A Raman spectroscopic study of the structural aspects of K2MgCl4 and Cs2MgCl4 as solid single crystals and molten salts

    International Nuclear Information System (INIS)

    Brooker, M.H.

    1975-01-01

    Polarized Raman spectra have been obtained for oriented single crystals of K 2 MgCl 4 and Cs 2 MgCl 4 at 77 and 298 K. The data are in excellent agreement with factor group analyses based on the space groups I 4 /mmm (D 17 4 /subh/) and Pnma (D 16 2 /subh/) for the K 2 MgCl 4 and Cs 2 MgCl 4 crystals. In K 2 MgCl 4 the magnesium is surrounded by six chloride ions in a distorted octahedral arrangement with a network structure such that neighboring octahedra share corners. In Cs 2 MgCl 4 a discrete tetrahedral MgCl 4 2- species is present. The 35 Cl-- 37 Cl isotopic splitting of the symmetric stetching mode of the tetrahedral MgCl 4 2- species has been resolved at 77 K and is similar to that observed for CCl 4 . Raman spectra for the high temperature solids and molten salts suggest that the coordination number of magnesium changes from six in solid K 2 MgCl 4 to four in the melt, whereas Cs 2 MgCl 4 melts with retention of the MgCl 4 2- tetrahedral complex. Additional evidence is presented to support previous reports that the MgCl 4 2- tetrahedral species is the principal complex ion in the melts, although a fraction of the magnesium appears to be present in a polynuclear complex, perhaps Mg 2 Cl 6 2-

  6. Thermodynamics of HfCl/sub 4/-KCl molten mixtures containing HfCl/sub 4/ up to 33. 3 mol. per cent

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, M V; Salyulev, A B; Kudyakov, V Ya [AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii

    1980-05-01

    Based on measurements of saturated vapour pressure in components of melted mixtures of HfCl/sub 4/-KCl, depending on temperature and concentration, calculated are the results of changes in activity coefficients of hafnium tetrachloride and potassium chloride on transition from diluted solutions, where the Henry law is met, to those concentrated where the law is disobeyed. Growth in the activity coefficient of HfCl/sub 4/ is due to dissociation of complex groups of HfCl/sub 6//sup 2 -/ into complexes with a lesser number of ligands and decreasing relative binding energy of Hf/sup 4 +/-Cl/sup -/ there. In this case, marked changes take place in partial enthalpy and entropy of hafnium tetrachloride mixing. Similar dependences are observed for potassium chloride, but they are expressed considerably weaker. Evaporation enthalpy and entropy are calculated for HfCl/sub 4/ and KCl monomers from their melted mixtures of various concentrations.

  7. Identification and analytical characterization of nine synthetic cathinone derivatives N-ethylhexedrone, 4-Cl-pentedrone, 4-Cl-α-EAPP, propylone, N-ethylnorpentylone, 6-MeO-bk-MDMA, α-PiHP, 4-Cl-α-PHP, and 4-F-α-PHP.

    Science.gov (United States)

    Liu, Cuimei; Jia, Wei; Li, Tao; Hua, Zhendong; Qian, Zhenhua

    2017-08-01

    Clinical and forensic toxicology laboratories are continuously confronted by analytical challenges when dealing with the new psychoactive substances (NPS) phenomenon. In this study, the analytical characterization of nine synthetic cathinones is described: 2-(ethylamino)-1-phenylhexan-1-one (N-ethylhexedrone 1), 1-(4-chlorophenyl)-2-(methylamino)pentan-1-one (4-Cl-pentedrone 2), 1-(4-chlorophenyl)-2-(ethylamino)pentan-1-one (4-Cl-α-EAPP 3), 1-(3,4-methylenedioxyphenyl)-2-propylaminopropan-1-one (propylone 4), 1-(3,4-methylenedioxyphenyl)-2-ethylaminopentan-1-one (N-ethylnorpentylone 5), 1-(6-methoxy-3,4-methylenedioxyphenyl)-2-methylaminopropan-1-one (6-MeO-bk-MDMA 6), 4-methyl-1-phenyl-2-(pyrrolidin-1-yl)pentan-1-one (α-PiHP 7), 1-(4-chlorophenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-Cl-α-PHP 8), and 1-(4-fluorophenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-F-α-PHP 9). The identification was based on ultra-high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (UHPLC-QTOF-MS), gas chromatography-mass spectrometry (GC-MS), and nuclear magnetic resonance (NMR) spectroscopy. The mass-spectral fragmentations of these compounds following collision-induced dissociation (CID) and electron ionization (EI) were studied to assist forensic laboratories in identifying these compounds or other substances with similar structure in their case work. To our knowledge, no analytical data about the compounds 1-4, 7, and 8 have appeared until now, making this the first report on these compounds. The GC-MS data of 5, 6 and 9 has been reported, but this study added the LC-MS, Fourier Transform Infrared (FTIR) and NMR data for additional characterization. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  8. Improvement of pre-treatment method for 36Cl/Cl measurement of Cl in natural groundwater by AMS

    International Nuclear Information System (INIS)

    Nakata, Kotaro; Hasegawa, Takuma

    2011-01-01

    Estimation of 36 Cl/Cl by accelerator mass spectrometry (AMS) is a useful method to trace hydrological processes in groundwater. For accurate estimation, separation of SO 4 2- from Cl - in groundwater is required because 36 S affects AMS measurement of 36 Cl. Previous studies utilized the difference in solubility between BaSO 4 and BaCl 2 (BaSO 4 method) to chemically separate SO 4 2- from Cl - . However, the accuracy of the BaSO 4 method largely depends on operator skill, and consequently Cl - recovery is typically incomplete (70-80%). In addition, the method is time consuming (>1 week), and cannot be applied directly to dilute solutions. In this study, a method based on ion-exchange column chromatography (column method) was developed for separation of Cl - and SO 4 2- . Optimum conditions were determined for the diameter and height of column, type and amount of resin, type and concentration of eluent, and flow rate. The recovery of Cl - was almost 100%, which allowed complete separation from SO 4 2- . The separation procedure was short ( 4 methods, and then analyzed by AMS to estimate 36 S counts and 36 Cl/Cl values. 36 S counts in samples processed by the column method were stable and lower than those from the BaSO 4 method. The column method has the following advantages over the BaSO 4 method: (1) complete and stable separation of Cl - and SO 4 2- , (2) less operator influence on results, (3) short processing time ( - , and (5) concentration of Cl - and separation from SO 4 2- in the one system for dilute solutions.

  9. Maximum on the electrical conductivity polytherm of molten TeCl{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Salyulev, Alexander B.; Potapov, Alexei M. [Russian Academy of Sciences, Ekaterinburg (Russian Federation). Inst. of High-Temperature Electrochemistry

    2017-09-01

    The electrical conductivity of molten TeCl{sub 4} was measured up to 761 K, i.e. 106 degrees above the normal boiling point of the salt. For the first time it was found that TeCl{sub 4} electrical conductivity polytherm has a maximum. It was recorded at 705 K (Κ{sub max}=0.245 Sm/cm), whereupon the conductivity decreases as the temperature rises. The activation energy of electrical conductivity was calculated.

  10. Etude structurale et vibrationnelle d'un nouveau composé complexe de cobalt: [Co(imidazole)4Cl]Cl.

    Science.gov (United States)

    Derbel, Amira; Mhiri, Tahar; Graia, Mohsen

    2015-10-01

    In the title complex, chlorido-tetra-kis-(1H-imidazole-κN (3))cobalt(II) chloride, [CoCl(C3H4N2)4]Cl, the Co(II) cation has a distorted square-pyramidal coordination environment. It is coordinated by four N atoms of four imidazole (Im) groups in the basal plane, and by a Cl atom in the apical position. It is isostructural with [Cu(Im)4Cl]Cl [Morzyk-Ociepa et al. (2012 ▸). J. Mol. Struct. 1028, 49-56] and [Cu(Im)4Br]Br [Hossaini Sadr et al. (2004 ▸). Acta Cryst. E60, m1324-m1326]. In the crystal, the [CoCl(C3H4N2)4](+) cations and Cl(-) anions are linked via N-H⋯Cl hydrogen bonds, forming layers parallel to (010). These layers are linked via C-H⋯Cl hydrogen bonds and C-H⋯π and π-π [inter-centroid distance = 3.794 (2) Å] inter-actions, forming a three-dimensional framework. The IR spectrum shows vibrational bands typical for imidazol groups. The monoclinic unit cell of the title compound emulates an ortho-rhom-bic cell as its β angle is close to 90°. The crystal is twinned, with the refined ratio of twin components being 0.569 (1):0.431 (1).

  11. Groundwater flowpaths and residence times inferred by 14C, 36Cl and 4He isotopes in the Continental Intercalaire aquifer (North-Western Africa)

    Science.gov (United States)

    Petersen, J. O.; Deschamps, P.; Hamelin, B.; Fourré, E.; Gonçalvès, J.; Zouari, K.; Guendouz, A.; Michelot, J.-L.; Massault, M.; Dapoigny, A.; ASTER Team

    2018-05-01

    In a semi-arid to arid climate context, dependency on groundwater resources may lead to overexploitation and deterioration of water quality. The Continental Intercalaire (CI) aquifer is one such continental-scale aquifer (more than a million of km2), which is mainly confined, poorly recharged but intensely abstracted. To date, the management of this resource relies on hydrogeological modelling and key parameters such as recharge/discharge rate and groundwater dynamics. We use a combination of residence time indicators (14C, 36Cl, 4He) and stable isotopes of water (2H and 18O) to give greater constraint on the groundwater residence time in the CI. In previous studies, 14C measurements and steady state modelling indicate a residence time of less than 100 ka whereas in others, 36Cl measurements and transient scenarios modelling suggest a longer residence time (>500 ka). In this study, most of the 14C measurements are below the limit of detection, establishing residence times greater than 40 ka and confirming the necessity of strict sampling protocols to exclude all air and AMS measurements when low 14C concentrations are expected. In the Tunisian recharge area, detectable 14C indicate sporadic recharge episodes (3-7 ka and 29-43 ka), whereas 4He and 36Cl concentrations in central areas suggest very old (water quality in the whole system.

  12. Electric conductivity of PCl{sub 5}-ZrCl{sub 4}, PCl{sub 5}-TaCl{sub 5}, and PCl{sub 5}-MoCl{sub 5} molten mixtures; Ehlektroprovodnost` rasplavlennykh sistem PCl{sub 5}-ZrCl{sub 4}, PCl{sub 5}-TaCl{sub 5}, i PCl{sub 5}-MoCl{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Salyulev, A B; Red` kin, A A; Moskalenko, N I [Inst. Vysokotemperaturnoj Ehlektrokhimii UrO RAN, Ekaterinburg (Russian Federation)

    1997-05-01

    When mixing individual molecular melts of PCl{sub 5} with ZrCl{sub 4}, TaCl{sub 5} or with MoCl{sub 5}, an essential (by several orders) increase in electric conductivity (up to 0.02-0.1 Ohm{sup -1}{center_dot}cm{sup -1}), which stems, in all probability, from the appearance of complex ions PCl{sub 4}{sup +}, ZrCl{sub 5}{sup -}, ZrCl{sub 6}{sup 2-}, TaCl{sub 5}{sup -} and MoCl{sub 6}{sup -} in the molten mixtures as a result of chemical interaction. 12 refs., 3 figs., 1 tab.

  13. Effect of NaCl-Stress on Metabolism of NO3-, NH4+ and NO2- at Several Rice Varieties

    Directory of Open Access Journals (Sweden)

    M Zulman Harja Utama

    2010-09-01

    Full Text Available This study was conducted to evaluate the effect of NaCl-stress on metabolism of NO3-, NH4+ and NO2- at several rice varieties. The results showed that an addition of NaCl had lesser effect on NaCl-tolerant varieties as compared to NaCl-sensitive in term of reduction in NO3-, NH4+, and NO2- uptake. Rice adaptation ability to NaCl stress occurred through the mechanism of NO3-, NH4+, and N02- metabolism physiology. It was indicated by the difference concentration of NO3-, NH4+ and N02- between the tolerant (Cisadane, moderate (Batang Lembang, Rendah Kuning, and Batang Piaman and sensitive (IR 66 varieties. Concentration of NH4+ and N02- of tolerant rice (Cisadane at NaCl treatment were about 1.16 and 2.6 times higher than that at control, respectively, while concentration of NO3- was only 0.03 times lower than control. In contrast, concentration of NO3-, NH4+, and N02- of sensitive rice (IR 66, were about 0.09, 0.27, and 0.41 times lower than that in control respecting at NaCl treatment, respectively.

  14. No solid solution compounds in between the binaries. Syntheses and crystal structures of Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and NbI{sub 2}Cl{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Reckeweg, Olaf; Schleid, Thomas [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2018-04-01

    The anion-mixed niobium tetrahalides Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and NbI{sub 2}Cl{sub 2} were obtained by heating NbBr{sub 5} with NbCl{sub 5} and NbI{sub 5} with NbCl{sub 5}, respectively, in equimolar ratios with niobium metal in evacuated, torch-sealed silica ampoules at 720 K for 3 days. The orthorhombic title compounds form as very brittle black needles and were characterized by single-crystal X-ray diffraction [space group: Immm, Z=4; a=704.27(6), b=824.13(7), c=929.64(8) pm for Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and a=753.76(6), b=829.38(7) and c=983.41(8) pm for NbI{sub 2}Cl{sub 2}]. Surprisingly enough, these mixed-anionic halides are not isostructural with either NbCl{sub 4}, NbBr{sub 4} or NbI{sub 4}, but crystallize isotypically with TaI{sub 2}Cl{sub 2}, thus being examples for differential site occupancy stabilized materials. Structural features of other niobium(IV) halides are compiled and compared to those of Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and NbI{sub 2}Cl{sub 2}. Except for NbF{sub 4}, they all exhibit chains of trans-edge connected [NbX{sub 6}]{sup 2-} octahedra, which allow Peierls distortions to form Nb-Nb single bonds. The packing of these chains differ, however, depending on the actual halide or mixed-halide combination.

  15. X-ray detection capability of a Cs2ZnCl4 single-crystal scintillator

    International Nuclear Information System (INIS)

    Yahaba, Natsuna; Koshimizu, Masanori; Sun, Yan; Asai, Keisuke; Yanagida, Takayuki; Fujimoto, Yutaka; Haruki, Rie; Nishikido, Fumihiko; Kishimoto, Shunji

    2014-01-01

    The X-ray detection capability of a scintillation detector equipped with a Cs 2 ZnCl 4 single crystal was evaluated. The scintillation decay kinetics can be expressed as the sum of two exponential decay components. The fast decay component had a decay time constant of 1.8 ns, and its relative intensity was 95%. The total light output was 630 photons/MeV, and a subnanosecond timing resolution of 0.66 ns was obtained. The detection efficiency of 67.4 keV X-rays was 80% for a detector equipped with a 2.2-mm-thick Cs 2 ZnCl 4 crystal. Thus, excellent timing resolution and high detection efficiency were achieved simultaneously. (author)

  16. Systematic Analysis of the 4-Coumarate:Coenzyme A Ligase (4CL Related Genes and Expression Profiling during Fruit Development in the Chinese Pear

    Directory of Open Access Journals (Sweden)

    Yunpeng Cao

    2016-10-01

    Full Text Available In plants, 4-coumarate:coenzyme A ligases (4CLs, comprising some of the adenylate-forming enzymes, are key enzymes involved in regulating lignin metabolism and the biosynthesis of flavonoids and other secondary metabolites. Although several 4CL-related proteins were shown to play roles in secondary metabolism, no comprehensive study on 4CL-related genes in the pear and other Rosaceae species has been reported. In this study, we identified 4CL-related genes in the apple, peach, yangmei, and pear genomes using DNATOOLS software and inferred their evolutionary relationships using phylogenetic analysis, collinearity analysis, conserved motif analysis, and structure analysis. A total of 149 4CL-related genes in four Rosaceous species (pear, apple, peach, and yangmei were identified, with 30 members in the pear. We explored the functions of several 4CL and acyl-coenzyme A synthetase (ACS genes during the development of pear fruit by quantitative real-time PCR (qRT-PCR. We found that duplication events had occurred in the 30 4CL-related genes in the pear. These duplicated 4CL-related genes are distributed unevenly across all pear chromosomes except chromosomes 4, 8, 11, and 12. The results of this study provide a basis for further investigation of both the functions and evolutionary history of 4CL-related genes.

  17. Studies of the effects of TiCl{sub 3} in LiBH{sub 4}/CaH{sub 2}/TiCl{sub 3} reversible hydrogen storage system

    Energy Technology Data Exchange (ETDEWEB)

    Liu Dongan [Ford Motor Company, Research and Advanced Engineering, MD 1170/RIC, Dearborn, MI 48121 (United States); Department of Mechanical Engineering, University of Michigan, 1023 H. H. Dow Building 2350 Hayward Street, Ann Arbor, MI 48109-2125 (United States); Yang Jun, E-mail: jyang27@ford.com [Ford Motor Company, Research and Advanced Engineering, MD 1170/RIC, Dearborn, MI 48121 (United States); Ni Jun [Department of Mechanical Engineering, University of Michigan, 1023 H. H. Dow Building 2350 Hayward Street, Ann Arbor, MI 48109-2125 (United States); Drews, Andy [Ford Motor Company, Research and Advanced Engineering, MD 1170/RIC, Dearborn, MI 48121 (United States)

    2012-02-15

    lowers the hydrogen desorption temperature. In addition, the solid-liquid nano-sized phase arrangement in the nano-composites improves the hydrogen reaction kinetics. The reversible incorporation/precipitation of LiCl at the hydrogen reaction temperature and during temperature cycling makes the 6LiBH{sub 4}/CaH{sub 2}/0.25TiCl{sub 3} nano-composite a fully reversible hydrogen storage material. These four states of LiCl in LiBH{sub 4}/CaH{sub 2}/TiCl{sub 3} system, i.e. 'formed-solid solution-molten solution-precipitation', are reported for the first time and the detailed study of this system is beneficial to further improve hydrogen storage property of complex hydrides.

  18. The oxidation of ReCl{sub 5} with oleum: synthesis and crystal structure of Re{sub 2}O{sub 4}Cl{sub 4}(SO{sub 4})

    Energy Technology Data Exchange (ETDEWEB)

    Betke, Ulf; Wickleder, Mathias S. [Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry (Germany)

    2012-01-15

    The reaction of ReCl{sub 5} and fuming sulfuric acid (25 % SO{sub 3}) in a sealed glass tube at 200 C led to red, needle shaped single crystals of Re{sub 2}O{sub 4}Cl{sub 4}(SO{sub 4}) (monoclinic, C2/c, a = 1501.8(2) pm, b = 1545.9(2) pm, c = 945.18(8) pm, β = 98.761(9) , Z = 8). In the crystal structure the [ReO{sub 2}] moieties are linked by [SO{sub 4}]{sup 2-} tetrahedra to chains along the [101] direction. Each sulfate ion connects four rhenium atoms, additional two chloride ions complete the octahedral coordination sphere of each rhenium atom according to {sup 1}{sub ∞}[ReO{sub 2/1}Cl{sub 2/1}(SO{sub 4}){sub 2/4}]. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Crystal structure of transition metal halides TiCl4, α-TiCl3, WCl4 and TiI2

    International Nuclear Information System (INIS)

    Troyanov, S.I.; Snigireva, E.M.

    2000-01-01

    Crystal structures of TiCl 4 , α-TiCl 3 , WCl 4 and TiI 2 are determined by x-ray diffraction method. For crystalline WCl 4 general for phases of this type space group C2/m is confirmed. Linear chains of WCl 6 octahedrons joined through the opposite edges exist in structure. Short W-W distances (2.69 A) in linear chains differentiate the structure of WCl 6 . Laminar structure of TiI 2 is belongs to CdI 2 structural type. Iodine atoms form slightly distorted hexagonal face-centered packing, titanium atoms fill up octahedral hollows in two-layer packing of iodine atoms with Ti-I distances equal 2.903 A [ru

  20. Structure and properties of Mn4Cl9: An antiferromagnetic binary hyperhalogen

    Science.gov (United States)

    Li, Yawei; Zhang, Shunhong; Wang, Qian; Jena, Puru

    2013-02-01

    Calculations based on density functional theory show that the structure of Mn4Cl9 anion is that of a Mn atom at the core surrounded by three MnCl3 moieties. Since Mn is predominantly divalent and MnCl3 is known to be a superhalogen with a vertical detachment energy (VDE) of 5.27 eV, Mn4Cl9 can be viewed as a hyperhalogen with the formula unit Mn(MnCl3)3. Indeed, the calculated VDE of Mn4Cl9 anion, namely 6.76 eV, is larger than that of MnCl3 anion. More importantly, unlike previously discovered hyperhalogens, Mn4Cl9 is the first such hyperhalogen species composed of only two constituent atoms. We further show that Mn4Cl9 can be used as a ligand to design molecules with even higher VDEs. For example, Li[Mn(MnCl3)3]2 anion has a VDE of 7.26 eV. These negatively charged clusters are antiferromagnetic with most of the magnetic moments localized at the Mn sites. Our studies show new pathways for creating binary hyperhalogens.

  1. Electrochemical Deposition and Dissolution of Aluminum in NaAlCl4 Melts

    DEFF Research Database (Denmark)

    Li, Qingfeng; Hjuler, H.A.; Berg, Rolf W.

    1990-01-01

    Effects of the additives MnCl2, sulfide, and their combined influence on aluminum deposition and dissolution inNaAlCl4 saturated with NaCl have been studied by polarization measurements, galvanostatic deposition, and current reversalchronopotentiometry (CRC). The solubility of MnCl2 was found...... to be 0.086 ± 0.006 m/o in the melt at 175°C. Aluminum-manganesealloys can be deposited in NaAlCl4 saturated with both NaCl and MnCl2, resulting in a slight increase incathodic overpotentials. The codeposition of the binary alloys at current densities below 4 mA/cm2 gave rise to formationof deposits so...

  2. Bonding in d9 complexes derived from EPR: Application to CuCl2-4, CuBr2-4, and CdCl2:Cu2+

    Science.gov (United States)

    Aramburu, J. A.; Moreno, M.

    1985-12-01

    In this work are reported the theoretical expressions for the [g], hyperfine, and superhyperfine (shf) tensors of a d9 square-planar complex within a molecular orbital (MO) scheme. These expressions include contributions arising from crystal field and charge transfer excitations calculated up to third and second order perturbations, respectively. This makes the present framework more general than those previously used. Through those expressions we have derived from the experimental EPR and optical data the MO coefficients corresponding to the valence b1g(x2-y2), b2g(xy), and eg(xz,yz) levels and also the core polarization contribution K to the hyperfine tensor for the systems CuCl2-4, CuBr2-4, and CdCl2:Cu2+. The 3d charge obtained for CuCl2-4 is equal to 0.61, 0.83, and 0.85 for the antibonding 3b1g, 2b2g, and 2eg levels, respectively. These figures are much closer to the Xα results by Bencini and Gatteschi [J. Am. Chem. Soc. 105, 5535 (1983)] than to those by Desjardins et al. [J. Am. Chem. Soc. 105, 4590 (1983)]. The σ and π covalency for CuBr2-4 are both higher than for CuCl2-4 in accord to the lower electronegativity for bromine. However, only for the antibonding 3b1g level of CuBr2-4 have we obtained an electronic charge lying mainly on ligands. The covalency of CdCl2:Cu2+ is smaller than that found for CuCl2-4, a fact associated to a higher metal-ligand distance for the former. Evidence of this statement are also given from the analysis of crystal-field spectra and isotropic shf constant. The values of K derived for CuCl2-4 (128.1×10-4 cm-1), CuBr2-4 (103.6×10-4 cm-1), and CdCl2:Cu2+ (123.9×10-4 cm-1) point out the dependence of K on the equatorial covalency but also on the existence of axial ligands. The [g] tensor of CuBr2-4 is dominated by the charge transfer contribution while the crystal field one is negative. Finally an analysis of the importance of each one of the involved contributions to the spin-Hamiltonian parameters is reported for the

  3. Synthesis, structure and optical properties of two isotypic crystals, Na3MO4Cl (M=W, Mo)

    International Nuclear Information System (INIS)

    Han, Shujuan; Bai, Chunyan; Zhang, Bingbing; Yang, Zhihua; Pan, Shilie

    2016-01-01

    Two isotypic compounds, Na 3 MO 4 Cl (M = W, Mo) have been obtained from the high temperature solution, and their structures were determined by single-crystal X-ray diffraction. Both of them crystallize in the space group P4/nmm of tetragonal system with the unit cells: a=7.5181(15), c=5.360(2) for Na 3 WO 4 Cl and a=7.4942(12), c=5.3409(18) for Na 3 MoO 4 Cl. The structure exhibits a 3D network built up by the ClNa 6 groups, and the MO 4 groups reside in the tunnels of the 3D network. The structural similarities and differences between Na 3 MO 4 Cl (M=W, Mo) and Sr 3 MO 4 F (M=Al, Ga) have been discussed. Meanwhile, detailed structure comparison analyses between Na 3 MO 4 Cl (M=W, Mo) and Na 3 MO 4 F (M=W, Mo) indicate that the different connection modes of ClNa 6 and FNa 6 make Na 3 MO 4 Cl and Na 3 MO 4 F crystallize in different structures. The IR spectra were used to verify the validity of the structure. The diffuse reflectance spectra show that the UV absorption edges are about 249 nm (4.99 eV) and 265 nm (4.69 eV) for Na 3 WO 4 Cl and Na 3 MoO 4 Cl, respectively. In addition, the first-principles theoretical studies are also carried out to aid the understanding of electronic structures and linear optical properties. - Graphical abstract: Two isotypic compounds, Na 3 MO 4 Cl (M=W, Mo) have been obtained from the high temperature solution. Both of them crystallize in the space group P4/nmm of tetragonal system. The structure exhibits a 3D network built up by the ClNa 6 groups, and the MO 4 groups reside in the tunnels of the 3D network. - Highlights: • Structure and properties of Na 3 MO 4 Cl (M=W, Mo) are reported for the first time. • They show a 3D network built by ClNa 6 , and WO 4 lies in the tunnels of the network. • IR spectra were used to verify the validity of the structure. • Band structures and density of states have been calculated.

  4. Interaction of different poisons with MgCl{sub 2}/TiCl{sub 4} based Ziegler-Natta catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bahri-Laleh, Naeimeh, E-mail: n.bahri@ippi.ac.ir

    2016-08-30

    Highlights: • The interactions between different classes of poison molecules and TiCl{sub 4}/MgCl{sub 2} type Ziegler-Natta catalyst is considered. • Poisons strongly stabilize MgCl{sub 2} crystal surfaces, mostly Ti active center relative to the unpoisoned solid. • Poison molecules decrease catalyst activity by increasing E{sub TS} in olefin polymerization. • Poison molecules do not have significant effect in stereospecifity of ZN catalysts in propylene polymerization. - Abstract: Adsorption of different poison molecules on activated MgCl{sub 2} is investigated within DFT using a cluster model of the MgCl{sub 2} surface with (MgCl{sub 2}){sub 16} formula containing four 4-coordinated and eight 5-coordinated Mg atoms as (110) and (104) surfaces, respectively. Studied poison molecules are chosen as possible impurities in hydrocarbon solvents and monomer feeds and contain water, hydrogensulfide, carbondioxide, molecular oxygen and methanol. First, adsorption of 1–4 molecules of different poisons to the (104) and (110) lateral cuts of MgCl{sub 2}, as well as their adsorption on [MgCl{sub 2}]/TiCl{sub 2}Et active center and AlEt{sub 3} cocatalyst is considered. Results reveal that poisons strongly stabilize both crystal surfaces, mostly Ti active center relative to the unpoisoned solid. Second, energy barrier (E{sub TS}) for ethylene insertion in the presence of different poisons located on the first and second Mg atom relative to the active Ti is calculated. While poison molecule located on the second Mg does not change E{sub TS}, coordination of it into the first Mg atom increases E{sub TS} by 0.9–1.2 kcal mol{sup −1}. In the last part of this manuscript, the stereoselective behavior of active Ti species, with and without poison molecules and external electron donor, is fully explored.

  5. Luminescence and scintillation properties of Ce-doped Cs2ZnCl4 crystals

    Science.gov (United States)

    Sugawara, K.; Koshimizu, M.; Yanagida, T.; Fujimoto, Y.; Haruki, R.; Nishikido, F.; Kishimoto, S.; Asai, K.

    2015-03-01

    In this study, we have synthesized scintillation materials based on Ce-doped Cs2ZnCl4 crystals. The light yield was enhanced by up to 20% by doping Cs2ZnCl4 with Ce3+ ions. In the scintillation time profiles, fast components exhibited decay time constants on the order of nanoseconds, which was ascribed to Auger-free luminescence (AFL). The light yield of the AFL component decreased at 10 mol% Ce3+ concentration, which is mainly attributed to the reabsorption of AFL photons inside the crystals by Ce3+ ions, as seen in the scintillation spectra. Long components had decay time constants of approximately 30 ns. In addition, at 10 mol% Ce3+ concentration, a prominent band appeared at approximately 500 nm in the scintillation spectrum, which was not observed in the photoluminescence spectra. The long components in the scintillation time profiles and the 500 nm band in the scintillation spectra were tentatively attributed to self-trapped excitons perturbed by Ce3+ ions.

  6. New Synthesis of Perhydrotriazolotriazoles Catalyzed by TiCl{sub 4} under Ambient Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Safari, J.; Gandomiravandi, S.; Ghotbinejad, M. [Univ. of Kashan, Kashan (Iran, Islamic Republic of)

    2012-02-15

    Aromatic 2,3-diazabuta-1,3-dienes in glacial acetic acid with isothiocyanate in the presence of catalyst TiCl{sub 4} at room temperature produced via criss-cross cycloaddition reactions the corresponding perhydro[1,2,4]triazolo[1,2-a][1,2,4] triazole-1,5-dithiones in relatively high yields and short reaction time.

  7. U4+ spectroscopic properties in Dsub(2d) with ThCl4, UCl4 and ThSiO4

    International Nuclear Information System (INIS)

    Khan Malek, C.

    1985-01-01

    This thesis is concerned with the study of the electronic structure of the tetravalent actinide ions in solid state. The technique used was high resolution optical spectroscopy. We deal with the U 4+ ion (sf 2 ) in the monocrystals ThCl 4 , UCl 4 , and ThSiO 4 where the U 4+ ion is substituded for the Th 4+ ion by doping. Visible and infrared optical spectra were recorded between 300 and 4.2K. With these three compounds, it is possible to compare the influence of different environments of Dsub(2d) symmetry: real symmetry for U 4+ in UCl 4 and ThSiO 4 ; approximate symmetry in ThCl 4 , whose structure is incommensurate and modulated at low temperature. The fitting of the data was carried out by diagonalizing the hamiltonian which describes the interactions of the U 4+ ion in a crystal field with its environment. This fitting procedure led to a coherent set of spectroscopic parameters. The fluorescence of U 4+ was observed in ThCl 4 and ThSiO 4 and the effect of the incommensurate structure of ThCl 4 on the optical spectra was studied. The symmetry of the U 4+ sites was identified by site selective excitation experiments and a relationship between the incommensurate structure and the lifetime of U 4+ energy levels was found. In conclusion, the U 4+ energy levels in a relatively low crystal field were determined for compounds that have a similar coordination polyhedron about the actinide ion. The values for these energy levels were then compared to those of lanthanide and 3d elements [fr

  8. Neutralization of Na2PO4: Reaction between Na3PO4 and CaCL2

    International Nuclear Information System (INIS)

    Xia Shenglan; Wang Luning

    1990-01-01

    The results of reaction Na 3 PO 4 with CaCl 2 in water at ambient and higher temperature are described. The reaction rate of Na 3 PO 4 with CaCl 2 is slow at ambient temperature and the reaction is complete at 260 deg C after 2 h. The products are Ca(OH) 2 and Ca 5 (PO 4 ) 3 (OH). The quantity of them is dependent upon the quanity of Na 3 PO 4 and CaCl 2 contained in water, all of them control pH of water

  9. Immobilization of Alkali Metal Fluorides via Recrystallization in a Cationic Lamellar Material, [Th(MoO4)(H2O)4Cl]Cl·H2O.

    Science.gov (United States)

    Lin, Jian; Bao, Hongliang; Qie, Meiying; Silver, Mark A; Yue, Zenghui; Li, Xiaoyun; Zhu, Lin; Wang, Xiaomei; Zhang, Linjuan; Wang, Jian-Qiang

    2018-06-05

    Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO 4 )(H 2 O) 4 Cl]Cl·H 2 O. The structure of TMC is composed of zigzagging cationic layers [Th(MoO 4 )(H 2 O) 4 Cl] + with Cl - as interlamellar charge-balancing anions. Instead of performing ion exchange, alkali thorium fluorides were formed after soaking TMC in AF (A = Na, K, and Cs) solutions. The mechanism of AF immobilization is elucidated by the combination of SEM-EDS, PXRD, FTIR, and EXAFS spectroscopy. It was observed that four water molecules coordinating with the Th 4+ center in TMC are vulnerable to competition with F - , due to the formation of more favorable Th-F bonds compared to Th-OH 2 . This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.

  10. Synthesis of palm-based polyurethane-LiClO{sub 4} via prepolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Sien, Jason Wong Chee [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi (Malaysia); School of Biosciences, Taylor’s University, Subang Jaya (Malaysia); Badri, Khairiah Haji [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi (Malaysia); Polymer Research Center, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi (Malaysia); Su’ait, Mohd Sukor [Polymer Research Center, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi (Malaysia); Solar Energy Research Institute Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi (Malaysia); Hassan, Nurul Izzati [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi (Malaysia)

    2015-09-25

    Palm-based polyurethane (pPU) with varying lithium salt (LiClO{sub 4}) content was synthesized. Higher loading percentage of LiClO{sub 4} in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li{sup +} ion. DSC thermogram showed the increase in the LiClO{sub 4} content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO{sub 4} increased from 10 to 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO{sub 4}.

  11. TETRACHLORO ZINCATE (II) [H2pymo][ZnCl4

    African Journals Online (AJOL)

    assembly of a hexa-palladium bowl-shaped cluster, ... mimic the properties of conventional porous solids. A number of ... mg (2 mmol) of [H2pymo]Cl were ground ... Figure 2: The anion environment in the structure of [H2pymo]2[ZnCl4]. Figure ...

  12. CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4: Infrared spectra, radiative efficiencies, and global warming potentials

    International Nuclear Information System (INIS)

    Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

    2016-01-01

    Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600–3500 cm"−"1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm"−"1 molecule"−"1): CH_3Cl, 660–780 cm"−"1, (3.89±0.19)×10"−"1"8; CH_2Cl_2, 650–800 cm"−"1, (2.16±0.11)×10"−"1"7; CHCl_3, 720–810 cm"−"1, (4.08±0.20)×10"−"1"7; and CCl_4, 730–825 cm"−"1, (6.30±0.31)×10"−"1"7. CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons. - Highlights: • Infrared spectra reported for CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4. • REs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1, respectively. • GWPs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 5, 8, 15, and 1775, respectively.

  13. Neutron scattering studies on phase transitions in (CD3ND3)2CuCl4 and MnCl2.4H2O

    International Nuclear Information System (INIS)

    Steijger, J.J.M.

    1982-10-01

    In this thesis the results of neutron scattering experiments and measurements of the susceptibility on some compounds which display magnetic and/or structural phase transitions, are described. Following an introductory chapter, chapter 2 shows that neutron scattering can be used as a tool for unravelling problems in crystallographic and magnetic structure. The qualitative different scattering patterns for scatters are described. In chapters 3 and 4 an investigation on the layered ferromagnets (CH 3 NH 3 ) 2 CuCl 4 and (CD 3 ND 3 ) 2 CuCl 4 is described. In these materials the copper ions, which carry the magnetic moment, are more closely spaced in the ab-planes, and consequently the magnetic interactions in these planes are stronger than those in the direction perpendicular to these planes by about a factor of 10 5 . Chapter 5 presents a discussion and a calculation of demagnetizing and dipole fields. The second part of this thesis is concerned with the transition from the antiferromagnetic to the paramagnetic phase in MnCl 2 .4H 2 O in the presence of a magnetic field applied perpendicular to the preferred direction of the magnetic moments. The theory is reviewed in chapter 6 and in chapter 7 the correction procedure for inhomogeneous internal fields is applied to the measurements on MnCl 2 .4H 2 O. (Auth./C.F.)

  14. The volumetric and thermochemical properties of Y(ClO4)3 (aq), Yb(ClO4)3 (aq), Dy(ClO4)3 (aq), and Sm(ClO4)3 (aq) at T=(288.15,298.15,313.15, and 328.15) K and p=0.1 MPa

    International Nuclear Information System (INIS)

    Hakin, Andrew W.; Lukacs, Michael J.; Liu, Jin Lian; Erickson, Kristy; Madhavji, Asha

    2003-01-01

    Relative densities and relative massic heat capacities have been measured for aqueous solutions of Y(ClO 4 ) 3 , Yb(ClO 4 ) 3 , Dy(ClO 4 ) 3 , and Sm(ClO 4 ) 3 at T=(288.15,298.15,313.15, and 328.15) K and p=0.1 MPa. These measurements were made in the concentration range 0.01624≤m/(mol·kg -1 )≤0.41822 using a Sodev 02D Vibrating Tube Densimeter and a Picker Microflow Calorimeter, respectively. To counter the potential effects of hydrolysis, aqueous solutions of the investigated salts were acidified with perchloric acid. After correcting for the presence of the acid, the measured properties were used to calculate apparent molar volumes and apparent molar heat capacities for solutions of the perchlorate salts in water. The calculated apparent molar properties were modeled at each investigated temperature using Pitzer ion interaction equations to produce estimates of apparent molar volumes and heat capacities at infinite dilution. In addition, the temperature dependences of the apparent molar properties of each salt were found to be well modeled by temperature dependent Pitzer ion interaction equations. The Helgeson, Kirham, and Flowers equations of state were incorporated into the Pitzer ion interaction equations in order to model the infinite dilution properties of the salts. Single ion volumes and heat capacities of the investigated trivalent metal cations have been calculated and compared to previously reported values

  15. Deposition, Accumulation, and Alteration of Cl(-), NO3(-), ClO4(-) and ClO3(-) Salts in a Hyper-Arid Polar Environment: Mass Balance and Isotopic Constraints

    Science.gov (United States)

    Jackson, Andrew; Davila, Alfonso F.; Boehlke, J. K.; Sturchio, Neil C.; Sevanthi, Ritesh; Estrada, Nubia; Brundrette, Megan; Lacell, Denis; McKay, Christopher P.; Poghosyan, Armen; hide

    2016-01-01

    The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl(-), NO3(-, ClO4(-)and ClO3(-)in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl(-) and NO3(-) isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4(-)/NO3(-) ratios and NO3(-) isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3(-)/ClO4(-) in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3(-), possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from approximately 10 to 30 kyr near the glacier to 70-200 kyr near the valley mouth. The relatively

  16. Quadruple-layered perovskite (CuCl)Ca2NaNb4O13

    International Nuclear Information System (INIS)

    Kitada, A.; Tsujimoto, Y.; Yamamoto, T.; Kobayashi, Y.; Narumi, Y.; Kindo, K.; Aczel, A.A.; Luke, G.M.; Uemura, Y.J.; Kiuchi, Y.; Ueda, Y.; Yoshimura, K.; Ajiro, Y.; Kageyama, H.

    2012-01-01

    We will present the synthesis, structure and magnetic properties of a new quadruple-layered perovskite (CuCl)Ca 2 NaNb 4 O 13 . Through a topotactic ion-exchange reaction with CuCl 2 , the precursor RbCa 2 NaNb 4 O 13 presumably having an incoherent octahederal tliting changes into (CuCl)Ca 2 NaNb 4 O 13 with a 2a p ×2a p ×2c p superstructure (tetragonal; a=7.73232(5) Å, c=39.2156(4) Å). The well-defined superstructure for the ion-exchanged product should be stabilized by the inserted CuCl 4 O 2 octahedral layers that firmly connect with neighboring perovskite layers. Magnetic studies show the absence of long-range magnetic ordering down to 2 K despite strong in-plane interactions. Aleksandrov′s group theory and Rietveld refinement of synchrotron X-ray diffraction data suggest the structure to be of I4/mmm space group with in-phase tilting along the a and b axes, a two-tilt system (++0). - Graphical Abstract: We present a quadruple-layered copper oxyhalide (CuCl)Ca 2 NaNb 4 O 13 synthesized through a topotactic ion-exchange reaction of RbCa 2 NaNb 4 O 13 with CuCl 2 . The compound has a well-defined superstructure. Magnetic studies suggest the absence of magnetic order even at 2 K. Highlights: ► (CuCl)Ca 2 NaNb 4 O 13 was prepared by ion-exchange reaction of RbCa 2 NaNb 4 O 13 with CuCl 2 . ► Compound has a 2a p ×2a p ×2c p superstructure (tetragonal; a=7.73 Å, c=39.21 Å). ► Such a well-defined superstructure was not observed in the precursor compound. ► Aleksandrov′s theory and Rietveld study suggest a (++0) octahedral tilting (I4/mmm). ► Magnetic studies revealed the absence of magnetic order down to 2 K.

  17. Apparent molar volumes for dilute solutions of NaClO4 and [Co(en) 3](ClO4)3 in D2O and H2O at 278-318 K

    International Nuclear Information System (INIS)

    Bottomley, G.A.; Glossop, L.G.

    1981-01-01

    Apparent molar volumes for dilute solutions of NaClO 4 and [Co(en) 3 ](ClO 4 ) 3 in D 2 O and H 2 O were measured by using a dilatometry technique at 278, 298 and 318K. Comparison of limiting slopes with the Debye-Huckel predictions from the dielectric constant and compressibility of H 2 O and D 2 O is complicated by ion pairing. The apparent molar volumes for NaClO 4 were less in D 2 O than in H 2 O. The complex [Co(en) 3 ](ClO 4 ) 3 when studied in D 2 O had its amine protons exchanged by deuterium; this did not allow a direct comparison of the apparent molar volumes of the protonated complex in each solvent system, but revealed a large isotope effect. The apparent molar volumes of the [Co(en) 3 ](ClO 4 ) 3 showed a much larger temperature dependence than that of NaClO 4

  18. Redox equilibrium of U4+/U3+ in molten NaCl-2CsCl by UV-Vis spectrophotometry and cyclic voltammetry

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Uehara, Akihiro; Fujii, Toshiyuki; Shirai, Osamu; Yamana, Hajimu; Sato, Nobuaki

    2005-01-01

    In order to investigate the redox equilibrium of uranium ions in molten NaCl-2CsCl, UV-Vis absorption spectro-photometry measurements were performed for U 4+ and U 3+ in molten NaCl-2CsCl at 923 K under simultaneous electrolytic control of their ratio. Prominent absorption bands at 480 and 570 nm were assigned to U 3+ , and their molar absorptivities were determined to be 1,260±42 and 963±32 mol -1 ·l·cm -1 respectively. From the dependence of the rest potential of the melt on the spectrophotometrically determined ratio of [U 4+ ]/[U 3+ ], the standard redox potential of the couple U 4+ /U 3+ at 923 K was determined to be -1.481±0.004 V vs. Cl 2 /Cl - . Cyclic voltammetry measurements were carried out for the couple U 4+ /U 3+ , and the results agreed well with this standard redox potential value. By the results of cyclic voltammetry, a temperature dependence of the standard redox potential was found to be -2.094+6.639 x 10 -4 T (T=823-923K). (author)

  19. Dielectric Study of the Phase Transitions in [P(CH3)4]2CuY4 (Y = Cl, Br)

    Science.gov (United States)

    Gesi, Kazuo

    2002-05-01

    Phase transitions in [P(CH3)4]2CuY4 (Y = Cl, Br) have been studied by dielectric measurements. In [P(CH3)4]2CuCl4, a slight break and a discontinuous jump on the dielectric constant vs. temperature curve are seen at the normal-incommensurate and the incommensurate-commensurate phase transitions, respectively. A small peak of dielectric constant along the b-direction exists just above the incommensurate-to-commensurate transition temperature. The anisotropic dielectric anomalies of [P(CH3)4]2CuBr4 at phase transitions were measured along the three crystallographic axes. The pressure-temperature phase diagram of [P(CH3)4]2CuCl4 was determined. The initial pressure coefficients of the normal-to-incommensurate and the incommensurate-to-commensurate transition temperatures are 0.19 K/MPa and 0.27 K/MPa, respectively. The incommensurate phase in [P(CH3)4]2CuCl4 disappears at a triple point which exists at 335 MPa and 443 K. The stability and the pressure effects of the incommensurate phases are much different among the four [Z(CH3)4]2CuY4 crystals (Z = N, P; Y = Cl, Br).

  20. Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl4.5H2O

    Directory of Open Access Journals (Sweden)

    Erik Hennings

    2014-12-01

    Full Text Available The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetrahedral coordination with Cl− and in an octahedral environment defined by five water molecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O5] (pentaaqua-μ-chlorido-trichloridodizinc. The trihydrate {hexaaquazinc tetrachloridozinc, [Zn(H2O6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetrahedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octahedrally surrounded by water molecules. The [ZnCl4] tetrahedra and [Zn(H2O6] octahedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexaaquazinc tetrachloridozinc trihydrate, [Zn(H2O6][ZnCl4]·3H2O}, consists of isolated octahedral [Zn(H2O6] and tetrahedral [ZnCl4] units, as well as additional lattice water molecules. O—H...O hydrogen bonds between the water molecules as donor and ZnCl4 tetrahedra and water molecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures.

  1. Evaluation report on CCTF CORE-I REFLOOD TEST Cl-4 (Run 13) and Cl-15 (Run 24)

    International Nuclear Information System (INIS)

    Sudoh, Takashi; Murao, Yoshio.

    1983-08-01

    The tests Cl-4 and Cl-15 were performed with the Cylindrical Core Test Facility (CCTF) to investigate the effects of the depressurization process to simulate the refill phase, and the effects of the nitrogen to be injected after the end of the accumulator injection on the thermo-hydraulic behavior in the core and primary loop system during refill and reflood phases. In these tests, after the lower plenum was filled to 0.9m level with saturated water at 0.6 MPa, the accumulator water was injected into three intact cold legs in the depressurization period from 0.6 MPa to 0.2 MPa. The water in the lower plenum voided during the depressurization and the significant steam condensation occurred in or near the intact cold legs. The condensation caused high steam flow rate in the intact loops and the lower plenum flashing resulted in suppressed core water accumulation. The slightly lower core heat transfer coefficient due to the less core water caused the higher turnaround temperature and the longer quench time than those of the normal reflood test without the depressurization process. The nitrogen injection followed the accumulator injection was allowed in the test Cl-15. However, significant effects of the nitrogen injection was not observed. (author)

  2. Room temperature photoinduced magnetism in [py.H]{sub 3}[FeCl{sub 4}]{sub 2}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Baniasadi, F. [Physics Department, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Tehranchi, M.M., E-mail: teranchi@sbu.ac.ir [Physics Department, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Fathi, M.B. [Physics Department, Kharazmi University, Tehran (Iran, Islamic Republic of); Hamidi, S.M. [Laser and Plasma Research Institute, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Safari, N.; Amani, V. [Faculty of Chemistry, Shahid Beheshti University, Tehran (Iran, Islamic Republic of)

    2015-11-15

    Photoinduced magnetism in a homogeneous solution of [py.H]{sub 3}[FeCl{sub 4}]{sub 2}Cl is measured by Faraday rotation in visible light (λ∼450–750 nm) at room temperature. The physics of this phenomenon may be attributed to electronic transitions caused by absorption of light. X-ray diffraction and Debye function analysis are therefore applied to find the abundant unit of molecules dissolved in the solution which are being further utilized to investigate the electronic structure and molecular orbitals by means of hybrid density function theory (B3LYP). Faraday rotation is observed at certain wavelengths consistent with energy differences of HOMO-LUMO energy levels. Thus this work puts forward a new material with certain photomagnetic properties which may be used in fabrication of room temperature magneto-optical switches. - Highlights: • Photoinduced magnetism in (FeCl{sub 4}){sub 2}(py.H){sub 3}Cl is illustrated via Faraday rotation. • The abundant unit of molecule is characterized by Debye function analysis of XRD. • PIM in the molecule is attributed to the charge transfer between HOMO-LUMO.

  3. Comparison on Mechanical Properties of SA508 Gr.3 Cl.1, Cl.2, and Gr.4N Low Alloy Steels for Pressure Vessels

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Min-Chul; Park, Sang-Gyu; Lee, Bong-Sang [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Lee, Ki-Hyoung [Korea Institute of Nuclear Safety, Daejeon (Korea, Republic of)

    2014-10-15

    In this study, microstructure and mechanical properties of SA508 Gr.3 Cl. 1, Cl.2, and Gr.4N low alloy steels are characterized to compare their properties. To evaluate the fracture toughness in the transition region, the master curve method according to ASTM E1921 was adopted in the cleavage transition region. Tensile tests and Charpy impact tests were also performed to evaluate the mechanical properties, and a microstructural investigation was carried out. The microstructure and mechanical properties of SA508 Gr.3 Cl.1, Cl2 and Gr.4N low alloy steels were characterized.. The predominant microstructure of SA508 Gr.4N model alloy is tempered martensite, while SA508 Gr.3 Cl.1 and Cl.2 steels show a typical tempered upper bainitic structure. SA508 Gr. 4N model alloy shows the best strength and transition behavior among the three SA508 steels. SA508 Gr.3 Cl.2 steel also has quite good strength, but there is a loss of toughness.

  4. Assessing toxic effects of [Omim]Cl and [Omim]BF4 in zebrafish adults using a biomarker approach.

    Science.gov (United States)

    Liu, Tong; Guo, Yingying; Wang, Jinhua; Wang, Jun; Zhu, Lusheng; Zhang, Jun; Zhang, Cheng

    2016-04-01

    In the present study, the toxic effects of 1-octyl-3-methylimidazolium chloride ([Omim]Cl) and 1-octyl-3-methylimidazolium tetrafluoroborate ([Omim]BF4) on the zebrafish livers were studied at 0, 5, 10, 20, and 40 mg L(-1) on the 7th and 14th days. In addition, the concentrations of [Omim]Cl and [Omim]BF4 in the test water, the acute toxicity of the two ionic liquids (ILs), and the influence of anions on the toxicity of the ILs were evaluated. The acute toxicity test results showed 50 % lethal concentration (LC50) values of 152.3 ± 12.1 mg L(-1) for [Omim]Cl and 144.0 ± 11.4 mg L(-1) for [Omim]BF4. At the lowest concentration investigated (5 mg L(-1)), [Omim]Cl and [Omim]BF4 did not significantly affect zebrafish during the exposure period. However, the toxic effects of these substances were enhanced as dosing concentrations and exposure times were increased. Levels of reactive oxygen species (ROS) were significantly enhanced on the 7th day after 20 mg L(-1) and on the 14th day after 10 mg L(-1) of either substance was applied, resulting in oxidative damage, such as lipid peroxidation and DNA damage. The experimental results also indicated little effect of the anions on the toxicity of ILs and consistent toxic effects of [Omim]Cl and [Omim]BF4. Graphical Abstract The graphical abstract for the present study after exposure to [Omim]Cl and [Omim]BF4. The letter R represents the anions Cl(-) and BF4 (.)

  5. Spectrophotometric study of closed-tube chemical transport of vanadium oxides with TeCl/sub 4/

    Energy Technology Data Exchange (ETDEWEB)

    Ohtani, T; Yamaoka, T; Shimamura, K

    1986-06-01

    The in situ observations of the gaseous species in the closed-tube chemical transport systems, V/sub 2/O/sub 3/-TeCl/sub 4/, V/sub 5/O/sub 9/-TeCl/sub 4/, VO/sub 2/-TeCl/sub 4/, V/sub 6/O/sub 13/-TeCl/sub 4/, and V/sub 2/O/sub 5/-TeCl/sub 4/ were made by using an UV and VIS spectrophotometer which was improved for the high-temperature measurements. The measurements showed that a great majority of gaseous species in the transport tube is VOCl/sub 3/ for all the systems, which is in agreement with the earlier result of the mass spectrometry on the VO/sub 2/-TeCl/sub 4/ system.

  6. Structural and electrochemical properties of Cl-doped LiFePO{sub 4}/C

    Energy Technology Data Exchange (ETDEWEB)

    Sun, C.S.; Zhang, Y.; Zhang, X.J.; Zhou, Z. [Institute of New Energy Material Chemistry, Nankai University, Tianjin 300071 (China)

    2010-06-01

    Cl-doped LiFePO{sub 4}/C cathode materials were synthesized through a carbothermal reduction route, and the microstructure and electrochemical performances were systematically studied. Cl-doped LiFePO{sub 4}/C cathode materials presented a high discharge capacity of {proportional_to}90 mAh g{sup -1} at the rate of 20 C (3400 mA g{sup -1}) at room temperature. Electrochemical impedance spectroscopy and cyclic voltamperometry indicated the optimized electrochemical reaction and Li{sup +} diffusion in the bulk of LiFePO{sub 4} due to Cl-doping. The improved Li{sup +} diffusion capability is attributed to the microstructure modification of LiFePO{sub 4} via Cl-doping. (author)

  7. DNA scanning mechanism of T4 endonuclease V. Effect of NaCl concentration on processive nicking activity

    International Nuclear Information System (INIS)

    Gruskin, E.A.; Lloyd, R.S.

    1986-01-01

    T4 endonuclease V is a pyrimidine dimer-specific endonuclease which generates incisions in DNA at the sites of pyrimidine dimers by a processive reaction mechanism. A model is presented in which the degree of processivity is directly related to the efficacy of the one-dimensional diffusion of endonuclease V on DNA by which the enzyme locates pyrimidine dimers. The modulation of the processive nicking activity of T4 endonuclease V on superhelical covalently closed circular DNA (form I) which contains pyrimidine dimers has been investigated as a function of the ionic strength of the reaction. Agarose gel electrophoresis was used to separate the three topological forms of the DNA which were generated in time course reactions of endonuclease V with dimer-containing form I DNA in the absence of NaCl, and in 25, 50, and 100 mM NaCl. The degree of processivity was evaluated in terms of the mass fraction of form III (linear) DNA which was produced as a function of the fraction of form I DNA remaining. Processivity is maximal in the absence of NaCl and decreases as the NaCl concentration is increased. At 100 mM NaCl, processivity is abolished and endonuclease V generates incisions in DNA at the site of dimers by a distributive reaction mechanism. The change from the distributive to a processive reaction mechanism occurs at NaCl concentrations slightly below 50 mM. The high degree of processivity which is observed in the absence of NaCl is reversible to the distributive mechanism, as demonstrated by experiments in which the NaCl concentration was increased during the time course reaction. In addition, unirradiated DNA inhibited the incision of irradiated DNA only at NaCl concentrations at which processivity was observed

  8. Investigation of the magnetic structure of KFeCl3, KFeBr3, Rb2MnCl4, and Rb3Mn2Cl7 compounds with magnetic correlations in one and two dimensions

    International Nuclear Information System (INIS)

    Gurewitz, E.

    1976-12-01

    The crystallographic structure of KFeCl 3 and KFeBr 3 consists of (FeCl) - octahedra packed in isolated zigzagging chains. These compounds order antiferromagnetically at Tsub(N) approximately 16 deg K and Tsub(N) approximately 9.5 deg K, respectively. Below Tsub(N) the Fe 2+ magnetic moments within a chain are ferromagnetically coupled, parallel to the chain axis, while the chains are coupled antiferromagnetically. In the temperatures Tsub(N) 3 has magnetic correlations within the chains only, whereas the correlations between the chains are negligible. Moessbauer effect measurements at these temperatures show a distinct hyperfine magnetic splitting, characteristic of relaxation phenomena. Cs 2 MnCl 4 , Rb 2 MnCl 4 and Rb 3 Mn 2 Cl 7 belong to the Asub(n+1)Bsub(n)Xsub(3n+1) family of compounds, with the Dsub(4h)sup(17) space group. These compounds order antiferromagnetically at Tsub(N) approximately 55 deg K for Cs 2 MnCl 4 and Rb 2 MnCl 4 , and Tsub(N) approximately 64.5 deg K for Rb 3 Mn 2 Cl 7 . Below Tsub(N) each Mn 2+ moment is along the c-axis and is coupled antiferromagnetically to the moments of its nearest neighbours (nn). These compounds behave like a two-dimensional antiferromagnet at T >= Tsub(N). Neutron scans of the reciprocal space exhibit rods of reflections along c vectorsup(*). The negligible interactions between next nn sets of MnCl 2 layers, a distance c vector apart, yield both in Rb 2 MnCl 4 and in Rb 3 Mn 2 Cl 7 , two distinctive magnetic structures (polytypes) below Tsub(N). (author)

  9. Saturated steams pressure of HfCl4-KCl molten mixtures

    International Nuclear Information System (INIS)

    Salyulev, A.B.; Smirnov, M.V.; Kudyakov, V.Ya.

    1980-01-01

    A bellows null pressure gauge and the dynamic method were used to measure the total and partial pressures of saturated vapors of individual components of molten HfCl 4 -KCl mixtures, as a function of temperature (260 to 1000 deg C) and composition (1.9 to 64.3 mol.% HfCl 4 ). Empirical equations expressing the relationship between pressure and temperature are presented. It is shown that in molten mixtures of hafnium tetrachloride with chlorides of alkaline metals its partial pressure dramatically increases when potassium chloride substitutes for cesium chloride

  10. Electrochemical and spectroscopie behaviour of iron in the molten NaCl-K2SO4 mixture

    DEFF Research Database (Denmark)

    Bjerrum, Niels; Petruchina, Irina; Volkov, S.V.

    1996-01-01

    The chemical and electrochemical dissolving of Armco iron in the NaCl-K2SO4 melt has been studied. In the case of the chemical dissolution, a sample becomes coated, as time goes on, with a dense film consisting of FeO, FeS and Fe3O4; precipitation in the melt is observed, the precipitate consisting...... not detect Fe(III) by electronic absorption spectra, possibly due to the superimposition of the charge transfer bands edge on low-intensity Fe(III) bands of the 5d electronic configuration. The solubility of Fe2O3 in the NaCl-K2SO4 melt is low and was determined to 2 x 10(-3) wt%....

  11. Characterization of the Fermi surface of BEDT-TTF4[Hg2Cl6].PhCl by electronic band structure calculations

    International Nuclear Information System (INIS)

    Veiros, L.F.; Canadell, E.

    1994-01-01

    Tight-binding band structure calculations for the room temperature structure of BEDT-TTF 4 [Hg 2 Cl 6 ]-PhCl show the existence of closed electron and hole Fermi surfaces, in agreement with the 2D metallic conductivity of this salt. It is shown that these closed Fermi surfaces result from the hybridization of two hidden 1D Fermi surfaces. However, our study also shows that a transition associated with either a usual or a hidden nesting type mechanism is unlikely. This explains why this salt retains its metallic properties without any resistivity anomaly down to 1.3 K. Our study suggests that BEDT-TTF 4 [Hg 2 Cl 6 ]-PhCl is somewhat anisotropic 2D semimetal and should exhibit Shubnikov-de Haas oscillations corresponding to a cross-sectional area of approximately 13% of the first Brillouin zone. (orig.)

  12. SEPARATION OF CsCl FROM LiCl-CsCl MOLTEN SALT BY COLD FINGER MELT CRYSTALLIZATION

    Directory of Open Access Journals (Sweden)

    JOSHUA R. VERSEY

    2014-06-01

    Full Text Available This study provides a fundamental understanding of a cold finger melt crystallization technique by exploring the heat and mass transfer processes of cold finger separation. A series of experiments were performed using a simplified LiCl-CsCl system by varying initial CsCl concentrations (1, 3, 5, and 7.5 wt%, cold finger cooling rates (7.4, 9.8, 12.3, and 14.9 L/min, and separation times (5, 10, 15, and 30 min. Results showed a potential recycling rate of 0.36 g/min with a purity of 0.33 wt% CsCl in LiCl. A CsCl concentrated drip formation was found to decrease crystal purity especially for smaller crystal formations. Dimensionless heat and mass transfer correlations showed that separation production is primarily influenced by convective transfer controlled by cooling gas flow rate, where correlations are more accurate for slower cooling gas flow rates.

  13. Seperation of CsCl from LiCl-CsCl molten salt by cold finger melt cryst allization

    Energy Technology Data Exchange (ETDEWEB)

    Versey, Joshua R. [Dept. of Chemical and Materials Engineering and Nuclear Engineering Program University of Idaho, Idaho (United States); Phongikaroon, Supathorn [Dept. of Mechanical and Nuclear Engineering Virginia Commonwealth University, Richmond (Korea, Republic of); Simpson, Michael F. [Dept. of Metallurgical Engineering University of Utah, Utah (Korea, Republic of)

    2014-06-15

    This study provides a fundamental understanding of a cold finger melt crystallization technique by exploring the heat and mass transfer processes of cold finger separation. A series of experiments were performed using a simplified LiCl-CsCl system by varying initial CsCl concentrations (1, 3, 5, and 7.5 wt%), cold finger cooling rates (7.4, 9.8, 12.3, and 14.9 L/min), and separation times (5, 10, 15, and 30 min). Results showed a potential recycling rate of 0.36 g/min with a purity of 0.33 wt% CsCl in LiCl. A CsCl concentrated drip formation was found to decrease crystal purity especially for smaller crystal formations. Dimensionless heat and mass transfer correlations showed that separation production is primarily influenced by convective transfer controlled by cooling gas flow rate, where correlations are more accurate for slower cooling gas flow rates.

  14. Synthesis, single-crystal structure determination and Raman spectrum of Ca{sub 2.57(4)}Sr{sub 0.43(4)}Cl{sub 2}[CBN

    Energy Technology Data Exchange (ETDEWEB)

    Reckeweg, Olaf; DiSalvo, Francis J. [Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology; Schulz, Armin [Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany)

    2017-05-01

    Solid-state reaction of Ca, CaCl{sub 2}, Sr, SrCl{sub 2}, C and BN at 900 C for 3 days yielded transparent red needles of Ca{sub 2.57(4)}Sr{sub 0.43(4)}Cl{sub 2}[CBN] as minority product (<10%) mixed with crystals of isotypic yellow Ca{sub 3}Cl{sub 2}[CBN] and orange Sr{sub 3}Cl{sub 2}[CBN]. Ca{sub 2.57(4)}Sr{sub 0.43(4)}Cl{sub 2}[CBN] crystallizes in the space group Pnma (no.62) with the unit cell parameters of a=1389.2(6), b=386.05(15) and c=1131.2(4)pm (Z=4). The Raman spectrum confirms the presence of the [CBN]{sup 4-} unit. The incremental volume of the [CBN]{sup 4-} is calculated to be 50.7(10) Aa{sup 3}.

  15. Dissociation dynamics of anionic and excited neutral fragments of gaseous SiCl4 following Cl 2p and Si 2p core-level excitations

    International Nuclear Information System (INIS)

    Chen, J M; Lu, K T; Lee, J M; Chou, T L; Chen, H C; Chen, S A; Haw, S C; Chen, T H

    2008-01-01

    The state-selective dissociation dynamics for anionic and excited neutral fragments of gaseous SiCl 4 following Cl 2p and Si 2p core-level excitations were characterized by combining measurements of the photon-induced anionic dissociation, x-ray absorption and UV/visible dispersed fluorescence. The transitions of core electrons to high Rydberg states/doubly excited states in the vicinity of both Si 2p and Cl 2p ionization thresholds of gaseous SiCl 4 lead to a remarkably enhanced production of anionic, Si - and Cl - , fragments and excited neutral atomic, Si*, fragments. This enhancement via core-level excitation near the ionization threshold of gaseous SiCl 4 is explained in terms of the contributions from the Auger decay of doubly excited states, shake-modified resonant Auger decay, or/and post-collision interaction. These complementary results provide insight into the state-selective anionic and excited neutral fragmentation of gaseous molecules via core-level excitation.

  16. Mechanism of H2O-Induced Conductance Changes in AuCl4-Functionalized CNTs

    KAUST Repository

    Murat, Altynbek

    2015-04-30

    We employ ab initio self-interaction corrected density functional theory combined with the nonequilibrium Green\\'s function method to study the electronic and quantum transport properties of carbon nanotubes (CNTs) functionalized with AuCl4 molecules. In particular, we investigate the electronic structure and characterize the conductance for different concentrations and configurations of randomly distributed AuCl4 molecules with and without the adsorption of H2O. We thus propose a mechanism that explains the origin of the recently observed resistivity changes of AuCl4-functionalized CNTs upon H2O adsorption. We find that water adsorption shifts the highest occupied Cl and Au states down in energy and thereby reduces the scattering of the electrons around the Fermi energy, hence enhancing the conductivity. Our results help in the development of highly sensitive nanoscale H2O vapor sensors based on AuCl4-functionalized CNTs. © 2015 American Chemical Society.

  17. Luminescence and energy transfer of Sm3+ and Eu3+ in Ca2PO4Cl

    International Nuclear Information System (INIS)

    Wang, Zhijun; Li, Panlai; Yang, Zhiping; Guo, Qinglin

    2014-01-01

    Sm 3+ , Eu 3+ , and Sm 3+ –Eu 3+ doped Ca 2 PO 4 Cl phosphors are synthesized by a solid-state method. Ca 2 PO 4 Cl:Sm 3+ can produce red emission under the 400 nm radiation excitation, and the emission peak is located at 601 nm, which is assigned to the 4 G 5/2 → 6 H 7/2 transition of Sm 3+ . Ca 2 PO 4 Cl:Eu 3+ can create red emission under the 392 nm radiation excitation, and the strongest peak is located at 620 nm, which is attributed to the 5 D 0 → 7 F 2 transition of Eu 3+ . The energy transfer from Sm 3+ to Eu 3+ in Ca 2 PO 4 Cl has been validated and the critical distance (R c ) of Sm 3+ to Eu 3+ in Ca 2 PO 4 Cl is calculated to be 1.14 nm. With increasing Eu 3+ doping concentration, the energy transfer efficiency (Sm 3+ →Eu 3+ ) gradually increases to 53.7%. The luminescence property of Ca 2 PO 4 Cl:Sm 3+ , Eu 3+ can be tuned by properly tuning the relative ratio of Sm 3+ –Eu 3+ , and the emission intensity of Ca 2 PO 4 Cl:Eu 3+ can be greatly enhanced by codoped Sm 3+ . - Highlights: • Ca 2 PO 4 Cl:Sm 3+ , Eu 3+ can produce red emission under the 400 nm radiation excitation. • The energy transfer from Sm 3+ to Eu 3+ in Ca 2 PO 4 Cl has been validated. • The critical distance of Sm 3+ to Eu 3+ in Ca 2 PO 4 Cl is calculated to be 1.14 nm

  18. Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

    Science.gov (United States)

    Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

    2001-11-05

    A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo

  19. Impedance spectroscopy study of dehydrated chitosan and chitosan containing LiClO4

    International Nuclear Information System (INIS)

    Costa, M.M.; Terezo, A.J.; Matos, A.L.; Moura, W.A.; Giacometti, Jose A.; Sombra, A.S.B.

    2010-01-01

    Cast films of chitosan and chitosan containing LiClO 4 were characterized using Fourier transform infrared spectroscopy and the thermogravimetric technique. The electric properties of hydrated and dehydrated films were investigated with impedance spectroscopy in the frequency range from 0.1 Hz to 1 MHz, at temperatures varying from 30 to 110 o C. The frequency dependence of the impedance for dehydrated chitosan and chitosan containing LiClO 4 films indicated ionic conduction. Two relaxation peaks were evident on the imaginary curve of the electric modulus, which were assigned to ionic conduction. The peak at higher frequency was found for chitosan and chitosan containing LiClO 4 films. The peak at lower frequency was attributed to Li + conduction since it appeared only for the chitosan containing LiClO 4 . The peak frequency varied with the temperature according to an Arrhenius process with activation energies of circa of 0.6 and 0.45 eV, for H + and Li + conduction, respectively.

  20. Influence of TiCl4 post-treatment condition on TiO2 electrode for enhancement photovoltaic efficiency of dye-sensitized solar cells.

    Science.gov (United States)

    Eom, Tae Sung; Kim, Kyung Hwan; Bark, Chung Wung; Choi, Hyung Wook

    2014-10-01

    Titanium tetrachloride (TiCl4) treatment processed by chemical bath deposition is usually adopted as pre- and post-treatment for nanocrystalline titanium dioxide (TiO2) film deposition in the dye-sensitized solar cells (DSSCs) technology. TiCl4 post-treatment is a widely known method capable of improving the performance of dye-sensitized solar cells. In this work, the effect of TiCl4 post-treatment on the TiO2 electrode is proposed and compared to the untreated film. A TiO2 passivating layer was deposited on FTO glass by RF magnetron sputtering. The TiO2 sol prepared sol-gel method, nanoporous TiO2 upper layer was deposited by screen printing method on the passivating layer. TiCl4 post-treatment was deposited on the substrate by hydrolysis of TiCl4 aqueous solution. Crystalline structure was adjusted by various TiCl4 concentration and dipping time: 20 mM-150 mM and 30 min-120 min. The conversion efficiency was measured by solar simulator (100 mW/cm2). The dye-sensitized solar cell using TiCl4 post-treatment was measured the maximum conversion efficiency of 5.04% due to electron transport effectively. As a result, the DSSCs based on TiCl4 post-treatment showed better photovoltaic performance than cells made purely of TiO2 nanoparticles. The relative DSSCs devices are characterized in terms of short circuit current density, open circuit voltage, fill factor, conversion efficiency.

  1. Effect of TiCl4 treatment on the refractive index of nanoporous TiO2 films

    Science.gov (United States)

    Lee, Jeeyoung; Lee, Myeongkyu

    2015-12-01

    We investigate the effect of TiCl4 treatment on the refractive index of a nanoporous TiO2 film. A nanoparticulate TiO2 film prepared on a glass substrate was immersed in a TiCl4 aqueous solution. The subsequent reaction of TiCl4 with H2O produces TiO2 and thus modifies the density and the refractive index of the film. With increasing TiCl4 concentration, the refractive index initially increased and then declined after being maximized (n = 2.02 at 633 nm) at 0.08 M concentration. A refractive index change as large as 0.45 could be obtained with the TiCl4 treatment, making it possible to achieve diffraction efficiency exceeding 80% in a diffraction grating-embedded TiO2 film. For high TiCl4 concentrations of 0.32 M and 0.64 M, the refractive index remained nearly unchanged. This was attributed to the limited permeability of high-viscosity TiCl4 solutions into the nanoporous films. The measured pore size distributions were in good agreement with the results of a diffraction analysis and refractive index measurement.

  2. Synthesis and the crystal and molecular structures of (H3L . Cl)[CoCl4] and H2L[CuBr4] (L is 2,4,6-Tri(N,N-dimethylamino)methylphenol)

    International Nuclear Information System (INIS)

    Kovalchukova, O. V.; Stash, A. I.; Strashnova, S. B.; Romashkina, E. P.; Zaitsev, B. E.

    2010-01-01

    The complex compounds (H 3 L . Cl)[CoCl 4 ] (I) and H 2 L[CuBr 4 ] (II), where L is 2,4,6-tri(N,N-dimethylamino)methylphenol, were isolated in the crystalline state and studied by X-ray diffraction. The organic cations were found to be outer-sphere ligands. All three nitrogen atoms of the tertiary amino groups are protonated. In compound I, the H 3 L 3+ cation exists as the cis tautomer. In compound II, the H 2 L 2+ dication exists as the trans isomer. In the crystal structure, the dications are arranged in layers via hydrogen bonds.

  3. Research and development on groundwater dating. Part 11. The proposal of separation method of chloride and sulfate ion for accurate measurement of 36Cl/Cl

    International Nuclear Information System (INIS)

    Nakata, Kotaro; Hasegawa, Takuma

    2010-01-01

    36 Cl is one of the most powerful tools to estimate the residence time of groundwater about 300-1800 thousand years. AMS(Accelerator Mass Spectroscopy) can provide accurate estimation of 36 Cl. However, estimation of 36 Cl by AMS is usually disturbed by isobar such as 36 S. Thus, separation of Cl (usually Cl - form in groundwater) and S (usually SO 4 -2 form in groundwater) is required for accurate estimation of 36 Cl. In previous studies, a methodology (BaSO 4 Method) that uses the difference in solubility between BaSO 4 and BaCl 2 , had been applied as pretreatment method for 36 Cl estimation by AMS. However BaSO 4 Method has following disadvantages; (1) Cl and SO 4 can not be separated completely, (2) accuracy of separation depends on the skills of operator, (3) it takes a long time for treatment, (4) it can not be applied to dilute solutions. Therefore, new methodology that can overcome disadvantages of BaSO 4 method is required for more accurate estimation of 36 Cl. In this study, Column Method based on column chromatography was investigated for pretreatment method for 36 Cl estimation by AMS to separate Cl and SO 4 ions. The conditions for Column Method were determined and adjusted so that Cl and SO 4 ions were separated completely and sufficient amount of Cl for 36 Cl estimation can be treated. The results of AMS measurement showed Column Method can remove SO 4 from Cl more effectively comparing with BaSO 4 method. Furthermore, Column Method was found to have following advantages over BaSO 4 Method; (1) dependence of accuracy of separation on the skills of operator is quite low, (2) treatment can be done within 6 h, (3) it can be applied to dilute solutions. (author)

  4. Saturated steams pressure of HfCl/sub 4/-KCl molten mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Salyulev, A B; Smirnov, M V; Kudyakov, V Ya [AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii

    1980-02-01

    A bellows null pressure gauge and the dynamic method were used to measure the total and partial pressures of saturated vapors of individual components of molten HfCl/sub 4/-KCl mixtures, as a function of temperature (260 to 1000 deg C) and composition (1.9 to 64.3 mol.% HfCl/sub 4/). Empirical equations expressing the relationship between pressure and temperature are presented. It is shown that in molten mixtures of hafnium tetrachloride with chlorides of alkaline metals its partial pressure dramatically increases when potassium chloride substitutes for cesium chloride.

  5. NMR insights on the properties of ZnCl2 molten salt hydrate medium through its interaction with SnCl4 and fructose

    DEFF Research Database (Denmark)

    Qiao, Yan; Pedersen, Christian Marcus; Wang, Yingxiong

    2014-01-01

    The solvent properties of ZnCl2 molten salt medium and its synergic effect with the Lewis acid catalyst, Sn4+, for biomass conversion, were investigated by nuclear magnetic resonance. The tautomeric distribution of fructose in the ZnCl2 molten salt medium was examined, and its effect for humins...... formation during the biomass conversion was evaluated. The ion complex composed by Sn4+ and Zn2+ indicated that there is a synergic catalytic effect between these two Lewis acid ions. 13C NMR spectra of fructose in different ZnCl2 molten salt hydrate concentrations revealed that the concentration of β...

  6. Neutron diffraction study of structural changes in ammonium halides ND4Br and ND4Cl under high pressure

    International Nuclear Information System (INIS)

    Balagurov, A.M.; Kozlenko, D.P.; Savenko, B.N.; Glazkov, V.P.; Somenkov, V.A.

    1997-01-01

    Structural changes in ammonium halides ND 4 Br and ND 4 Cl at pressures up to 45 kbar and up to 35 kbar, respectively, have been studied with the DN-12 diffractometer at the IBR-2 pulsed reactor. For both systems, the equation of state and the position parameter of deuterium atoms as functions of pressure were obtained. The obtained equations of state are nearly the same as the ones for the nondeuterated systems NH 4 Br and NH 4 Cl obtained by the piston displacement technique. It was found that the order - disorder phase transition from the phase in which the ammonium tetrahedra are randomly oriented (CsCl-type cubic structure, space group Pm3m) into the phase in which the ammonium tetrahedra are oriented in parallel (CsCl-type cubic structure, space group P4 bar 3m), occurs at equal critical value of the position parameter u=0.153 ± 0.002 in both systems. It appears to be valid for all of the ammonium halides, and, possibly, for other similar compounds. (author)

  7. Thermodynamic modeling of neptunium(V) solubility in concentrated Na-CO3-HCO3-Cl-ClO4-H-OH-H2O systems

    International Nuclear Information System (INIS)

    Novak, C.F.; Roberts, K.E.

    1994-01-01

    Safety assessments of nuclear waste repositories often require estimation of actinide solubilities as a function of groundwater composition. Although considerable amount of research has been done on the solubility and speciation of actinides, relatively little has been done to unify these data into a model applicable to concentrate brines. Numerous authors report data on the aqueous chemical properties of Np(V) in NaClO 4 , Na 2 CO 3 , and NaCl media, but a consistent thermodynamic model for predicting these properties is not available. To meet this need, a model was developed to describe the solubility of Np(V) in Na-Cl-ClO 4 -CO 3 aqueous systems, based on the Pitzer activity coefficient formalism for concentrated electrolytes. Hydrolysis and/or carbonate complexation are the dominant aqueous reactions with neptunyl in these systems. Literature data for neptunyl extraction and solubility, and solubility data that the authors developed, are used to parameterize an integrated model for Np(V) solubility in the Np(V)-Na-CO 3 -HCO 3 -Cl-ClO 4 -H-OH-H 2 O system. The resulting model is tested against additional solubility data, and compared with Np(V) solubility experiments in complex synthetic brines

  8. The dynamics of ammonium ions in K1-x(NH4)xCl mixed crystals by the neutron scattering study

    International Nuclear Information System (INIS)

    Smirnov, L.S.; Natkanets, I.; Shuvalov, L.A.; Dolbinina, V.V.

    2004-01-01

    The study of vibrational spectrum of the K 1-x (NH 4 ) x Cl mixed crystals in a dynamically disordered cubic α-phase at 10 K is carried out by means of inelastic incoherent neutron scattering on the NERA-PR time-of-flight spectrometer set at the IBR-2 reactor (JINR, Dubna). It is shown that low-energy modes of ammonium ions with the energies 19-23 and 62-63 cm -1 at 10 K are observed only within the disordered cubic α-phase and are absent in the ordered cubic δ-phase of NH 4 Cl. The energies of local translation and libration modes of ammonium ions are determined in the α- and δ-phases of the K 1-x (NH 4 ) x Cl mixed crystals

  9. Insulators containing CuCl4X22- (X=H2O, NH3) units: Origin of the orthorhombic distortion observed only for CuCl4(H2O)22-

    DEFF Research Database (Denmark)

    García-Fernández, P.; García Lastra, Juan Maria; Trueba, A.

    2012-01-01

    The origin of the difference in structure between compounds containing CuCl4X22- (X=H2O, NH3) units is analyzed by means of first-principles calculations. While NH3-containing compounds display tetragonal symmetry, H2O-containing ones display an orthorhombic distortion at low temperature where...... the equatorial Cl- ions are no longer equivalent. Our simulations of optical and vibrational transitions show good agreement with all available experimental optical absorption and Raman data. As a salient feature, the value of the force constant for the B1g mode, K(B1g), driving the orthorhombic distortion......CuCl4(H2O)2 has a local origin....

  10. Quasielastic neutron scattering and infra-red band contour study of H2O reorientations in [Ni(H2O)6] (ClO4)2

    International Nuclear Information System (INIS)

    Janik, J.A.; Janik, J.M.; Otnes, K.; Stanek, T.

    1980-01-01

    IR band contour measurements carried out for [Ni(H 2 O) 6 ] (ClO 4 ) 2 revealed an existence of fast H 2 O 180 deg flips around Ni-O axes at room temperatures. These flips were subjected to a more accurate study by the quasielastic neutron scattering method. Correlation times of the order of picosecond were obtained for room temperatures and the barrier to rotation of ca. 7 kcal/mole. The results are compared to those previously obtained for [Mg(H 2 O) 6 ] (ClO 4 ) 2 and also to those for [Ni(NH 3 ) 6 ] (ClO 4 ) 2 and [Mg(NH 3 ) 6 ] (ClO 4 ) 2 . (author)

  11. Study of NaBH4 reaction with RhCl4H2O and H2PtCl6·6H2O in dimethylformamide

    International Nuclear Information System (INIS)

    Khain, V.S.; Val'kova, V.P.

    1988-01-01

    Data on study of NaBH 4 reactions with RhCl 3 x4H 2 O and H 2 PtCl 6 x6H 2 O in dimethylformamide, which is a good solvent of both complex hydride and compounds of platinum metals are presented. Rhodium (3) and platinum (4) reduction by sodium tetrahydridoborate in dimethylformamide proceeds quantitatively up to element state. Depositions of powder-like rhodium and platinum or their sols stable up to 8 months are formed depending on the ratio of concentrations of the reacting substances. Stoichiometry of redox-reactions is established based on spectrophotometric, gasovolumetric measurements,

  12. X-ray photoelectron investigation of UO2(ClO4)2 interaction with diabase

    International Nuclear Information System (INIS)

    Teterin, Yu.A.; Nefedov, V.I.; Ivanov, K.E.; Baev, A.S.; Gajpel', G.; Rajkh, T.; Niche, Kh.

    1996-01-01

    X-ray diffraction study was made on interaction of soluble uranyl perchlorate with diabase, composing rocks in regions of Chelyabinsk and Chernobyl accidents and in places of radioactive waste burials. Absence of ClO 4 - anion in analyzed products of UO 2 (ClO 4 ) 2 interaction with diabase testifies to the absence of physio- or chemosorbed UO 2 (ClO 4 ) 2 layer on its surface. Formation of uranyl compounds (uranyl hydroxides) on diabase surface was confirmed, and bond lengths for these compounds were determined. Reaction of substitution of uranium ions for calcium ions proceeds more actively in the surface layers of diabase grains. 4 refs.; 3 tabs

  13. Apparent molar heat capacities and apparent molar volumes of Pr(ClO4)3(aq), Gd(ClO4)3(aq), Ho(ClO4)3(aq), and Tm(ClO4)3(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

    International Nuclear Information System (INIS)

    Hakin, Andrew W.; Lian Liu, Jin; Erickson, Kristy; Munoz, Julie-Vanessa

    2004-01-01

    Acidified aqueous solutions of Pr(ClO 4 ) 3 (aq), Gd(ClO 4 ) 3 (aq), Ho(ClO 4 ) 3 (aq), and Tm(ClO 4 ) 3 (aq) were prepared from the corresponding oxides by dissolution in dilute perchloric acid. Once characterized with respect to trivalent metal cation and acid content, the relative densities of the solutions were measured at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa using a Sodev O2D vibrating tube densimeter. The relative massic heat capacities of the aqueous systems were also determined, under the same temperature and pressure conditions, using a Picker Flow Microcalorimeter. All measurements were made on solutions containing rare earth salt in the concentration range 0.01 ≤ m/(mol · kg -1 ) ≤ 0.2. Relative densities and relative massic heat capacities were used to calculate the apparent molar volumes and apparent molar heat capacities of the acidified salt solutions from which the apparent molar properties of the aqueous salt solutions were extracted by the application of Young's Rule. The concentration dependences of the isothermal apparent molar volumes and heat capacities of each aqueous salt solution were modelled using Pitzer ion-interaction equations. These models produced estimates of apparent molar volumes and apparent molar heat capacities at infinite dilution for each set of isothermal V phi,2 and C pphi,2 values. In addition, the temperature and concentration dependences of the apparent molar volumes and apparent molar heat capacities of the aqueous rare earth perchlorate salt solutions were modelled using modified Pitzer ion-interaction equations. The latter equations utilized the Helgeson, Kirkham, and Flowers equations of state to model the temperature dependences (at p=0.1 MPa) of apparent molar volumes and apparent molar heat capacities at infinite dilution. The results of the latter models were compared to those previously published in the literature. Apparent molar volumes and apparent heat capacities at infinite dilution

  14. Magnetic properties of 1 : 4 complexes of CoCl2 and pyridines carrying carbenes (S(0) = 4/2, 6/2, and 8/2) in diluted frozen solution; influence of carbene multiplicity on heterospin single-molecule magnets.

    Science.gov (United States)

    Karasawa, Satoru; Nakano, Kimihiro; Tanokashira, Jun-ichi; Yamamoto, Noriko; Yoshizaki, Takahito; Koga, Noboru

    2012-11-28

    The microcrystalline sample of a parent complex, [CoCl(2)(py)(4)], showed a single-molecule magnet (SMM) behavior with an effective activation barrier, U(eff)/k(B), of 16 K for reversal of the magnetism in the presence of a dc field of 3 kOe. Pyridine ligands having 2-4 diazo moieties, DYpy; Y = 2, 3l, 3b, and 4, were prepared and confirmed to be quintet, septet, septet, and nonet in the ground state, respectively, after irradiation. The 1 : 4 complexes, CoCl(2)(DYpy)(4); Y = 2, 3l, 3b, and 4 in frozen solutions after irradiation showed the magnetic behaviors of SMMs with total spin multiplicity, S(total) = 17/2, 25/2, 25/2, and 33/2, respectively. Hysteresis loops depending on the temperature were observed and the values of coercive force, H(c), at 1.9 K were 12, 8.4, 11, and 8.1 kOe for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively. In dynamic magnetic susceptibility experiments, ac magnetic susceptibility data obeyed the Arrhenius law to give U(eff)/k(B) values of 94, 92, 93, and 87 K for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively, while the relaxation times for CoCl(2)(CYpy)(4); Y = 2 and 3l, obtained by dc magnetization decay in the range of 3.5-1.9 K slightly deviated downward from Arrhenius plots on cooling. The dynamic magnetic behaviors for CoCl(2)(CYpy)(4) including [CoCl(2)(py)(4)] and CoCl(2)(C1py)(4) suggested that the generated carbenes interacted with the cobalt ion to increase the relaxation time, τ(q), due to the spin quantum tunneling magnetization, which became larger with increasing S(total) of the complex.

  15. Life-time resolved emission spectra in CdCl2 crystals

    International Nuclear Information System (INIS)

    Kawabata, S.; Nakagawa, H.; Kitaura, M.

    2005-01-01

    The emission spectrum of CdCl 2 is composed of ultraviolet (UV) and yellow (Y) bands peaking at 3.70 and 2.30 eV, respectively. In order to determine the initial states of the Y-luminescence, decay curves of the Y-emission were measured at 8K by varying emission energy in the range from 1.64 eV to 3.13 eV. The observed decay curves are composed of two or three exponential components. The values of lifetime for them were 900, 460 and 60 μs. The emission spectrum for each decay component, i.e., life-time resolved emission spectrum, was analyzed by the observed decay curves. The emission spectrum for the component of 460 μs lifetime exhibits a dominant band at 2.30 eV and a satellite band at 3.03 eV. The emission spectrum for the component of 60 μs lifetime is reproduced by the three Gaussian bands peaking at 2.21, 2.65 and 2.87 eV. For the component of 900 μs lifetime, only a single band appears at 1.73 eV. The origin of the emission bands in life-time resolved emission spectra is briefly discussed, and the initial states of Y-luminescence are explained by the excited states of a [Cd 2+ Cl - 6 ] 4- complex molecular ion. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. A hydrochemical investigation using 36Cl/Cl in groundwaters

    International Nuclear Information System (INIS)

    Metcalfe, Richard

    2003-03-01

    This report describes 36 Cl studies which were undertaken during the H14 financial year. The results of this study suggest that, if 36 Cl data can be obtained for groundwaters at spatial scales comparable with, or smaller than, the spatial scales of the variability in in-situ 36 Cl production in the host rock, the data could potentially be useful for interpreting groundwater origins and flow paths. Four groundwater samples and one onsen water sample from the Tono area were collected for 36 Cl analysis. The groundwater samples came from boreholes MSB-2 and MSB-4 in the MIU Construction Site, whereas the onsen water was taken from Oniiwa Onsen (Komatsuya). In addition, a single sample from borehole HDB-1 at Horonobe was also sent for analysis. Supporting rock chemical data and wireline geophysical data have also been evaluated, to provide a basis for interpreting the 36 Cl data. Rock analyses and spectral gamma wireline data were used to estimate theoretical limiting equilibrium 36 Cl/Cl ratios in the rock. These have been compared with the compositions measured for groundwater samples, enabling a judgement to be made as to: whether the waters have resided for long enough in the rock to approach equilibrium (> c. 1.5 Ma); the spatial scales of mixing of the dissolved Cl in the groundwater. The estimates of in-situ 36 Cl/Cl production made with the newly available rock chemical data and wireline geophysical data have enabled 36 Cl data obtained previously from MIU-4, KNA-6 and DH-12 during H12 and H13 to be interpreted more confidently. In particular it seems that 36 Cl/Cl ratios measured previously in groundwater samples from MIU-4 are not in equilibrium with in-situ production in the granite. Furthermore, they imply that the Cl is homogenised, at least on the scale of the upper half of borehole. In contrast, the data from DH-12 imply that the Cl could be in equilibrium with in-situ 36 Cl production in the granite, which would be consistent with a relatively long

  17. Substitution and Redox Chemistry of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)].

    Science.gov (United States)

    Prokopuk, Nicholas; Kennedy, Vance O.; Stern, Charlotte L.; Shriver, Duward F.

    1998-09-21

    Two sequential electrochemical reductions occur for the cluster anion [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) at 0.89 and 0.29 V vs Ag/AgCl, with the generation [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) and [Ta(6)Cl(12)(OSO(2)CF(3))(6)](4)(-). Chemical reduction of [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) by ferrocene produces [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) with the concomitant shift of the nu(SO(2)) stretch from 1002 to 1018 cm(-)(1). Reaction of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)] (1) with [Bu(4)N]X (X = Cl, Br, I, NCS) occurs by reduction and substitution, yielding [Bu(4)N](3)[Ta(6)Cl(12)X(6)], where the clusters with X = Br, I, and NCS are new. Spectroscopic (IR and UV-vis) evidence indicates that the reduced cluster core {Ta(6)Cl(12)}(2+) is produced in reaction mixtures of 1 with the halide and pseudohalide ions. Concomitant substitution of the triflate ligands of 1 by X(-) occurs and the rates for the overall reduction and substitution increase in the order X(-) = Cl(-) < Br(-) < NCS(-) < I(-) < CN(-). Reduction of 1 with ferrocene followed by addition of [Bu(4)N]O(2)CCH(3) produces the new cluster [Ta(6)Cl(12)(O(2)CCH(3))(6)](3)(-) isolated as the tetrabutylammonium salt. Cyclic voltammetry and UV-vis spectroscopy on the new clusters [Bu(4)N](3)[Ta(6)Cl(12)X(6)] (X = Br, I, NCS, and O(2)CCH(3)) are reported. Crystal data for [Bu(4)N](3)[Ta(6)Cl(12)(NCS)(6)].CH(2)Cl(2): monoclinic, space group, P2(1)/c (No. 14); a = 25.855(6) Å, b = 21.843(6) Å, c = 16.423(3) Å; beta = 100.03(2) degrees; V = 9133(3) Å(3); Z = 4.

  18. Preparation and characterization of organic-inorganic hybrid perovskite (C4H9NH3)2CuCl4

    International Nuclear Information System (INIS)

    Xiao Zelong; Chen Hongzheng; Shi Minmin; Wu Gang; Zhou Renjia; Yang Zhisheng; Wang Mang; Tang Benzhong

    2005-01-01

    Organic-inorganic hybrid perovskite (C 4 H 9 NH 3 ) 2 CuCl 4 was prepared via the reaction between copper chloride and butylammonium chloride. Its chemical structure was characterized by FT-IR and elemental analysis. Its thin film was obtained by spin-coating, and X-ray diffraction (XRD) measurements indicated the formation of two-dimensional layered perovskites structure, with the c-axis perpendicular to the substrate surface. The electronic structure, thermal properties and electrical properties of the hybrid perovskite (C 4 H 9 NH 3 ) 2 CuCl 4 were also studied by UV-vis, photoluminescience (PL), TGA, DSC, and Hall measurement

  19. Leaching of dieldrin, permethrin, phenyl urea and 4-CL phenyl urea pesticides from soil

    International Nuclear Information System (INIS)

    Onal, G.

    1978-01-01

    Leaching of four 14 C-labelled pesticides (dieldrin, permethrin, phenyl urea and 4-Cl phenyl urea) were investigated. It was found that dieldrin and permethrin were not leached from soil but adsorbed by the soil; phenyl urea and 4-CL phenyl urea were leached to a 7.5 cm depth

  20. Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy

    International Nuclear Information System (INIS)

    Chu, Li-Kang; Han, Hui-Ling; Lee, Yuan-Pern

    2007-01-01

    A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl 2 CS and N 2 or CO 2 with a KrF excimer laser at 248 nm. A transient band in the region of 1160-1220 cm -1 , which diminished on prolonged reaction, is assigned to the C-S stretching (ν 1 ) mode of ClCS. Calculations with density-functional theory (B3P86 and B3LYP/aug-cc-pVTZ) predict the geometry, vibrational wave numbers, and rotational parameters of ClCS. The rotational contour of the spectrum of ClCS simulated based on predicted rotational parameters agrees satisfactorily with experimental observation; from spectral simulation, the band origin is determined to be at 1194.4 cm -1 . Reaction kinetics involving ClCS, CS, and CS 2 are discussed

  1. Solid state physics and actinide spectroscopy with ThBr4 and ThCl4

    International Nuclear Information System (INIS)

    Genet, M.

    1984-01-01

    From the solid state physics to the optical spectroscopy of 5 f elements, we have described in details how ThBr 4 and ThCl 4 are acting an important role in the applied and basic research field. The possible applications are based on the scintillation properties of these crystals while the fundamental aspect is related to their special incommensurate structure which modulates the host properties of these matrices at low temperature. This very small perturbation of bromine atom positions have optical consequences on the absorption and emission of the actinide studied ions which are interpreted in function of the modulated structure parameters determined by inelastic and elastic neutron scattering and by Raman spectroscopy. The structural model proposed shows, for the first time, how the optical properties of the investigated ion are influenced by the sinusoidal displacements of the bromine atoms, leading to an energy continuum in the absorption and reducing the site symmetry from Dsub(2d) to a multisite of D 2 symmetry

  2. Chronic effects of the ionic liquid [C4mim][Cl] towards the microalga Scenedesmus quadricauda

    International Nuclear Information System (INIS)

    Deng, Yun; Beadham, Ian; Wu, Jie; Chen, Xiao-Di; Hu, Lan; Gu, Jun

    2015-01-01

    Chronic effects of the ionic liquid [C 4 mim][Cl] (mp 73 °C) towards the microalga, Scenedesmus quadricauda were studied by flow cytometry, monitoring multiple endpoints of cell density, esterase activity, membrane integrity, reactive oxygen species and chlorophyll fluorescence. Toxicity was clearly in evidence, and although increased esterase activity indicated hormesis during initial exposure to [C 4 mim][Cl], inhibition of both esterase activity and chlorophyll fluorescence became apparent after 3 days. Cell density was also decreased by culturing with [C 4 mim][Cl], but this effect was clearly concentration-dependent and only became significant during the second half of the experiment. In contrast, [C 4 mim][Cl] had only a modest effect on reactive oxygen species (ROS) and caused little damage to cell membranes. - Highlights: • Use of an advanced biological technique, flow cytometry, to elucidate ionic liquid toxicity. • Chronic effects of ionic liquid. • Membrane integrity and ROS studied. • Mechanism of ionic liquid toxicity. - [C 4 mim][Cl] significantly inhibited esterase activity, chlorophyll fluorescence and cell density, having only a modest effect on reactive oxygen species and cell membranes

  3. Anisotropy in Ba2Cu3O4Cl2 single crystals grown by the traveling solvent floating zone method

    International Nuclear Information System (INIS)

    Yamada, Shigeki; Iwagaki, Yohei; Noro, Sumiko

    2007-01-01

    Magnetic and electrical properties of layered copper oxychloride Ba 2 Cu 3 O 4 Cl 2 single crystals are measured. Single crystal growth of Ba 2 Cu 3 O 4 Cl 2 by the traveling solvent floating zone method is attempted using Ba 3 Cu 2 O 4 Cl 2 as solvent. By optimization of the growth conditions, large single crystals of (φ5mmx30mm) of Ba 2 Cu 3 O 4 Cl 2 are grown. The resistivity with the current parallel to the c-axis is 10 2 -10 3 times larger than that with the current perpendicular to the a-axis. The temperature dependence of the dielectric spectrum for each direction is measured and analyzed by using the Debye model. The spectrum width, which is related to the effective number of electrons (n/m), does not show an appreciable dependence on temperature. The characteristic frequencies at which the dielectric constant changes, which are related to the dissipation (γ), increase with warming. The temperature dependence is almost the same as the resistivity curve. This indicates that the hopping process dominates both DC- and AC-type electrical transport. The spectrum width with the electric field parallel to the a-axis is 30 times larger than that with the electric field parallel to the c-axis. On the other hand, the characteristic frequencies do not show an appreciable dependence on electric field direction

  4. Kinetic isotope effects in the gas phase reactions of OH and Cl with CH3Cl, CD3Cl, and 13CH3Cl

    Directory of Open Access Journals (Sweden)

    A. A. Gola

    2005-01-01

    Full Text Available The kinetic isotope effects in the reactions of CH3Cl, 13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2 K and 1013±10 mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of 13CH3Cl and CD3Cl with OH and Cl were determined relative to CH3Cl as: kOH+CH3ClkOH+CH3Cl/kOH+13CH3Cl}kOH+13CH3Cl=1.059±0.008, kOH+CH3ClkOH+CH3Cl/kOH+CD3ClkOH+CD3Cl=3.9±0.4, kCl+CH3ClkCl+CH3Cl/kCl+13CH3ClkCl+13CH3Cl =1.070±0.010 and kCl+CH3ClkCl+CH3Cl/kCl+CD3ClkCl+CD3Cl=4.91±0.07. The uncertainties given are 2σ from the statistical analyses and do not include possible systematic errors. The unexpectedly large 13C kinetic isotope effect in the OH reaction of CH3Cl has important implications for the global emission inventory of CH3Cl.

  5. Further studies on hydration of alkynes by the PtCl4-CO catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Israelsohn, Osnat; Vollhardt, K. Peter C.; Blum, Jochanan

    2002-01-18

    Under CO atmosphere, between 80 and 120 C, a glyme solution of PtCl{sub 4} forms a carbonyl compound that promotes hydration of internal as well as terminal alkynes to give aldehyde-free ketones. The catalytic process depends strongly on the electronic and steric nature of the substrates. Part of the carbonyl functions of the catalyst can be replaced by phosphine ligands. Chiral DIOP reacts with the PtCl{sub 4}-CO compound to give a catalyst that promotes partial kinetic resolution of a racemic alkyne. Replacement of part of the CO by polystyrene-bound diphenylphosphine enables to attach the catalyst to the polymeric support. Upon entrapment of the platinum compound in a silica sol-gel matrix, it reacts as a partially recyclable catalyst. A reformulated mechanism for the PdCl{sub 4}-CO catalyzed hydration is suggested on the basis of the present study.

  6. Photoluminescence properties of X5SiO4Cl6:Tb (X = Sr, Ba) green ...

    Indian Academy of Sciences (India)

    attracted more attention due to their potential applications ... materials were thoroughly mixed and ground in an agate mortar. ... Figure 2. Excitation spectra of Ba5SiO4Cl6:Tb3+ phosphor. spectrum of Tb3+ singly doped phosphor Ba5SiO4Cl6,.

  7. Cu ion disordering in high ionic conductor Rb4Cu16I7Cl13

    International Nuclear Information System (INIS)

    Kawaji, Hitoshi; Atake, Tooru; Kanno, Ryoji; Izumi, Fujio; Yamamoto, Osamu.

    1993-01-01

    The properties of a high ionic conductor Rb 4 Cu 16 I 7+x Cl 13-x were studied by neutron and X-ray diffraction, and heat capacity measurements. The structure parameters of Rb 4 Cu 16 I 7.2 Cl 12.8 were obtained by the Rietveld analysis of TOF neutron diffraction data between 50 and 300 K, which showed gradual excitation of migration of Cu ions from Cu(3) site into Cu(2) site with increasing temperature from about 100 K to room temperature. The heat capacity was measured between 10 and 300 K using a high precision adiabatic calorimeter. An abnormal increase was observed in the heat capacity curve above about 100 K. The excess heat capacity showed a broad anomaly with a maximum at about 190 K. The measurements were also made of Rb 4 Cu 16 I 7 Cl 13 which showed slight different properties from Rb 4 Cu 16 I 7.2 Cl 12.8 . (author)

  8. Study on technology for laboratory scale production of Zirconium Chloride (ZrCl4) by chlorinating Zirconium dioxide (ZrO2)

    International Nuclear Information System (INIS)

    Nguyen Van Sinh

    2007-01-01

    ZrCl 4 is used as a main material for producing metallic zirconium. There are four methods for obtaining ZrCl 4 . The method of chlorination of ZrO 2 was selected and some instruments have been made for the study (to produce ZrCl 4 in laboratory scale). A procedure of preparing ZrCl 4 on the obtained instruments was set up and a small amount of ZrCl 4 was successfully obtained. (author)

  9. Complexation of Am(III) by oxalate in NaClO4 media

    International Nuclear Information System (INIS)

    Choppin, G.R.; Chen, J.F.

    1995-01-01

    The complexation of Am(III) by oxalate has been investigated in solutions of NaClO 4 up to 9.0 M ionic strength at 25 degrees C. The dissociation constants of oxalic acid were determined by potentiometric titration, while the stability constants of the Am(III)-oxalate complexation were measured by the solvent extraction technique. A thermodynamic model was constructed to predict the apparent equilibrium constants at different ionic strengths by applying the Pitzer equation using parameters for the Na + -HOx - , Na + -Ox - , AmOx + -ClO 4 - , and Na + -Am(Ox) 2 - interactions obtained by fitting the data

  10. Electrochemical Deposition of Aluminum from NaCl-AlCl3 Melts

    DEFF Research Database (Denmark)

    Li, Qingfeng; Hjuler, H. A.; Berg, Rolf W.

    1990-01-01

    Electrochemical deposition of aluminum from NaAlCl4 melts saturated with NaCl onto a glassy carbon electrode at175°C has been studied by voltammetry, chronoamperometry, and constant current deposition. The deposition of aluminumwas found to proceed via a nucleation/growth mechanism, and the nucle......Electrochemical deposition of aluminum from NaAlCl4 melts saturated with NaCl onto a glassy carbon electrode at175°C has been studied by voltammetry, chronoamperometry, and constant current deposition. The deposition of aluminumwas found to proceed via a nucleation/growth mechanism......, and the nucleation process was found to be progressive.The morphology of aluminum deposits was examined with photomicroscopy. It was shown that depending on the currentdensities (c.d.) applied, three types of aluminum deposits could be obtained, namely, spongy deposits formed at lower c.d.(below 0.7 mA/cm2), smooth...... layers deposited at intermediate c.d. (between 2 and 10 mA/cm2), and dendritic or porous depositsobtained at high c.d. (above 15 mA/cm2). However, the smooth aluminum deposits were about five times more voluminousthan the theoretical value. The spongy deposits were formed due to difficulties...

  11. Hydrostatic Compression of 2,4,6,8,10,12 hexanitrohexaaza isowurtzitane (CL20) Co Crystals

    Science.gov (United States)

    2016-12-01

    ARL-TR-7901 ● DEC 2016 US Army Research Laboratory Hydrostatic Compression of 2,4,6,8,10,12- hexanitrohexaaza-isowurtzitane (CL20... Hydrostatic Compression of 2,4,6,8,10,12- hexanitrohexaaza-isowurtzitane (CL20) Co-Crystals by DeCarlos Taylor Weapons and Materials...Technical Report 3. DATES COVERED (From - To) October 2015–September 2016 4. TITLE AND SUBTITLE Hydrostatic Compression of 2,4,6,8,10,12

  12. Sources and behavior of perchlorate ions (ClO4-) in chalk aquifer of Champagne-Ardenne, France: preliminary results

    Science.gov (United States)

    Cao, Feifei; Jaunat, Jessy; Ollivier, Patrick; Cancès, Benjamin; Morvan, Xavier; Hubé, Daniel; Devos, Alain; Devau, Nicolas; Barbin, Vincent; Pannet, Pierre

    2018-06-01

    Perchlorate (ClO4-) is an environmental contaminant of growing concern due to its potential human health effects and widespread occurrence in surface water and groundwater. Analyses carried out in France have highlighted the presence of ClO4- in drinking water of Champagne-Ardenne (NW of France), with two potential sources suspected: a military source related to the First World War and an agricultural source related to the past use of Chilean nitrates. To determine the sources of ClO4- in groundwater, major and trace elements, 2H and 18O, ClO3- and ClO4- ions and a list of 39 explosives were analyzed from 35 surface water and groundwater sampling points in the east of the city of Reims. ClO4- ions were found in almost all sampling points (32 out of 35) with a max value of 33 µg L-1. ClO4- concentrations were highest in groundwater ranging from 0.7 to 33 µg L-1 (average value of about 6.2 µg L-1) against from 4 µg L-1) were collected near a military camp, where huge quantities of ammunitions have been used, stored and destroyed during and after the First World War.

  13. Growth of NH4Cl Single Crystal from Vapor Phase in Vertical Furnace

    Science.gov (United States)

    Nigara, Yutaka; Yoshizawa, Masahito; Fujimura, Tadao

    1983-02-01

    A pure and internally stress-free single crystal of NH4Cl was grown successfully from the vapor phase. The crystal measured 1.6 cmφ× 2 cm and had the disordered CsCl structure, which was stable below 184°C. The crystal was grown in an ampoule in a vertical furnace, in which the vapor was efficiently transported both by diffusion and convection. In line with the growth mechanism of a single crystal, the temperature fluctuation (°C/min) on the growth interface was kept smaller than the product of the temperature gradient (°C/cm) and the growth rate (cm/min). The specific heat of the crystal was measured around -31°C (242 K) during cooling and heating cycles by AC calorimetry. The thermal hysteresis (0.4 K) obtained here was smaller than that (0.89 K) of an NH4Cl crystal grown from its aqueous solution with urea added as a habit modifier.

  14. The Effect of WNK4 on the Na+-Cl- Cotransporter Is Modulated by Intracellular Chloride.

    Science.gov (United States)

    Bazúa-Valenti, Silvana; Chávez-Canales, María; Rojas-Vega, Lorena; González-Rodríguez, Xochiquetzal; Vázquez, Norma; Rodríguez-Gama, Alejandro; Argaiz, Eduardo R; Melo, Zesergio; Plata, Consuelo; Ellison, David H; García-Valdés, Jesús; Hadchouel, Juliette; Gamba, Gerardo

    2015-08-01

    It is widely recognized that the phenotype of familial hyperkalemic hypertension is mainly a consequence of increased activity of the renal Na(+)-Cl(-) cotransporter (NCC) because of altered regulation by with no-lysine-kinase 1 (WNK1) or WNK4. The effect of WNK4 on NCC, however, has been controversial because both inhibition and activation have been reported. It has been recently shown that the long isoform of WNK1 (L-WNK1) is a chloride-sensitive kinase activated by a low Cl(-) concentration. Therefore, we hypothesized that WNK4 effects on NCC could be modulated by intracellular chloride concentration ([Cl(-)]i), and we tested this hypothesis in oocytes injected with NCC cRNA with or without WNK4 cRNA. At baseline in oocytes, [Cl(-)]i was near 50 mM, autophosphorylation of WNK4 was undetectable, and NCC activity was either decreased or unaffected by WNK4. A reduction of [Cl(-)]i, either by low chloride hypotonic stress or coinjection of oocytes with the solute carrier family 26 (anion exchanger)-member 9 (SLC26A9) cRNA, promoted WNK4 autophosphorylation and increased NCC-dependent Na(+) transport in a WNK4-dependent manner. Substitution of the leucine with phenylalanine at residue 322 of WNK4, homologous to the chloride-binding pocket in L-WNK1, converted WNK4 into a constitutively autophosphorylated kinase that activated NCC, even without chloride depletion. Elimination of the catalytic activity (D321A or D321K-K186D) or the autophosphorylation site (S335A) in mutant WNK4-L322F abrogated the positive effect on NCC. These observations suggest that WNK4 can exert differential effects on NCC, depending on the intracellular chloride concentration. Copyright © 2015 by the American Society of Nephrology.

  15. Ca8Mg(SiO4)4Cl2:Ce3+, Tb3+: A potential single-phased phosphor for white-light-emitting diodes

    International Nuclear Information System (INIS)

    Zhu Ge; Wang Yuhua; Ci Zhipeng; Liu Bitao; Shi Yurong; Xin Shuangyu

    2012-01-01

    A single-phased white-light-emitting phosphor Ca 8 Mg(SiO 4 ) 4 Cl 2 :Ce 3+ , Tb 3+ (CMSC:Ce 3+ , Tb 3+ ) is synthesized by a high temperature solid-state reaction method, and its photoluminescence properties are investigated. The obtained phosphor exhibits a strong excitation band between 250 and 410 nm, matching well with the dominant emission band of a UV light-emitting-diode (LED) chip. Energy transfer from Ce 3+ to Tb 3+ ions has been investigated and demonstrated to be a resonant type via a dipole–dipole mechanism. The energy transfer efficiency as well as the critical distance is also estimated. Furthermore, the phosphors can generate light from yellow-green through white and eventually to blue by properly tuning the relative ratio of Ce 3+ to Tb 3+ ions grounded on the principle of energy transfer. The results show that this phosphor has potential applications as a single-phased phosphor for UV white-light LEDs. - Highlights: ► The luminescence properties of Ca 8 Mg(SiO 4 ) 4 Cl 2 :Ce 3+ , Tb 3+ were investigated for the first time. ► The strong absorption of phosphors matches well with the emission band of UV LED chips. ► The energy transfer from Ce 3+ to Tb 3+ in Ca 8 Mg(SiO 4 ) 4 Cl 2 was investigated in detail. ► The white light (CIE=(0.29, 0.34)) is generated by tuning the relative ratio of Ce 3+ to Tb 3+ .

  16. 87Rb-NMR in Rb2ZnCl4 below the incommensurable phase

    International Nuclear Information System (INIS)

    Grande, S.; Moskvich, Yu.N.; Aleksandrova, I.P.

    1983-01-01

    In Rb 2 ZnCl 4 crystals the curly polar phase, which changes into the incommensurable phase below 192 K, has been investigated by pulsed NMR. The angular correlations of the second-order quadrupole shifts have been measured and the corresponding tensors of the electric field gradient have been calculated. The six Rb layers change differently in magnitude and orientation compared to the paraelectric phase. The temperature dependences within the C-phase are also different. The spin-lattice relaxation times have been measured and discussed for each layer in the C-phase. All relaxation times show an anomaly at a further phase transition occurring at 72 K connected with an increase of the number of spectral lines

  17. Synthesis and characterization of technetium(III) complexes containing 2,2'-bipyridine and 1,10-phenanthroline. X-ray crystal structures of cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(bpy)]B(C6H5)4, cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(phen)]B(C6H5)4, and cis (Cl),trans(P)-[TcCl2(P(CH3CH2)(C6H5)2)2(bpy)]SO3CF3

    International Nuclear Information System (INIS)

    Wilcox, B.E.; Ho, D.M.; Deutsch, E.

    1989-01-01

    Technetium(III) complexes of the general formula cis(Cl),trans(P)-[TcCl 2 (P) 2 L] + , where (P) is dimethylphenylphosphine (PMe 2 Ph) or ethyldiphenylphosphine (PEtPh 2 ) and L is 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy), or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by L substitution onto, with concomitant displacement of one chloride and one phosphine ligand from, the mer-TcCl 3 (P) 3 starting material in refluxing ethanol. Analysis of these complexes by fast atom bombardment mass spectrometry (in the positive ion mode) provides fingerprint mass spectra that exhibit peaks assigned to the molecular ion M + as well as peaks assigned to M + minus one or more monodentate ligands. Results of single-crystal x-ray structure determinations of cis(Cl),trans(P)-[TcCl 2 (PMe 2 Ph) 2 (bpy)]BPh 4 (A), cis(Cl),trans(P)-[TcCl 2- (PMe 2 Ph) 2 (phen)]BPh 4 (B), and cis(Cl),trans(P)-[TcCl 2 (PEtPh 2 ) 2 (bpy)]SO 3 CF 3 (C), with formula weights of 921.62, 945.64, and 903.65, respectively are reported. 26 refs., 5 figs., 5 tabs

  18. Low-temperature heat capacities and thermodynamic properties of ethylenediammonium tetrachlorozincate chloride (C2H10N2)2(ZnCl4)Cl2

    International Nuclear Information System (INIS)

    He, Dong-Hua; Di, You-Ying; Wang, Bin; Dan, Wen-Yan; Tan, Zhi-Cheng

    2010-01-01

    The ethylenediammonium tetrachlorozincate chloride (C 2 H 10 N 2 ) 2 (ZnCl 4 )Cl 2 was synthesized. Chemical analysis, elemental analysis, and X-ray crystallography were applied to characterize the composition and crystal structure of the complex. Low-temperature heat capacities of the compound were measured by a precision automatic adiabatic calorimeter over the temperature range from T = 77-377 K. A polynomial equation of heat capacities as a function of the reduced temperature was fitted by a least square method. Based on the polynomial equation, the smoothed heat capacities and thermodynamic functions of the title compound relative to the standard reference temperature 298.15 K were calculated at intervals of 5 K. A thermochemical cycle was designed and the enthalpy change of the solid phase reaction of ethylenediamine dihydrochloride with zinc chloride was determined to be Δ r H m o =-(17.9±0.6)kJmol -1 by an isoperibol solution-reaction calorimeter. Finally, the standard molar enthalpy of formation of the title compound was derived to be Δ f H m o [(C 2 H 10 N 2 ) 2 (ZnCl 4 )Cl 2 ,s]=-(1514.4±2.7)kJmol -1 in accordance with Hess law.

  19. Hydrogen Generation from Al-NiCl2/NaBH4 Mixture Affected by Lanthanum Metal

    Directory of Open Access Journals (Sweden)

    Wen Qiang Sun

    2012-01-01

    Full Text Available The effect of La on Al/NaBH4 hydrolysis was elaborated in the present paper. Hydrogen generation amount increases but hydrogen generation rate decreases with La content increasing. There is an optimized composition that Al-15 wt% La-5 wt% NiCl2/NaBH4 mixture (Al-15 wt% La-5 wt% NiCl2/NaBH4 weight ratio, 1 : 3 has 126 mL g−1 min−1 maximum hydrogen generation rate and 1764 mL g−1 hydrogen generation amount within 60 min. The efficiency is 88%. Combined with NiCl2, La has great effect on NaBH4 hydrolysis but has little effect on Al hydrolysis. Increasing La content is helpful to decrease the particle size of Al-La-NiCl2 in the milling process, which induces that the hydrolysis byproduct Ni2B is highly distributed into Al(OH3 and the catalytic reactivity of Ni2B/Al(OH3 is increased therefore. But hydrolysis byproduct La(OH3 deposits on Al surface and leads to some side effect. The Al-La-NiCl2/NaBH4 mixture has good stability in low temperature and its hydrolytic performance can be improved with increasing global temperature. Therefore, the mixture has good safety and can be applied as on board hydrogen generation material.

  20. Hydrogen generation from Al-NiCl2/NaBH4 mixture affected by lanthanum metal.

    Science.gov (United States)

    Sun, Wen Qiang; Fan, Mei-Qiang; Fei, Yong; Pan, Hua; Wang, Liang Liang; Yao, Jun

    2012-01-01

    The effect of La on Al/NaBH(4) hydrolysis was elaborated in the present paper. Hydrogen generation amount increases but hydrogen generation rate decreases with La content increasing. There is an optimized composition that Al-15 wt% La-5 wt% NiCl(2)/NaBH(4) mixture (Al-15 wt% La-5 wt% NiCl(2)/NaBH(4) weight ratio, 1 : 3) has 126 mL g(-1 )min(-1) maximum hydrogen generation rate and 1764 mL g(-1) hydrogen generation amount within 60 min. The efficiency is 88%. Combined with NiCl(2), La has great effect on NaBH(4) hydrolysis but has little effect on Al hydrolysis. Increasing La content is helpful to decrease the particle size of Al-La-NiCl(2) in the milling process, which induces that the hydrolysis byproduct Ni(2)B is highly distributed into Al(OH)(3) and the catalytic reactivity of Ni(2)B/Al(OH)(3) is increased therefore. But hydrolysis byproduct La(OH)(3) deposits on Al surface and leads to some side effect. The Al-La-NiCl(2)/NaBH(4) mixture has good stability in low temperature and its hydrolytic performance can be improved with increasing global temperature. Therefore, the mixture has good safety and can be applied as on board hydrogen generation material.

  1. Ternary g-C{sub 3}N{sub 4}/ZnO/AgCl nanocomposites: Synergistic collaboration on visible-light-driven activity in photodegradation of an organic pollutant

    Energy Technology Data Exchange (ETDEWEB)

    Akhundi, Anise; Habibi-Yangjeh, Aziz, E-mail: ahabibi@uma.ac.ir

    2015-12-15

    Graphical abstract: - Highlights: • Novel ternary g-C{sub 3}N{sub 4}/ZnO/AgCl nanocomposites were prepared using a facile method. • g-C{sub 3}N{sub 4}/ZnO/AgCl (40%) has superior activity in degradation of RhB under visible-light. • The activity is 7.5 and 6-fold higher than g-C{sub 3}N{sub 4}/ZnO and g-C{sub 3}N{sub 4}/AgCl, respectively. • There are synergistic collaboration between ZnO and AgCl in enhancing the activity. - Abstract: The present work demonstrates the preparation of ternary g-C{sub 3}N{sub 4}/ZnO/AgCl nanocomposites, as novel visible-light-driven photocatalysts, using a facile large-scale methodology. The microstructure, morphology, purity, thermal, and spectroscopic properties of the prepared samples were studied using XRD, TEM, EDX, TG, UV–vis DRS, FT-IR, and PL techniques. Compared with the g-C{sub 3}N{sub 4}/ZnO and g-C{sub 3}N{sub 4}/AgCl nanocomposites, the g-C{sub 3}N{sub 4}/ZnO/AgCl nanocomposites displayed higher photocatalytic activity for degradation of rhodamine B under visible-light irradiation. Photocatalytic activity of the g-C{sub 3}N{sub 4}/ZnO/AgCl (40%) nanocomposite is about 9.5, 7.5, and 6-fold higher than those of the g-C{sub 3}N{sub 4}, g-C{sub 3}N{sub 4}/ZnO, and g-C{sub 3}N{sub 4}/AgCl samples, respectively. The enhanced photocatalytic activity of the nanocomposites was mainly attributed to efficiently separation of the charge carriers by synergistic collaboration of ZnO and AgCl in removing photogenerated electrons from g-C{sub 3}N{sub 4}. Furthermore, the results showed that the photocatalytic activity of the nanocomposite considerably depends on the preparation time, calcination temperature, and scavengers of the reactive species. Finally, the nanocomposite was found to be a reusable photocatalyst.

  2. Reduction behavior of UO22+ in molten LiCl-RbCl and LiCl-KCl eutectics by using tungsten

    Science.gov (United States)

    Nagai, Takayuki; Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu

    2013-08-01

    The reduction of uranium from UO22+ to UO2+ or U4+ in molten LiCl-RbCl and LiCl-KCl eutectics was examined by using tungsten and chlorine gas. Spectrophotometric technique was adopted to determine the concentration of uranium species. When tungsten was immersed into the LiCl-RbCl eutectic melt at 400 °C without supplying chlorine gas, 36% of the total weight of the hexavalent of UO22+ was reduced to the pentavalent of UO2+. Under purging chlorine gas into the melt, 96% of UO22+ was reduced to the tetravalent of U4+. Tungsten oxy-chloride of WOCl4 was produced via the reductions of UO22+, which was volatized from the melt and adsorbed on the upper part of experimental cell. On the other hand, 84% of UO22+ in the LiCl-KCl eutectic melt at 500 °C was reduced to U4+ by using tungsten and chlorine gas.

  3. The role of electrolyte anions (ClO4-, NO3-, and Cl-) in divalent metal (M2+) adsorption on oxide and hydroxide surfaces in salt solutions

    International Nuclear Information System (INIS)

    Criscenti, L.J.; Sverjensky, D.A.

    1999-01-01

    Adsorption of divalent metal ions (M 2+ ) onto oxide and hydroxide surfaces from solutions of strong electrolytes has typically been inferred to take place without the involvement of the electrolyte anion. Only in situations where M 2+ forms a strong enough aqueous complex with the electrolyte anion (for example, CdCl + or PbCl + ) has it been frequently suggested that the metal and the electrolyte anion adsorb simultaneously. A review of experimental data for the adsorption of Cd 2+ , Pb 2+ , Co 2+ , UO 2 2+ , Zn 2+ , Cu 2+ , Ba 2+ , Sr 2+ , and Ca 2+ onto quartz, silica, goethite, hydrous ferric oxide, corundum, γ-alumina, anatase, birnessite, and magnetite, from NaNO 3 , KNO 3 , NaCl, and NaClO 4 solutions over a wide range of ionic strengths (0.0001 M-1.0 M), reveals that transition and heavy metal adsorption behavior with ionic strength is a function of the type of electrolyte. In NaNO 3 solutions, metal adsorption exhibits little or no dependence on the ionic strength of the solution. However, in NaCl solutions, transition and heavy metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption exhibits little dependence on ionic strength but is often suggestive of an increase in metal adsorption with increasing ionic strength. Analysis of selected adsorption edges was carried out using the extended triple-layer model and aqueous speciation models that included metal-nitrate, metal-chloride, and metal-hydroxide complexes

  4. Quaternary system LiF-LiCl-LiVO3-Li2MoO4

    International Nuclear Information System (INIS)

    Anipchenko, B.V.; Garkushin, I.K.

    2000-01-01

    Interactions in the LiF-LiCl-LiVO 3 -Li 2 MoO 4 system are studied by differential thermal analysis. Rate of heating/cooling of the samples comprised 15 Grad/min, mass of sample composed 0.2 g. The system was investigated in the 300-650 Deg C range. X-ray diffraction method was used for determination of purity of the reagents. Composition and temperature of quaternary component eutectics are determined: 16.5 mol. % of LiF, 47.0 mol. % of LiCl, 28.8 mol. % of LiVO 3 , 7.6 mol. % of Li 2 MoO 4 ; 387 Deg C. Mean value of melting enthalpy of quaternary eutectics mixture in the LiF-LiCl-LiVO 3 -Li 2 MoO 4 system on the results of the tests was in the range of 222 kJ/kg [ru

  5. Study of ZrO2-H2SO4-(NH4)2SO4(NH4Cl)-H2O systems

    International Nuclear Information System (INIS)

    Motov, D.L.; Sozinova, Yu.P.; Rys'kina, M.P.

    1988-01-01

    Regions of formation, composition and solubility of ammonium sulfatozirconates (ASZ) in ZrO 2 -H 2 SO 4 -(NH 4 ) 2 SO 4 (NH 4 Cl)-H 2 O systems at 25 and 75 deg C are studied by the isothermal method. Five ASZ: (NH 4 ) 2 Zr(OH) 2 (SO 4 ) 2 , NH 4 ZrOH(SO 4 ) 2 xH 2 O, NH 4 ZrO 0.5 (OH) 2 SO 4 x1.5H 2 O, (NH 4 ) 2 Zr(SO 4 ) 3 x2H 2 O, (NH 4 ) 4 Zr(SO 4 ) 4 x4H 2 O are detected, their properties are investigated. Main sulfates are new compounds never described ealier

  6. Crystal structure of zdenekite NaPbCu5(AsO4)4Cl · 5H2O

    International Nuclear Information System (INIS)

    Zubkova, N.V.; Pushcharovsky, D.Yu.; Sarp, H.; Teat, S. J.; MacLean, E. J.

    2003-01-01

    The crystal structure of the mineral zdenekite NaPbCu 5 (AsO 4 ) 4 Cl · 5H 2 O was established (Bruker SMART CCD diffractometer, synchrotron radiation, λ = 0.6843 A, R = 0.096 for 1356 reflections). Single-crystal X-ray diffraction study demonstrated that zdenekite belongs to the monoclinic system with the unit-cell parameters a = 10.023(7) A, b 19.55(1) A, c = 10.023(6) A, β = 90.02(1) deg., sp. gr. P2 1 /n, Z = 4. The structure consists of polyhedral layers parallel to the (010) plane. These layers are formed by Cuφ 5 polyhedra (φ = O, Cl, H 2 O) and AsO 4 tetrahedra. Distorted Na octahedra and Pb 7-vertex polyhedra and H 2 O molecules coordinated to these metal atoms are located between the layers

  7. Synthesis and characterization of PVA blended LiClO4 as electrolyte material for battery Li-ion

    Science.gov (United States)

    Gunawan, I.; Deswita; Sugeng, B.; Sudaryanto

    2017-07-01

    It have been synthesized the materials for Li ion battery electrolytes, namely PVA with the addition of LiClO4 salt were varied 0, 5, 10, 15 and 20% by weight respectively. The objective of this study is to control the ionic conductivity in traditional polymer electrolytes, to improve ionic conductivity with the addition of lithium perchlorat (LiClO4). These electrolyte materials prepared by PVA powder was dissolved into distilled water and added LiClO4 salt were varied. After drying the solution, PVA sheet blended LiClO4 salt as electrolyte material for Li ion battery obtained. PVA blended LiClO4 salt crystallite form was confirmed using X-Ray Difraction (XRD) equipment. Observation of the morphology done by using Scanning Electron Microscope (SEM). While the electrical conductivity of the material is measured using LCR meter. The results of XRD pattern of LiClO4 shows intense peaks at angles 2θ = 23.2, 32.99, and 36.58°, which represent the crystalline nature of the salt. Particles morphology of the sample revealed by scanning electron microscopy are irregular in shape and agglomerated, with mean size 200-300 nm. It can be concluded that polycrystalline particles are composed of large number of crystallites. The study of conductivity by using LCR meter shows that all the graphs represent the DC and AC conductivity phenomena.

  8. A Layered Solution Crystal Growth Technique and the Crystal Structure of (C 6H 5C 2H 4NH 3) 2PbCl 4

    Science.gov (United States)

    Mitzi, D. B.

    1999-07-01

    Single crystals of the organic-inorganic perovskite (C6H5C2H4NH3)2PbCl4 have been grown at room temperature using a layered solution approach. The bottom solution layer, contained within a long straight tube, consists of PbCl2 dissolved in concentrated aqueous HCl. A less dense layer of methanol is carefully placed on top of the HCl/PbCl2 solution using a syringe. Finally, a stoichiometric quantity of C6H5C2H4NH2 (relative to the PbCl2) is added to the top of the column. As the layers slowly diffuse together, well-formed crystals of (C6H5C2H4NH3)2PbCl4 appear near the interface between the HCl/PbCl2 and C6H5C2H4NH2 solutions. The thick, plate-like crystals are well suited for X-ray crystallography studies. Room temperature intensity data were refined using a triclinic (Poverline1) cell (a=11.1463(3) Å, b=11.2181(3) Å, c=17.6966(5) Å, α= 99.173(1)°, β=104.634(1)°, γ=89.999(1)°, V=2111.8(1) Å3, Z=4, Rf/Rw=0.031/0.044). The organic-inorganic layered perovskite structure features well-ordered sheets of corner-sharing distorted PbCl6 octahedra separated by bilayers of phenethylammonium cations. Tilting and rotation of the PbCl6 octahedra within the perovskite sheets, coupled with organic cation ordering, leads to the unusual in-sheet 2ap×2ap superstructure, where ap is the lattice constant for the ideal cubic perovskite.

  9. Domain structure of human complement C4b extends with increasing NaCl concentration: implications for its regulatory mechanism.

    Science.gov (United States)

    Fung, Ka Wai; Wright, David W; Gor, Jayesh; Swann, Marcus J; Perkins, Stephen J

    2016-12-01

    During the activation of complement C4 to C4b, the exposure of its thioester domain (TED) is crucial for the attachment of C4b to activator surfaces. In the C4b crystal structure, TED forms an Arg 104 -Glu 1032 salt bridge to tether its neighbouring macroglobulin (MG1) domain. Here, we examined the C4b domain structure to test whether this salt bridge affects its conformation. Dual polarisation interferometry of C4b immobilised at a sensor surface showed that the maximum thickness of C4b increased by 0.46 nm with an increase in NaCl concentration from 50 to 175 mM NaCl. Analytical ultracentrifugation showed that the sedimentation coefficient s 20,w of monomeric C4b of 8.41 S in 50 mM NaCl buffer decreased to 7.98 S in 137 mM NaCl buffer, indicating that C4b became more extended. Small angle X-ray scattering reported similar R G values of 4.89-4.90 nm for C4b in 137-250 mM NaCl. Atomistic scattering modelling of the C4b conformation showed that TED and the MG1 domain were separated by 4.7 nm in 137-250 mM NaCl and this is greater than that of 4.0 nm in the C4b crystal structure. Our data reveal that in low NaCl concentrations, both at surfaces and in solution, C4b forms compact TED-MG1 structures. In solution, physiologically relevant NaCl concentrations lead to the separation of the TED and MG1 domain, making C4b less capable of binding to its complement regulators. These conformational changes are similar to those seen previously for complement C3b, confirming the importance of this salt bridge for regulating both C4b and C3b. © 2016 The Author(s).

  10. Enhancement in CO2 Adsorption Capacity and Selectivity in the Chalcogenide Aerogel CuSb2S4 by Post-synthetic Modification with LiCl

    KAUST Repository

    Ahmed, Ejaz

    2015-09-11

    The new chalcogel CuSb2S4 was obtained by reacting Cu(OAc)2·H2O with KSbS2 in a water/formamide mixture at room temperature. In order to modify the gas adsorption capacity the synthesized CuSb2S4 aerogel was loaded with different amounts of LiCl. CO2 adsorption measurements on the CuSb2S4 aerogel before and after treatment with LiCl showed more than three times increased uptake of the LiCl-modified chalcogel. The selectivities of the gas pairs CO2/H2 and CO2/CH4 in the LiCl-treated chalcogel are 235 and 105 respectively and amongst the highest reported for chalcogenide-based aerogels. In comparison with other porous materials like zeolites, activated carbon and most of the Metal Organic Frameworks (MOFs) or Porous Organic Frameworks (POFs), our synthesized aerogels show good air and moisture stability. Although, the CO2 storage capacity of our aerogels is relatively low, however the selectivity of CO2 over H2 or CH4 in LiCl-loaded aerogels are higher than in zeolites, activated carbon as well as some MOFs like Cu-BTC and MOF-5 etc.

  11. Apparent molar heat capacities and apparent molar volumes of Pr(ClO{sub 4}){sub 3}(aq), Gd(ClO{sub 4}){sub 3}(aq), Ho(ClO{sub 4}){sub 3}(aq), and Tm(ClO{sub 4}){sub 3}(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

    Energy Technology Data Exchange (ETDEWEB)

    Hakin, Andrew W. E-mail: hakin@uleth.ca; Lian Liu, Jin; Erickson, Kristy; Munoz, Julie-Vanessa

    2004-09-01

    Acidified aqueous solutions of Pr(ClO{sub 4}){sub 3}(aq), Gd(ClO{sub 4}){sub 3}(aq), Ho(ClO{sub 4}){sub 3}(aq), and Tm(ClO{sub 4}){sub 3}(aq) were prepared from the corresponding oxides by dissolution in dilute perchloric acid. Once characterized with respect to trivalent metal cation and acid content, the relative densities of the solutions were measured at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa using a Sodev O2D vibrating tube densimeter. The relative massic heat capacities of the aqueous systems were also determined, under the same temperature and pressure conditions, using a Picker Flow Microcalorimeter. All measurements were made on solutions containing rare earth salt in the concentration range 0.01 {<=} m/(mol {center_dot} kg{sup -1}) {<=} 0.2. Relative densities and relative massic heat capacities were used to calculate the apparent molar volumes and apparent molar heat capacities of the acidified salt solutions from which the apparent molar properties of the aqueous salt solutions were extracted by the application of Young's Rule. The concentration dependences of the isothermal apparent molar volumes and heat capacities of each aqueous salt solution were modelled using Pitzer ion-interaction equations. These models produced estimates of apparent molar volumes and apparent molar heat capacities at infinite dilution for each set of isothermal V{sub phi,2} and C{sub pphi,2} values. In addition, the temperature and concentration dependences of the apparent molar volumes and apparent molar heat capacities of the aqueous rare earth perchlorate salt solutions were modelled using modified Pitzer ion-interaction equations. The latter equations utilized the Helgeson, Kirkham, and Flowers equations of state to model the temperature dependences (at p=0.1 MPa) of apparent molar volumes and apparent molar heat capacities at infinite dilution. The results of the latter models were compared to those previously published in the literature. Apparent

  12. Tetraammineplatinum(II) aquapentachloroiridate(III) dihydrate, [Pt(NH3)4][IrCl5(H2O)

    International Nuclear Information System (INIS)

    Garnier, E.; Bele, M.

    1994-01-01

    The crystal is built up from planar Pt(NH 3 ) 4 2+ cations, octahedral IrCl 5 (H 2 O) 2- anions and two H 2 O molecules. The coordination of these ions is 6/6, thus leading to a NaCl crystal structure. Electrostatic interactions and N..Cl, N..O and N..N short contacts (possible hydrogen bonds) take part in the packing of the structure and form a three-dimensional network. (orig.)

  13. TeX4 (X = F, Cl, Br) as Lewis acids--complexes with soft thio- and seleno-ether ligands.

    Science.gov (United States)

    Hector, Andrew L; Jolleys, Andrew; Levason, William; Reid, Gillian

    2012-08-28

    TeF(4) reacts with OPR(3) (R = Me or Ph) in anhydrous CH(2)Cl(2) to give the colourless, square based pyramidal 1 : 1 complexes [TeF(4)(OPR(3))] only, in which the OPR(3) is coordinated basally in the solid state, (R = Me: d(Te-O) = 2.122(2) Å; R = Ph: d(Te-O) = 2.1849(14) Å). Variable temperature (19)F{(1)H}, (31)P{(1)H} and (125)Te{(1)H} NMR spectroscopic studies strongly suggest this is the low temperature structure in solution, although the systems are dynamic. The much softer donor ligands SMe(2) and SeMe(2) show a lower affinity for TeF(4), although unstable, yellow products with spectroscopic features consistent with [TeF(4)(EMe(2))] are obtained by the reaction of TeF(4) in neat SMe(2) or via reaction in CH(2)Cl(2) with SeMe(2). TeX(4) (X = F, Cl or Br) causes oxidation and halogenation of TeMe(2) to form X(2)TeMe(2). The Br(2)TeMe(2) hydrolyses in trace moisture to form [BrMe(2)Te-O-TeMe(2)Br], the crystal structure of which has been determined. TeX(4) (X = Cl or Br) react with the selenoethers SeMe(2), MeSe(CH(2))(3)SeMe or o-C(6)H(4)(SeMe)(2) (X = Cl) in anhydrous CH(2)Cl(2) to give the distorted octahedral monomers trans-[TeX(4)(SeMe(2))(2)], cis-[TeX(4){MeSe(CH(2))(3)SeMe}] and cis-[TeCl(4){o-C(6)H(4)(SeMe)(2)}], which have been characterised by IR, Raman and multinuclear NMR ((1)H, (77)Se{(1)H} and (125)Te{(1)H}) spectroscopy, and via X-ray structure determinations of representative examples. Tetrahydrothiophene (tht) can form both 1 : 1 and 1 : 2 Te : L complexes. For X = Br, the former has been shown to be a Br-bridged dimer, [Br(3)(tht)Te(μ-Br)(2)TeBr(3)(tht)], by crystallography with the tht ligands anti, whereas the latter are trans-octahedral monomers. Like its selenoether analogue, MeS(CH(2))(3)SMe forms distorted octahedral cis-chelates, [TeX(4){MeS(CH(2))(3)SMe}], whereas the more rigid o-C(6)H(4)(SMe)(2) unexpectedly forms a zig-zag chain polymer in the solid state, [TeCl(4){o-C(6)H(4)(SMe)(2)}](n), in which the dithioether adopts an

  14. Luminescent Properties of Sr4Si3O8Cl4:Eu2+, Bi3+ Phosphors for Near UV InGaN-Based Light-Emitting-Diodes

    Directory of Open Access Journals (Sweden)

    Wangqing Shen

    2015-12-01

    Full Text Available Sr4Si3O8Cl4 co-doped with Eu2+, Bi3+ were prepared by the high temperature reaction. The structure and luminescent properties of Sr4Si3O8Cl4:Eu2+, Bi3+ were investigated. With the introduction of Bi3+, luminescent properties of these phosphors have been optimized. Compared with Sr3.90Si3O8Cl4:0.10Eu2+, the blue-green phosphor Sr3.50Si3O8Cl4:0.10Eu2+, 0.40Bi3+ shows stronger blue-green emission with broader excitation in near-UV range. Bright blue-green light from the LED means this phosphor can be observed by the naked eye. Hence, it may have an application in near UV LED chips.

  15. Synthesis, crystal structure, thermal analysis and dielectric properties of [(C{sub 4}H{sub 9}){sub 4}N]{sub 3}Bi{sub 2}Cl{sub 9} compound

    Energy Technology Data Exchange (ETDEWEB)

    Trigui, W., E-mail: walatrigui@yahoo.fr; Oueslati, A.; Chaabane, I.; Hlel, F.

    2015-07-15

    A new organic–inorganic tri-tetrabutylammonium nonachlorobibismuthate(III) compound was prepared. It was found to crystallize in the monoclinic system (P2{sub 1}/n space group) with the following lattice parameters: a=11.32(2) Å, b=22.30(3) Å, c=28.53(2) Å and β=96.52(0)°. The [Bi{sub 2}Cl{sub 9}]{sup 3−} anions are surrounded by six [(C{sub 4}H{sub 9})N]{sup +} cations, forming an octahedral configuration. These octahedra are sharing corners in order to provide the tri-dimensional network cohesion. The differential scanning calorimetry reveals four order-disorder reversible phase transitions located at 214, 238, 434 and 477 K. The Raman and infrared spectra confirm the presence of both cationic [(C{sub 4}H{sub 9})N]{sup +} and anionic [Bi{sub 2}Cl{sub 9}]{sup 3−} parts. The dielectric parameters, real and imaginary dielectric permittivity (ε′ and ε″), and dielectric loss tangent (tg δ), were measured in the frequency range of 209 kHz–5 MHz at different temperatures. The variations of dielectric dispersion (ε') and dielectric absorption (ε″) with frequency show a distribution of relaxation times, which is probably related to the change in the dynamical state of the [(C{sub 4}H{sub 9}){sub 4}N]{sup +} cations and the [Bi{sub 2}Cl{sub 9}]{sup 3−} anions. - Graphical abstract: Projection of the atomic arrangement of the [(C{sub 4}H{sub 9}){sub 4}N]{sub 3}Bi{sub 2}Cl{sub 9} compound along the b axis. - Highlights: • The structure of the (TBA){sub 3}Bi{sub 2}Cl{sub 9} compound was solved and reported. • The cristal belongs to the monoclinic system with P2{sub 1}/n space group. • DSC discloses four order–disorder reversible phases transitions. • The temperature-dependent permittivity ε' and ε″ has been investigated.

  16. Chlorination of UO2, PuO2, and rare-earth oxides using ZrCl4

    International Nuclear Information System (INIS)

    Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

    2001-01-01

    A new chlorination method using ZrCl 4 , which has a high reactivity with oxygen, has been investigated for more efficient oxide treatment. After actinide oxides are chlorinated and dissolved in a molten salt bath, actinide metals can be selectively collected using the electrorefining process. This process is well suited for pyrochemical reprocessing of metallic fuels. In LiCl-KCI eutectic melts, rare-earth oxides (Y 2 O 3 , La 2 O 3 , CeO 2 , and Nd 2 O 3 ) and actinide oxides (UO 2 and PuO 2 ) were chlorinated by adding ZrCl 4 . As a result, rare-earth and actinide elements were dissolved into the salt as trivalent ions and ZrO 2 was precipitated. When an excess of ZrCI 4 was added, oxides in powder form were completely chlorinated in five hours. It was demonstrated that the ZrCI 4 chlorination method, free from corrosive gas such as chlorine, was very simple and useful. (author)

  17. A mass spectrometric study of the neutral and ionic vapor components of ytterbium chlorides; formation enthalpies of YbCl2 and YbCl3 molecules, and YbCl3- and YbCl4- ions in the gas phase

    International Nuclear Information System (INIS)

    Kuznetsov, F.Yh.; Kudin, L.S.; Pogrebnoj, A.M.; Butman, M.F.; Burdukovskaya, G.G.

    1997-01-01

    Ionic and neutral components of saturated vapour over the ytterbium di-and trichloride is studied through the Knudsen effusive method with mass-spectromic registration of evaporated products within the temperature range of 1000-1300 K. It is found that ytterbium trichloride is subjected to thermal decomposition with formation of ytterbium dichloride and molecular chloride. Sublimation enthalpy and enthalpy of YbCl 2 and YbCl 3 molecules formation in a gaseous phase at 298 K, comprising 356±6, 293±8, -425±6 and -667±6 kJ/mole correspondingly, are determined with application of 2 and 3 thermodynamical laws. Enthalpies of YbCl 3 - and YbCl 4 - negative ions formation in a gaseous phase at 298 K equal to -895 and -1211±30 kJ/mole correspondingly are calculated by measured equilibrium constants ion-molecular reaction. 30 refs., 3 figs., 3 tabs

  18. Microstructure and Thermal Properties of Polypropylene/Clay Nanocomposites with TiCl4/MgCl2/Clay Compound Catalyst

    Directory of Open Access Journals (Sweden)

    Limei Wang

    2015-01-01

    Full Text Available Polypropylene (PP/clay nanocomposites were synthesized by in situ intercalative polymerization with TiCl4/MgCl2/clay compound catalyst. Microstructure and thermal properties of PP/clay nanocomposites were studied in detail. Fourier transform infrared (FTIR spectra indicated that PP/clay nanocomposites were successfully prepared. Both wide-angle X-ray diffraction (XRD and transmission electron microscopy (TEM examination proved that clay layers are homogeneously distributed in PP matrix. XRD patterns also showed that the α phase was the dominate crystal phase of PP in the nanocomposites. Thermogravimetric analysis (TGA examinations confirmed that thermal stability of PP/clay nanocomposites was markedly superior to pure PP. Differential scanning calorimetry (DSC scans showed that the melt temperature and the crystallinity of nanocomposites were slightly lower than those of pure PP due to crystals imperfections.

  19. CO2 Absorption and Magnesium Carbonate Precipitation in MgCl2–NH3–NH4Cl Solutions: Implications for Carbon Capture and Storage

    Directory of Open Access Journals (Sweden)

    Chen Zhu

    2017-09-01

    Full Text Available CO2 absorption and carbonate precipitation are the two core processes controlling the reaction rate and path of CO2 mineral sequestration. Whereas previous studies have focused on testing reactive crystallization and precipitation kinetics, much less attention has been paid to absorption, the key process determining the removal efficiency of CO2. In this study, adopting a novel wetted wall column reactor, we systematically explore the rates and mechanisms of carbon transformation from CO2 gas to carbonates in MgCl2–NH3–NH4Cl solutions. We find that reactive diffusion in liquid film of the wetted wall column is the rate-limiting step of CO2 absorption when proceeding chiefly through interactions between CO2(aq and NH3(aq. We further quantified the reaction kinetic constant of the CO2–NH3 reaction. Our results indicate that higher initial concentration of NH4Cl ( ≥ 2 mol · L − 1 leads to the precipitation of roguinite [ ( NH 4 2 Mg ( CO 3 2 · 4 H 2 O ], while nesquehonite appears to be the dominant Mg-carbonate without NH4Cl addition. We also noticed dypingite formation via phase transformation in hot water. This study provides new insight into the reaction kinetics of CO2 mineral carbonation that indicates the potential of this technique for future application to industrial-scale CO2 sequestration.

  20. Identification of the pH sensor and activation by chemical modification of the ClC-2G Cl- channel.

    Science.gov (United States)

    Stroffekova, K; Kupert, E Y; Malinowska, D H; Cuppoletti, J

    1998-10-01

    Rabbit and human ClC-2G Cl- channels are voltage sensitive and activated by protein kinase A and low extracellular pH. The objective of the present study was to investigate the mechanism involved in acid activation of the ClC-2G Cl- channel and to determine which amino acid residues play a role in this acid activation. Channel open probability (Po) at +/-80 mV holding potentials increased fourfold in a concentration-dependent manner with extracellular H+ concentration (that is, extracellular pH, pHtrans), with an apparent acidic dissociation constant of pH 4.95 +/- 0.27. 1-Ethyl-3(3-dimethylaminopropyl)carbodiimide-catalyzed amidation of the channel with glycine methyl ester increased Po threefold at pHtrans 7.4, at which the channel normally exhibits low Po. With extracellular pH reduction (protonation) or amidation, increased Po was due to a significant increase in open time constants and a significant decrease in closed time constants of the channel gating, and this effect was insensitive to applied voltage. With the use of site-directed mutagenesis, the extracellular region EELE (amino acids 416-419) was identified as the pH sensor and amino acid Glu-419 was found to play the key or predominant role in activation of the ClC-2G Cl- channel by extracellular acid.

  1. Excitation function measurements of sup 4 sup 0 Ar(p,3n) sup 3 sup 8 K, sup 4 sup 0 Ar(p,2pn) sup 3 sup 8 Cl and sup 4 sup 0 Ar(p,2p) sup 3 sup 9 Cl reactions

    CERN Document Server

    Nagatsu, K; Suzuki, K

    1999-01-01

    For the production of sup 3 sup 8 K, excitation functions of the sup 4 sup 0 Ar(p,3n) sup 3 sup 8 K reaction and its accompanying reactions sup 4 sup 0 Ar(p,2pn) sup 3 sup 8 Cl, and sup 4 sup 0 Ar(p,2p) sup 3 sup 9 Cl were measured at the proton energy of 20.5-39.5 MeV to determine the optimum conditions of irradiation. Target cells containing argon gas were prepared using specially developed tools in an argon-replaced glove box. In the sup 4 sup 0 Ar(p,3n) sup 3 sup 8 K, sup 4 sup 0 Ar(p,2pn) sup 3 sup 8 Cl, and sup 4 sup 0 Ar(p,2p) sup 3 sup 9 Cl reactions, the maximum cross sections were 6.7+-0.7, 34+-3.3 and 11+-1.2mbarn at 37.6, 39.5 and 32.0 MeV, respectively, and the saturation thick target yields were calculated to be 560, 2200, and 1300 sup * MBq/mu A, respectively, at an incident energy of 39.5 MeV ( sup * integral yield above 21 MeV).

  2. Distribution of {sup 36}Cl/Cl in a river-recharged aquifer: Implications for the fallout rate of bomb-produced {sup 36}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Tosaki, Yuki, E-mail: tosaki@tac.tsukuba.ac.j [Sustainable Environmental Studies, Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8572 (Japan); Massmann, Gudrun [Institute of Geological Sciences, Department of Earth Sciences, Freie Universitaet Berlin, Malteserstrasse 74-100, 12249 Berlin (Germany); Tase, Norio [Sustainable Environmental Studies, Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8572 (Japan); Sasa, Kimikazu; Takahashi, Tsutomu [Tandem Accelerator Complex, Research Facility Center for Science and Technology, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Matsushi, Yuki [Department of Nuclear Engineering and Management, School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Tamari, Michiko [Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571 (Japan); Nagashima, Yasuo [Tandem Accelerator Complex, Research Facility Center for Science and Technology, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Bessho, Kotaro; Matsumura, Hiroshi [Radiation Science Center, High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

    2010-04-15

    Distribution of {sup 36}Cl/Cl ratios in a river-recharged aquifer was investigated in the Oderbruch area, northeastern Germany. The aquifer is confined up to 3.5-4 km inland, where it changes to an unconfined condition. The {sup 36}Cl/Cl ratios in the confined area were in the range between 4.6 x 10{sup -14} and 23.1 x 10{sup -14}, showing a peak at 2-3 km away from the river. A plot of {sup 36}Cl/Cl vs. reciprocal Cl{sup -} concentrations indicated possible effect of the Cl{sup -} concentration variation on the observed {sup 36}Cl/Cl ratios. After accounting for this effect, the estimated {sup 36}Cl fallout rates for the last 30 yrs show reasonable agreement with the Dye-3 data and the mid-latitude background value. The results suggest that a local {sup 36}Cl fallout curve can be constructed from groundwater when dispersive mixing is of minor importance.

  3. Mixed-valence, layered, cation radical salts of the ethane-bridged dimeric tetrathiafulvalene [(EDT-TTF-CH2-)2#centre dot#+] [X-][THF]0.5, X-=FeCl4-, GaCl4-

    DEFF Research Database (Denmark)

    Mézière, C.; Fourmigué, M.; Canadell, E.

    2000-01-01

    The synthesis and X-ray crystal structure of the ethane-linked dimeric tetrathiafulvalene [(EDT-TTF-CH2)(2)], 1,2-bis(ethylenedithiotetrathiafulvalenyl)ethane (1), is reported. It oxidizes reversibly at 0.45 and 0.90 V vs SCE. Electrocrystallization in the presence of [n-Bu4N][FeCl4] or [n-Bu4N...

  4. Synthesis, Structure, and Li-Ion Conductivity of LiLa(BH4)3X, X = Cl, Br, I

    DEFF Research Database (Denmark)

    Payandeh GharibDoust, SeyedHosein; Brighi, Matteo; Sadikin, Yolanda

    2017-01-01

    In this work, a new type of addition reaction between La(BH4)3 and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)3Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)3X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4)...

  5. Inhibitory Effect of NH4Cl Treatment on Renal Tgfß1 Signaling Following Unilateral Ureteral Obstruction

    Directory of Open Access Journals (Sweden)

    Martina Feger

    2015-09-01

    Full Text Available Background/Aims: Consequences of obstructive nephropathy include tissue fibrosis, a major pathophysiological mechanism contributing to development of end-stage renal disease. Transforming growth factor β 1 (Tgfβ1 is involved in the progression of renal fibrosis. According to recent observations, ammonium chloride (NH4Cl prevented phosphate-induced vascular remodeling, effects involving decrease of Tgfβ1 expression and inhibition of Tgfβ1-dependent signaling. The present study, thus, explored whether NH4Cl influences renal Tgfβ1-induced pro-fibrotic signaling in obstructive nephropathy induced by unilateral ureteral obstruction (UUO. Methods: UUO was induced for seven days in C57Bl6 mice with or without additional treatment with NH4Cl (0.28 M in drinking water. Transcript levels were determined by RT-PCR as well as protein abundance by Western blotting, blood pH was determined utilizing a blood gas and chemistry analyser. Results: UUO increased renal mRNA expression of Tgfb1, Tgfβ-activated kinase 1 (Tak1 protein abundance and Smad2 phosphorylation in the nuclear fraction of the obstructed kidney tissues, effects blunted in NH4Cl treated mice as compared to control treated mice. The mRNA levels of the transcription factors nuclear factor of activated T cells 5 (Nfat5 and SRY (sex determining region Y-box 9 (Sox9 as well as of tumor necrosis factor α (Tnfα, interleukin 6 (Il6, plasminogen activator inhibitor 1 (Pai1 and Snai1 were up-regulated in the obstructed kidney tissues following UUO, effects again significantly ameliorated following NH4Cl treatment. Furthermore, the increased protein and mRNA expression of α-smooth muscle actin (α-Sma, fibronectin and collagen type I in the obstructed kidney tissues following UUO were significantly attenuated following NH4Cl treatment. Conclusion: NH4Cl treatment ameliorates Tgfβ1-dependent pro-fibrotic signaling and renal tissue fibrosis markers following obstructive nephropathy.

  6. Reactivity toward alcohols of (Ru/sup IV/ = O/sup 2-/) unit in trans-(RuCl(O)(py)/sub 4/)/sup +/

    Energy Technology Data Exchange (ETDEWEB)

    Aoyagi, Kimitake; Nagao, Hirotaka; Yukawa, Yasuhiko; Ogura, Mariko; Kuwayama, Akito; Howell, F S; Mukaida, Masao; Kakihana, Hidetake

    1986-12-01

    The reactivity with alcohol of trans-(RuCl(O)(py)/sub 4/)/sup +/ was investigated. In MeOH, trans-(RuCl(OH)(py)/sub 4/)/sup +/ was confirmed to exist as a precursor in the formation of trans-(RuCl(OMe)(py)/sub 4/)/sup +/. The reaction progress was traced by spectrometrical and /sup 18/O-labelling experiments.

  7. Antisense down-regulation of 4CL expression alters lignification, tree growth, and saccharification potential of field-grown poplar

    Science.gov (United States)

    Steven L. Voelker; Barbara Lachenbruch; Frederick C. Meinzer; Michael Jourdes; Chanyoung Ki; Ann M. Patten; Laurence B. Davin; Norman G. Lewis; Gerald A. Tuskan; Lee Gunter; Stephen R. Decker; Michael J. Selig; Robert Sykes; Michael E. Himmel; Peter Kitin; Olga Shevchenko; Steven H. Strauss

    2010-01-01

    Transgenic down-regulation of the Pt4CL1 gene family encoding 4-coumarate:coenzyme A ligase (4CL) has been reported as a means for reducing lignin content in cell walls and increasing overall growth rates, thereby improving feedstock quality for paper and bioethanol production. Using hybrid poplar (Populus tremula...

  8. Changing structural properties of mixed crystals [N(CH{sub 3}){sub 4}]{sub 2}Zn{sub 1-x}Co{sub x}Cl{sub 4} (x = 0, 0.5, 0.7, 0.9, and 1) by magic angle spinning nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Ae Ran, E-mail: aeranlim@hanmail.net [Department of Science Education, Jeonju University, Jeonju 560-759 (Korea, Republic of); Department of Carbon Fusion Engineering, Jeonju University, Jeonju 560-759 (Korea, Republic of)

    2016-03-01

    Temperature dependences of the chemical shift and spin-lattice relaxation time in the rotating frame T{sub 1ρ} were measured for {sup 1}H and {sup 13}C nuclei in mixed crystals of the form [N(CH{sub 3}){sub 4}]{sub 2}Zn{sub 1-x} Co{sub x}Cl{sub 4} (x = 0, 0.5, 0.7, 0.9, and 1). The mixed crystals varied in color according to the amount of Co{sup 2+} ions, whereas the phase transition temperatures remained nearly unchanged. [N(CH{sub 3}){sub 4}]{sub 2}ZnCl{sub 4} and [N(CH{sub 3}){sub 4}]{sub 2}CoCl{sub 4} crystals contain two nonequivalent types of a-N(CH{sub 3}){sub 4} and b-N(CH{sub 3}){sub 4}. The two crystallographically different ions a-N(CH{sub 3}){sub 4} and b-N(CH{sub 3}){sub 4} were distinguished using {sup 13}C CP/MAS NMR spectroscopy. The NMR spectrum and T{sub 1ρ} for {sup 1}H and {sup 13}C in case of x = 0.5 and x = 0.7 were similar to those for [N(CH{sub 3}){sub 4}]{sub 2}ZnCl{sub 4}, whereas those for x = 0.9 were absolutely different. Additionally, [N(CH{sub 3}){sub 4}]{sub 2}Zn{sub 0.1}Co{sub 0.9}Cl{sub 4} exhibited the structural properties of both [N(CH{sub 3}){sub 4}]{sub 2}ZnCl{sub 4} and [N(CH{sub 3}){sub 4}]{sub 2}CoCl{sub 4}. - Highlights: • Chemical shift and spin-lattice relaxation time in rotating frame. • Two crystallographically different ions a-N(CH{sub 3}){sub 4} and b-N(CH{sub 3}){sub 4}. • Structural properties of mixed crystals.

  9. NbCl 5 and CrCl 3 catalysts effect on synthesis and hydrogen ...

    Indian Academy of Sciences (India)

    Two kinds of novel materials, Mg–1.6 mol% Ni–0.4 mol% NiO–2 mol% MCl (MCl = NbCl5, CrCl3), along with Mg–1.6 mol% Ni–0.4 mol% NiO for comparison, were examined for their potential use in hydrogen storage applications, having been fabricated via cryomilling. The effects of NbCl5 and CrCl3 on hydrogen storage ...

  10. Orientation correlation and intermolecular structure of GeCl4, VCl4 and other tetrachloride liquids

    International Nuclear Information System (INIS)

    Nath, P.P.; Sarkar, S.; Joarder, R.N.

    2007-01-01

    The intermolecular structure and correlation of GeCl 4 , VCl 4 and other tetrachloride liquids can be well described by Misawa's orientation correlation model originally applied to liquid CCl 4 . The model supports on average a specific 'corner' to 'face' correlation, but evidently very different from 'Apollo' type model. The Misawa model appears to work, in some respect, even better than reference interaction site model (RISM) used for long to describe intermolecular structure of such molecular systems. The test and comparison are made through the calculation of small asymmetric part of the intermolecular structure and evaluation of partial atom-atom distribution functions

  11. Influence of Substrates on the Electrochemical Deposition and Dissolution of Aluminum in NaAlCl4 Melts

    DEFF Research Database (Denmark)

    Li, Qingfeng; Hjuler, Hans Aage; Berg, Rolf W.

    1991-01-01

    The deposition and dissolution of aluminum in NaAlCl4 melts saturated with NaCl have been investigated by voltammetryand potentiometry for different electrode materials at 175°C. The tungsten and glassy carbon electrodes are shownto be electrochemically inert in the melts, whereas copper is elect......The deposition and dissolution of aluminum in NaAlCl4 melts saturated with NaCl have been investigated by voltammetryand potentiometry for different electrode materials at 175°C. The tungsten and glassy carbon electrodes are shownto be electrochemically inert in the melts, whereas copper...... is electrochemically active; it dissolves into the melts at a lowanodic potential. On a nickel substrate, nickel dichloride will be formed at a potential of ca. 1.0 V vs. an aluminum referenceelectrode. The reversibility (of deposition and dissolution of aluminum) is found to be strongly affected by currentdensity...... investigated. Nickel and, to some extent,tungsten electrodes proved to be appropriate as working anodes in the Al/NaCl-AlCl3/Ni battery system....

  12. Electron paramagnetic resonance of gamma irradiated (CH3)3NHClO4 and CH3NH3ClO4 single crystals

    International Nuclear Information System (INIS)

    Yavuz, Metin; Koeksal, Fevzi

    1999-01-01

    Gamma irradiation damage centers in (CH 3 ) 3 NHClO 4 and CH 3 NH 3 ClO 4 single crystals have been investigated at room temperature by the electron paramagnetic resonance (EPR) technique. It has been found that γ-irradiation produces the (CH 3 ) 3 N + radical in the first, and NH + 3 and ClO 3 radicals in the second compound. The EPR parameters of the observed radicals have been determined and discussed

  13. Gas Phase Homo- and Co-polymerization of Ethylene over Mg(O Et){sub 2}/T HF/Si Cl{sub 4}/Ti Cl{sub 4}/ Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Min-Chul, Chung [Korea Advanced Institute of Science and Techology., Taejeon (Korea, Republic of); Il, Kim [Univ. of Ulsan., Ulsan (Korea, Republic of); Jae-Ha, Kim [Korea Petrochemial Ind., Kyungnam (Korea, Republic of); Hong-Ki Choi [Korea Advanced Institute of Science and Technology., Taejeon (Korea, Republic of); Seung-Ihl, Woo

    1994-08-01

    Homo- and co-polymerization of ethylene were carried out in both gas and slurry phases over Mg(O Et)2/T HF/Si Cl{sub 4}/Ti Cl{sub 4}-Al Et{sub 3} catalysts in the range of temperature 20-70{sup o} C and pressure 2-10 psig. In gas phase polymerization, maximum activity was measured at the Al/Ti mole ratio of 377, and reaction rate dependence on Al Et{sub 3} concentration could be explained with the Langmuir-Hinshelwood adsorption model. Even though maximum activities were obtained at the same temperature, 60{sup o} C in both gas and slurry phases, overall activation energy was higher for the slurry phase(13 kCal/mol) than for the gas phase(4.7 kCal/mol) polymerization. The molecular weight behavior has been examined by measuring intrinsic viscosity. The molecular weight was increased as the ethylene pressure increased, and as the temperature and the concentration of Al Et{sub 3} and hydrogen decreased. Using two different co monomers(propylene and butene-1), the copolymerization of ethylene was carried out. The intrinsic viscosity and the melt index were decreased as co monomer concentration increased, and the maximum activity was observed when the concentration of comonomer is about 20 mol%. (author). 28 refs. 6 tabs. 13 figs.

  14. A simple access to pure thorium(IV) halides (ThCl{sub 4}, ThBr{sub 4}, and ThI{sub 4})

    Energy Technology Data Exchange (ETDEWEB)

    Deubner, H. Lars; Rudel, Stefan Sebastian; Kraus, Florian [Fachbereich Chemie, Philipps-Universitaet Marburg (Germany)

    2017-12-13

    In this work we present a facile, lab scale synthesis for thorium tetrahalides ThX{sub 4} (X = Cl, Br, and I). The reaction between the easily available ThO{sub 2} and AlX{sub 3} (X = Cl, Br, and I) and a subsequent in situ chemical vapor transport (CVT) leads to a product of high purity, which is obtained in the form of crystals or large aggregates of crystals. Their identity and purity was evidenced by X-ray powder diffraction and IR spectroscopy. The usage of ThO{sub 2} avoids, unlike earlier syntheses, the utilization of scarcely available thorium metal or of other reactants, such as CCl{sub 4}, which leads to impurities. Furthermore, the reaction tolerates even less pure ThO{sub 2}. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Thermodynamics of the production of condensed phases in the chemical vapor deposition of ZrC in the ZrCl{sub 4}–CH{sub 4}–H{sub 2}–Ar system

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Haiping [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China); Deng, Juanli, E-mail: dengjl@chd.edu.cn [School of Materials Science and Engineering, Chang' an University, Xi' an, Shaanxi 710064 (China); Yang, Lianli [College of Chemistry and Chemical Engineering, Xianyang Teachers College, Xianyang, Shaanxi 712000 (China); Cheng, Laifei; Luo, Lei; Zhu, Yan [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China); Su, Kehe [Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China); Zhang, Litong [Science and Technology on Thermostructure Composite Materials Laboratory, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China)

    2014-05-02

    Production conditions of ZrC, Zr and C(graphite) condensed phases in the chemical vapor deposition process with ZrCl{sub 4}–CH{sub 4}–H{sub 2}–Ar precursor system have been investigated based on thermodynamic analyses using the FactSage code. The yields of condensed phases have been examined as functions of the injected reactant ratios of ZrCl{sub 4}/(ZrCl{sub 4} + CH{sub 4}), H{sub 2}/(ZrCl{sub 4} + CH{sub 4}) and Ar/(ZrCl{sub 4} + CH{sub 4}), the temperature and the pressure. The results show that the yields strongly depend on the molar ratios of the ZrCl{sub 4}/(ZrCl{sub 4} + CH{sub 4}) and H{sub 2}/(ZrCl{sub 4} + CH{sub 4}) injected reactant and on the temperature, but are insensitive to the inert gas Ar ratio and pressure. The co-deposition of ZrC with Zr or C(graphite) can be easily controlled by changing the ratios of ZrCl{sub 4}/CH{sub 4} and H{sub 2}/(ZrCl{sub 4} + CH{sub 4}). Process conditions such as high input amount of H{sub 2}, relatively low amount of Ar, low pressure and temperature above 1300 K are favorable for the deposition of ZrC. The results of this work will be helpful for further experimental investigation on different deposition conditions. - Highlights: • Control of the composition of deposits via adjustment of precursor ratios • Carbon enrichment can be avoided using a low amount of argon diluting gas. • The deposition process is significantly influenced by the presence of hydrogen.

  16. First remote sensing measurements of ClOOCl along with ClO and ClONO2 in activated and deactivated Arctic vortex conditions using new ClOOCl IR absorption cross sections

    Directory of Open Access Journals (Sweden)

    M. Birk

    2010-02-01

    Full Text Available Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007 yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007. Under this aspect, nocturnal Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B from Kiruna (Sweden on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2. New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established polar chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007. Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC using

  17. Zero-Pressure Organic Superconductor: Di-(Tetramethyltetraselenafulvalenium)-Perchlorate [(TMTSF)2ClO4

    DEFF Research Database (Denmark)

    Bechgaard, Klaus; da Costa Carneiro, Kim; Olsen, Malte

    1981-01-01

    Evidence for superconductivity in the organic conductor di-(tetramethyltetraselenafulvalenium)-perchlorate [(TMTSF)2ClO4] has been found by resistance measurements in the absence of applied pressure. For different crystals the transitions are approximately 0.3 K wide and are centered around...

  18. Osmotic and ionic effects of NaCl and Na2SO4 salinity on Phragmites australis

    DEFF Research Database (Denmark)

    Pagter, Majken; Bragato, Claudia; Malagoli, Mario

    2009-01-01

    Osmotic and ion-specific effects of NaCl and Na2SO4 on Phragmites australis (Cav.) Trin ex. Steud. were investigated in a laboratory experiment by examining effects of iso-osmotic solutions of NaCl and Na2SO4 on growth, osmolality of cell sap, proline content, elemental composition and gas exchange....... Plants were supplied with a control standard nutrient solution (Ψ = -0.09 MPa) or solutions of NaCl or Na2SO4 at water potentials of -0.50, -1.09 or -1.74 MPa. Salt treatments increased root concentrations of Na and S or Cl, whereas P. australis had efficient mechanisms for exclusion of Na and S...... and partly Cl ions from the leaves. Incomplete exclusion of Cl from the leaves may affect aboveground biomass production, which was significantly more reduced by NaCl than Na2SO4. Stomatal conductance was negatively influenced by decreasing water potentials caused by NaCl or Na2SO4, implying that a non...

  19. Chemistry of Frozen NaCl and MgSO4 Brines - Implications for Surface Expression of Europa's Ocean Composition

    Science.gov (United States)

    Johnson, P. V.; Hodyss, R. P.; Choukroun, M.; Vu, T. H.

    2015-12-01

    The composition of Europa's subsurface ocean is a critical determinant of its habitability, but current analysis of the ocean composition is limited to its expression on the Europan surface. While there is observational evidence indicating that ocean materials make their way to the surface, our understanding of the chemical processes that can alter this material under Europan surface conditions is limited. We present experimental data on the chemistry of mixed solutions of NaCl and MgSO4 as they are frozen to 100 K, replicating the conditions that may occur when subsurface ocean fluids are emplaced onto Europa's surface. Confocal micro-Raman spectroscopy is used to study the formation of salts during the freezing process, and the interaction of ions in the frozen brines. Our data indicate that mixed aqueous solutions of NaCl and MgSO4 form Na2SO4 and MgCl2 preferentially when frozen, rather than making NaCl and MgSO4 precipitates. The detection of epsomite (MgSO4Ÿ•7H2O) on Europa's surface may therefore imply an ocean composition relatively low in sodium, unless radiolytic chemistry converts MgCl2 to MgSO4 as suggested by Hand and Brown 2013 (ApJ 145 110). These results have important implications for the interpretation of remote sensing data of Europa's surface.

  20. Aspect ratio control of Au nanorods via covariation of the total amount of HAuCl{sub 4} and ascorbic acid

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Xiao [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, 122 Luoshi Road, Hongshan District, Wuhan 430070, Hubei (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Feng, Jinyang [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, 122 Luoshi Road, Hongshan District, Wuhan 430070, Hubei (China); Zhao, Xiujian, E-mail: opluse@whut.edu.cn [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, 122 Luoshi Road, Hongshan District, Wuhan 430070, Hubei (China)

    2015-07-15

    Highlights: • The AR value decreased as the total amount of [HAuCl{sub 4}] and [AA] increasing. • The UV–vis absorption spectra showed the peak wavelength of TSPR at around 530 nm. • The wavelength of LSPR had a red-shifted effect. - Abstract: Controlling the aspect ratio (AR) of gold nanorods (GNRs) via covariation of the total concentrations of HAuCl{sub 4} ([HAuCl{sub 4}]) and ascorbic acid ([AA]) has been studied. Characteristics of GNRs were examined by transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) absorption spectrophotometry. TEM results showed that single crystalline GNRs grew along an elongated growth direction of [100]. TEM results also revealed that the quantity of plate shaped and nearly spherical nanoparticles increased as the total amount of [HAuCl{sub 4}] and [AA] decreased. The AR value measured from TEM images decreased from 4.74 to 2.41 as the total amount of [HAuCl{sub 4}] and [AA] was increased from 0.305 to 2.44 mM. The UV–vis absorption spectra of all samples showed that the wavelength of transverse surface plasmon resonance (TSPR) peak appeared at around 530 nm for all samples. The wavelength of longitudinal surface plasmon resonance (LSPR) peak increased from 640 to 894 nm as the total amount of [HAuCl{sub 4}] and [AA] decreased from 2.44 to 0.305 mM. The wavelength of LSPR peak shows a red-shifted effect except when the total amount of [HAuCl{sub 4}] and [AA] was 0.122 mM.

  1. Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8.

    Science.gov (United States)

    Dell'Amico, Daniela Belli; Calderazzo, Fausto; Marchetti, Fabio; Ramello, Stefano; Samaritani, Simona

    2008-02-04

    The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.

  2. Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

    Energy Technology Data Exchange (ETDEWEB)

    Billaud, D.; Naji, A.; Ghanbaja, J. [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P. [Centre National d`Etudes Spatiales (CNES), 31 - Toulouse (France)

    1996-12-31

    The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

  3. Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

    Energy Technology Data Exchange (ETDEWEB)

    Billaud, D; Naji, A; Ghanbaja, J [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P [Centre National d` Etudes Spatiales (CNES), 31 - Toulouse (France)

    1997-12-31

    The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

  4. Potentiometric study of cadmium (2) complexing with chloride-ions in aqueous solutions of Mg(ClO/sub 4/, Cl)/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Prokuev, V A; Belousov, E A

    1985-05-01

    By the method of potentiometric titration using cadmium amalgam electrode at ionic forces 1.0; 2.0; 3.0; 4.5; 6.0; 7.5 and 9.0 of (Mg(ClO/sub 4/)/sub 2/ general constants of cadmium chloride compleses stability are determined. By the Vasiliev extrapolation equation thermodynamic constants of CdClsub(n)sup(2-n) ion formation, where n=1-3 are evaluated.

  5. Electronic structure and optical properties of Cs2HgCl4: DFT calculations and X-ray photoelectron spectroscopy measurements

    Science.gov (United States)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Parasyuk, O. V.; Fedorchuk, A. O.; Khyzhun, O. Y.

    2016-10-01

    A high-quality single crystal of cesium mercury tetrabromide, Cs2HgCl4, was synthesized by using the vertical Bridgman-Stockbarger method and its electronic structure was studied from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectra were measured for both pristine and Ar+ ion-bombarded Cs2HgCl4 single crystal surfaces. The present XPS measurements indicate that the Cs2HgCl4 single crystal surface is sensitive with respect to Ar+ ion-bombardment: such a treatment changes substantially its elemental stoichiometry. With the aim of exploring total and partial densities of states within the valence band and conduction band regions of the Cs2HgCl4 compound, band-structure calculations based on density functional theory (DFT) using the augmented plane wave + local orbitals (APW + lo) method as incorporated within the WIEN2k package are performed. The calculations indicate that the Cl 3p states are the principal contributors in the upper portion of the valence band, while the Hg 5d and Cs 5p states dominate in its lower portion. In addition, the calculations allow for concluding that the unoccupied Cl p and Hg s states are the main contributors to the bottom of the conduction band. Furthermore, main optical characteristics of Cs2HgCl4, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity, are elucidated based on the DFT calculations.

  6. NaCl islands decorated with 2D or 3D 3,4,9,10-perylene-tetracarboxylic-dianhydride nanostructures

    International Nuclear Information System (INIS)

    Sun Xiaonan; Silly, Fabien

    2010-01-01

    The formation of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) nanostrutures on Au(1 1 1)-(22x√(3)) covered with NaCl islands has been studied using scanning tunneling microscopy (STM). Atomically resolved STM images show that NaCl grows as (1 0 0)-terminated layers on Au(1 1 1)-(22x√(3)). Local atomic hexagonal packing has also been observed in the NaCl(1 0 0) layer. At submonolayer NaCl coverage, PTCDA forms two-dimensional islands on the Au(1 1 1) surface and nucleate preferentially at the NaCl island step edges. When the Au surface is fully covered with NaCl layers, PTCDA molecules form three-dimensional molecular clusters decorating the step edges of NaCl layers.

  7. NaCl islands decorated with 2D or 3D 3,4,9,10-perylene-tetracarboxylic-dianhydride nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Sun Xiaonan [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands); Silly, Fabien, E-mail: Fabien.silly@cea.fr [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands); CEA, IRAMIS, SPCSI, Nanostructures and Organic Semiconductors Laboratory, F-91191 Gif-sur-Yvette (France); UPMC, IPCM, UMR CNRS 7201, 4 place Jussieu, F-75005 Paris (France)

    2010-01-15

    The formation of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) nanostrutures on Au(1 1 1)-(22x{radical}(3)) covered with NaCl islands has been studied using scanning tunneling microscopy (STM). Atomically resolved STM images show that NaCl grows as (1 0 0)-terminated layers on Au(1 1 1)-(22x{radical}(3)). Local atomic hexagonal packing has also been observed in the NaCl(1 0 0) layer. At submonolayer NaCl coverage, PTCDA forms two-dimensional islands on the Au(1 1 1) surface and nucleate preferentially at the NaCl island step edges. When the Au surface is fully covered with NaCl layers, PTCDA molecules form three-dimensional molecular clusters decorating the step edges of NaCl layers.

  8. Deposition, accumulation, and alteration of Cl−, NO3−, ClO4− and ClO3− salts in a hyper-arid polar environment: Mass balance and isotopic constraints

    Science.gov (United States)

    Jackson, Andrew; Davila, Alfonso F.; Böhlke, John Karl; Sturchio, Neil C.; Sevanthi, Ritesh; Estrada, Nubia; Brundrett, Maeghan; Lacelle, Denis; McKay, Christopher P.; Poghosyan, Armen; Pollard, Wayne; Zacny, Kris

    2016-01-01

    The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl−, NO3−, ClO4− and ClO3− in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl− and NO3−isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4−/NO3− ratios and NO3− isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3−/ClO4− in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3−, possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from ∼10 to 30 kyr near the glacier to 70–200 kyr near the valley mouth. The relatively young age

  9. Influence of gold species (AuCl4(-) and AuCl2(-)) on self-assembly of PS-b-P2VP in solutions and morphology of composite thin films fabricated at the air/liquid interfaces.

    Science.gov (United States)

    Zhao, Xingjuan; Wang, Qian; Zhang, Xiaokai; Lee, Yong-Ill; Liu, Hong-Guo

    2016-01-21

    Composite thin films doped with Au species were fabricated at an air/liquid interface via a series of steps, including the mass transfer of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) across the liquid/liquid interface between a DMF/CHCl3 solution and an aqueous solution containing either AuCl4(-) or AuCl2(-), self-assembly of PS-b-P2VP in a mixed DMF-water solution, and adsorption and further self-organization of the formed aggregates at the air/liquid interface. This is a new approach for fabricating composite polymer films and can be completed within a very short time. AuCl4(-) and AuCl2(-) ions were found to significantly influence the self-assembly behavior of the block copolymer and the morphologies of the composite films, leading to the formation of nanowire arrays and a foam structure at the air/liquid interface, respectively, which originated from rod-like micelles and microcapsules that had formed in the respective solutions. The effect of the metal complex was analyzed based on the packing parameters of the amphiphilic polymer molecules in different microenvironments and the interactions between the pyridine groups and the metal chloride anions. In addition, these composite thin films exhibited stable and durable performance as heterogeneous catalysts for the hydrogenation of nitroaromatics in aqueous solutions.

  10. Adsorption of the reactive azo dyes onto NH4Cl-induced activated carbon

    Directory of Open Access Journals (Sweden)

    Sakine Shekoohiyan

    2016-03-01

    Full Text Available Background: The efficacy of NH4Cl-induced activated carbon (NAC was examined in order to adsorb RR198, an azo reactive model dye, from an aqueous solution. Methods: The effects of pH (3 to 10, adsorbent dose (0.1 to 1.2 g/L, dye concentration and contact time on the adsorption efficiency were investigated. Results: The results showed that the removal of dye was highest at a solution pH of 7 and a powder dose of 1.1 g/L. The 85.9%, 72.6% and 65.4% removal of RR198 was obtained for a concentration of 25, 50 and 100 mg/L, respectively, at a relatively short contact time of 30 minutes, and at optimum pH and NAC concentrations of 1 g/L. The experimental data for kinetic analysis illustrated a best fit to the pseudo-second-order model. The study data on equilibrium were modeled using Langmuir, Freundlich and Dubinin–Radushkevich models; the Langmuir equation provided the best fit for the data. Conclusion: Therefore, the NAC appears to be an efficient and appropriate adsorbent for the removal of reactive azo dyes from waste streams.

  11. La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Synthesis, structure and {sup 31}P solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Eul, Matthias; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. of Physics

    2016-04-01

    The phosphide oxides La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} were synthesized from lanthanum, copper(I) oxide, red phosphorus, and lanthanum(III) chloride through a ceramic technique. Single crystals can be grown in a NaCl/KCl flux. Both structures were refined from single crystal X-ray diffractometer data: I4/mmm, a = 403.89(4), c = 2681.7(3) pm, wR2 = 0.0660, 269 F{sup 2} values, 19 variables for La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and a = 407.52(5), c = 4056.8(7) pm, wR2 = 0.0905, 426 F{sup 2} values, 27 variables for La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Refinement of the occupancy parameters revealed full occupancy for the oxygen sites in both compounds. The structures are composed of cationic (La{sub 2}O{sub 2}){sup 2+} layers and covalently bonded (Cu{sub 4}P{sub 4}){sup 5-} polyanionic layers with metallic characteristics, and an additional La{sup 3+} between two adjacent (Cu{sub 4}P{sub 4}){sup 5-} layers. The structure of La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} comprises two additional LaOCl slabs per unit cell. Temperature-dependent magnetic susceptibility studies revealed Pauli paramagnetism. The phosphide substructure of La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} was studied by {sup 31}P solid state NMR spectroscopy. By using a suitable dipolar re-coupling approach the two distinct resonances belonging to the P{sub 2}{sup 4-} and the P{sup 3-} units could be identified.

  12. Chlorellestadite, Ca5(SiO4)1.5(SO4)1.5Cl, a new ellestadite- group mineral from the Shadil-Khokh volcano, South Ossetia

    Science.gov (United States)

    Środek, Dorota; Galuskina, Irina O.; Galuskin, Evgeny; Dulski, Mateusz; Książek, Maria; Kusz, Joachim; Gazeev, Viktor

    2018-05-01

    Chlorellestadite (IMA2017-013), ideally Ca5(SiO4)1.5(SO4)1.5Cl, the Cl-end member of the ellestadite group was discovered in a calcium-silicate xenolith in rhyodacite lava from the Shadil Khokh volcano, Greater Caucasus, South Ossetia. Chlorellestadite forms white, tinged with blue or green, elongate crystals up to 0.2-0.3 mm in length. Associated minerals include spurrite, larnite, chlormayenite, rondorfite, srebrodolskite, jasmundite and oldhamite. The empirical crystal chemical formula of the holotype specimen is Ca4.99Na0.01(SiO4)1.51(SO4)1.46(PO4)0.03(Cl0.61OH0.21F0.11)Σ0.93. Unit-cell parameters of chlorellestadite are: P63/m, a = 9.6002(2), c = 6.8692(2) Å, V = 548.27(3)Å3, Z = 2. Chlorellestadite has a Mohs hardness of 4-4.5 and a calculated density of 3.091 g/cm3. The cleavage is indistinct, and the mineral shows irregular fracture. The Raman spectrum of chlorellestadite is similar to the spectra of other ellestadite group minerals, with main bands located at 267 cm-1 (Ca-O vibrations), and between 471 and 630 cm-1 (SiO4 4- and SO4 2- bending vibrations) and 850-1150 cm-1 (SiO4 4- and SO4 2- stretching modes). Chlorellestadite forms in xenoliths of calcium-silicate composition when they are exposed to Cl-bearing volcanic exhalations at about 1000 °C under low pressure conditions.

  13. The TiCl{sub 3} catalyst in NaAlH{sub 4} for hydrogen storage induces grain refinement and impacts on hydrogen vacancy formation

    Energy Technology Data Exchange (ETDEWEB)

    Singh, S.; Eijt, S.W.H. [Fundamental Aspects of Materials and Energy, Department of Radiation, Radionuclides and Reactors, Faculty of Applied Sciences, Delft University of Technology, Delft (Netherlands); Huot, J. [Universite du Quebec a Trois Rivieres, Quebec (Canada); Kockelmann, W.A. [ISIS, Rutherford Appleton Laboratory, Chilton, Oxfordshire (United Kingdom); Wagemaker, M. [Fundamental Aspects of Materials and Energy, Department of Radiation, Radionuclides and Reactors, Faculty of Applied Sciences, Delft University of Technology, Delft (Netherlands); Mulder, F.M. [Fundamental Aspects of Materials and Energy, Department of Radiation, Radionuclides and Reactors, Faculty of Applied Sciences, Delft University of Technology, Delft (Netherlands)], E-mail: f.m.mulder@tudelft.nl

    2007-09-15

    TiCl{sub 3} acts as an efficient catalyst for NaAlH{sub 4} (sodium alanate), altering its hydrogen sorption kinetics and reversibility considerably. In order to clarify its role, we performed in situ neutron diffraction experiments on protonated catalysed and uncatalysed NaAlH{sub 4}. The phase transformations were monitored in the first two reaction steps during hydrogen release and in the second step during reloading. Our study for the first time provides clear indications that both Ti{sub x}Al{sub 1-x} and NaCl formed act as grain refiner for Al and NaH, respectively, preventing particle growth. Particle sizes generally stay small upon desorption and reloading of TiCl{sub 3} catalysed NaAlH{sub 4}, while significant particle growth is observed for uncatalysed NaAlH{sub 4}. The small crystallite sizes and observed hydrogen vacancy formation greatly facilitate the mass transfer during loading and unloading. This study underlines the importance of grain refining for achieving reversibility and faster kinetics of the hydrogen sorption processes, with a crucial double role played by the catalyst.

  14. Synthesis of [PtCl2(4,4'-dialkoxy-2,2'-bipyridine)] complexes and their in vitro anticancer properties.

    Science.gov (United States)

    Vo, Van; Tanthmanatham, Ontida; Han, Haesook; Bhowmik, Pradip K; Spangelo, Bryan L

    2013-08-01

    A series of [Pt(II)Cl2(4,4'-dialkoxy-2,2'-bipyridine)] complexes of the general formula of [Pt(II)Cl2(4,4'-bis(RO)-2,2'-bipyridine)] (where R = -(CH2)n-1CH3, n = 2-6, 8) were synthesized and characterized using (1)H NMR, (13)C NMR spectroscopy, elemental analysis, mass spectroscopy, and differential scanning calorimetry measurements. The in vitro anti-proliferative activities of these compounds were evaluated against human cancer cell lines A549 (lung adenocarcinoma), DU145 (prostate carcinoma), MCF-7 (breast adenocarcinoma), and MDA-MB-435 (melanoma) using the MTS cell proliferation assay. Several Pt(II) coordination compounds were found to have greatly enhanced activity compared to cisplatin after a one hour treatment in all cell lines tested. A structure-activity relationship was observed, that is, the activity increases as the carbon chain length of the alkyl group increases. The activity was maximum when the carbon chain length reached four or five carbons and decreased with the longer carbon chain length. Fluorescence microscopy and flow cytometry data indicate that the main mode of cell death is through apoptosis with some necrotic responses.

  15. Origin of the fast magnetization tunneling in [Ni(hmp)(tBuEtOH)Cl]4

    Science.gov (United States)

    Lawrence, Jon; Yang, En-Che

    2005-03-01

    High-frequency (40-360 GHz), angle-dependent EPR data have been collected for single-crystals of [Ni(hmp)(dmb)Cl]4, and [Ni0.02Zn0.98(hmp)(dmb)Cl]4. The all-nickel complex behaves as a single-molecule magnet (SMM) at low temperatures, displaying hysteresis and magnetic quantum tunneling. However, in spite of its high symmetry (S4), the relaxation is found to be very fast. We show that the origin of this behavior is related to a 4^th-order transverse crystal-field interaction, B4^4(S+^4 + S-^4), which produces a significant tunnel-splitting (˜10 MHz) of the ms = ±4 ground state of this S = 4 SMM. The fourth-order (B4^4) and uniaxial (D) crystal-field strengths can be related to the directionality and magnitude of the single-ion interactions (Di and Ei) at the individual Ni^II sites, as determined for the doped crystals. Variable-temperature EPR measurements also reveal the locations of excited spin states (S = 3, 2, etc..), enabling estimates of intra-molecular exchange coupling strengths.

  16. Tb3O2Cl[SeO3]2 and Tb5O4Cl3[SeO3]2: Oxide Chloride Oxoselenates(IV) of Trivalent Terbium with ''Lone-Pair'' Channel or Layer Structures

    International Nuclear Information System (INIS)

    Wontcheu, Joseph; Schleid, Thomas

    2005-01-01

    Orthorhombic Tb 3 O 2 Cl[SeO 3 ] 2 (Pnma; a = 535.16(4), b = 1530.51(9), c = 1081.72(7) pm; Z = 4) is formed by reacting a stoichiometric mixture of Tb 4 O 7 , Tb, TbCl 3 , and SeO 2 in a suitable molar ratio (12: 8: 7: 42) within seven days in an evacuated sealed silica tube at 850 C. The needle-shaped, colourless single crystals (light, water and air stable) exhibit one-dimensional strands [(Tb1) 3/3 (Tb2) 2/1 O 4/2 ] 5+ [O 2 Tb 3 ] 5+ along [100] formed by two parallel chains [OTb 4/2 ] 4+ of trans-edge connected [OTb 4 ] 10+ tetrahedra (d(O-Tb) = 220 - 231 pm) which share an extra edge per chain link. The crystal structure contains two crystallographically different Tb 3+ cations: Tb1 is coordinated as bicapped trigonal prism, while Tb2 resides in square antiprismatic coordination. The Se 4+ coordination is best described as Ψ 1 tetrahedral ([SeO 3 E] 2- ; E: non-binding electron pair). The non-binding ''lone-pair'' electrons of four [SeO 3 ] 2- groups and two Cl - anions form pseudo-hexagonal empty channels along [100] between four cationic double chains. Tb 5 O 4 Cl 3 [SeO 3 ] 2 was prepared likewise as plate-like, colourless single crystals by solid-state reaction of an admixture of Tb 4 O 7 , Tb, TbOCl, TbCl 3 , and SeO 2 (molar ratio: 9: 6: 21: 7: 28) in an evacuated sealed silica tube during seven days at 850 C. This compound crystallizes in the monoclinic system (C2/m; a = 1229.13(9), b = 546.17(4), c = 978.79(7) pm, β = 90.485(6) ; Z = 2) and contains three crystallographically different Tb 3+ cations in seven- and eightfold coordination of O 2- and Cl - anions, respectively. The crystal structure of Tb 5 O 4 Cl 3 [SeO 3 ] 2 is layered and built up of corrugated terbium-oxygen sheets [O 4 Tb 5 ] 7+ formed by edge- and vertex-shared [OTb 4 ] 10+ tetrahedra (d(O-Tb) = 226-232 pm) spreading parallel (001). The structure is strongly related to the ''lone-pair'' channel structures of Tb 2 O[SeO 3 ] 2 and Tb 3 O 2 Cl[SeO 3 ] 2 , where single ([OTb 2 ] 4

  17. Thermal expansion at the incommensurate phase transition in [N(CH3)4]2ZnCl4-xBrx crystals

    NARCIS (Netherlands)

    Maior, M.M.; Loosdrecht, P.H.M. van; Kempen, H. van; Molnar, S.B.; Slivka, V.Yu.

    1994-01-01

    The temperature dependence of the thermal expansion in the vicinity of the incommensurate phase transition in [N(CH3)4]2ZnCl4-xBrx mixed crystals is found to deviate from that predicted within the Landau theory of phase transitions. It is shown that the dominant contribution to this deviation in the

  18. Interaction of a 29 MeV 3{sup H}e particle beam with a Cl{sub 4}C vapour target; Interacciones de He{sup 3} de 29 MeV en un blanco de Cl{sub 4}C

    Energy Technology Data Exchange (ETDEWEB)

    Lleo Morilla, A

    1963-07-01

    The interactions of a 29 MeV 3{sup H}e particles beam on a Cl{sub 4}C vapour target have been studied using the photographic method. differential cross-sections for the Cl({sup 3}He, {sup 3}He)Cl elastic scattering and {sup 1}2C({sup 3}He, {alpha}){sup 1}1C pick-up reaction are shown; the corresponding angular distributions in the centre-of-mass system have been compared with the predictions of optical model and A.B.M. theories. (Author) 21 refs.

  19. Action spectroscopy of SrCl{sup +} using an integrated ion trap time-of-flight mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Puri, Prateek, E-mail: teek24@ucla.edu; Schowalter, Steven J.; Hudson, Eric R. [Department of Physics and Astronomy, University of California, Los Angeles, California 90095 (United States); Kotochigova, Svetlana; Petrov, Alexander [Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States)

    2014-07-07

    The photodissociation cross-section of SrCl{sup +} is measured in the spectral range of 36 000–46 000 cm{sup −1} using a modular time-of-flight mass spectrometer (TOF-MS). By irradiating a sample of trapped SrCl{sup +} molecular ions with a pulsed dye laser, X{sup 1}Σ{sup +} state molecular ions are electronically excited to the repulsive wall of the A{sup 1}Π state, resulting in dissociation. Using the TOF-MS, the product fragments are detected and the photodissociation cross-section is determined for a broad range of photon energies. Detailed ab initio calculations of the SrCl{sup +} molecular potentials and spectroscopic constants are also performed and are found to be in good agreement with experiment. The spectroscopic constants for SrCl{sup +} are also compared to those of another alkaline earth halogen, BaCl{sup +}, in order to highlight structural differences between the two molecular ions. This work represents the first spectroscopy and ab initio calculations of SrCl{sup +}.

  20. Coagulation performance and floc characteristics of polytitanium tetrachloride (PTC) compared with titanium tetrachloride (TiCl4) and ferric chloride (FeCl3) in algal turbid water

    KAUST Repository

    Chekli, L.; Eripret, C.; Park, S.H.; Tabatabai, S. Assiyeh Alizadeh; Vronska, O.; Tamburic, B.; Kim, J.H.; Shon, H.K.

    2016-01-01

    Seasonal green algae blooms in freshwaters have raised attention on the need to develop novel effective treatment processes for the removal of algae in water. In the present study, the performance of newly developed polytitanium tetrachloride (PTC) coagulant for the removal of freshwater microalga Chlorella vulgaris has been investigated and compared with titanium tetrachloride (TiCl4) coagulant and the conventional ferric chloride (FeCl3) coagulant. The main benefit of using titanium-based coagulants is that the sludge produced after flocculation may be recycled into a valuable product: titanium dioxide photocatalyst. Both titanium-based coagulants achieved good flocculation over a broader pH range and coagulant dose compared to conventional FeCl3 coagulant. All three coagulants achieved comparable performance in terms of turbidity removal (i.e. turbidity removal efficiency >97%); although TiCl4 performed slightly better at the lower tested dose (i.e. <9 mg/L). Zeta potential measurements indicated that charge neutralisation may not be the sole mechanism involved in the coagulation of algae for all three coagulants. Analysis of the dynamic floc size variation during floc breakage showed no regrowth after floc breakage for the three coagulants. The flocs formed by both Ti-based coagulants were larger than those formed by FeCl3 and also grew at a faster rate. This study indicates that Ti-based coagulants are effective and promising coagulants for algae removal in water.

  1. Coagulation performance and floc characteristics of polytitanium tetrachloride (PTC) compared with titanium tetrachloride (TiCl4) and ferric chloride (FeCl3) in algal turbid water

    KAUST Repository

    Chekli, L.

    2016-11-11

    Seasonal green algae blooms in freshwaters have raised attention on the need to develop novel effective treatment processes for the removal of algae in water. In the present study, the performance of newly developed polytitanium tetrachloride (PTC) coagulant for the removal of freshwater microalga Chlorella vulgaris has been investigated and compared with titanium tetrachloride (TiCl4) coagulant and the conventional ferric chloride (FeCl3) coagulant. The main benefit of using titanium-based coagulants is that the sludge produced after flocculation may be recycled into a valuable product: titanium dioxide photocatalyst. Both titanium-based coagulants achieved good flocculation over a broader pH range and coagulant dose compared to conventional FeCl3 coagulant. All three coagulants achieved comparable performance in terms of turbidity removal (i.e. turbidity removal efficiency >97%); although TiCl4 performed slightly better at the lower tested dose (i.e. <9 mg/L). Zeta potential measurements indicated that charge neutralisation may not be the sole mechanism involved in the coagulation of algae for all three coagulants. Analysis of the dynamic floc size variation during floc breakage showed no regrowth after floc breakage for the three coagulants. The flocs formed by both Ti-based coagulants were larger than those formed by FeCl3 and also grew at a faster rate. This study indicates that Ti-based coagulants are effective and promising coagulants for algae removal in water.

  2. Nqrs Data for C3H2Cl10N2PSb[C3HCl4N2P·Cl6HSb](Subst. No. 0601)

    Science.gov (United States)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C3H2Cl10N2PSb [C3HCl4N2P·Cl6HSb] (Subst. No. 0601)

  3. Stable Chloro- and Bromoxenate Cage Anions; [X3(XeO3)3]3- and [X4(XeO3)4]4- (X = Cl or Br).

    Science.gov (United States)

    Goettel, James T; Haensch, Veit G; Schrobilgen, Gary J

    2017-06-28

    The number of isolable compounds which contain different noble-gas-element bonds is limited for xenon and even more so for krypton. Examples of Xe-Cl bonds are rare, and prior to this work, no Xe-Br bonded compound had been isolated in macroscopic quantities. The syntheses, isolation, and characterization of the first compounds to contain Xe-Br bonds and their chlorine analogues are described in the present work. The reactions of XeO 3 with [N(CH 3 ) 4 ]Br and [N(C 2 H 5 ) 4 ]Br have provided two bromoxenate salts, [N(C 2 H 5 ) 4 ] 3 [Br 3 (XeO 3 ) 3 ] and [N(CH 3 ) 4 ] 4 [Br 4 (XeO 3 ) 4 ], in which the cage anions have Xe-Br bond lengths that range from 3.0838(3) to 3.3181(8) Å. The isostructural chloroxenate anions (Xe-Cl bond lengths, 2.9316(2) to 3.101(4) Å) were synthesized by analogy with their bromine analogues. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy and low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe-Br and Xe-Cl bonds are very weakly covalent and can be viewed as σ-hole interactions, similar to those encountered in halogen bonding. However, the halogen atoms in these cases are valence electron lone pair donors, and the σ* Xe-O orbitals are lone pair acceptors.

  4. Quasi-self-trapped Frenkel-exciton near-UV luminescence with large Stokes shift in wide-bandgap Cs4PbCl6 nanocrystals

    Science.gov (United States)

    Zhang, Yumeng; Fan, Baolu; Liu, Yuzhen; Li, Hongxia; Deng, Kaiming; Fan, Jiyang

    2018-04-01

    Inorganic lead halide perovskite nanocrystals (NCs) have attracted great interest owing to their superior luminescence and optoelectronic properties. In comparison to cubic CsPbX3 (X = Cl, Br, or I) that has visible luminescence, trigonal Cs4PbX6 has a much larger bandgap and distinct optical properties. Little has been known about the luminescence properties of the Cs4PbX6 NCs. In this study, we synthesize the well-crystallized Cs4PbCl6 NCs with sizes of 2.2-11.8 nm, which exhibit stable and near-UV luminescence (with a lifetime of 19.7-24.2 ns) with a remarkable quantum confinement effect at room temperature. In comparison to the negligible Stokes shift in the CsPbCl3 NCs, the Stokes shift of the Cs4PbCl6 NCs is very large (0.91 eV). The experimental results in combination with the first-principles calculations reveal that the near-UV luminescence of the Cs4PbCl6 NCs stems from the Frenkel excitons self-trapped in the isolated PbCl64- octahedrons. This is different from the CsPbCl3 NCs whose luminescence originates from the free Wannier excitons. The theoretical model based on the lattice relaxation is proposed to account for the large Stokes shift and its abnormal decrease with the decreasing particle size.

  5. The French accelerator mass spectrometry facility ASTER after 4 years: Status and recent developments on {sup 36}Cl and {sup 129}I

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Maurice; Aumaitre, Georges; Bourles, Didier L.; Keddadouche, Karim [ASTER-Team, CNRS-IRD Aix-Marseille Universite, F-13545 Aix-en-Provence (France); CEREGE, CNRS-IRD Aix-Marseille,Universite, F-13545 Aix-en-Provence (France); Braucher, Regis [CEREGE, CNRS-IRD Aix-Marseille,Universite, F-13545 Aix-en-Provence (France); Finkel, Robert C. [CEREGE, CNRS-IRD Aix-Marseille,Universite, F-13545 Aix-en-Provence (France); Earth and Planetary Science Dept., UC Berkeley, Berkeley, CA 94720-4767 (United States); Nottoli, Emmanuelle; Benedetti, Lucilla [CEREGE, CNRS-IRD Aix-Marseille,Universite, F-13545 Aix-en-Provence (France); Merchel, Silke, E-mail: s.merchel@hzdr.de [Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden (Germany)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer Yearly sample throughput as high as over 3300 unknowns for {sup 10}Be in 2010. Black-Right-Pointing-Pointer {sup 35}Cl/{sup 37}Cl samples proved time dependent mass fractionation and/or source memory. Black-Right-Pointing-Pointer Need for improvement in measurement strategies, data evaluation and ion sources. Black-Right-Pointing-Pointer Cross-calibration of secondary in-house {sup 129}I standards vs. NIST 3231. Black-Right-Pointing-Pointer Cross-contamination for iodine {approx}0.5% within first 20 h of source running. - Abstract: Since the acceptance tests of the French 5 MV accelerator mass spectrometry facility ASTER in 2007, routine measurement conditions for the long-lived radionuclides {sup 10}Be and {sup 26}Al have been established. Yearly sample throughput as high as over 3300 unknowns has been reached for {sup 10}Be in 2010. Cross-contamination for volatile elements has been largely solved by an ion source upgrade allowing {sup 36}Cl measurements at ASTER. However, recent long-term tests using {sup 35}Cl/{sup 37}Cl samples with strongly varying ratios have shown that identical targets lead to different {sup 35}Cl/{sup 37}Cl results at the 2-4% level when being measured after a time gap of 24 h while the source is running other samples. Besides time dependent mass fractionation, another likely reason for this effect might be source memory, thus, asking for sophisticated measurement strategies and improved data evaluation and eventually further ion source improvement. Finally, after establishing quality assurance by cross-calibration of secondary in-house {sup 26}Al and {sup 41}Ca standards and taking part in round-robin exercises of {sup 10}Be and {sup 36}Cl, a two-step cross-calibration of secondary in-house {sup 129}I standards has been performed. The NIST 3231 standard containing {sup 129}I/{sup 127}I at (0.981 {+-} 0.012) Multiplication-Sign 10{sup -6} has been used for step-wise dilution with NaI to produce

  6. Analysis of temperature dependence of {sup 35}Cl-NQR frequency in 2,4-D herbicide (2,4-dichlorophenoxy acetic acid); Analiza temperaturowej zaleznosci czestosci {sup 35}Cl-NQR w herbicydzie 2,4-D (kwas dichlorofenoksyoctowy)

    Energy Technology Data Exchange (ETDEWEB)

    Mazurek, P.; Ostafin, M.; Kasprzak, J.; Nogaj, B. [Inst. Fizyki, Uniwersytet A. Mickiewicza, Poznan (Poland)

    1994-12-31

    Biological activity of herbicide depends on electronic structure and molecule dynamics. The former parameter has been investigated by means of NQR spectra on {sup 35}Cl nuclei of 2,4-dichlorophenoxy acetic acid. The analysis of temperature dependency of observed frequency has been done. 12 refs, 3 figs, 1 tab.

  7. Comparative study of the catalytic activity of the complexes Cp*RuCl(PAr3)2 [Ar = -C6H5 and 4-CF3-C6H4] in the ATRP of styrene

    International Nuclear Information System (INIS)

    Villa-Hernandez, Alejandro M.; Rosales-Velazquez, Claudia P.; Torres-Lubian, Jose R.; Saldivar-Guerra, Enrique

    2011-01-01

    Styrene polymerization by ATRP was conducted independently using the complexes Cp * RuCl(PPh 3 ) 2 , and Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 as catalysts, in order to evaluate the influence of the electronic properties of the phosphine ligands on the rate and control of the polymerization. The kinetic data for polymerizations carried out with Cp * RuCl(PPh 3 ) 2 , show that molecular weights increase linearly with conversion with an average initiation efficiency of 0.77. The molecular weights obtained in the kinetic study with Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 also increase with conversion but show a marked deviation below the theoretical molecular weights. This behavior was explained by the gradual, irreversible, oxidation of catalyst Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 as confirmed by 31 P-NMR spectroscopy. Catalyst Cp * RuCl(PPh 3 ) 2 promotes the polymerization with a rate of polymerization higher than that obtained using Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 ; this is consistent with the better electron donating properties of PPh 3 versus P(4-CF 3 -C 6 H 4 ) 3 . Preliminary studies of styrene polymerization by ATRP in supercritical CO 2 , shows that only catalyst Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 , with fluorinated ligands, was active. (author)

  8. Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic perchlorates: (C6H18N3)·(ClO4)3H2O (I) and (C9H11N2)·ClO4(II)

    Science.gov (United States)

    Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Ferretti, V.; Ben Nasr, C.

    2018-06-01

    The reaction of perchloric acid with 1-(2-aminoethyl)piperazine or 5,6-dimethyl-benzimidazole results in the formation of 1-(2-amonioethyl)piperazine-1,4-dium triperchlorate hydrate (C6H18N3)·(ClO4)3·H2O (I) or 5,6-dimethyl-benzylimidazolium perchlorate (C9H11N2)·ClO4(II). Both compounds were fully structurally characterized including single crystal X-ray diffraction analysis. Compound (I) crystallizes in the centrosymmetric triclinic space group P 1 bar with the lattice parameters a = 7.455 (2), b = 10.462 (2), c = 10.824 (2) Å, α = 80.832 (2), β = 88.243 (2), γ = 88.160 (2) °, Z = 2 and V = 832.77 (3) Å3. Compound (II) has been found to belong to the P21/c space group of the monoclinic system, with a = 7.590 (3), b = 9.266 (3), c = 16.503 (6) Å, β = 107.38 (2) °, V = 1107.69 (7) Å3 and Z = 4. The structures of (I) and (II) consist of slightly distorted [ClO4]- tetrahedra anions and 1-(2-amonioethyl)piperazine-1,4-dium trication (I) or 5,6-dimethyl-benzylimidazolium cations (II) and additionally a lattice water in (I). The crystal structures of (I) and (II) exhibit complex three-dimensional networks of H-bonds connecting all their components. In the atomic arrangement of (I), the ClO4- anions form corrugated chains, while in (II) the atomic arrangement exhibits wide pseudo-hexagonal channels of ClO4 tetrahedra including the organic entities. The lattice water serves as a link between pairs of cations and pairs of anions via several Osbnd H⋯O and N-H⋯O interactions in compound (I). The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived.

  9. GeSn growth kinetics in reduced pressure chemical vapor deposition from Ge2H6 and SnCl4

    Science.gov (United States)

    Aubin, J.; Hartmann, J. M.

    2018-01-01

    We have investigated the low temperature epitaxy of high Sn content GeSn alloys in a 200 mm industrial Reduced Pressure - Chemical Vapor Deposition tool from Applied Materials. Gaseous digermane (Ge2H6) and liquid tin tetrachloride (SnCl4) were used as the Ge and Sn precursors, respectively. The impact of temperature (in the 300-350 °C range), Ge2H6 and SnCl4 mass-flows on the GeSn growth kinetics at 100 Torr has been thoroughly explored. Be it at 300 °C or 325 °C, a linear GeSn growth rate increase together with a sub-linear Sn concentration increase occurred as the SnCl4 mass-flow increased, irrespective of the Ge2H6 mass flow (fixed or varying). The Sn atoms seemed to catalyze H desorption from the surface, resulting in higher GeSn growth rates for high SnCl4 mass-flows (in the 4-21 nm min-1 range). The evolution of the Sn content x with the F (SnCl4) 2 ·/F (Ge2H6) mass-flow ratio was fitted by x2/(1 - x) = n ·F (SnCl4) 2 ·/F (Ge2H6), with n = 0.25 (325 °C) and 0.60 (300 °C). We have otherwise studied the impact of temperature, in the 300-350 °C range, on the GeSn growth kinetics. The GeSn growth rate exponentially increased with the temperature, from 15 up to 32 nm min-1. The associated activation energy was low, i.e. Ea = 10 kcal mol-1. Meanwhile, the Sn content decreased linearly as the growth temperature increased, from 15% at 300 °C down to 6% at 350 °C.

  10. Experimental determination of the H2O + 15 wt% NaCl and H2O + 25 wt% NaCl liquidi to 1.4 GPa

    Science.gov (United States)

    Valenti, P.; Schmidt, C.

    2009-12-01

    The binary H2O+NaCl is one of the most important model systems for chloridic fluids in many geologic environments such as the Earth’s crust, upper mantle, and subducting slabs, and is also applicable to extraterrestrial icy planetary bodies (e.g., Manning 2004, Zolensky et al., 1999). The knowledge on phase equilibria and PVTx properties of this system is still fragmentary at high pressures, e.g., very little has been reported on liquidi at compositions Daniel 2008). In this study, we investigated the liquidus of 15 and 25 wt% NaCl solutions at pressures up to 1.4 GPa. The experiments were performed using a hydrothermal diamond-anvil cell (Bassett et al. 1993) modified for Raman spectroscopy and accurate temperature measurements. A quartz chip, halite, and water were loaded into the sample chamber, which also contained a small trapped air bubble (10 vol%) when it was sealed. The actual salinity was then determined from measurement of the vapor-saturated liquidus temperature. The sample chamber was then compressed until the bubble disappeared. After freezing, phase transitions occurring with increasing temperature were observed optically, and the pressure was determined from the frequency shift of the 464 cm-1 Raman line of quartz (Schmidt and Ziemann 2000). The sample chamber was then compressed further, and the experiment was repeated at various bulk densities until a pressure of ~1.4 GPa was attained. At some conditions, Raman spectra were acquired for identification of the phase assemblage. The solution always crystallized to a single phase upon cooling above ~0.15 GPa at 25 wt% NaCl and above ~1 GPa at 15 wt% NaCl. Raman spectra in the OH stretching region indicate that this phase contains or is a NaCl hydrate other than hydrohalite, probably in solid solution with ice. Melting of this phase produced liquid and hydrohalite and/or ice VI. Ice VI was the last solid that dissolved upon heating, between 1100 MPa, 3 °C and 1370 MPa, 17 °C for 15 wt% NaCl and at

  11. Inland Concentrations of Cl2 and ClNO2 in Southeast Texas Suggest Chlorine Chemistry Significantly Contributes to Atmospheric Reactivity

    Directory of Open Access Journals (Sweden)

    Cameron B. Faxon

    2015-10-01

    Full Text Available Measurements of molecular chlorine (Cl2, nitryl chloride (ClNO2, and dinitrogen pentoxide (N2O5 were taken as part of the DISCOVER-AQ Texas 2013 campaign with a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS using iodide (I- as a reagent ion. ClNO2 concentrations exceeding 50 ppt were regularly detected with peak concentrations typically occurring between 7:00 a.m. and 10:00 am. Hourly averaged Cl2 concentrations peaked daily between 3:00 p.m. and 4:00 p.m., with a 29-day average of 0.9 ± 0.3 (1σ ppt. A day-time Cl2 source of up to 35 ppt∙h−1 is required to explain these observations, corresponding to a maximum chlorine radical (Cl• production rate of 70 ppt∙h−1. Modeling of the Cl2 source suggests that it can enhance daily maximum O3 and RO2• concentrations by 8%–10% and 28%–50%, respectively. Modeling of observed ClNO2 assuming a well-mixed nocturnal boundary layer indicates O3 and RO2• enhancements of up to 2.1% and 38%, respectively, with a maximum impact in the early morning. These enhancements affect the formation of secondary organic aerosol and compliance with air quality standards for ozone and particulate matter.

  12. Electrochemical behavior of Th(IV) and its electrodeposition from ThF_4-LiCl-KCl melt

    International Nuclear Information System (INIS)

    Wang, Xianbin; Huang, Wei; Gong, Yu; Jiang, Feng; Zheng, Haiyang; Zhu, Tiejian; Long, Dewu; Li, Qingnuan

    2016-01-01

    The electrochemical behavior of Th(IV) ion on molybdenum (Mo) electrode was studied by cyclic voltammetry (CV) and square wave voltammetry (SWV) technologies at 773 K in ThF_4-LiCl-KCl melt. The reduction of Th(IV) to metal Th at −1.67 V (vs. Ag/AgCl) is a four-electron exchange process, which is quasi-reversible and diffusion-controlled. The diffusion coefficient (D) and activation energy of diffusion process for Th(IV) were determined to be 3.77 × 10"−"5 cm"2 s"−"1 and 59.2 kJ mol"−"1. The pulse potential electrolysis of ThF_4-LiCl-KCl melt revealed that 86.8% of Th(IV) can be separated from the melt based on the inductively coupled plasma atomic emission spectrometer (ICP-AES) results.

  13. Intrinsic and extrinsic photoluminescence in the NH sub 4 MnCl sub 3 cubic perovskite: a spectroscopic study

    CERN Document Server

    Hernandez, I

    2003-01-01

    This work investigates the photoluminescence (PL) properties of the cubic chloroperovskite NH sub 4 MnCl sub 3. Like in most concentrated materials, the Mn sup 2 sup + PL which is located at 2.10 eV at T = 10 K strongly depends on the temperature. Optical absorption (OA), emission, and excitation spectroscopy, as well as lifetime measurements, performed on NH sub 4 MnCl sub 3 indicate that the PL is mainly intrinsic at T = 10 K and consists of a broad band located at 2.10 eV. Above this temperature, the PL gradually transforms to extrinsic PL due to exciton migration and subsequent trapping. Further temperature increase above 100 K yields transfer to killers of excitation which are responsible for the PL quenching, and hence the absence of PL at ambient conditions. The exciton traps are identified with perturbed Mn sup 2 sup + sites with the effective activation energy of 52 meV, whilst the activation energy for energy transfer is 47 meV. The existence of these traps has been directly revealed by time-resolve...

  14. Electrochemistry Study on PVC-LiClO4 Polymer Electrolyte Supported by Bengkulu Natural Bentonite for Lithium Battery

    Directory of Open Access Journals (Sweden)

    Ghufira

    2012-04-01

    Full Text Available In this research bentonite was used as filler to produce polymer electrolyte (PVCLiClO4. Some weight variation of bentonite have been made by addition, such as 0% wt/wt; 5% wt/wt ; 10% wt/wt ; 15% wt/wt ; 20% wt/wt ; and 25% wt/wt of bentonite to the mixture of 0,5 gramof PVC and 0,125 gram of LiClO4. Ionic conductivity of polymer electrolyte was tested using impedance spectroscopy. The result of the research was showed that a mixture of PVCBentonite(10% wt/wt-LiClO4 gives the highest ionic conductivity (4,86 x 10-3 S.Cm-1. This result indicated that the presence of natural bentonite can be used as a filler in the current composite polymer electrolyte and can increase the ionic conductivity of the polymer electrolyte.

  15. Evaluation report on CCTF core-I reflood tests Cl-5 (Run 14), Cl-10 (Run 19) and Cl-12 (Run 21)

    International Nuclear Information System (INIS)

    Akimoto, Hajime; Murao, Yoshio

    1983-06-01

    Three tests Cl-5 (Run 14), Cl-10 (Run 19) and Cl-12 (Run 21) were performed using the Cylindrical Core Test Facility to study the effect of the containment pressure on the core cooling and the system behaviors during the reflood phase of a PWR-LOCA. The containment pressures of these tests were 0.15, 0.20 and 0.30 MPa for the tests Cl-10, Cl-5 and Cl-12, respectively. Through the comparison of the test results from these three tests, the following results were obtained. (1) The higher containment pressure gave the higher heat transfer coefficient in the core. This resulted in the lower turnaround temperature, the shorter turnaround time and the shorter quench time at the higher containment pressure. (2) In the higher containment pressure test, the higher core water head, the higher upper plenum water head, the higher downcomer water head in the early period and the lower downcomer water head in the later period were observed than those in the lower containment pressure test. This resulted in the higher pressure drop through the intact loop in the early period of the tests and the lower pressure drop in the later period of the test with the containment pressure. (3) The pressure drop through the broken cold leg pressurized the primary system. The pressure drop through the broken cold leg was decreased with the containment pressure. (4) The core inlet mass flow rate was increased with the containment pressure as observed in the FLECHT-SET phase B1 test. In quantity, however, the effect of the containment pressure on the increase of the core inlet mass flow rate was less in the CCTF than that in the FLECHT-SET. The less sensitivity in the CCTF was attributed mainly to the great pressure drop through the broken cold leg, which was not observed in the FLECHT-SET with big broken cold leg. (5) The system effect of the containment pressure was explained quantitatively. (author)

  16. Interaction of a 29 MeV 3He particle beam with a Cl4C vapour target

    International Nuclear Information System (INIS)

    Lleo Morilla, A.

    1963-01-01

    The interactions of a 29 MeV 3 H e particles beam on a Cl 4 C vapour target have been studied using the photographic method. differential cross-sections for the Cl( 3 He, 3 He)Cl elastic scattering and 1 2C( 3 He, α) 1 1C pick-up reaction are shown; the corresponding angular distributions in the centre-of-mass system have been compared with the predictions of optical model and A.B.M. theories. (Author) 21 refs

  17. Phase transitions and molecular motions in [Ni(ND3)6](ClO4)2

    International Nuclear Information System (INIS)

    Migdal-Mikuli, Anna; Mikuli, Edward; Gorska, Natalia; Kowalska, Aneta; Ulanski, Jacek

    2004-01-01

    [Ni(ND 3 ) 6 ](ClO 4 ) 2 has three solid phases between 100 and 300 K. The phase transitions temperatures at heating (T C1 h =164.1 K and T C2 h =145.1 K) are shifted, as compared to the non-deuterated compound, towards the lower temperature of ca. 8 and 5 K, respectively. The ClO 4 - anions perform fast, picosecond, isotropic reorientation with the activation energy of 6.6 kJ mol -1 , which abruptly slow down at T C1 c phase transition, during sample cooling. The ND 3 ligands perform fast uniaxial reorientation around the Ni-N bond in all three detected phases, with the effective activation energy of 2.9 kJ mol -1 . The reorientational motion of ND 3 is only slightly distorted at the T C1 phase transition due to the dynamical orientational order-disorder process of anions. The low value of the activation energy for the ND 3 reorientation suggests that this reorientation undergoes the translation-rotation coupling, which makes the barrier to the rotation of the ammonia ligands not constant but fluctuating. The phase polymorphism and the dynamics of the molecular reorientations of the title compound are similar but not quite identical with these of the [Ni(NH 3 ) 6 ](ClO 4 ) 2

  18. Ternary rare-earth halides of the A2MX5 type (A = K, In, NH4, Rb, Cs; X = Cl, Br, I)

    International Nuclear Information System (INIS)

    Meyer, G.; Soose, J.; Moritz, A.; Vitt, V.; Holljes, T.

    1985-01-01

    Ternary rare-earth (=M) chlorides, bromides, and iodides In 2 MCl 5 , (NH 4 ) 2 MCl 5 , Rb 2 MCl 5 , Cs 2 MCl 5 , CsRbMCl 5 , K 2 MBr 5 , Rb 2 MBr 5 , K 2 MI 5 , and Rb 2 MI 5 have been synthesized. Single crystals of In 2 PrCl 5 , Rb 2 PrCl 5 , K 2 PrBr 5 , and K 2 PrI 5 were grown and the structures refined. The other halides were characterized by X-ray powder patterns. They are isotypic either with K 2 PrCl 5 (orthorhombic, Pnma, Z = 4, hexagonal arrangement of chains of edge-connected polyhedra [PrX 7 ]) or with Cs 2 DyCl 5 (orthorhombic, Pbnm, Z = 4, hexagonal arrangement of cis-corner-connected octahedra [DyCl 6 ]) which may be discriminated in structure field diagrams. The thermal expansion was investigated for Cs 2 LuCl 5 and Rb 2 PrX 5 (X = Cl, Br, I). (author)

  19. Crystal and molecular structure of new fullerides (Ph4P)2C60Hal (Hal = Br, I) and (Ph4As)2C60Cl

    International Nuclear Information System (INIS)

    Gritsenko, V.V.; D'yachenko, O.A.; Shilov, G.V.; Spitsyn, N.G.; Yagubskij, E h.B.

    1997-01-01

    New stable on air fullerides (Ph 4 P) 2 C 60 Hal (Hal = Br, I) and (Ph 4 As) 2 C 60 Cl were synthesized and their crystal structure were determined. On the basis of their relative crystallochemical analysis fullerides obtained were shown to be isostructural. They are described by general formula (Ph 4 X) 2 C 60 Hal (X = H, As; Hal = Cl, Br, I) and crystallized in triclinic system. Anions C 60 - and Hal - occupy the centre-symmetrical positions, cations (PH 4 P) + and (Ph 4 As) + occupy the general positions. The main parameters of molecular structure are presented

  20. Ferroelastoelectric phase transition in (NH4)2CuCl4·2H2O single crystal

    International Nuclear Information System (INIS)

    Tylczyński, Zbigniew; Wiesner, Maciej

    2015-01-01

    The (NH 4 ) 2 CuCl 4 ·2H 2 O crystal exhibits anomalous thermal, piezoelectric, dielectric and elastic properties in the vicinity of the ferroelastoelectric phase transition at T C  = 200 K. Macroscopic order parameter is the h 36 component of the spontaneous piezoelectric tensor connecting polarisation P 3 and strain η 6 . The temperature change in h 36 component was proportional to (T C  − T) α , where α = 0.58 ± 0.05. Close to T C changes in dielectric permittivity were negligible. High value of ac conductivity in the high-temperature phase results from protons jumping between disordered ions NH 4 + and between molecules of crystallisation water. Only longitudinal ultrasonic waves exhibited an abrupt change upon the phase transition. The relaxation time of the order parameter was determined from anomalous changes in attenuation of the longitudinal waves. - Highlights: • Low-temperature phase shows higher-order ferroicity: ferroelastoelectricity. • Temperature change of spontaneous piezoelectricity was studied in the ordered phase. • Dispersion of complex dielectric constant was investigated in wide temperature range. • At high-temperature phase ac conductivity is caused by proton jumps. • Anomalies of ultrasonic waves at T C were analysed using phenomenological theory

  1. NMR Insights into the Unexpected Interaction of SnCl4 with D-Glucosamine and Its Effect on 5-HMF Preparation in ZnCl2 Molten Salt Hydrate Medium

    DEFF Research Database (Denmark)

    Chen, Chunyan; Ge, Wenzhi; Jia, Lingyu

    2016-01-01

    SnCl4, a versatile Lewis acid catalyst in the biomass conversion, plays a positive role for the cellulose biomass conversion but negative for chitin biomass conversion as realized in our previous research. In this report, the unexpected effects of SnCl4 on the conversion of d-glucosamine (GlcNH2)...

  2. An oil-in-water self-assembly synthesis, characterization and photocatalytic properties of nano Ag@AgCl surface-sensitized K2Ti4O9

    International Nuclear Information System (INIS)

    Liang, Yinghua; Lin, Shuanglong; Liu, Li; Hu, Jinshan; Cui, Wenquan

    2014-01-01

    Highlights: • The plasmatic Ag@AgCl surface-sensitized K 2 Ti 4 O 9 composite photocatalysts. • Ag@AgCl greatly increased visible light absorption for K 2 Ti 4 O 9 . • The photocatalysts exhibited enhanced photocatalytic dye degradation. - Abstract: Nano-sized plasmonic Ag@AgCl surface-sensitized K 2 Ti 4 O 9 composite photocatalysts (hereafter designated as Ag@AgCl/K 2 Ti 4 O 9 ) was synthesized via a facile oil-in-water self-assembly method. The photocatalytic activity of the prepared materials for RhB (Rhodamine B) degradation was examined under visible light irradiation. The results reveal that the size of Ag@AgCl, which evenly dispersed on the surface of K 2 Ti 4 O 9 , distributes about 20–50 nm. The UV–vis diffuse reflectance spectra indicate that Ag@AgCl/K 2 Ti 4 O 9 samples have a significantly enhanced optical absorption in 380–700 nm. The photocatalytic activities of the Ag@AgCl/K 2 Ti 4 O 9 samples increase first and then decrease with increasing amount of loading Ag@AgCl and the Ag@AgCl(20 wt.%)/K 2 Ti 4 O 9 sample exhibits the best photocatalytic activity and 94.47% RhB was degraded after irradiation for 2 h. Additionally, studies performed using radical scavengers indicated that O 2 · − and Cl 0 acted as the main reactive species. The electronic interaction was systematically studied and confirmed by the photo-electrochemical measurements

  3. Controllable hydrothermal synthesis of rutile TiO2 hollow nanorod arrays on TiCl4 pretreated Ti foil for DSSC application

    International Nuclear Information System (INIS)

    Xi, Min; Zhang, Yulan; Long, Lizhen; Li, Xinjun

    2014-01-01

    Rutile TiO 2 nanorod arrays (TNRs) were achieved by hydrothermal process on TiCl 4 pretreated Ti foil. Subsequently, TNRs were hydrothermally etched in HCl solution to form hollow TiO 2 nanorod arrays (H-TNRs). The TiCl 4 pretreatment plays key roles in enhancement of Ti foil corrosion resistance ability and crystal nucleation introduction for TNRs growth. TNRs with desired morphology can be obtained by controlling TiCl 4 concentration and the amount of tetrabutyl titanate (TTB) accordingly. TNRs with the length of ∼1.5 μm and diameter of ∼200 nm, obtained on 0.15 M TiCl 4 pretreated Ti foil with 0.6 mL TTB, exhibits relatively higher photocurrent. The increased pore volume of the H-TNRs has contributed to the increased surface area which is benefit for Dye-Sensitized Solar Cells (DSSC) application. And the 180 °C-H-TNRs photoanode obtained from the 0.15-TiCl 4 -TNRs sample demonstrated 128.9% enhancement of photoelectric efficiency of DSSC compared to that of the original TNR photoanode. - Graphical abstract: Rutile hollow TiO 2 nanorod array photoanode obtained from original TiO 2 nanorod array photoanode by hydrothermal etching demonstrates enhanced photoelectric efficiency of DSSC. - Highlights: • TiO 2 nanorods are prepared via hydrothermal process on TiCl 4 -pretreated Ti foil. • Hollow TiO 2 nanorods are obtained by hydrothermal etching of TiO 2 nanorods. • TiCl 4 pretreatment plays a key role in protecting Ti foil from chemical corrosion. • Hollow TiO 2 nanorods photoanode shows enhanced photoelectric efficiency for DSSC

  4. Synthesis, Structure, and Li-Ion Conductivity of LiLa(BH4)3X, X = Cl, Br, I

    DEFF Research Database (Denmark)

    GharibDoust, Seyed Hosein Payandeh; Brighi, Matteo; Sadikin, Yolanda

    2017-01-01

    In this work, a new type of addition reaction between La(BH4)3 and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)3Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)3X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4...... with increasing lattice parameter, that is, increasing size of the halide ion in the structure. Thus, we conclude that the sizes of both windows are important for the lithium ion conduction in LiLa(BH4)3X compounds. The lithium ion conductivity is measured over one to three heating cycles and with different...

  5. Assessment of Aquifer Age and Replenishment Rate by Utilizing 36Cl-Pulse

    International Nuclear Information System (INIS)

    Challan, M.B.; Challan, M.B.; Labib, A.A.; Labib, A.A.

    2015-01-01

    The present study aims at estimating the residence-time of groundwater based on bomb-produced 36 Cl. Water samples were collected from some selected wells located around Al-Zulfi province, Riyadh central region, Saudi Arabia. 36 The Cl/Cl ratios in the water samples were determined by Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Liquid Scintillation Counting(LSC). 36 The Cl/Cl ratios in the groundwater were estimated to be 1.0-2.0×10 -10 . The shallow unconfined aquifer of the area is mainly replenished by the water infiltration from the seasonal rains. Estimates of residence time were obtained by comparing the measured bomb-derived 36 Cl concentrations in groundwater with the background reference. Dating based on a 36 Cl bomb pulse may be more reliable and sensitive for groundwater recharged before 1975, back as far as the mid-1950s.The above 36 Cl-background concentration was deduced by determining accurately the background corrected Dye-3 ice core data from the frozen Arctic Data, according to the estimated total 3 '6Cl resources, including bomb-produced '3 6 Cl fallout. An estimated residence time of 7.81×10 4 y was obtained from extrapolated flow velocity. It was noticed that 36 Cl concentration in groundwater does not reflect the input of bomb pulse 36 Cl, it belongs to the era before 1950

  6. Use of Chitosan-modified Bentonite for Removal of Cu2+, Cl- and 2,4-Dichlorophenoxyacetic Acid (2,4-D from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Ba, K.

    2014-07-01

    Full Text Available Batch experiments were performed to investigate the removal of Cu2+ , Cl- , and 2,4-dichlorophe- noxyacetic acid (2,4-D from aqueous solution using chitosan-modified bentonite. When the chi-tosan was loaded on the bentonite, the inter-layer space of the montmorillonite increased and the adsorption efficiency enhanced, as chitosan contains large numbers of -NH2 and -OH functional groups that could serve as coordination sites to bind heavy metals. In this study, the bentonite that was prepared through three procedures: Na2CO3 treatment, thermal treatment and compound treatment, was modified by chitosan. Experimental results demonstrated that the average removal rates of Cu2+ , Cl-, and 2,4-D effectively were 94.87 %, 86.19 % and 91.06 %, respectively.

  7. Refractive indices of K2ZnCl4 crystals in an incommensurate phase under uniaxial stresses

    International Nuclear Information System (INIS)

    Gaba, V.M.; Kogut, Z.O.; Brezvin, R.S.; Stadnik, V.I.

    2010-01-01

    The influence of uniaxial mechanical stresses directed along the principal crystallophysical axes on refractiveindex temperature dependences in K 2 ZnCl 4 crystals was studied. It is established that the refractive indices ni are quite sensitive to uniaxial stresses. Significant baric shifts of the paraphase-incommensurate-commensurate phase transition points to different temperature regions were observed, which is due to the effect of the uniaxial stress on the K 2 ZnCl 4 crystal structure. It is found that applying uniaxial pressure increases the value of the temperature hysteresis of the commensurate-incommensurate phase transition. (authors)

  8. Density evaluation of remotely-supplied hydrogen radicals produced via tungsten filament method for SiCl4 reduction

    Science.gov (United States)

    Zohra Dahmani, Fatima; Okamoto, Yuji; Tsutsumi, Daiki; Ishigaki, Takamasa; Koinuma, Hideomi; Hamzaoui, Saad; Flazi, Samir; Sumiya, Masatomo

    2018-05-01

    Effect of the hydrogen radical on the reduction of a silicon tetrachloride (SiCl4) source was studied. The hydrogen radicals were generated using a tungsten (W) filament in a generation chamber, and were remotely supplied to another reaction chamber. The density of the hydrogen radical was estimated from the optical transmittance of 600-nm-wavelength light through phosphate glass doped with tungsten oxide (WO3). Lifetime of the hydrogen radical seemed sufficiently long, and its density as supplied to the reaction chamber was estimated to be on the order of 1012 cm‑3. Signal intensity of the peak corresponding to SiCl4 (m/z = 170) detected by quadrupole-mass measurement was confirmed to decrease owing to the reaction with the remotely-supplied hydrogen radical. This indicates the possibility that chemically-stable SiCl4, as one of the by-products of the Siemens process, can be reduced to produce silicon.

  9. Effect of Ce{sup 3+} ion on Dy{sup 3+} or Mn{sup 2+} in KMgSO{sub 4}Cl synthesized by centrifuge method

    Energy Technology Data Exchange (ETDEWEB)

    Shinde, Nita [Department of Physics R.T.M. Nagpur University, Nagpur 440033 (India); Dhoble, N.S. [Department of Chemistry, Sevadal Mahila Mahavidyalaya, Nagpur 440018 (India); Gedam, S.C., E-mail: gedam_sc@rediffmail.com [K.Z.S. Science College, Kalmeshwar, Nagpur 441501 (India); Dhoble, S.J. [Department of Physics R.T.M. Nagpur University, Nagpur 440033 (India)

    2016-04-15

    In this paper effect of Ce{sup 3+} ion on Dy{sup 3+} and Mn{sup 2+} ions in microcrystalline KMgSO{sub 4}Cl host prepared by ethanol (centrifuge technique) method has been discussed. In KMgSO{sub 4}Cl sample X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) characteristics have been studied. Powder X-ray diffraction analysis shows the crystalline nature of the phosphor prepared by this new route. The morphological structures of the samples were conducted using SEM technique. An average crystallite size was found to be 5 μm. Photoluminescence in KMgSO{sub 4}Cl:Ce{sup 3+} is observed at 324 nm and 344 nm along with red emission broad band at around 644 nm. In KMgSO{sub 4}Cl: Ce, Dy phosphor Ce{sup 3+} emission around 324 and 344 nm overlaps rather well with Dy{sup 3+} excitation. The addition of Ce{sup 3+} showed higher photoluminescence (PL) intensity for the Dy{sup 3+} emissions around 482 and 576 nm excited via Ce{sup 3+} ions at 284 nm due to {sup 4}F{sub 9/2} to {sup 6}H{sub 15/2} and {sup 6}H{sub 13/2} levels. Ce{sup 3+}→Mn{sup 2+} energy transfer process occurs in KMgSO{sub 4}Cl host. KMgSO{sub 4}Cl: Mn does not give PL at 284 nm excitation but for co-doped samples with cerium, Mn{sup 2+} ions exhibits efficient fluorescence at around 560 nm due to {sup 4}T{sub 1}–{sup 6}A{sub 1} transition. KMgSO{sub 4}Cl: Dy or KMgSO{sub 4}Cl: Mn directly exciting does not show any emission while addition of Mn{sup 2+}, enhances red emission of Ce{sup 3+} at 644 nm. The CIE co-ordinates of KMgSO{sub 4}Cl:Ce; KMgSO{sub 4}Cl:Ce, Dy and KMgSO{sub 4}Cl:Ce, Mn phosphors reveals that the emission colour varies from blue to deep-red. Hence this material may be a potential lamp phosphor. - Highlights: • KMgSO{sub 4}Cl: Ce3{sup +} along with Dy3{sup +} and Mn2{sup +} was prepared by centrifuge method. • Particle size was found to be 5 μm using SEM technique. • The emission varies from blue to deep-red.

  10. Densities and apparent molar volumes of HClO4(aq) and Yb(ClO4)3(aq) at elevated temperatures and pressures

    International Nuclear Information System (INIS)

    Hakin, Andrew W.; Lukacs, Michael J.; Jin Lianliu

    2004-01-01

    Relative densities have been measured for acidified aqueous solutions of ytterbium perchlorate {Yb(ClO 4 ) 3 } at approximately T=(348.15, 373.15, 398.15, and 423.15) K and p=(10.0, 20.0, and 30.0) MPa over the concentration range 0.01624≤m 2 /(mol · kg -1 ) ≤ 0.2531 using an optically coupled vibrating tube densimeter (OCVTD). Experimental apparent molar volumes have been calculated from the density measurements, and apparent molar volumes for the aqueous perchlorate salt have been calculated using Young's rule. The application of Young's rule requires apparent molar volumes for aqueous perchloric acid (HClO 4 ) solutions over extended temperature and pressure ranges. These values were calculated from densities for aqueous HClO 4 solutions that were measured using the OCVTD at the same temperatures and pressures as those used to investigate the density surface of the acidified aqueous Yb(ClO 4 ) 3 solutions. The temperature, pressure, and composition surfaces of the apparent molar volumes for Yb(ClO 4 ) 3 (aq) and HClO 4 (aq) have been modelled using Pitzer ion-interaction equations. Apparent molar volumes at infinite dilution obtained from these models have been compared to those which can be calculated using the semi-empirical Helgeson, Kirkham, and Flowers equations of state. Values for the apparent molar volume at infinite dilution of the ytterbium trivalent cation have also been calculated using simple additivity principles

  11. Strong crystal field effect in Np{sup 4+}:ThCl{sub 4} - optical absorption study

    Energy Technology Data Exchange (ETDEWEB)

    Gajek, Z. [Instytut Niskich Temperatur i Badan Strukturalnych, Polska Akademia Nauk, 50-950 Wroclaw 2, Skr. Poczt. 1410 (Poland); Krupa, J.C. [Laboratoire de Radiochimie, Institut de Physique Nucleaire, BP 1, 91406 Orsay Cedex (France)

    1998-12-21

    Results of optical absorption measurements in polarized light on tetravalent neptunium diluted in a ThCl{sub 4} single crystal are reported. The recorded spectra are complex, pointing to the presence of an Np{sup 3+} impurity. The electronic transitions assigned to the Np{sup 4+} ion are interpreted in terms of the usual model, following the actual understanding of the neptunium electronic structure and independent theoretical predictions. R.m.s. deviations of the order of 36 cm{sup -1} have been obtained for 42 levels fitted with 11 free parameters. The crystal field effect resulting from the fitting is considerably larger than that observed for the uranium ion in the same host. (author)

  12. Determination of hydrolysis constants for gadolinium in ion strength media 2M of NaCl, NaClO4 and KCl at 303 K

    International Nuclear Information System (INIS)

    Serna M, S.; Jimenez R, M.; Solache R, M.

    1999-01-01

    This work was made with the purpose to extend information about the hydrolysis constants of gadolinium (III) in ion strength media 2M of NaCl, NaClO 4 , KCl at 303 K using the potentiometric method for this determination, and analysing starting from those data, the influence of anions and cations. It is concluded that the media which were determined the hydrolysis constants are very important and it is recommended the sodium perchlorate as the more adequate salt for those determinations. Also it was obtained the distribution diagrams of chemical species in each one of the media studied. (Author)

  13. High-level expression of a novel chromoplast phosphate transporter ClPHT4;2 is required for flesh color development in watermelon.

    Science.gov (United States)

    Zhang, Jie; Guo, Shaogui; Ren, Yi; Zhang, Haiying; Gong, Guoyi; Zhou, Ming; Wang, Guizhang; Zong, Mei; He, Hongju; Liu, Fan; Xu, Yong

    2017-02-01

    Chromoplast development plays a crucial role in controlling carotenoid content in watermelon flesh. Modern cultivated watermelons with colorful flesh are believed to originate from pale-colored and no-sweet progenitors. But the molecular basis of flesh color formation and regulation is poorly understood. More chromoplasts and released carotenoid globules were observed in the red-fleshed fruit of the 97103 cultivar than in the pale-colored fruits of the PI296341-FR line. Transcriptome profiles of these two materials identified Cla017962, predicted as ClPHT4;2, was dramatically up-regulated during flesh color formation. High ClPHT4;2 expression levels were closely correlated with increased flesh carotenoid contents among 198 representative watermelon accessions. Down-regulation of ClPHT4;2 expression in transgenic watermelons reduced the fruit carotenoid accumulation. ClPHT4;2 as a function of chromoplast-localized phosophate transporter was tested by heterologous expression into a yeast phosphate-uptake-defective mutant, western blotting, subcellular localization, and immunogold electron microscopy analysis. Two transcription factors, ClbZIP1 and ClbZIP2, were identified, which responded to ABA and sugar signaling to regulate ClPHT4;2 transcription only in cultivated watermelon species. Our findings suggest that elevated ClPHT4;2 gene expression is necessary for carotenoid accumulation, and may help to characterize the co-development of flesh color and sweetness during watermelon development and domestication. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

  14. Response to Comment on "Synthesis and characterization of the pentazolate anion cyclo-N5- in (N5)6(H3O)3(NH4)4Cl".

    Science.gov (United States)

    Jiang, Chao; Zhang, Lei; Sun, Chengguo; Zhang, Chong; Yang, Chen; Chen, Jun; Hu, Bingcheng

    2018-03-16

    Huang and Xu argue that the cyclo -N 5 - ion in (N 5 ) 6 (H 3 O) 3 (NH 4 ) 4 Cl we described in our report is theoretically unfavorable and is instead protonated. Their conclusion is invalid, as they use an improper method to assess the proton transfer in a solid crystal structure. We present an in-depth experimental and theoretical analysis of (N 5 ) 6 (H 3 O) 3 (NH 4 ) 4 Cl that supports the results in the original paper. Copyright © 2018, American Association for the Advancement of Science.

  15. Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

    International Nuclear Information System (INIS)

    Faradzhev, N.S.; Perry, C.C.; Kusmierek, D.O.; Fairbrother, D.H.; Madey, T.E.

    2004-01-01

    The kinetics of decomposition and subsequent chemistry of adsorbed CF 2 Cl 2 , activated by low-energy electron irradiation, have been examined and compared with CCl 4 . These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF 2 Cl 2 and CCl 4 dissociation increase in an H 2 O (D 2 O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H 2 O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2x10 -15 cm 2 for CF 2 Cl 2 and 2.5±0.2x10 -15 cm 2 for CCl 4 . RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl - and F - anions in the halocarbon/water films and production of H 3 O + , CO 2 , and intermediate compounds COF 2 (for CF 2 Cl 2 ) and COCl 2 , C 2 Cl 4 (for CCl 4 ) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation

  16. Neutron scattering from (CD3ND3)2MnCl4

    International Nuclear Information System (INIS)

    Lehner, N.

    1978-12-01

    For the perovskite-type crystal (CD 3 ND 3 ) 2 MnCl 4 neutron scattering experiments were performed concerning the magnetic behaviour, critical phenomena and lattice dynamics. The crystal is built up from layers, resulting in a quasi two-dimensional antiferromagnetic order, whereas the lattice dynamics shows a more three-dimensional behaviour; this can be explained by long-range Coulomb forces. Only the correlation lengths, which were determined by critical scattering, show a pronounced anisotropy. (orig.) [de

  17. Etching characteristic and mechanism of BST thin films using inductively coupled Cl2/Ar plasma with additive CF4 gas

    International Nuclear Information System (INIS)

    Kim, Gwan-Ha; Kim, Kyoung-Tae; Kim, Dong-Pyo; Kim, Chang-Il

    2004-01-01

    BST thin films were etched with inductively coupled CF 4 /(Cl 2 +Ar) plasmas. The maximum etch rate of the BST thin films was 53.6 nm/min for a 10% CF 4 to the Cl 2 /Ar gas mixture at RF power of 700 W, DC bias of -150 V, and chamber pressure of 2 Pa. Small addition of CF 4 to the Cl 2 /Ar mixture increased chemical effect. Consequently, the increased chemical effect caused the increase in the etch rate of the BST thin films. To clarify the etching mechanism, the surface reaction of the BST thin films was investigated by X-ray photoelectron spectroscopy

  18. One-Step Nonaqueous Synthesis of Pure Phase TiO2 Nanocrystals from TiCl4 in Butanol and Their Photocatalytic Properties

    Directory of Open Access Journals (Sweden)

    Tieping Cao

    2011-01-01

    Full Text Available Pure phase TiO2 nanomaterials were synthesized by an autoclaving treatment of TiCl4 with butanol as a single alcohol source. It was found that the control of molar ratio of TiCl4 to butanol played an important role in determining the TiO2 crystal phase and morphology. A high molar ratio of TiCl4 to butanol favored the formation of anatase nanoparticles, whereas rutile nanorods were selectively obtained at a low molar ratio of TiCl4 to butanol. Evaluation of the photocatalytic activity of the synthesized TiO2 was performed in terms of decomposition of organic dye rhodamine B under ultraviolet irradiation. It turned out that the as-synthesized TiO2 crystallites possessed higher photocatalytic activities toward bleaching rhodamine B than Degussa P25, benefiting from theirhigh surface area, small crystal size as well as high crystallinity.

  19. Polymeric anionic networks using dibromine as a crosslinker; the preparation and crystal structure of [(C4H9)4N]2[Pt2Br10].(Br2)7 and [(C4H9)4N]2[PtBr4Cl2].(Br2)6.

    Science.gov (United States)

    Berkei, Michael; Bickley, Jamie F; Heaton, Brian T; Steiner, Alexander

    2002-09-21

    The reaction of M[PtX3(CO)] (M+ = [(C4H9)4N]+, X = Br, Cl) with an excess of Br2 gives the new platinum(IV) salts, [(C4H9)4N]2[Pt2Br10].(Br2)7, 1, and [(C4H9)4N]2[PtBr4Cl2].(Br2)6, 2, which, in the solid state, contain strong Br Br interactions resulting in the formation of polymeric networks; they could provide useful solid storage reservoirs for elemental bromine.

  20. Dielectric spectroscopy of PMMA-LiClO4 based polymer electrolyte plasticized with ethylene carbonate EC

    Science.gov (United States)

    Pal, P.; Ghosh, A.

    2018-04-01

    Dielectric spectroscopy covering the frequency range 0.01 Hz - 2 MHz for PMMA-LiClO4 based polymer electrolyte embedded with different concentration of ethylene carbonate (x = 0, 20 and 40 wt%) has been analyzed using Havrilliak-Negami formalism. The reciprocal temperature dependence of inverse relaxation time obtained from the analysis of dielectric spectra follows Vogel-Tammann-Fulcher behaviour. The shape parameters obtained from this analysis change with ethylene carbonate concentrations. From the fits of the experimental result using Kohlrausch-Williams-Watts function. We have obtained stretched exponent β which indicates that the relaxation is highly non-exponential. The decay function obtained from electric modulus data is highly asymmetric.

  1. Pitting corrosion of Al and Al-Cu alloys by ClO4- ions in neutral sulphate solutions

    International Nuclear Information System (INIS)

    Amin, Mohammed A.; Abd El Rehim, Sayed S.; Moussa, S.O.; Ellithy, Abdallah S.

    2008-01-01

    The influence of various concentrations of NaClO 4 , as a pitting corrosion agent, on the corrosion behaviour of pure Al, and two Al-Cu alloys, namely (Al + 2.5 wt% Cu) and (Al + 7 wt% Cu) alloys in 1.0 M Na 2 SO 4 solution was investigated by potentiodynamic polarization and potentiostatic techniques at 25 deg. C. Measurements were conducted under the influence of various experimental conditions, complemented by ex situ energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) examinations of the electrode surface. In free perchlorate sulphate solutions, for the three Al samples, the anodic polarization exhibits an active/passive transition. The active dissolution region involves an anodic peak (peak A) which is assigned to the formation of Al 2 O 3 passive film on the electrode surface. The passive region extends up to 1500 mV with almost constant current density (j pass ) without exhibiting a critical breakdown potential or showing any evidence of pitting attack. For the three Al samples, addition of ClO 4 - ions to the sulphate solution stimulates their active anodic dissolution and tends to induce pitting corrosion within the oxide passive region. Pitting corrosion was confirmed by SEM examination of the electrode surface. The pitting potential decreases with increasing ClO 4 - ion concentration indicating a decrease in pitting corrosion resistance. The susceptibility of the three Al samples towards pitting corrosion decreases in the order: Al > (Al + 2.5 wt% Cu) alloy > (Al + 7 wt% Cu) alloy. Potentiostatic measurements showed that the rate of pitting initiation increases with increasing ClO 4 - ion concentration and applied step anodic potential, while it decreases with increasing %Cu in the Al samples. The inhibitive effect of SO 4 2- ions was also discussed

  2. Synthesis of [PtCl2(4,4′-dialkoxy-2,2′-bipyridine)] complexes and their in vitro anticancer properties

    Science.gov (United States)

    Vo, Van; Tanthmanatham, Ontida; Han, Haesook; Bhowmik, Pradip K.; Spangelo, Bryan L.

    2013-01-01

    A series of [Pt(II)Cl2(4,4′-dialkoxy-2,2′-bipyridine)] complexes of the general formula of[Pt(II)Cl2(4,4′-bis(RO)-2,2′-bipyridine)] (where R = −(CH2)n−1CH3, n = 2–6,8) were synthesized and characterized using 1H NMR, 13C NMR spectroscopy, elemental analysis, mass spectroscopy, and differential scanning calorimetry measurements. The in vitro anti-proliferative activities of these compounds were evaluated against human cancer cell lines A549 (lung adenocarcinoma), DU145 (prostate carcinoma), MCF-7 (breast adenocarcinoma), and MDA-MB-435 (melanoma) using the MTS cell proliferation assay. Several Pt(II) coordination compounds were found to have greatly enhanced activity compared to cisplatin after a one hour treatment in all cell lines tested. A structure-activity relationship was observed, that is, the activity increases as the carbon chain length of the alkyl group increases. The activity was maximum when the carbon chain length reaches four or five carbons and decreased with the longer carbon chain length. Fluorescence microscopy and flow cytometry data indicate that the main mode of cell death is through apoptosis with some necrotic responses. PMID:23817622

  3. Apparent and standard molar volumes and heat capacities of aqueous Ni(ClO4)2 from 25 to 85oC

    International Nuclear Information System (INIS)

    Pan, P.; Campbell, A.B.

    1997-01-01

    Apparent molar heat capacities and volumes of aqueous Ni(ClO 4 ) 2 were measured from 25 to 85 o C over a concentration range of 0.02 to 0.8 mol-kg -1 using a Picker flow microcalorimeter and a Picker vibrating-tube densimeter. An extended Debye-Huckel equation was fitted to the experimental data to obtain expressions for the apparent molar properties as functions of ionic strength for Ni(ClO 4 ) 2 (aq). The standard-state partial molar properties for Ni(ClO 4 ) 2 (aq) in the temperature range 25 to 85 o C were obtained and can be expressed by empirical equations. The standard partial molar heat capacities and volumes for Ni 2+ (aq) from 25 to 86 o C were obtained by using the additivity rule and data for ClO - 4 (aq) in the literature. These values were extrapolated to 300 o C by employing the Helgeson-Kirkham-Flower (HKF) equations, amended to include a standard-state correction term. (author)

  4. Genome Wide Transcriptome Analysis reveals ABA mediated response in Arabidopsis during Gold (AuCl4- treatment

    Directory of Open Access Journals (Sweden)

    Devesh eShukla

    2014-11-01

    Full Text Available The unique physico-chemical properties of gold nanoparticles (AuNPs find manifold applications in diagnostics, medicine and catalysis. Chemical synthesis produces reactive AuNPs and generates hazardous by-products. Alternatively, plants can be utilized to produce AuNPs in an eco-friendly manner. To better control the biosynthesis of AuNPs, we need to first understand the detailed molecular response induced by AuCl4- In this study, we carried out global transcriptome analysis in root tissue of Arabidopsis grown for 12- hours in presence of gold solution (HAuCl4 using the novel unbiased Affymetrix exon array. Transcriptomics analysis revealed differential regulation of a total of 704 genes and 4900 exons. Of these, 492 and 212 genes were up- and downregulated, respectively. The validation of the expressed key genes, such as glutathione-S-transferases, auxin responsive genes, cytochrome P450 82C2, methyl transferases, transducin (G protein beta subunit, ERF transcription factor, ABC, and MATE transporters, was carried out through quantitative RT-PCR. These key genes demonstrated specific induction under AuCl4- treatment relative to other heavy metals, suggesting a unique plant-gold interaction. GO enrichment analysis reveals the upregulation of processes like oxidative stress, glutathione binding, metal binding, transport, and plant hormonal responses. Changes predicted in biochemical pathways indicated major modulation in glutathione mediated detoxification, flavones and derivatives, and plant hormone biosynthesis. Motif search analysis identified a highly significant enriched motif, ACGT, which is an abscisic acid responsive core element (ABRE, suggesting the possibility of ABA- mediated signaling. Identification of abscisic acid response element (ABRE points to the operation of a predominant signaling mechanism in response to AuCl4- exposure. Overall, this study presents a useful picture of plant-gold interaction with an identification of

  5. Studies on the Electrochemical Dissolution for the Treatment of 10 g-Scale Zircaloy-4 Cladding Hull Wastes in LiCl-KCl Molten Salts

    International Nuclear Information System (INIS)

    Lee, You Lee; Lee, Jang Hwa; Jeon, Min Ku; Kang, Kweon Ho

    2012-01-01

    The electrochemical behaviors of 10 g-scale fresh and oxidized Zircaloy-4 cladding hulls were examined in 500 degree C LiCl-KCl molten salts to confirm the feasibility of the electrorefining process for the treatment of hull wastes. In the results of measuring the potential-current response using a stainless steel basket filled with oxidized Zircaloy-4 hull specimens, the oxidation peak of Zr appears to be at -0.7 to -0.8 V vs. Ag/AgCl, which is similar to that of fresh Zircaloy-4 hulls, while the oxidation current is found to be much smaller than that of fresh Zircaloy-4 hulls. These results are congruent with the outcome of current-time curves at -0.78 V and of measuring the change in the average weight and thickness after the electrochemical dissolution process. Although the oxide layer on the surface affects the uniformity and rate of dissolution by decreasing the conductivity of Zircaloy-4 hulls, electrochemical dissolution is considered to occur owing to the defect of the surface and phase properties of the Zr oxide layer.

  6. On the structural phase transitions of the perovskite-type layer structures (Csub(n)Hsub(2n+1)NH3)2MeCl4

    International Nuclear Information System (INIS)

    Heger, G.

    1978-01-01

    The perovskite-type layer compounds (Csub(n)Hsub(2n+1)NH 3 ) 2 MeCl 4 show a variety of different structural modifications. They differ from oneanother by the order and dynamical behaviour of the CH 3 -CH 2 -...-CH 2 -NH 3 chain molecules and the [MeCl 6 ] octahedra layers. These two structural members are coupled together by N-H...Cl hydrogen bonds. According to group theoretical relations the modifications of (Csub(n)Hsub(2n+1)NH 3 ) 2 MeCl 4 were ordered in the scheme of a 'family tree'. Taking (CH 3 NH 3 ) 2 MnCl 4 as an example, various experimental investigations incorporated neutron diffraction are reported. They lead to a sequence of phase transitions. For these phase transitions a model is developed based on the orientations of the CH 3 NH 3 dump-bell molecules and their interactions with the [MnCl 6 ] layers. (orig./HPOE) [de

  7. FeCl3-catalyzed ethanol pretreatment of sugarcane bagasse boosts sugar yields with low enzyme loadings and short hydrolysis time.

    Science.gov (United States)

    Zhang, Hongdan; Zhang, Shuaishuai; Yuan, Hongyou; Lyu, Gaojin; Xie, Jun

    2018-02-01

    An organosolv pretreatment system consisting of 60% ethanol and 0.025 mol·L -1 FeCl 3 under various temperatures was developed in this study. During the pretreatment, the highest xylose yield was 11.4 g/100 g raw material, representing 49.8% of xylose in sugarcane bagasse. Structural features of raw material and pretreated substrates were characterized to better understand how hemicellulose removal and delignification affected subsequent enzymatic hydrolysis. The 160 °C pretreated solid presented a remarkable glucose yield of 93.8% for 72 h. Furthermore, the influence of different additives on the enzymatic hydrolysis of pretreated solid was investigated. The results indicated that the addition of Tween 80 shortened hydrolysis time to 6 h and allowed a 50% reduction of enzyme loading to achieve the same level of glucose yield. This work suggested that FeCl 3 -catalyzed organosolv pretreatment could improve the enzymatic hydrolysis significantly and reduce the hydrolysis time and enzyme dosage with the addition of Tween 80. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. NaCl islands decorated with 2D or 3D 3,4,9,10-perylene-tetracarboxylic-dianhydride nanostructures

    NARCIS (Netherlands)

    Sun, Xiaonan; Silly, Fabien

    2010-01-01

    The formation of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) nanostrutures on Au(1 1 1)-(22 x root 3) covered with NaCl islands has been studied using scanning tunneling microscopy (STM). Atomically resolved STM images show that NaCl grows as (1 0 0)-terminated layers on Au(1 1 1)-(22 x

  9. Isopiestic Investigation of the Osmotic and Activity Coefficients of {yMgCl2 + (1 - y)MgSO4}(aq) and the Osmotic Coefficients of Na2SO4.MgSO4(aq) at 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Miladinovic, J; Ninkovic, R; Todorovic, M; Rard, J A

    2007-06-06

    Isopiestic vapor pressure measurements were made for {l_brace}yMgCl{sub 2} + (1-y)MgSO{sub 4}{r_brace}(aq) solutions with MgCl{sub 2} ionic strength fractions of y = 0, 0.1997, 0.3989, 0.5992, 0.8008, and (1) at the temperature 298.15 K, using KCl(aq) as the reference standard. These measurements for the mixtures cover the ionic strength range I = 0.9794 to 9.4318 mol {center_dot} kg{sup -1}. In addition, isopiestic measurements were made with NaCl(aq) as reference standard for mixtures of {l_brace}xNa{sub 2}SO{sub 4} + (1-x)MgSO{sub 4}{r_brace}(aq) with the molality fraction x = 0.50000 that correspond to solutions of the evaporite mineral bloedite (astrakanite), Na{sub 2}Mg(SO{sub 4}){sub 2} {center_dot} 4H{sub 2}O(cr). The total molalities, m{sub T} = m(Na{sub 2}SO{sub 4}) + m(MgSO{sub 4}), range from m{sub T} = 1.4479 to 4.4312 mol {center_dot} kg{sup -1} (I = 5.0677 to 15.509 mol {center_dot} kg{sup -1}), where the uppermost concentration is the highest oversaturation molality that could be achieved by isothermal evaporation of the solvent at 298.15 K. The parameters of an extended ion-interaction (Pitzer) model for MgCl2(aq) at 298.15 K, which were required for an analysis of the {l_brace}yMgCl{sub 2} + (1-y)MgSO{sub 4}{r_brace}(aq) mixture results, were evaluated up to I = 12.025 mol {center_dot} kg{sup -1} from published isopiestic data together with the six new osmotic coefficients obtained in this study. Osmotic coefficients of {l_brace}yMgCl{sub 2} + (1-y)MgSO{sub 4}{r_brace}(aq) solutions from the present study, along with critically-assessed values from previous studies, were used to evaluate the mixing parameters of the extended ion-interaction model.

  10. Biodegradation of the Nitramine Explosive CL-20

    OpenAIRE

    Trott, Sandra; Nishino, Shirley F.; Hawari, Jalal; Spain, Jim C.

    2003-01-01

    The cyclic nitramine explosive CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) was examined in soil microcosms to determine whether it is biodegradable. CL-20 was incubated with a variety of soils. The explosive disappeared in all microcosms except the controls in which microbial activity had been inhibited. CL-20 was degraded most rapidly in garden soil. After 2 days of incubation, about 80% of the initial CL-20 had disappeared. A CL-20-degrading bacterial strain, Agrobact...

  11. Using isotope 36Cl to study utilization of Cl by crops and distribution and movement of Cl in soil

    International Nuclear Information System (INIS)

    Pan Jiarong; Wen Xianfang; Tang Nianxin

    1991-06-01

    Results from using isotope 36 Cl show that a large quantity of Cl is absorbed and utilized by spring wheat, cotton and tobacco from the chloride fertilizers. The utilization coefficient of Cl increases with the growing time of plants and reaches peak at mature stage. The utilization coefficient of above plants are 26.72%, 3317% and 26.19% respectively. The absorption and utilization of residual Cl in soil is much smaller than that in fertilizers, and the utilization coefficient is decreasing with the increasing of growth season. For spring wheat, utilization coefficient is 12.7% in second season and 9.3% in third season. The ability of absorbing and utilizing Cl from organic materials by crops is very low and the utilization coefficient is 10% or less, that depends on circumstances. For rice the utilization coefficient is 3.1% in dry land and 24.3% in flooded land. The distribution of absorbed Cl is mainly in stalk, a little in husk and a few in seeds and roots. After irrigating water it is equivalent to 9.1 mm of rainfall in soil, the Cl moves rapidly to depth 10∼12 cm. Cl moves faster in porous soil than in clay soil, and faster in horizontal direction than in vertical direction

  12. Preparation and characterization of a layered perovskite-type organic-inorganic hybrid compound (C8NH6-CH2CH2NH3)2CuCl4

    International Nuclear Information System (INIS)

    Zheng Yingying; Wu Gang; Deng Meng; Chen Hongzheng; Wang Mang; Tang, B.-Z.

    2006-01-01

    The organic-inorganic hybrid compound (C 8 NH 6 -CH 2 CH 2 NH 3 ) 2 CuCl 4 (AEI-CuCl 4 ) was synthesized from ethanol solution containing copper chloride and 3-2-(aminoethyl) indole hydrochloride (AEI-HCl). High order diffraction peaks corresponding to (0 0 l; l = 2, 4, 6, ...) observed in the X-ray diffraction profile of AEI-CuCl 4 indicated the formation of hybrid crystal with layered perovskite structure. The organic-inorganic hybrid crystal thin film can be easily prepared by spin-coating method from the ethanol solution of the AEI-CuCl 4 perovskite and it showed characteristic absorptions of CuCl-based layered perovskite centered at 288 and 388 nm, as well as the photoluminescence peak at around 420 nm. The unaided-eye-detectable blue fluorescence emission comes from the cooperation of AEI-HCl and AEI-CuCl 4 perovskite, in which protonized aminoethyl indole dominates the shape of the spectrum and the enhancement of emission intensity is due to the formation of the perovskite structure. The thermal analysis presented that the AEI-CuCl 4 perovskite started to melt at 182 deg. C, together with the beginning of the decomposition of the hybrids. Compared with the organic-inorganic perovskite hybrids reported previously, the AEI-CuCl 4 perovskite shows a novel stepwise decomposition behavior

  13. (nBuCp)2ZrCl2-catalyzed Ethylene-4M1P Copolymerization: Copolymer Backbone Structure, Melt Behavior, and Crystallization

    KAUST Repository

    Atiqullah, Muhammad

    2016-01-08

    The judicious design of methylaluminoxane (MAO) anions expands the scope for developing industrial metallocene catalysts. Therefore, the effects of MAO anion design on the backbone structure, melt behavior, and crystallization of ethylene−4-methyl-1-pentene (E−4M1P) copolymer were investigated. Ethylene was homopolymerized, as well as copolymerized with 4M1P, using (i) MAO anion A (unsupported [MAOCl2]−) premixed with dehydroxylated silica, (nBuCp)2ZrCl2, and Me2SiCl2; and (ii) MAO anion B (Si−O−Me2Si−[MAOCl2]−) supported with (nBuCp)2ZrCl2 on Me2SiCl2-functionalized silica. Unsupported Me2SiCl2, opposite to the supported analogue, acted as a co-chain transfer agent with 4M1P. The modeling of polyethylene melting and crystallization kinetics, including critical crystallite stability, produced insightful results. This study especially illustrates how branched polyethylene can be prepared from ethylene alone using particularly one metallocene-MAO ion pair, and how a compound, that functionalizes silica as well as terminates the chain, can synthesize ethylene−α-olefin copolymers with novel structures. Hence, it unfolds prospective future research niches in polyethyne systhesis. This article is protected by copyright. All rights reserved.

  14. Timing of Pleistocene glaciations in the High Atlas, Morocco: New 10Be and 36Cl exposure ages

    Science.gov (United States)

    Hughes, Philip D.; Fink, David; Rodés, Ángel; Fenton, Cassandra R.; Fujioka, Toshiyuki

    2018-01-01

    This paper presents data from 42 new samples yielding Late Pleistocene cosmogenic 10Be and 36Cl exposure ages of moraine boulders across a series of glaciated valleys in the Toubkal Massif (4167 m a.s.l.), High Atlas, Morocco. This represents the first comprehensive Pleistocene glacial chronology in North Africa and one of the largest datasets from the Mediterranean region. The timing of these glacier advances has major implications for understanding the influence of Atlantic depressions on moisture supply to North Africa and the Mediterranean basin during the Pleistocene. The oldest and lowest moraines which span elevations from ∼1900 to 2400 m a.s.l. indicate that the maximum glacier advance occurred from MIS 5 to 3 with a combined mean 10Be and 36Cl age of 50.2 ± 19.5 ka (1 SD; n = 12, 7 outliers). The next moraine units up-valley at higher elevations (∼2200-2600 m a.s.l.) yielded exposure ages close to the global Last Glacial Maximum (LGM) with a combined mean 10Be and 36Cl age of 22.0 ± 4.9 ka (1 SD; n = 9, 7 outliers). The youngest exposure ages are from moraines that were emplaced during the Younger Dryas with a combined mean 10Be and 36Cl age of 12.3 ± 0.9 ka (1 SD; n = 7, no outliers) and are found in cirques at the highest elevations ranging from ∼2900 to 3300 m a.s.l. From moraines predating the Younger Dryas, a large number of young outliers are spread evenly between 6 and 13 ka suggesting a continuing process of exhumation or repositioning of boulders during the early to mid-Holocene. This attests to active seismic processes and possibly intense erosion during this period.

  15. A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

    Science.gov (United States)

    Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

    2018-04-01

    Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

  16. Thermodynamic modeling of Cl(-), NO3(-) and SO4(2-) removal by an anion exchange resin and comparison with Dubinin-Astakhov isotherms.

    Science.gov (United States)

    Dron, Julien; Dodi, Alain

    2011-03-15

    The removal of chloride, nitrate, and sulfate ions from wastewaters by a macroporous ion-exchange resin is studied through the experimental results obtained for six ion exchange systems, OH(-)/Cl(-), OH(-)/NO3(-), OH(-)/SO4(2-), and HCO3(-)/Cl(-), Cl(-)/NO3(-), Cl(-)/SO4(2-). The results are described through thermodynamic modeling, considering either an ideal or a nonideal behavior of the ionic species in the liquid and solid phases. The nonidealities are determined by the Davies equation and Wilson equations in the liquid and solid phases, respectively. The results show that the resin has a strong affinity for all the target ions, and the order of affinity obtained is OH(-) < HCO3(-) < Cl(-) < NO3(-) < SO4(2-). The calculation of the changes in standard Gibbs free energies (ΔG(0)) shows that even though HCO3(-) has a lower affinity to the resin, it may affect the removal of Cl(-), and in the same way that Cl(-) may affect the removal of NO3(-) and SO4(2-). The application of nonidealities in the thermodynamic model leads to an improved fit of the model to the experimental data with average relative deviations below 1.5% except for the OH(-)/SO4(2-) system. On the other hand, considering ideal or nonideal behaviors has no significant impact on the determination of the selectivity coefficients. The thermodynamic modeling is also compared with the Dubinin-Astakhov adsorption isotherms obtained for the same ion exchange systems. Surprisingly, the latter performs significantly better than the ideal thermodynamic model and nearly as well as the nonideal thermodynamic model.

  17. Thermodynamic investigation of the ternary mixed aqueous electrolyte (MgCl{sub 2} + MgSO{sub 4}) system by potentiometric method at T = 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Bagherinia, Mohammad A., E-mail: mabagherinia@yahoo.com [Department of Chemistry, Faculty of Science, Lahijan Branch, Islamic Azad University, Lahijan (Iran, Islamic Republic of); Giahi, Masoud; Pournaghdy, Mohammad; Vaghar, Gholam R. [Department of Chemistry, Faculty of Science, Lahijan Branch, Islamic Azad University, Lahijan (Iran, Islamic Republic of)

    2012-01-15

    Highlights: > In this study we investigated the thermodynamic properties of MgCl{sub 2} + MgSO{sub 4} + H{sub 2}O. > The method used in this work was potentiometric method. > Mg-ISE and the Ag/AgCl electrodes used in this work had a good Nernst response. > The experimental results obeyed the Harned rule. > The Pitzer model could be used to describe this ternary system satisfactorily. - Abstract: This work reports the results of thermodynamic investigation of the ternary mixed-electrolyte system (MgCl{sub 2} + MgSO{sub 4} + H{sub 2}O). The investigation was performed based on Pitzer ion interaction model by using the potentiometric technique at T = 298.15 K. The mean activity coefficients of MgCl{sub 2} in the mixed aqueous electrolyte system were determined on the galvanic cell without liquid junction of the type: Mg-ISE|MgCl{sub 2} (m{sub A}), MgSO{sub 4} (m{sub B}), H{sub 2}O|Ag/AgCl over total ionic strengths from (0.001 to 8.000) mol . kg{sup -1} for different series of salt ratio r (r=m{sub MgCl{sub 2}}/m{sub MgSO{sub 4}}=2.5,5.0,7.5,10.0,15.0 and pure MgCl{sub 2}). The PVC based magnesium ion-selective electrode (Mg-ISE) and the Ag/AgCl electrode used in this work were made in our laboratory and had a reasonably good Nernst response. The experimental results obeyed the Harned rule, and the Pitzer model could be used to describe this ternary system satisfactorily. Pitzer ion-interaction parameters for mixed salts were determined for this system. Then, these parameters ({theta}{sub ClSO{sub 4}}=0.0252{+-}0.0042, {psi}{sub MgClSO{sub 4}}=-0.0049{+-}0.0003) were used to calculate the values of the mean activity coefficients of MgSO{sub 4}, the osmotic coefficients of water ({phi}) and the excess Gibbs free energies of solution (G{sup E}) for the whole series of the studied electrolyte systems.

  18. Comparison of adsorption equilibrium models for the study of CL-, NO3- and SO4(2-) removal from aqueous solutions by an anion exchange resin.

    Science.gov (United States)

    Dron, Julien; Dodi, Alain

    2011-06-15

    The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), and HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-), Cl(-)/SO(4)(2-). They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH(-)Cl(-)4)(2-), and distinguish high energy processes (OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), Cl(-)/SO(4)(2-)) from lower energy systems (HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-)). The D-A and D-R models provide the best fit to the experimental points, indicating that the micropore volume filling theory is the best representation of the ion exchange processes under study among other adsorption isotherms. The nonlinear regression results are also compared with linear regressions. While the parameter values are not affected, the evaluation of the best fitting model is biased by linearization. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Overexpression of artificially fused bifunctional enzyme 4CL1-CCR: a method for production of secreted 4-hydroxycinnamaldehydes in Escherichia coli.

    Science.gov (United States)

    Liu, Shuxin; Qi, Qi; Chao, Nan; Hou, Jiayin; Rao, Guodong; Xie, Jin; Lu, Hai; Jiang, Xiangning; Gai, Ying

    2015-08-12

    4-Hydroxycinnamaldehydes are important intermediates in several secondary metabolism pathways, including those involved in the biosynthesis of phenolic acids, flavonoids, terpenoids and monolignols. They are also involved in the biosynthesis and degradation of lignins, which are important limiting factors during the processes of papermaking and biofuel production. Access to these aromatic polymers is necessary to explore the secondary biometabolic pathways they are involved in. Coniferaldehyde, sinapaldehyde, p-coumaraldehyde and caffealdehyde are members of the 4-hydroxycinnamaldehyde family. Although coniferaldehyde and sinapaldehyde can be purchased from commercial sources, p-coumaraldehyde and caffealdehyde are not commercially available. Therefore, there is increasing interest in producing 4-hydroxycinnamaldehydes. Here, we attempted to produce 4-hydroxycinnamaldehydes using engineered Escherichia coli. 4-Coumaric acid: coenzyme A ligase (4CL1) and cinnamoyl coenzyme A reductase (CCR) were fused by means of genetic engineering to generate an artificial bifunctional enzyme, 4CL1-CCR, which was overexpressed in cultured E. coli supplemented with phenylpropanoic acids. Three 4-hydroxycinnamaldehydes, p-coumaraldehyde, caffealdehyde and coniferaldehyde, were thereby biosynthesized and secreted into the culture medium. The products were extracted and purified from the culture medium, and identically characterized by the HPLC-PDA-ESI-MSn. The productivity of this new metabolic system were 49 mg/L for p-coumaraldehyde, 19 mg/L for caffealdehyde and 35 mg/L for coniferaldehyde. Extracellular hydroxycinnamoyl-coenzyme A thioesters were not detected, indicating that these thioesters could not pass freely through the cellular membrane. The fusion enzyme 4CL1-CCR can catalyze sequential multistep reactions, thereby avoiding the permeability problem of intermediates, which reveals its superiority over a mixture of individual native enzymes. Moreover, we have described a

  20. Luminescence and scintillation properties of Rb2HfCl6 crystals

    International Nuclear Information System (INIS)

    Saeki, Keiichiro; Wakai, Yuki; Fujimoto, Yutaka; Koshimizu, Masanori; Asai, Keisuke; Yanagida, Takayuki; Nakauchi, Daisuke

    2016-01-01

    We developed a scintillator based on a Rb 2 HfCl 6 crystal as a ternary halide crystal with intrinsic luminescence. In the photoluminescence spectra, two emission bands are observed at 383 and 434 nm. The 434 nm emission band for Rb 2 HfCl 6 may be attributed to [HfCl 6 ] 2- complex ion or [ZrCl 6 ] 2- impurity, since the Rb 2 HfCl 6 contained Zr as impurity at 0.62 mol %. The radioluminescence band is observed at 420 nm and can be attributed to the same origin as the photoluminescence band at 434 nm. The scintillation decay-time constants were 0.84 and 5.4 μs. The light yield was estimated to be 24,100 photons/MeV. (author)

  1. Nitroreductase catalyzed biotransformation of CL-20

    International Nuclear Information System (INIS)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2004-01-01

    Previously, we reported that a salicylate 1-monooxygenase from Pseudomonas sp. ATCC 29352 biotransformed CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane) (C 6 H 6 N 12 O 12 ) and produced a key metabolite with mol. wt. 346Da corresponding to an empirical formula of C 6 H 6 N 10 O 8 which spontaneously decomposed in aqueous medium to produce N 2 O, NH4+, and HCOOH [Appl. Environ. Microbiol. (2004)]. In the present study, we found that nitroreductase from Escherichia coli catalyzed a one-electron transfer to CL-20 to form a radical anion (CL-20 - ) which upon initial N-denitration also produced metabolite C 6 H 6 N 10 O 8 . The latter was tentatively identified as 1,4,5,8-tetranitro-1,3a,4,4a,5,7a,8,8a-octahydro-diimidazo[4,5-b:4',5'-e] pyrazine [IUPAC] which decomposed spontaneously in water to produce glyoxal (OHCCHO) and formic acid (HCOOH). The rates of CL-20 biotransformation under anaerobic and aerobic conditions were 3.4+/-0.2 and 0.25+/-0.01nmolmin -1 mg of protein -1 , respectively. The product stoichiometry showed that each reacted CL-20 molecule produced about 1.8 nitrite ions, 3.3 molecules of nitrous oxide, 1.6 molecules of formic acid, 1.0 molecule of glyoxal, and 1.3 ammonium ions. Carbon and nitrogen products gave mass-balances of 60% and 81%, respectively. A comparative study between native-, deflavo-, and reconstituted-nitroreductase showed that FMN-site was possibly involved in the biotransformation of CL-20

  2. Dynamics of the OH stretching mode in crystalline Ba(ClO4)2.3H2O

    Science.gov (United States)

    Hutzler, Daniel; Brunner, Christian; Petkov, Petko St.; Heine, Thomas; Fischer, Sighart F.; Riedle, Eberhard; Kienberger, Reinhard; Iglev, Hristo

    2018-02-01

    The vibrational dynamics of the OH stretching mode in Ba(ClO4)2 trihydrate are investigated by means of femtosecond infrared spectroscopy. The sample offers plane cyclic water trimers in the solid phase that feature virtually no hydrogen bond interaction between the water molecules. Selective excitation of the symmetric and asymmetric stretching leads to fast population redistribution, while simultaneous excitation yields quantum beats, which are monitored via a combination tone that dominates the overtone spectrum. The combination of steady-state and time-resolved spectroscopy with quantum chemical simulations and general theoretical considerations gives indication of various aspects of symmetry breakage. The system shows a joint population lifetime of 8 ps and a long-lived coherence between symmetric and asymmetric stretching, which decays with a time constant of 0.6 ps.

  3. 75 FR 37994 - Airworthiness Directives; Bombardier, Inc. Model CL-600-1A11 (CL-600), CL-600-2A12 (CL-601), CL...

    Science.gov (United States)

    2010-07-01

    ... provides data for replacement of the accumulators. The commenter requests that stronger language be... numbers 1004 through 1085 inclusive; (2) Bombardier, Inc. CL-600-2A12 (CL-601) airplanes, serial numbers 3001 through 3066 inclusive; and (3) Bombardier, Inc. CL-600-2B16 (CL-601-3A, CL-601-3R, and CL- 604...

  4. Controllable hydrothermal synthesis of rutile TiO{sub 2} hollow nanorod arrays on TiCl{sub 4} pretreated Ti foil for DSSC application

    Energy Technology Data Exchange (ETDEWEB)

    Xi, Min [Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhang, Yulan; Long, Lizhen [Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Li, Xinjun, E-mail: lixj@ms.giec.ac.cn [Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2014-11-15

    Rutile TiO{sub 2} nanorod arrays (TNRs) were achieved by hydrothermal process on TiCl{sub 4} pretreated Ti foil. Subsequently, TNRs were hydrothermally etched in HCl solution to form hollow TiO{sub 2} nanorod arrays (H-TNRs). The TiCl{sub 4} pretreatment plays key roles in enhancement of Ti foil corrosion resistance ability and crystal nucleation introduction for TNRs growth. TNRs with desired morphology can be obtained by controlling TiCl{sub 4} concentration and the amount of tetrabutyl titanate (TTB) accordingly. TNRs with the length of ∼1.5 μm and diameter of ∼200 nm, obtained on 0.15 M TiCl{sub 4} pretreated Ti foil with 0.6 mL TTB, exhibits relatively higher photocurrent. The increased pore volume of the H-TNRs has contributed to the increased surface area which is benefit for Dye-Sensitized Solar Cells (DSSC) application. And the 180 °C-H-TNRs photoanode obtained from the 0.15-TiCl{sub 4}-TNRs sample demonstrated 128.9% enhancement of photoelectric efficiency of DSSC compared to that of the original TNR photoanode. - Graphical abstract: Rutile hollow TiO{sub 2} nanorod array photoanode obtained from original TiO{sub 2} nanorod array photoanode by hydrothermal etching demonstrates enhanced photoelectric efficiency of DSSC. - Highlights: • TiO{sub 2} nanorods are prepared via hydrothermal process on TiCl{sub 4}-pretreated Ti foil. • Hollow TiO{sub 2} nanorods are obtained by hydrothermal etching of TiO{sub 2} nanorods. • TiCl{sub 4} pretreatment plays a key role in protecting Ti foil from chemical corrosion. • Hollow TiO{sub 2} nanorods photoanode shows enhanced photoelectric efficiency for DSSC.

  5. Magnetic phase transition in layered inorganic-organic hybrid (C12H25NH3)2CuCl4

    Science.gov (United States)

    Bochalya, Madhu; Kumar, Sunil; Kanaujia, Pawan K.; Prakash, G. Vijaya

    2018-05-01

    Inorganic-organic (IO) hybrids are material systems which have become an interesting theme of research for physicist and chemists recently due to the possibility of engineering specific magnetic, thermal or optoelectronic properties by playing around with the transition metal, halides and the organic components. Our experiments on (C12H25NH3)2CuCl4 show that the system exhibits a long range ferromagnetic order below ˜11 K. In such an inorganic-organic hybrid system, Jahn-Teller distortion of the copper ions results into a weak ferromagnetic order as compared to the antiferromagnetic spin-spin exchange in the pure inorganic CuCl2 compound. Moreover, this particular hybrid system also exhibits photoluminescence when excited below absorption maximum related to charge transfer peak though the effect is much weaker as compared to that in extensively studied other MX4-based (M = Sn, Pb; X = Cl, Br, I) counterparts.

  6. Experimental Charge Density Study of Trichromium Linear Metal String Complex – Cr3(dpa)4Cl2

    DEFF Research Database (Denmark)

    Wu, Lai-Chin; Cheng, Ming-Chuan; Thomsen, Maja Krüger

    An experimental and theoretical charge density study, based on Bader’s Quantum Theory: Atoms in Molecule (QTAIM), on a trichromium metal string complex, Cr3(dpa)4Cl2(C2H5OC2H5)x(CH2Cl2)1-x (1, dpa- = bis(2-pyridyl)amido)) is performed. The structure and multipole model of 1 are performed by using...... experimental X-ray diffraction data which are collected at both 100 K using conventional X-ray source (DS1) and 15 K using synchrotron source (DS2). The three chromium metal string is bridged by four dpa- ligands. These tri-chromium metal ions are bonded to each other and terminated by two Cl- ions on the both...... ends, forming a [Cl(1)Cr(1)Cr(2)Cr(3)Cl(2)] linear string. Each Cr atoms are coordinated by four N atoms of each dpa- ligand. This metal string is slightly unsymmetrical at both data sets. The bond distance, from DS1 (DS2), of Cr(1)Cr(2), 2.3480(2) (2.3669(1)) Å, is 0.03 (0.003) Å shorter than Cr...

  7. Characterization of glial cell K-Cl cotransport.

    Science.gov (United States)

    Gagnon, Kenneth B E; Adragna, Norma C; Fyffe, Robert E W; Lauf, Peter K

    2007-01-01

    The molecular mechanism of K-Cl cotransport (KCC) consists of at least 4 isoforms, KCC 1, 2, 3, and 4 which, in multiple combinations, exist in most cells, including erythrocytes and neuronal cells. We utilized reverse-transcriptase-polymerase chain reaction (RT-PCR) and ion flux studies to characterize KCC activity in an immortalized in vitro cell model for fibrous astrocytes, the rat C6 glioblastoma cell. Isoform-specific sets of oligonucleotide primers were synthesized for NKCC1, KCC1, KCC2, KCC3, KCC4, and also for NKCC1 and actin. K-Cl cotransport activity was determined by measuring either the furosemide-sensitive, or the Cl(-)-dependent bumetanide-insensitive Rb(+) (a K(+) congener) influx in the presence of the Na/K pump inhibitor ouabain. Rb(+) influx was measured at a fixed external Cl concentrations, [Cl(-)](e), as a function of varying external Rb concentrations, [Rb(+)](e), and at a fixed [Rb(+)](e) as a function of varying [Cl(-)](e), and with equimolar Cl replacement by anions of the chaotropic series. RT-PCR of C6 glioblastoma (C6) cells identified mRNA for three KCC isoforms (1, 3, and 4). NKCC1 mRNA was also detected. The apparent K(m) for KCC-mediated Rb(+) influx was 15 mM [Rb(+)](e), and V(max) 12.5 nmol Rb(+) * mg protein(-1) * minute(-1). The calculated apparent K(m) for external Cl(-) was 13 mM and V(max) 14.4 nmol Rb(+) * mg protein(-1) * minute(-1). The anion selectivity sequence of the furosemide-sensitive Rb(+) influx was Cl(-)>Br-=NO(3)(-)>I(-)=SCN(-)>Sfm(-) (sulfamate). Established activators of K-Cl cotransport, hyposmotic shock and N-ethylmaleimide (NEM) pretreatment, stimulated furosemide-sensitive Rb(+) influx. A ñ50% NEM-induced loss of intracellular K(+) was prevented by furosemide. We have identified by RT-PCR the presence of three distinct KCC isoforms (1, 3, and 4) in rat C6 glioblastoma cells, and functionally characterized the anion selectivity and kinetics of their collective sodium-independent cation-chloride cotransport

  8. Coexisting Ferromagnetic and Ferroelectric Order in a CuCl4-based Organic-Inorganic Hybrid

    NARCIS (Netherlands)

    Polyakov, Alexey O.; Arkenbout, Anne H.; Baas, Jacob; Blake, Graeme R.; Meetsma, Auke; Caretta, Antonio; van Loosdrecht, Paul H. M.; Palstra, Thomas T. M.

    2012-01-01

    We investigate the structural, magnetic, and dielectric properties of the organic-inorganic hybrid material CuCl4(C6H5CH2CH2NH3)(2) and demonstrate that spontaneous ferroelectric order sets in below 340 K, which coexists with ferromagnetic ordering below 13 K. We use X-ray diffraction to show that

  9. ac impedance, DSC and FT-IR investigations on (x)PVAc-(1 - x)PVdF blends with LiClO4

    International Nuclear Information System (INIS)

    Baskaran, R.; Selvasekarapandian, S.; Kuwata, N.; Kawamura, J.; Hattori, T.

    2006-01-01

    The blended polymer electrolytes comprising poly(vinyl acetate) (PVAc)-poly(vinylidene fluoride) (PVdF) have been prepared for different blend composition with constant lithium perchlorate (LiClO 4 ) ratio by solution casting technique. The formation of the blend polymer electrolyte complex has been confirmed by FT-IR spectroscopy analysis. DSC analysis has been performed in order to observe the change in transition temperature that is caused by the blending of polymers and addition of LiClO 4 . The ac impedance and dielectric spectroscopy studies are carried out on the blended matrix to identify the optimized blend composition, which is having high ionic conductivity. The temperature dependence of conductivity of the polymer electrolytes is found to follow VTF type equation. The high ionic conductivity of 6.4 x 10 -4 S cm -1 at 343 K has been observed for blended polymer electrolyte having blend ratio 75:25 (PVAc:PVdF). The ionic transference number of mobile ions has been estimated by Wagner's polarization method and the value is reported to be t ion is 0.95-0.98 for all the blended samples. The modulus spectra reveal the non-Debye nature and distribution of relaxation times of the samples. The dielectric spectra show the low frequency dispersion, which implies the space charge effects arising from the electrodes

  10. Partial molar volumes and viscosities of aqueous hippuric acid solutions containing LiCl and MnCl2 · 4H2O at 303.15 K

    Science.gov (United States)

    Deosarkar, S. D.; Tawde, P. D.; Zinjade, A. B.; Shaikh, A. I.

    2015-09-01

    Density (ρ) and viscosity (η) of aqueous hippuric acid (HA) solutions containing LiCl and MnCl2 · 4H2O have been studied at 303.15 K in order to understand volumetric and viscometric behavior of these systems. Apparent molar volume (φv) of salts were calculated from density data and fitted to Massons relation and partial molar volumes (φ{v/0}) at infinite dilution were determined. Relative viscosity data has been used to determine viscosity A and B coefficients using Jones-Dole relation. Partial molar volume and viscosity coefficients have been discussed in terms of ion-solvent interactions and overall structural fittings in solution.

  11. Structure and redox properties of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20 adsorbed on a silica surface. M05 computational study

    Directory of Open Access Journals (Sweden)

    Liudmyla K. Sviatenko

    2016-03-01

    Full Text Available The cluster approximation was applied at M05/tzvp level to model adsorption of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20 on (001 surface of α-quartz. Structures of the obtained CL-20–silica complexes confirm close to parallel orientation of the nitrocompound toward surface. The binding between CL-20 and silica surface was analyzed and bond energies were calculated applying the atoms in molecules (AIM method. Hydrogen bonds were found to significantly contribute in adsorption energy. An attaching of electron leads to significant deviation from coplanarity in complexes and to strengthening of hydrogen bonding. Redox properties of adsorbed CL-20 were compared with those of gas-phase and hydrated species by calculation of electron affinity, ionization potential, reduction Gibbs free energy, oxidation Gibbs free energy, reduction and oxidation potentials. It was shown that adsorbed CL-20 has lower ability to redox transformation as compared with hydrated one.

  12. Computing OpenSURF on OpenCL and General Purpose GPU

    Directory of Open Access Journals (Sweden)

    Wanglong Yan

    2013-10-01

    Full Text Available Speeded-Up Robust Feature (SURF algorithm is widely used for image feature detecting and matching in computer vision area. Open Computing Language (OpenCL is a framework for writing programs that execute across heterogeneous platforms consisting of CPUs, GPUs, and other processors. This paper introduces how to implement an open-sourced SURF program, namely OpenSURF, on general purpose GPU by OpenCL, and discusses the optimizations in terms of the thread architectures and memory models in detail. Our final OpenCL implementation of OpenSURF is on average 37% and 64% faster than the OpenCV SURF v2.4.5 CUDA implementation on NVidia's GTX660 and GTX460SE GPUs, repectively. Our OpenCL program achieved real-time performance (>25 Frames Per Second for almost all the input images with different sizes from 320*240 to 1024*768 on NVidia's GTX660 GPU, NVidia's GTX460SE GPU and AMD's Radeon HD 6850 GPU. Our OpenCL approach on NVidia's GTX660 GPU is more than 22.8 times faster than its original CPU version on Intel's Dual-Core E5400 2.7G on average.

  13. Copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone - ({sup 64}Cu)(H2Ac4oT)Cl - internal dosimetry: animal model and human extrapolation

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Josianne L.; Silva, Paulo R.O.; Santos, Raquel G.; Ferreira, Andrea V., E-mail: jlr@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2011-07-01

    Thiosemicarbazones have attracted great pharmacological interest because of their biological properties, such as cytotoxic activity against multiple strains of human tumors. Due to the excellent properties of {sup 64}Cu, the copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone (({sup 64}Cu)(H2Ac4oT)Cl) was developed for tumor detection by positron emission tomography. The radiopharmaceuticals were produced in the nuclear reactor TRIGA-IPR-R1 from CDTN. At the present work, ({sup 64}Cu)(H2Ac4oT)Cl biokinetic data (evaluated in mice bearing Ehrlich tumor) were treated by MIRD formalism to perform Internal Dosimetry studies. Doses in several organs of mice were determinate, as well as in implanted tumor, for ({sup 64}Cu)(H2Ac4oT)Cl. Doses results obtained for animal model were extrapolated to humans assuming a similar concentration ratio among various tissues between mouse and human. In the extrapolation, it was used human organ masses from Cristy/Eckerman phantom. Both penetrating and non-penetrating radiation from {sup 64}Cu in the tissue were considered in dose calculations. (author)

  14. Liquid-vapor equilibrium in LaCl3-LuCl3 and PrCl3-NdCl3 systems

    International Nuclear Information System (INIS)

    Nisel'son, L.A.; Lyzlov, Yu.N.; Solov'ev, S.I.

    1978-01-01

    The liquid-vapour equilibrium in the systems LaCl 3 -LuCl 3 and PrCl 3 -NdCl 3 was studied by the boiling-point method. It was established that the system LaCl 3 -LuCl 3 is near-ideal. In the PrCl 3 -NdCl 3 system, a considerable positive deviation from the ideal with the formation of an azeotrope was detected. The azeotrope has a ''smeared-out'' minimum, which falls on a mixture containing approximately 65 mol.% neodymium trichloride. The boiling point of this mixture at a pressure of 1 mm Hg is approximately 975 deg C. The relative volatility coefficients in both systems were studied by the Raleigh distillation method. The presence of the azeotrope in the system PrCl 3 -NdCl 3 is confirmed by the nature of the dependence of the relative volatility coefficient on the composition of the mixture

  15. Improved 36Cl performance at the ASTER HVE 5 MV accelerator mass spectrometer national facility

    International Nuclear Information System (INIS)

    Finkel, R.; Arnold, M.; Aumaître, G.; Benedetti, L.; Bourlès, D.; Keddadouche, K.; Merchel, S.

    2013-01-01

    The HVE 5 MV ASTER AMS national facility at CEREGE was accepted in 2007. Since then we have continued to optimize performance for 36 Cl. Cl-36 analyses use AgCl, a Cs negative ion sputter source, Ar stripping to +5 in the terminal of the Tandetron™ accelerator at 5 MV and a silicon nitride post-acceleration stripper foil to enhance suppression of 36 S relative to 36 Cl. The major challenges to obtaining the desired performance for Earth science applications are ion source memory, mass fractionation effects, 36 S isobar suppression and sensitivity. Redesign of the SO110 ion source by HVE to change the size of the aperture and the shape of cathode significantly reduced ion source memory to less than ∼0.1%, a level that can be compensated for by matching standards to samples. We observe small systematic drifts in 35 Cl/ 37 Cl ratios over time, the source of which is not yet determined. Measurement of standards indicates that this effect limits the precision of 35 Cl/ 37 Cl ratio determination to about 2%. 36 S is suppressed in several ways. First, the sample chemistry has been designed to reduce S to low levels. Second, cathodes are constructed of low-S nickel, enabling direct target loading without the use of AgBr pre-packing. Third, a post-acceleration Si 3 N 4 stripper foil differentially absorbs energy from 36 Cl and 36 S. A subsequent electrostatic deflector is then able to suppress 36 S by a factor of ∼240 relative to 36 Cl. Differential energy loss in the detector further suppresses 36 S by about 10 −4 , for an overall suppression factor of 4 × 10 −7 . 36 S count rates are typically equivalent to a background 36 Cl/Cl of ∼10 −15 . At typical 35 Cl currents of ∼20 μA Cl 5+ samples with 36 Cl/ 35 Cl of 6 × 10 −14 can be measured to ±5% statistical uncertainty with 1 h of analysis time. Typical machine blanks have 36 Cl/Cl ∼2 × 10 −15 .

  16. Structural phase transitions in CsPbCl/sub 3/ and RbCdCl/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Plesko, S; Kind, R; Roos, J [Swiss Federal Inst. of Technology, Zuerich. Lab. of Solid State Physics

    1978-08-01

    Structural phase transitions in CsPbCl/sub 3/ have been investigated by /sup 133/Cs and /sup 87/Rb nuclear magnetic resonance. The space groups of the room temperature phase in CsPbCl/sub 3/ and of two unknown phases in RbCdCl/sub 3/ could be clarified. Thus both perovskites show the same phase sequence from cubic Pm3m-O sub(h)sup(1) to tetragonal P4/mbm-D sub(4h)sup(5), orthorhombic Cmcm-D sub(2h)sup(17) and further orthorhombic Pnma-D sub(2h)sup(16).

  17. Cl--HCO-3 antiport in rat lacrimal gland

    International Nuclear Information System (INIS)

    Lambert, R.W.; Bradley, M.E.; Mircheff, A.K.

    1988-01-01

    With the use of analytical subcellular fractionation and tracer uptake methods the authors have demonstrated the presence of a Cl - -HCO - 3 antiport mechanism in the rat exorbital lacrimal gland. They find that outwardly directed gradients of HCO - 3 and of 35 Cl - accelerated the flux of 36 Cl - into isolated membrane vesicles. Because vesicle membrane potentials were clamped to 0 mV with K + -valinomycin, the observed anion gradient-dependent acceleration of Cl - influx could not be attributed to conductive fluxes. The antiporter had an apparent K 0.5 for Cl - between 6 and 10 mM. It was sensitive to the stilbene derivatives 4-acetamido-4'-isothiocyanostilbene-2,2'-disulfonic acid (SITS) and 4,4'-diisothiocyanostilbene-2,2'-disulfonic acid (DIDS). It was also sensitive to the loop diuretic furosemide, which has frequently been used in tests for NaKCl 2 symporter activity. Other anions inhibited anion gradient-driven Cl - influx in the sequence SCN - > NO - 3 > Cl - HCO - 3 > SO 2- 4 . The density distribution of Cl - -HCO - 3 antiport activity indicated that ∼80% of the transporter was associated with intracellular membranes, suggesting the presence of cytoplasmic pools of functional antiporters. Because several studies have already shown the presence of Na + -H + antiporter activity in lacrimal acinar cell basolateral membranes, a cellular model for lacrimal acinar electrolyte secretion is proposed in which a parallel array of Cl - -HCO - 3 and Na + -H + antiporters mediates the Na + -dependent accumulation of Cl - against its electrochemical potential gradient

  18. Multicomponent Biginelli's synthesis of 3,4-dihydropyrimidin-2(1H-ones promoted by SnCl2.2H2O

    Directory of Open Access Journals (Sweden)

    Russowsky Dennis

    2004-01-01

    Full Text Available The ability of SnCl2.2H2O as catalyst to promote the Biginelli three-component condensation reaction from a diversity of aromatic aldehydes, ethyl acetoacetate and urea or thiourea is described. The reaction was carried out in acetonitrile or ethanol as solvents in neutral media and represents an improvement of the classical Biginelli protocol and an advantage in comparison with FeCl3.6H2O, NiCl2.6H2O and CoCl2.6H2O which were used with HCl as co-catalyst. The synthesis of 3,4-dihydropyrimidinones was achieved in good to excelent yields.

  19. Systematic study of spin crossover and structure in [Co(terpyRX)2](Y)2 systems (terpyRX = 4'-alkoxy-2,2':6',2''-terpyridine, X = 4, 8, 12, Y = BF4(-), ClO4(-), PF6(-), BPh4(-))

    DEFF Research Database (Denmark)

    Nielsen, Pia; Nielsen, Hans Toftlund; Bond, Andrew

    2009-01-01

    A family of spin crossover cobalt(II) complexes of the type [Co(terpyRX)(2)](Y)(2) x nH(2)O (X = 4, 8, 12 and Y = BF(4)(-), ClO(4)(-), PF(6)(-), BPh(4)(-)) has been synthesized, whereby the alkyl chain length, RX, and counteranion, Y, have been systematically varied. The structural (single crystal...

  20. Experimental Thermodynamics of [Na-Mg-Cl-SO4] Aqueous Solutions at GPa Pressure With Application to Icy Worlds.

    Science.gov (United States)

    Brown, J. M.; Bollengier, O.; Vance, S.

    2017-12-01

    Water competes with silicates as the main constituent of solid bodies in the outer solar system. Ganymede and Titan, the Mercury-sized satellites of Jupiter and Saturn, are made up half of water present as massive hydrospheres where pressure can reach up to 1.5 GPa. Geophysical data and planetary models unequivocally support the existence of global aqueous oceans trapped in these hydrospheres. However, the extent of these oceans and their role in the processes governing the internal structure of these moons remain unresolved. At issue is the poor to non-existent characterization, at the relevant pressures, of the properties of the aqueous fluids of significance to the outer solar system (with notably the Na-Mg-Cl-SO4 salts found in primitive chondrites), forcing current models to rely on pure water only. Our team at the University of Washington has developed an experimental apparatus to acquire the speed of sound of aqueous solutions in the 0 - 0.7 GPa and 250 - 350 K pressure and temperature ranges covering most of the conditions of existence of these extra-terrestrial oceans. Speeds of sound measured over a grid of pressures and temperatures allow calculation of the thermodynamic quantities (G, ρ, μ...) required for planetary science. Early analysis of pure water samples indicates our experimental results are on par with (at lower pressures), or better than, the IAPWS water laboratory standard, with sound speeds determined to 0.02% over our entire pressure range. For the first time at the high pressures of interest for large icy moons, we achieved the exploration of H2O-NaCl, H2O-MgSO4, H2O-Na2SO4 and H2O-MgCl2 solutions, from dilute concentrations to saturation. We are now in the process of acquiring the first data for H2O-NaCl-MgSO4 mixtures. We will briefly present our experimental setup and the underlying sound speed theory, and will then compare our results for the four endmembers, with an emphasis on their different association behavior under pressure as

  1. The centrifugal sudden distorted wave method for chemical reactions: Application to Cl+HCl → ClH+Cl

    International Nuclear Information System (INIS)

    Amaee, B.; Connor, J.N.L.; Schatz, G.C.

    1987-01-01

    The authors describe a method for calculating cross sections for atom plus diatom reactive collisions based on the centrifugal sudden distorted wave (CSDW) approximation. This method is nearly exact at low energies where reactive cross sections are small. Representative CPU times are given for applications of CSDW method to the Cl + HCl → ClH + Cl reaction using CDC 7600, Cyber 176, Cyber 205, Cray XMP and Cray 2 computers. Calculations show that the product HCl molecule is highly rotationally excited, (receiving 40-50% of the available energy) and that the shape of the product rotational distribution is nearly independent of reagent rotational state. The authors also calculated product differential cross sections and find them to be backward peaked at low energies

  2. Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis

    KAUST Repository

    Credendino, Raffaele; Minenkov, Yury; Liguori, Dario; Piemontesi, Fabrizio; Melchior, Andrea; Morini, Giampiero; Tolazzi, Marilena; Cavallo, Luigi

    2017-01-01

    Adducts of TiCl4 with Lewis bases used as internal or external donors in heterogeneous Ziegler-Natta (ZN) catalysis represents a fundamental interaction contributing to the final composition of MgCl2 supported ZN-catalysts. This study presents

  3. Blue photoluminescence and long lasting phosphorescence properties of a novel chloride phosphate phosphor: Sr5(PO4)3Cl:Eu2+

    International Nuclear Information System (INIS)

    Wu, Chuanqiang; Zhang, Jiachi; Feng, Pengfei; Duan, Yiming; Zhang, Zhiya; Wang, Yuhua

    2014-01-01

    A novel blue emitting long lasting phosphorescence phosphor Sr 5 (PO 4 ) 3 Cl:Eu 2+ is synthesized by solid state method at 1223 K in reducing atmosphere. The afterglow emission spectrum shows one broad band centered at 441 nm due to the 5d–4f transition of Eu 2+ at six coordinated Sr(II) sites and the color coordinates are calculated to be (0.149, 0.095) which is close to the light blue region. The excitation band is in 240–430 nm and partly overlaps the solar irradiation on Earth's surface. The long lasting phosphorescence of the optimal sample doping by 0.1 mol%Eu 2+ can be recorded for about 1040 s (0.32 mcd/m 2 ). Thermoluminescence shows that there are at least three types of traps corresponding to peaks at 340 K, 382 K, 500 K, respectively. The filling and fading experiments reveal that the traps in Sr 5 (PO 4 ) 3 Cl:Eu 2+ are independent. The shallow traps (340 K) essentially contribute to the visible long lasting phosphorescence, while the deep traps (382 K and 500 K) are proved to be very stable. Thus, the Sr 5 (PO 4 ) 3 Cl:Eu 2+ material shows potential applications as not only a long lasting phosphorescence phosphor, but also an optical storage material. -- Highlights: • The blue long lasting phosphorescence of Sr 5 (PO 4 ) 3 Cl:Eu 2+ is first reported. • Filling and fading experiments are carried out for revealing natures of traps. • The afterglow mechanism for independent traps of Sr 5 (PO 4 ) 3 Cl:Eu 2+ is proposed

  4. Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

    Science.gov (United States)

    Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

    2017-01-01

    RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification

  5. Improved performance of dye-sensitized solar cell based on TiO_2 photoanode with FTO glass and film both treated by TiCl_4

    International Nuclear Information System (INIS)

    Li, Jinlun; Zhang, Haiyan; Wang, Wenguang; Qian, Yannan; Li, Zhenghui

    2016-01-01

    The dye-sensitized solar cell (DSSC) based on TiO_2 photoanode with FTO glass and TiO_2 film co-treated by TiCl_4 were fabricated. The effects of TiCl_4 treatment on the photovoltaic performance of the DSSCs were investigated. TiCl_4 treatment of the FTO glass resulted in the formation of a compact TiO_2 thin layer on its surface, which could increase the electron collection efficiency. Meanwhile, TiCl_4 treatment of the TiO_2 film could fill gaps between nanoparticles in the TiO_2 film, leading to better electron transfer. These advantages make the DSSC exhibit a highest conversion efficiency of 3.34% under a simulated solar irradiation with an intensity of 100 mW/cm"2 (1 sun), increased by 38% compared with that of the untreated DSSC.

  6. Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

    Science.gov (United States)

    Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

    2003-03-24

    Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

  7. Thermodynamics of curium(III) in concentrated electrolyte solutions: formation of sulfate complexes in NaCl/Na2SO4 solutions

    International Nuclear Information System (INIS)

    Paviet, P.; Fanghaenel, T.; Klenze, R.; Kim, J.I.

    1996-01-01

    The formation of sulfate complexes of Curium in aqueous solutions is studied by time resolved laser fluorescence spectroscopy (TRLFS) at 25 C. The species Cm 3+ , Cm(SO 4 ) - , Cm(SO 4 ) - 2 and Cm(SO 4 ) 3- 3 are quantified spectroscopically in the trace concentration range by peak deconvolution of fluorescence emission spectra. The complex formation equilibria are measured in NaCl/ Na 2 SO 4 solutions of constant ionic strength (3 molal) as a function of the sulfate concentration. The stability constants of Cm(SO 4 ) + and Cm(SO 4 ) - 2 are determined to be log β 1 = 0.93±0.08 and log β 2 = 0.61±0.08, respectively. The complex Cm(SO 4 ) 3- 3 is found to be stable only at very high sulfate concentrations (above 1 molal) and therefore not considered for further evaluation. (orig.)

  8. Emission spectrum of an electric-discharge ClF laser

    International Nuclear Information System (INIS)

    Deryugin, A A; Razhev, A M; Kochetov, Igor' V

    1998-01-01

    Experiments revealed a complex structure of the emission spectrum of an electric-discharge ClF laser, corresponding to the D'-A' transitions with a maximum near 285 nm. The vibrational bands in the emission spectrum overlapped at the base in the range 282-286 nm because of a high pressure in the gaseous active medium. Theoretical calculations were made and an interpretation was provided of the vibrational structure of the emission spectrum of the ClF molecules. The emission spectrum of the electric-discharge ClF laser was shown to consist of the 0-4, 0-5, 0-6, 1-6, 1-7, and 2-8 bands of the D'-A' transition. A total efficiency of 0.1% was achieved for the first time for the ClF laser and lasing was observed in a gaseous He - F 2 -BCl 3 active medium. (lasers, active media)

  9. A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

    Science.gov (United States)

    Watson, R.; Machado, G.; Fischer, S.; Davis, D. D.

    1976-01-01

    The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

  10. Characterization of the human pH- and PKA-activated ClC-2G(2 alpha) Cl- channel.

    Science.gov (United States)

    Sherry, A M; Stroffekova, K; Knapp, L M; Kupert, E Y; Cuppoletti, J; Malinowska, D H

    1997-08-01

    A ClC-2G(2 alpha) Cl- channel was identified to be present in human lung and stomach, and a partial cDNA for this Cl- channel was cloned from a human fetal lung library. A full-length expressible human ClC-2G(2 alpha) cDNA was constructed by ligation of mutagenized expressible rabbit ClC-2G(2 alpha) cDNA with the human lung ClC-2G(2 alpha) cDNA, expressed in oocytes, and characterized at the single-channel level. Adenosine 3',5'-cyclic monophosphate-dependent protein kinase (PKA) treatment increased the probability of opening of the channel (Po). After PKA activation, the channel exhibited a linear (r = 0.99) current-voltage curve with a slope conductance of 22.1 +/- 0.8 pS in symmetric 800 mM tetraethylammonium chloride (TEACl; pH 7.4). Under fivefold gradient conditions of TEACl, a reversal potential of +21.5 +/- 2.8 mV was measured demonstrating anion-to-cation discrimination. As previously demonstrated for the rabbit ClC-2G(2 alpha) Cl- channel, the human analog, hClC-2G(2 alpha), was active at pH 7.4 as well as when the pH of the extracellular face of the channel (trans side of the bilayer; pHtrans) was asymmetrically reduced to pH 3.0. The extent of PKA activation was dependent on pHtrans. With PKA treatment, Po increased fourfold with a pHtrans of 7.4 and eightfold with a pHtrans of 3.0. Effects of sequential PKA addition followed by pHtrans reduction on the same channel suggested that the PKA- and pH-dependent increases in channel Po were separable and cumulative. Northern analysis showed ClC-2G(2 alpha) mRNA to be present in human adult and fetal lung and adult stomach, and quantitative reverse transcriptase-polymerase chain reaction showed this channel to be present in the adult human lung and stomach at about one-half the level found in fetal lung. The findings of the present study suggest that the ClC-2G(2 alpha) Cl- channel may play an important role in Cl- transport in the fetal and adult human lung.

  11. Thermal behaviour of the thermoluminescent dosemeter CaSO4: Dy + NaCl

    International Nuclear Information System (INIS)

    Antonio Filho, J.

    1988-01-01

    Thermoluminescent materials are widely applied in radiation dosimetry. Nevertheless to obtain a good degree of reliability, it is necessary to subject the materials to an adequate thermal treatment, before and after irradiation, conveniently controlling temperature, heating time and cooling rate. It has been observed that the TLD CaSO 4 : Dy + NaCl loses 10% of its sensivity after each utilization cycle with the thermal treatment usually recomended. This fact establishes a severe limitation in works requiring a good measurement precision. Several alternative procedures, which overcome this limitation, have been studied. Two of the procedures yielded excellent results, with a coefficient of variation of 1 to 1.3%. One of them consist of two heating cycles at 300 0 C during 15 and three hours respectively, before irradiation, followed by a heating cycle at 100 0 C during 15 minutes, after irradiation. In a second procedure the material is heated at 300 0 C during three hours, pre-irradiation, followed by a heating cycle at 100 0 C. during 15 minutes, after irradiation. In all cases the heating cycle are followed by fast cooling periods. (author) [pt

  12. Phase formation in the systems ZrO2-H2SO4-Na2SO4 (NaCl)-H2O

    International Nuclear Information System (INIS)

    Sozinova, Yu.P.; Motov, D.L.; Rys'kina, M.P.

    1988-01-01

    Formation of solid phases in the systems ZrO 2 - H 2 SO 4 - Na 2 SO 4 (NaCl) - H 2 O at 25 and 75 deg C is studied. Three basic Na 2 Zr(OH) 2 (SO 4 ) 2 x (0.2 - 0.4)H 2 O, NaZrOH(SO 4 ) 2 x H 2 O, NaZrO 0.5 (OH) 2 SO 4 x 2H 2 O and three normal sodium sulfatozirconates Na 2 Zr(SO 4 ) 3 x 3H 2 O, Na 4 Zr(SO 4 ) 4 x 3H 2 O, Na 6 Zr(SO 4 ) 5 x 4H 2 O have been isolated, their solubility and crystal optical properties are determined

  13. Photoluminescence properties and thermal stability of blue-emitting Ba5-xCl(PO4)3:xEu2+ (0.004≤x≤0.016) phosphors.

    Science.gov (United States)

    Liu, Jie; Zhang, Zhi-Ming; Wu, Zhan-Chao; Wang, Fang-Fang; Li, Zhen-Jiang; Kuang, Shao-Ping; Wu, Ming-Mei

    2017-01-15

    A series of blue-emitting Ba 5-x Cl(PO 4 ) 3 :xEu 2+ (0.004≤x≤0.016) phosphors were synthesized by conventional high-temperature solid state reaction. The structure and photoluminescence (PL) properties of the phosphors were investigated. The as-prepared phosphors exhibit broad excitation band ranging from 250 to 420nm, and strong asymmetric blue emission band peaking at 436nm. The optimum concentration of Eu 2+ in the Ba 5 Cl(PO 4 ) 3 :Eu 2+ phosphor is x=0.01, and the concentration quenching mechanism is verified to be the combined actions of dipole-dipole interaction and radiation re-absorption mechanism. The thermal stability of Ba 5 Cl(PO 4 ) 3 :Eu 2+ was evaluated by temperature-dependent PL spectra. Compared with that of commercial BaMgAl 10 O 17 :Eu 2+ (BAM) phosphor, the Ba 5-x Cl(PO 4 ) 3 :xEu 2+ phosphors exhibit similarly excellent thermal quenching property. In addition, the CIE chromaticity coordinates of Ba 5-x Cl(PO 4 ) 3 :xEu 2+ (0.004≤x≤0.016) were calculated to evaluate the color quality. All the results indicate that Ba 5 Cl(PO 4 ) 3 :Eu 2+ is a promising candidate phosphor for near-ultraviolet (n-UV) pumped LED. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Vacuum ultraviolet photoabsorption spectroscopy of CH2Cl2 and CD2Cl2 in the energy region 50,000-95,000 cm-1

    Science.gov (United States)

    Mandal, Anuvab; Singh, Param Jeet; Shastri, Aparna; Jagatap, B. N.

    2014-12-01

    A consolidated study of the VUV absorption spectra of CH2Cl2 and CD2Cl2 in the 50,000-95,000 cm-1 region using synchrotron radiation is presented. Rydberg series and vibronic analysis are carried out and supported by quantum chemical calculations. The broad absorption band of CH2Cl2 in the region 50,000-60,000 cm-1 is attributed to the valence states 11B2, 11B1 and 11A1. Most of the bands in the 60,000-95,000 cm-1 region are fitted to Rydberg series of ns, np and nd type converging to the first four ionization potentials 11.320, 11.357, 12.152 and 12.271 eV of CH2Cl2 arising from excitation of an electron from one of the four outermost Cl non-bonding orbitals (2b1, 3b2, 1a2 and 4a1). Vertical excited states of CH2Cl2 calculated using TDDFT are correlated with experimentally observed electronic states based on the symmetries of the initial and final MOs involved in a transition. A few Rydberg transitions viz. 2b1→5s, 4p, 5p, 6p; 3b2→4p, 5p; 1a2→4p are accompanied by vibronic features. Observed vibronic bands are assigned mainly to the CCl symmetric stretch (ν3‧) mode with smaller contributions from the CH symmetric stretch (ν1‧), CH2 bend (ν2‧) and CH2 wag (ν8‧) modes. Assignments are corroborated by comparison with the VUV absorption spectrum of the deuterated isotopologue CD2Cl2, reported here for the first time. The high underlying intensities seen in several sub-regions are explained by valence or valence-Rydberg mixed type transitions predicted with high oscillator strengths by the TDDFT calculations.

  15. Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

    KAUST Repository

    Kumar, Rajeev Ananda; De, Priyadarsi; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

    2015-01-01

    The kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3·ether complexes in hexane at 0°C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR′FeCl4 - complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR′FeCl4 - ⇋ HCl + FeCl3·ROR′.

  16. Densities and apparent molar volumes of HClO{sub 4}(aq) and Yb(ClO{sub 4}){sub 3}(aq) at elevated temperatures and pressures

    Energy Technology Data Exchange (ETDEWEB)

    Hakin, Andrew W. E-mail: hakin@uleth.ca; Lukacs, Michael J.; Jin Lianliu

    2004-09-01

    Relative densities have been measured for acidified aqueous solutions of ytterbium perchlorate {l_brace}Yb(ClO{sub 4}){sub 3}{r_brace} at approximately T=(348.15, 373.15, 398.15, and 423.15) K and p=(10.0, 20.0, and 30.0) MPa over the concentration range 0.01624{<=}m{sub 2}/(mol {center_dot} kg{sup -1}) {<=} 0.2531 using an optically coupled vibrating tube densimeter (OCVTD). Experimental apparent molar volumes have been calculated from the density measurements, and apparent molar volumes for the aqueous perchlorate salt have been calculated using Young's rule. The application of Young's rule requires apparent molar volumes for aqueous perchloric acid (HClO{sub 4}) solutions over extended temperature and pressure ranges. These values were calculated from densities for aqueous HClO{sub 4} solutions that were measured using the OCVTD at the same temperatures and pressures as those used to investigate the density surface of the acidified aqueous Yb(ClO{sub 4}){sub 3} solutions. The temperature, pressure, and composition surfaces of the apparent molar volumes for Yb(ClO{sub 4}){sub 3}(aq) and HClO{sub 4}(aq) have been modelled using Pitzer ion-interaction equations. Apparent molar volumes at infinite dilution obtained from these models have been compared to those which can be calculated using the semi-empirical Helgeson, Kirkham, and Flowers equations of state. Values for the apparent molar volume at infinite dilution of the ytterbium trivalent cation have also been calculated using simple additivity principles.

  17. Cross Sections of the 36Ar(d,α)34mCl, 40Ar(d,α)38Cl and 40Ar(d,p)41Ar Nuclear Reactions below 8.4 MeV

    Science.gov (United States)

    Engle, J W; Severin, G W; Barnhart, T E; Knutson, L D; Nickles, R J

    2011-01-01

    We have measured the cross section for production of the medically interesting isotope 34mCl, along with 38Cl and 41Ar, using deuteron bombardments of 36Ar and 40Ar below 8.4 MeV. ALICE/ASH analytical codes were employed to determine the shape of nuclear excitation functions, and experiments were performed using the University of Wisconsin tandem electrostatic accelerator to irradiate thin targets of argon gas. PMID:22041299

  18. Metal-ligand delocalization and spin density in the CuCl2 and [CuCl4](2-) molecules: Some insights from wave function theory.

    Science.gov (United States)

    Giner, Emmanuel; Angeli, Celestino

    2015-09-28

    The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl2 and [CuCl4](2-) systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that each valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.

  19. Facile synthesis of hollow Co3O4 microspheres and its use as a rapid responsive CL sensor of combustible gases.

    Science.gov (United States)

    Teng, Fei; Yao, Wenqing; Zheng, Youfei; Ma, Yutao; Xu, Tongguang; Gao, Guizhi; Liang, Shuhui; Teng, Yang; Zhu, Yongfa

    2008-09-15

    The hollow Co(3)O(4) microspheres (HCMs) were prepared by the carbonaceous templates, which did not need the surface pretreatment. The chemiluminescence (CL) and catalytic properties for CO oxidation over these hollow samples were evaluated. The samples were characterized by scanning electron microscopy (SEM), energy disperse spectra (EDS), transmission electron microscopy (TEM), selected area electron diffraction (ED), X-ray diffraction (XRD), temperature-programmed desorption (TPD) and N(2) adsorption. The influences of filter' band length, flow rate of gas, test temperature, and particle structure on CL intensities were mainly investigated. It was found that compared with the solid Co(3)O(4) particles (SCPs), HCMs had a stronger CL intensity, which was ascribed to its hollow structure; and that CL properties of the catalysts were well correlated with their reaction activities. Moreover, HCMs were used to fabricate a highly sensitive gas detector, which is a rapid and effective method for the selection of catalysts or the detection of environmental deleterious gases.

  20. Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br, I- )

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei [Physical; Govind, Niranjan [Environmental; Xantheas, Sotiris S. [Advanced; Department; Wang, Xue-Bin [Physical

    2018-01-16

    Four new Zeise’s family ions with mixed-halide ligands, i.e., PtClnX3-n(C2H4)- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl3(C2H4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl3) > 4.56 (–Cl2Br) > 4.53 (–ClBr2) > 4.34 (–Cl2I) > 4.30 eV (–ClI2). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl2X, and the trans-isomer for –ClX2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

  1. The 4D evolution of porosity during ongoing pressure-solution processes in NaCl using x-ray microtomography

    Science.gov (United States)

    Macente, Alice; Fusseis, Florian; Butler, Ian; Tudisco, Erika; Hall, Stephen; Andò, Edward

    2016-04-01

    Pressure-solution creep is a common deformation mechanism in the upper crust. It represents a mass transfer via dissolution-reprecipitation that critically affects the hydraulic properties of rocks. Successful management of safe radioactive storage sites in rock-salt deposits critically depends on an accurate knowledge of the hydro-mechanical behaviour of salt deposits. Despite numerous lab experiments that have been conducted, many aspects of pressure-solution are still poorly understood. There is little knowledge about the spatio-temporal evolution of porosity and permeability during pressure-solution creep. While rates of pressure-solution creep in silicates and carbonates are slow, which makes laboratory investigations of these materials impractical, compaction experiments have demonstrated that NaCl samples deform sufficiently fast to study pressure-solution creep in a lab environment at room temperature and modest loads. We present results from novel experiments that quantify the 4-dimensional (three spatial dimensions plus time) evolution of pressure-solution processes using in-situ x-ray microtomography. Our experiments are performed in custom made x-ray transparent presses. 5 mm diameter NaCl powder samples with a grain size of 250-300 μm are loaded dry into the press and pre-compacted to produce a starting aggregated material. The sample is then flooded with saturated NaCl solution and loaded uniaxially by means of a pneumatic actuator to a constant uniaxial stress. Different sample mixtures were tested, as well as different uniaxial loads. The resulting deformation of the samples is documented in 3-dimensional microtomographic datasets, acquired at regular time intervals. Image analysis allowed characterization of the microstructural evolution of the NaCl grains and the spatio-temporal distribution of porosity during ongoing mechanical and chemical compaction. The microtomography data have also been analysed with 3D Digital Image Correlation (3D-DIC or

  2. Alterações fisiológicas do sistema nervoso central de rã pelas toxinas de Cl. perfringens, Cl. oedematiens e Cl. septicum

    Directory of Open Access Journals (Sweden)

    Genésio Pacheco

    1947-09-01

    Full Text Available The authors carried on experiences in order to confirm the neurotoxic theory of gas gangrene explained by Pacheco & Costa, uning preparations of isolated cord-posterior train of Leptodactylus ocellatus as described by OZORIO DE ALMEIDA & Cols. Frogs were intoxicated 3 days before the test with parcially purified toxins of Cl. perfringens, Cl. oedematiens and Cl. septicum. The intoxication produced a shortening of spinal reflexes duration time of such preparations, showing a typical alteration of the reflex activity of the spinal cord.

  3. Formation Mechanism and Dispersion of Pseudo-Tetragonal BaTiO3-PVP Nanoparticles from Different Titanium Precursors: TiCl4 and TiO2

    Directory of Open Access Journals (Sweden)

    Jinhui Li

    2017-12-01

    Full Text Available Nano-sized tetragonal BaTiO3 (BT particles that are well dispersed in solution are essential for the dielectric layer in multilayer ceramic capacitor technology. A hydrothermal process using TiCl4 and BaCl2, as source of Ti and Ba, respectively, or the precursor TiO2 as seed for the formation of BT, and poly(vinylpyrrolidone (PVP as a surfactant, was employed in this study to enhance both the dispersibility and tetragonality (c/a simultaneously in a single reaction process. The process parameters, i.e., the ratio of TiO2 substitution of TiCl4, the reaction time, and PVP content were systematically studied, and the growth mechanism and relation between the tetragonality and the particle size are discussed. Dynamic light scattering (DLS analysis was used to show that truncated pseudo-tetragonal BT-PVP particles with an average size of 100 nm, having a narrow size distribution and a coefficient of variation (CV as low as 20% and being mono-dispersed in water, were produced. The narrow particle size distribution is attributed to the ability of PVP to inhibit the growth of BT particles, and the high c/a of BT-PVP to heterogeneous particle growth using TiO2 seeds.

  4. Magnetic properties of the new π -d organic superconductor β -(BDA-TTP){2}FeCl{4}

    Science.gov (United States)

    Tokumoto, M.; Ishii, K.; Tanaka, H.; Akutsu, H.; Yamada, J.; Choi, E. S.; Brooks, J. S.; Ishida, K.

    2004-04-01

    We have investigated complete anisotropy in the magnetic properties of the charge transfer salt β -(BDA-TTP){2}FeCl{4} [BDA-TTP = 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene] and revealed that the anisotropy in both the temperature and the field dependences of magnetization below TN show behaviours different from those for typical antiferromagnets. Key words. Antiferromagnet anisotropy Smagnetization.

  5. Cross sections of the 36Ar(d,α)34mCl, 40Ar(d,α)38Cl, and 40Ar(d,p)41Ar nuclear reactions below 8.4 MeV.

    Science.gov (United States)

    Engle, J W; Severin, G W; Barnhart, T E; Knutson, L D; Nickles, R J

    2012-02-01

    We have measured the cross section for production of the medically interesting isotope (34m)Cl, along with (38)Cl and (41)Ar, using deuteron bombardments of (36)Ar and (40)Ar below 8.4 MeV. ALICE/ASH analytical codes were employed to determine the shape of nuclear excitation functions, and experiments were performed using the University of Wisconsin tandem electrostatic accelerator to irradiate thin targets of argon gas. Copyright © 2011 Elsevier Ltd. All rights reserved.

  6. Proteomic changes in Debaryomyces hansenii upon exposure to NaCl stress

    DEFF Research Database (Denmark)

    Gori, Klaus; Hébraud, Michel; Chambon, Christophe

    2007-01-01

    The proteome of the highly NaCl-tolerant yeast Debaryomyces hansenii was investigated by two-dimensional polyacrylamide gel electrophoresis (2D PAGE), and 47 protein spots were identified by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) followed by mass spectrometry (MS...... 7% and 4% of the rate in medium without NaCl. In addition, the number of protein spots detected on 2D gels prepared from cells exposed to 8% and 12% (w/v) NaCl exceeded less than 28% of the number of protein spots detected on 2D gels prepared from cells without added NaCl. Several proteins were...

  7. Synthesis and characterization of novel Na15 (SO4 )5 F4 Cl:Ce3+ halosulfate phosphors.

    Science.gov (United States)

    Bhake, A M; Nair, Govind B; Zade, G D; Dhoble, S J

    2016-12-01

    A series of Na 15 (SO 4 ) 5 F 4 Cl phosphors doped with Ce 3+ ions was prepared using the wet chemical method. X-Ray diffraction studies were used to determine their phase formation and purity. Fourier transform infrared spectroscopy effectively identified the chemical bonds present in the molecule. The photoluminescence properties of the as-prepared phosphors were investigated and the Ce 3+ ions in these hosts were found to give broadband emission in the UV range. For the thermoluminescence study, phosphors were irradiated with a 5 Gy dose of γ-rays from a 60 Co source. Chen's half-width method was employed to calculate the trapping parameters from the thermoluminescence glow curve. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  8. Thermodynamic study on co-deposition of ZrB2–SiC from ZrCl4–BCl3–CH3SiCl3–H2–Ar system

    International Nuclear Information System (INIS)

    Deng, Juanli; Cheng, Laifei; Zheng, Guopeng; Su, Kehe; Zhang, Litong

    2012-01-01

    Thermodynamics phase diagram of ZrB 2 –SiC co-deposited from precursors of ZrCl 4 –BCl 3 –CH 3 SiCl 3 (methyltrichlorosilane, MTS)–H 2 –Ar has been investigated in detail by using the FactSage code and its embedded database (130 species being involved). The yields of condensed phases in the co-deposition process have been examined as the functions of the inject reactant ratios of BCl 3 / (BCl 3 + MTS) and H 2 / (ZrCl 4 + BCl 3 + MTS), and the temperature at a fixed pressure of 5 kPa. The results show that their yields strongly depend on the molar ratios of the inject reactants and the temperature. Consequently, the pure ZrB 2 –SiC composite without free C, B 4 C, ZrC and ZrSi can be co-deposited under the ideal condition by adjusting the reactant ratios and the temperature. The gas-phase equilibrium concentration distribution shows that the high input amount of H 2 is favorable for the co-deposition of ZrB 2 and SiC at a fixed ratio of ZrCl 4 :BCl 3 :MTS:Ar. In the end, the theoretical results can lay down guidelines for increasing the experimental yields of ZrB 2 and SiC. - Highlights: ► The exact ratio of ZrB 2 and SiC could be obtained by adjusting input gas ratios. ► The other condensed phase species could appear under some suitable conditions ► The H 2 acting as reaction species directly influences the deposition process. ► The high H 2 input amount is favorable for the co-deposition of ZrB 2 and SiC. ► The flow rate range of the H 2 pump should be increased in the experimental study.

  9. 133Cs NMR investigation of 2D frustrated Heisenberg antiferromagnet, Cs2CuCl4

    Science.gov (United States)

    Vachon, M.-A.; Kundhikanjana, W.; Straub, A.; Mitrovic, V. F.; Reyes, A. P.; Kuhns, P.; Coldea, R.; Tylczynski, Z.

    2006-10-01

    We report 133Cs nuclear magnetic resonance (NMR) measurements on the 2D frustrated Heisenberg antiferromagnet Cs2CuCl4 down to 2 K and up to 15 T. We show that 133Cs NMR is a good probe of the magnetic degrees of freedom in this material. Cu spin degrees of freedom are sensed through a strong anisotropic hyperfine coupling. The spin excitation gap opens above the critical saturation field. The gap value was determined from the activation energy of the nuclear spin-lattice relaxation rate in a magnetic field applied parallel to the Cu chains (\\skew3\\hat{b} axis). The values of the g-factor and the saturation field are consistent with the neutron-scattering and magnetization results. The measurements of the spin spin relaxation time are exploited to show that no structural changes occur down to the lowest temperatures investigated.

  10. Luminescence properties of undoped CsCaCl3 and CsSrCl3 crystalline scintillators

    International Nuclear Information System (INIS)

    Fujimoto, Yutaka; Saeki, Keiichiro; Koshimizu, Masanori; Asai, Keisuke; Yanagida, Takayuki

    2015-01-01

    Intrinsic luminescence properties of undoped CsCaCl 3 and CsSrCl 3 crystalline scintillators were studied. The crystal samples were grown by a vertical Bridgman method. Photoluminescence spectra of the crystals showed Auger-free luminescence (AFL) at 310 nm and self-trapped emission (STE) at 400 nm for CsCaCl 3 and 465 nm for CsSrCl 3 , when vacuum ultraviolet (VUV) light at 84 nm and 160 nm excited the crystals. X-ray excited radioluminescence spectra of the crystals showed some emission bands in the 280-600 nm wavelength range, which are owing to AFL, STE, and other origins such as lattice defects and impurities. Scintillation light yield was 400-300 ph/MeV, and the principal scintillation decay time about 2.5 ns and 12 ns for CsCaCl 3 and 1.8 ns and 13 ns for CsSrCl 3 . (author)

  11. Luminescence properties of Na2Sr2Al2PO4Cl9:Sm3+ phosphor

    Science.gov (United States)

    Tamboli, Sumedha; Shahare, D. I.; Dhoble, S. J.

    2018-04-01

    A series of Sm3+ ions doped Na2Sr2Al2PO4Cl9 phosphors were synthesized via solid state synthesis method. Photoluminescence (PL) emission spectra were obtained by keeping excitation wavelength at 406 nm. Emission spectra show three emission peaks at 563 nm, 595 nm and 644 nm. The CIE chromaticity diagram shows emission colour of the phosphor in the orange-red region of the visible spectrum, indicating that the phosphor may be useful in preparing orange light-emitting diodes. Na2Sr2Al2PO4Cl9:Sm3+ phosphors were irradiated by γ-rays from a 60Co source and β-rays from a 90Sr source. Their thermoluminescence (TL) glow curves were obtained by Nucleonix 1009I TL reader. TL Trapping parameters such as activation energy of trapped electrons and order of kinetics were obtained by using Chen's peak shape method, Glow curve fitting method and initial rise method.

  12. Diphosphine- and CO-Induced Fragmentation of Chloride-bridged Dinuclear Complex and Cp*Ir(mu-Cl)(3)Re(CO)(3) and Attempted Synthesis of Cp*Ir(mu-Cl)(3)Mn(CO)(3): Spectroscopic Data and X-ray Diffraction Structures of the Pentamethylcyclopentadienyl Compounds [Cp*IrCl{(Z)-Ph2PCH = CHPPh2}][Cl]center dot 2CHCl(3) and Cp*Ir(CO)Cl-2

    Energy Technology Data Exchange (ETDEWEB)

    Hammons, Casey [University of North Texas; Wang, Xiaoping [ORNL; Nesterov, Vladimir [University of North Texas; Richmond, Michael G. [University of North Texas

    2010-01-01

    The confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (1) undergoes rapid fragmentation in the presence of the unsaturated diphosphine ligand (Z)-Ph2PCH = CHPPh2 to give the mononuclear compounds [Cp*IrCl {(Z)-Ph2PCH = CHPPh2}][Cl] (2) and fac-ClRe(CO)(3)[(Z)-Ph2PCH = CHPPh2] (3). 2 has been characterized by H-1 and P-31 NMR spectroscopy and X-ray diffraction analysis. 2 center dot 2CHCl(3) crystallizes in the monoclinic space group C2/c, a = 35.023 (8) angstrom, b = 10.189 (2) angstrom, c = 24.003 (6) angstrom, b = 103.340 (3), V = 8,335 (3) angstrom 3, Z = 8, and d(calc) = 1.647 Mg/m(3); R = 0.0383, R-w = 0.1135 for 8,178 reflections with I> 2 sigma(I). The Ir(III) center in 2 exhibits a six-coordinate geometry and displays a chelating diphosphine group. Compound 1 reacts with added CO with fragmentation to yield the known compounds Cp*Ir(CO)Cl-2 (4) and ClRe(CO)(5) (5) in near quantitative yield by IR spectroscopy. Using the protocol established by our groups for the synthesis of 1, we have explored the reaction of [Cp*IrCl2](2) with ClMn(CO)(5) as a potential route to Cp*Ir(mu-Cl)(3)Mn(CO)(3); unfortunately, 4 was the only product isolated from this reaction. The solid-state structure of 4 was determined by X-ray diffraction analysis. 4 crystallizes in the triclinic space group P-1, a = 7.4059 (4) angstrom, b = 7.8940 (4) angstrom, c = 11.8488 (7) angstrom, alpha = 80.020 (1), beta = 79.758 (1), gamma = 68.631 (1), V = 630.34 (6) angstrom(3), Z = 2, and d(calc) = 2.246 Mg/m(3); R = 0.0126, R-w = 0.0329 for 2,754 reflections with I> 2 sigma(I). The expected three-legged piano-stool geometry in 4 has been crystallographically confirmed.

  13. Lead-Free MA2CuCl(x)Br(4-x) Hybrid Perovskites.

    Science.gov (United States)

    Cortecchia, Daniele; Dewi, Herlina Arianita; Yin, Jun; Bruno, Annalisa; Chen, Shi; Baikie, Tom; Boix, Pablo P; Grätzel, Michael; Mhaisalkar, Subodh; Soci, Cesare; Mathews, Nripan

    2016-02-01

    Despite their extremely good performance in solar cells with efficiencies approaching 20% and the emerging application for light-emitting devices, organic-inorganic lead halide perovskites suffer from high content of toxic, polluting, and bioaccumulative Pb, which may eventually hamper their commercialization. Here, we present the synthesis of two-dimensional (2D) Cu-based hybrid perovskites and study their optoelectronic properties to investigate their potential application in solar cells and light-emitting devices, providing a new environmental-friendly alternative to Pb. The series (CH3NH3)2CuCl(x)Br(4-x) was studied in detail, with the role of Cl found to be essential for stabilization. By exploiting the additional Cu d-d transitions and appropriately tuning the Br/Cl ratio, which affects ligand-to-metal charge transfer transitions, the optical absorption in this series of compounds can be extended to the near-infrared for optimal spectral overlap with the solar irradiance. In situ formation of Cu(+) ions was found to be responsible for the green photoluminescence of this material set. Processing conditions for integrating Cu-based perovskites into photovoltaic device architectures, as well as the factors currently limiting photovoltaic performance, are discussed: among them, we identified the combination of low absorption coefficient and heavy mass of the holes as main limitations for the solar cell efficiency. To the best of our knowledge, this is the first demonstration of the potential of 2D copper perovskite as light harvesters and lays the foundation for further development of perovskite based on transition metals as alternative lead-free materials. Appropriate molecular design will be necessary to improve the material's properties and solar cell performance filling the gap with the state-of-the-art Pb-based perovskite devices.

  14. Radiological assessment of 36Cl in the disposal of used CANDU fuel

    International Nuclear Information System (INIS)

    Johnson, L.H.; Goodwin, B.W.; Sheppard, S.C.; Tait, J.C.; Wuschke, D.M.; Davison, C.C.

    1995-06-01

    An assessment of the potential radiological impact of 36 Cl in the disposal of used CANDU fuel has been performed. The assessment was based on new data on chlorine impurity levels in used fuel. Data bases for the vault, geosphere, and biosphere models used in the EIS postclosure assessment case study (Goodwin et al. 1994) were modified to include the necessary 36 Cl data. The resulting safety analysis shows that estimated radiological risks from 36 Cl are forty times lower than from 129 I at 10 4 a; this, incorporation of 36 Cl into the models does not change the overall conclusions of the study of Goodwin et al. (1994a). For human intrusion scenarios, an analysis using the methodology of Wuschke (1992) showed that the maximum risk is unaffected by the inclusion of 36 Cl. (author). 51 refs., 5 tabs., 15 figs

  15. Rayleigh-Brillouin scattering in NH4Cl under hydrostatic pressure

    International Nuclear Information System (INIS)

    Hikita, Tomoyuki; Kitabatake, Makoto; Ikeda, Takuro

    1981-01-01

    Rayleigh-Brillouin scattering in NH 4 Cl has been studied under hydrostatic pressure. Brillouin shifts of the longitudinal phonons propagating along the and directions and of the transverse phonons propagating along the direction are measured as a function of temperature at four fixed pressures up to 2.3 kbar. All components increase almost linearly with decreasing temperature in the disordered phase and show incremental increases similar to the temperature dependence of the long range order parameter in the ordered phase. It was found that the longitudinal modes exhibit large despersion effect even at high pressures. On the other hand, the transverse mode appears to give no dispersion effect. The intensity of the Rayleigh component in the VV polarization condition increases as the temperature approaches the transition point, while that in the VH polarization does not show such anomalous increase. (author)

  16. Crystal structure, thermochromic and magnetic properties of organic-inorganic hybrid compound: (C7H7N2S)2CuCl4

    Science.gov (United States)

    Vishwakarma, Ashok K.; Kumari, Reema; Ghalsasi, Prasanna S.; Arulsamy, Navamoney

    2017-08-01

    The synthesis, thermal analysis, crystal structure and magnetic properties of (2-aminobenzothiazolium)2CuCl4, organic-inorganic hybrid compound, have been described. The compound crystallizes in the monoclinic space group P21/c with two formula units in a unit cell of dimensions a = 6.9522(4) Å, b = 9.6979(4) Å, c = 13.9633(6) Å, β = 97.849(3)° and volume 930.83(8) Å3 at 150(2) K. The structure consists of isolated nearly square planer [CuC14]2- units, with somewhat longer than normal Cusbnd Cl bond lengths [Cusbnd Cl (average) = 2.2711 Å]. The magnetic measurements of (2-aminobenzothiazolium)2CuCl4 using SQUID magnetometer show paramagnetic nature of the compound. Thermal measurements (TG-DTA and DSC) on this compound showed reversible phase transition at 83 °C. This transition is accompanied by the reversible change in colour of the prismatic crystal from green to dark brown, thermochromic behaviour. Temperature dependent EPR measurements on powdered sample ascertain change in coordination sphere around Cu(II) with shift in g|| = 2.150 and g⊥ = 2.071 at room temperature, typical of square planar, to g|| = 2.201 and g⊥ = 2.182 at 170 °C, typical of distorted tetrahedral geometry.

  17. Cl36 and the age of the cosmic rays

    International Nuclear Information System (INIS)

    Casse, M.; Goret, P.; Regnier, S.

    1975-01-01

    The radioactive isotope 36 Cl (tau=γx3.10 5 y) is used as a time reference for the propagation of cosmic rays. New measurements of the production cross section of 36 Cl in Ti and Fe at 24GeV will be presented. A critical analysis of the cross sections leads to an estimate of the ratio 36 Cl/Cl=0.030+0.007 in the arriving cosmic rays. The comparison between the expected abundance of Cl in the arriving cosmic rays and the observations tend to support the decay of 36 Cl. The inferred cosmic ray confinement time is about 10 6 y [fr

  18. 3-Amino-1,2,4-triazolium ion in [24(3at)]Cl and [24(3at)]2SnCl6·H2O. Comparative X-ray, vibrational and theoretical studies

    Science.gov (United States)

    Daszkiewicz, Marek; Marchewka, Mariusz K.

    2012-09-01

    Crystal structures of 3-amino-1,2,4-triazolium chloride and bis(3-amino-1,2,4-triazolium) hexachloridostannate monohydrate were determined by means of X-ray single crystal diffraction. The route of protonation of organic molecule and tautomer equilibrium constants for the cationic forms were calculated using B3LYP/6-31G* method. The most stable protonated species is 2,4-H2-3-amino-1,2,4-triazolium ion, 24(3at)+. Very good agreement between theoretical and experimental frequencies was achieved due to very weak interactions existing in studied compounds. Significantly weaker intermolecular interactions are found in [24(3at)]2SnCl6·H2O than in [24(3at)]Cl. The differences in strength of interactions are manifested in red and blue shifts for stretching and bending motions, respectively. PED calculations show that for 24(3at)+ ion the stretching type of motion of two Nringsbnd H bonds is independent, whereas bending is coupled.

  19. Comparative study of the catalytic activity of the complexes Cp{sup *}RuCl(PAr{sub 3}){sub 2} [Ar = -C{sub 6H}5 and 4-CF{sub 3}-C{sub 6}H{sub 4}] in the ATRP of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Villa-Hernandez, Alejandro M.; Rosales-Velazquez, Claudia P.; Torres-Lubian, Jose R., E-mail: rtorres@ciqa.mx [Departamento de Sintesis de Polimeros, Centro de Investigacion en Quimica Aplicada, Coah. (Mexico); Saldivar-Guerra, Enrique [Departamento de Procesos de Polimerizacion, Centro de Investigacion en Quimica Aplicada, Coah. (Mexico)

    2011-09-15

    Styrene polymerization by ATRP was conducted independently using the complexes Cp{sup *}RuCl(PPh{sub 3}){sub 2}, and Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} as catalysts, in order to evaluate the influence of the electronic properties of the phosphine ligands on the rate and control of the polymerization. The kinetic data for polymerizations carried out with Cp{sup *}RuCl(PPh{sub 3}){sub 2}, show that molecular weights increase linearly with conversion with an average initiation efficiency of 0.77. The molecular weights obtained in the kinetic study with Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} also increase with conversion but show a marked deviation below the theoretical molecular weights. This behavior was explained by the gradual, irreversible, oxidation of catalyst Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} as confirmed by {sup 31}P-NMR spectroscopy. Catalyst Cp{sup *}RuCl(PPh{sub 3}){sub 2} promotes the polymerization with a rate of polymerization higher than that obtained using Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2}; this is consistent with the better electron donating properties of PPh{sub 3} versus P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}. Preliminary studies of styrene polymerization by ATRP in supercritical CO{sub 2}, shows that only catalyst Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2}, with fluorinated ligands, was active. (author)

  20. Surfactant-promoted reactions of Cl2 and Br2 with Br- in glycerol.

    Science.gov (United States)

    Faust, Jennifer A; Dempsey, Logan P; Nathanson, Gilbert M

    2013-10-17

    Gas-liquid scattering experiments are used to explore reactions of gaseous Cl2 and Br2 with a 0.03 M solution of the surfactant tetrahexylammonium bromide (THABr) dissolved in glycerol. At thermal collision energies, 79 ± 2% of incident Cl2 molecules react with Br(-) to form Cl2Br(-) in the interfacial region. This reaction probability is three times greater than the reactivity of Cl2 with 3 M NaBr-glycerol, even though the interfacial Br(-) concentrations are similar in each solution. We attribute the high 79% uptake to the presence of surface THA(+) ions that stabilize the Cl2Br(-) intermediate as it is formed in the charged, hydrophobic pocket created by the hexyl chains. Cl2Br(-) generates the single exchange product BrCl in a 1% yield close to the surface, while the remaining 99% desorbs as the double exchange product Br2 over >0.1 s after diffusing deeply into the bulk. When NaCl is added to the surfactant solution in a 20:1 Cl(-)/Br(-) ratio, the Cl2 reaction probability drops from 79% to 46 ± 1%, indicating that Cl(-) in the interfacial region only partially blocks reaction with Br(-). In parallel, we observe that gaseous Br2 molecules dissolve in 0.03 M THABr for 10(4) times longer than in 3 M NaBr. We attribute this change to formation of stabilizing interfacial and bulk-phase THA(+)Br3(-) ion pairs, in analogy with the capture of Cl2 and formation of THA(+)Cl2Br(-) pairs. The THA(+) ion appears to be a powerful interfacial catalyst for promoting reaction of Cl2 and Br2 with Br(-) and for ferrying the resultant ions into solution.

  1. Electrocrystallization of Au nanoparticles on glassy carbon from HClO4 solution containing [AuCl4]-

    International Nuclear Information System (INIS)

    Komsiyska, L.; Staikov, G.

    2008-01-01

    The mechanism and kinetics of electrocrystallization of Au nanoparticles on glassy carbon (GC) were investigated in the system GC/1 mM KAuCl 4 + 0.1 M HClO 4 . Experimental results show that the gold electrodeposition follows the so-called Volmer-Weber growth mechanism involving formation and growth of 3D Au nanoparticles on an unmodified GC substrate. The analysis of current transients shows that at relatively positive electrode potentials (E ≥ 0.84 V) the deposition kinetics corresponds to the theoretical model for progressive nucleation and diffusion-controlled 3D growth of Au nanoparticles. The potential dependence of the nucleation rate extracted from the current transients is in agreement with the atomistic theory of nucleation. At sufficiently negative electrode potentials (E ≤ 0.64 V) the nucleation frequency becomes very high and the nucleation occurs instantaneously. Based on this behaviour is applied a potentiostatic double-pulse routine, which allows controlled electrodeposition of Au nanoparticles with a relatively narrow size distribution

  2. Hydrolysis of CuCl{sub 2} in the Cu-Cl thermochemical cycle for hydrogen production: Experimental studies using a spray reactor with an ultrasonic atomizer

    Energy Technology Data Exchange (ETDEWEB)

    Ferrandon, Magali S.; Lewis, Michele A. [Argonne National Laboratory, Chemical Sciences and Engineering Division, 9700 S. Cass Ave., Argonne, IL 60439 (United States); Alvarez, Francisco; Shafirovich, Evgeny [The University of Texas at El Paso, Mechanical Engineering Department, 500 W. University Ave., El Paso, TX 79968 (United States)

    2010-03-15

    The Cu-Cl thermochemical cycle is being developed as a hydrogen production method. Prior proof-of-concept experimental work has shown that the chemistry is viable while preliminary modeling has shown that the efficiency and cost of hydrogen production have the potential to meet DOE's targets. However, the mechanisms of CuCl{sub 2} hydrolysis, an important step in the Cu-Cl cycle, are not fully understood. Although the stoichiometry of the hydrolysis reaction, 2CuCl{sub 2} + H{sub 2}O <-> Cu{sub 2}OCl{sub 2} + 2HCl, indicates a necessary steam-to-CuCl{sub 2} molar ratio of 0.5, a ratio as high as 23 has been typically required to obtain near 100% conversion of the CuCl{sub 2} to the desired products at atmospheric pressure. It is highly desirable to conduct this reaction with less excess steam to improve the process efficiency. Per Le Chatelier's Principle and according to the available equilibrium-based model, the needed amount of steam can be decreased by conducting the hydrolysis reaction at a reduced pressure. In the present work, the experimental setup was modified to allow CuCl{sub 2} hydrolysis in the pressure range of 0.4-1 atm. Chemical and XRD analyses of the product compositions revealed the optimal steam-to-CuCl{sub 2} molar ratio to be 20-23 at 1 atm pressure. The experiments at 0.4 atm and 0.7 atm showed that it is possible to lower the steam-to-CuCl{sub 2} molar ratio to 15, while still obtaining good yields of the desired products. An important effect of running the reaction at reduced pressure is the significant decrease of CuCl concentration in the solid products, which was not predicted by prior modeling. Possible explanations based on kinetics and residence times are suggested. (author)

  3. Observed and simulated time evolution of HCl, ClONO2, and HF total column abundances

    Directory of Open Access Journals (Sweden)

    B.-M. Sinnhuber

    2012-04-01

    Full Text Available Time series of total column abundances of hydrogen chloride (HCl, chlorine nitrate (ClONO2, and hydrogen fluoride (HF were determined from ground-based Fourier transform infrared (FTIR spectra recorded at 17 sites belonging to the Network for the Detection of Atmospheric Composition Change (NDACC and located between 80.05° N and 77.82° S. By providing such a near-global overview on ground-based measurements of the two major stratospheric chlorine reservoir species, HCl and ClONO2, the present study is able to confirm the decrease of the atmospheric inorganic chlorine abundance during the last few years. This decrease is expected following the 1987 Montreal Protocol and its amendments and adjustments, where restrictions and a subsequent phase-out of the prominent anthropogenic chlorine source gases (solvents, chlorofluorocarbons were agreed upon to enable a stabilisation and recovery of the stratospheric ozone layer. The atmospheric fluorine content is expected to be influenced by the Montreal Protocol, too, because most of the banned anthropogenic gases also represent important fluorine sources. But many of the substitutes to the banned gases also contain fluorine so that the HF total column abundance is expected to have continued to increase during the last few years. The measurements are compared with calculations from five different models: the two-dimensional Bremen model, the two chemistry-transport models KASIMA and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. Thereby, the ability of the models to reproduce the absolute total column amounts, the seasonal cycles, and the temporal evolution found in the FTIR measurements is investigated and inter-compared. This is especially interesting because the models have different architectures. The overall agreement between the measurements and models for the total column abundances and the seasonal cycles is good. Linear trends of HCl, ClONO2, and HF are calculated from both

  4. A new organic superconductor, beta-(BDA-TTP)2GaCl4 [BDA-TTP = 2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene].

    Science.gov (United States)

    Yamada, Jun-ichi; Toita, Takashi; Akutsu, Hiroki; Nakatsuji, Shin'ichi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Koichi; Choi, Eun S; Graf, David; Brooks, James S

    2003-09-07

    The preparation, crystal structure and physical properties of beta-(BDA-TTP)2GaCl4 has been investigated; the salt exhibits superconductivity at 3.1 K (onset) under a hydrostatic pressure of 7.6 kbar.

  5. Phase diagram of pressure-induced superconductor β-(BDA-TTP)2MX4 (M=Fe, Ga and X=Cl, Br) with localized magnetic moments

    Science.gov (United States)

    Choi, E. S.; Graf, D.; Tokumoto, T.; Brooks, J. S.; Yamada, Jun-Ichi

    2007-03-01

    We have investigated transport and magnetization properties of β-(BDA-TTP)2MX4 (M=Fe, Ga and X=Cl, Br) as a function of pressure, temperature and magnetic field. The title material undergoes metal-insulator transitions above 100 K at ambient pressure. The insulating phase is suppressed with pressure and superconductivity eventually appears above Pc= 4.5 kbar (X=Cl) and 13 kbar (X=Br). The general temperature-pressure (TP) phase diagram is similar each other, while higher pressure is required for X=Br compounds to suppress the insulating state and induce the superconductivity. Pressure dependent DC magnetization studies on β-(BDA-TTP)2FeCl4 compound revealed that the AFM ordering persist well above Pc. In spite of similarity of phase diagram between M=Fe and M=Ga compounds, magnetoresistance results show distinct behaviors, which indicates the magnetic interaction with the conduction electrons are still effective. The comparison between X=Cl and X=Br compounds suggests the anion-size effect rather than the existence of localized magnetic moments plays more important role in determining the ground state.

  6. Hybrid model of atmospheric pressure Ar/O{sub 2}/TiCl{sub 4} radio-frequency capacitive discharge for TiO{sub 2} deposition

    Energy Technology Data Exchange (ETDEWEB)

    Leblanc, A. [ENS Cachan, UPMC, Paris (France); Ding, Ke [College of Science, Donghua University, Shanghai 201620 (China); Lieberman, M. A., E-mail: lieber@eecs.berkeley.edu [Department of Electrical Engineering, University of California, Berkeley, California 94720 (United States); Wang, De Xin; Zhang, Jing; Jun Shi, Jian [College of Materials Science and Engineering, Donghua University, Shanghai 201620 (China)

    2014-05-14

    A hybrid global-analytical model of an atmospheric pressure radio-frequency driven capacitive discharge is applied to determine the plasma conditions for TiO{sub 2} film deposition. The feed gas is mainly argon with a small fraction of O{sub 2} and a smaller fraction of TiCl{sub 4}. Variations of the discharge parameters and species densities with O{sub 2} concentration, discharge power, and flow rate are determined. A simplified chemistry model is developed and compared with the simulation results, showing good agreement. For a base case with Ar/O{sub 2}/TiCl{sub 4} flow rates of 203/30/0.17 sccm, the results indicate that a minimum O{sub 2} fraction of 7.3 × 10{sup −4} is required for pure (un-chlorinated) TiO{sub 2} film deposition that the active precursor species is TiO{sub 2}Cl{sub 3}, with subsequent abstraction of Cl atoms by dissociative electron attachment and that the deposition rates are around 1 nm/s.

  7. Biodegradation of the High Explosive Hexanitrohexaazaiso-wurtzitane (CL-20

    Directory of Open Access Journals (Sweden)

    Steve Nicolich

    2009-04-01

    Full Text Available The aerobic biodegradability of the high explosive CL-20 by activated sludge and the white rot fungus Phanerochaete chrysosporium has been investigated. Although activated sludge is not effective in degrading CL-20 directly, it can mineralize the alkaline hydrolysis products. Phanerochaete chrysosporium degrades CL-20 in the presence of supplementary carbon and nitrogen sources. Biodegradation studies were conducted using various nutrient media under diverse conditions. Variables included the CL-20 concentration; levels of carbon (as glycerol and ammonium sulfate and yeast extract as sources of nitrogen. Cultures that received CL-20 at the time of inoculation transformed CL-20 completely under all nutrient conditions studied. When CL-20 was added to pre-grown cultures, degradation was limited. The extent of mineralization was monitored by the 14CO2 time evolution; up to 51% mineralization was achieved when the fungus was incubated with [14C]-CL-20. The kinetics of CL-20 biodegradation by Phanerochaete chrysosporium follows the logistic kinetic growth model.

  8. On chlorization of uranium and plutonium oxides in NaCl-KCl-MgCl2 molten eutectic

    International Nuclear Information System (INIS)

    Vorobej, M.P.; Desyatnik, V.N.; Pirogov, S.M.

    1978-01-01

    The chlorination process of U 3 O 8 , UO 2 , and PuO 2 in a melt of anhydrous NaCl-KCl-MgCl 2 with gaseous chlorine and carbon tetrachloride has been studied. The chlorination rate of uranium oxides has been studied within a temperature range 500-800 deg C at a chlorine feeding rate of 10 ml/min. Thermoqravimetric and X-ray analyses have shown that K 2 UO 2 Cl 4 compound is the final product of chlorination of uranium oxides. The mechanism of chlorination has been proposed. THe rate of PuO 2 chlorination has been studied within the same temperature range. It has been established that PuO 2 is readily chlorinated with CCl 4 vapours at a feeding rate of 10 ml/min. In contrast to uranium, chloride forms of plutonium in a highest oxidized state are unstable and are reduced in the melt to Pu(3) and Pu(4). The oxygen being released is retained by CCl 4 and by the products of CCl 4 pyrolysis

  9. Time-domain seismic modeling in viscoelastic media for full waveform inversion on heterogeneous computing platforms with OpenCL

    Science.gov (United States)

    Fabien-Ouellet, Gabriel; Gloaguen, Erwan; Giroux, Bernard

    2017-03-01

    Full Waveform Inversion (FWI) aims at recovering the elastic parameters of the Earth by matching recordings of the ground motion with the direct solution of the wave equation. Modeling the wave propagation for realistic scenarios is computationally intensive, which limits the applicability of FWI. The current hardware evolution brings increasing parallel computing power that can speed up the computations in FWI. However, to take advantage of the diversity of parallel architectures presently available, new programming approaches are required. In this work, we explore the use of OpenCL to develop a portable code that can take advantage of the many parallel processor architectures now available. We present a program called SeisCL for 2D and 3D viscoelastic FWI in the time domain. The code computes the forward and adjoint wavefields using finite-difference and outputs the gradient of the misfit function given by the adjoint state method. To demonstrate the code portability on different architectures, the performance of SeisCL is tested on three different devices: Intel CPUs, NVidia GPUs and Intel Xeon PHI. Results show that the use of GPUs with OpenCL can speed up the computations by nearly two orders of magnitudes over a single threaded application on the CPU. Although OpenCL allows code portability, we show that some device-specific optimization is still required to get the best performance out of a specific architecture. Using OpenCL in conjunction with MPI allows the domain decomposition of large models on several devices located on different nodes of a cluster. For large enough models, the speedup of the domain decomposition varies quasi-linearly with the number of devices. Finally, we investigate two different approaches to compute the gradient by the adjoint state method and show the significant advantages of using OpenCL for FWI.

  10. Synchrotron radiation studies on luminescence of Eu2+-doped LaCl3 microcrystals embedded in a NaCl matrix

    International Nuclear Information System (INIS)

    Savchyn, P.V.; Vistovskyy, V.V.; Pushak, A.S.; Voloshinovskii, A.S.; Gektin, A.V.; Pankratov, V.; Popov, A.I.

    2012-01-01

    LaCl 3 :Eu 2+ microcrystals dispersed in the NaCl matrix have been obtained in the NaCl–LaCl 3 (1 mol.%)–EuCl 3 (0.1 mol.%) crystalline system. The low-temperature luminescent properties of these microcrystals have been studied upon the VUV and UV excitation by the synchrotron radiation. The spectroscopic parameters as well as decay time constants of Eu 2+ -doped LaCl 3 host have been established. The excitation mechanism of divalent europium centers through energy transfer and reabsorption is discussed.

  11. Active Ti Species in TiCl3-Doped NaAlH4. Mechanism for Catalyst Deactivation

    NARCIS (Netherlands)

    Balde, C.P.; Stil, H.A.; van der Eerden, A.M.J.; de Jong, K.P.; Bitter, J.H.

    2007-01-01

    The nature of the active Ti species in TiCl3-doped NaAlH4, a promising hydrogen storage material, was studied as a function of the desorption temperature with Ti K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, Ti K-edge X-ray absorption near-edge structure (XANES) spectroscopy,

  12. EFFECT OF DIFFERENT K2 HPO4, NaCl LEVELS AND TWO DIFFERENT TEMPARATURES ON SOME EMULSION PROPERTIES OF GOAT MEAT

    OpenAIRE

    Mustafa KARAKAYA; Hüsnü Yusuf GÖKALP; Ramazan BAYRAK

    1996-01-01

    Different levels of K2 HPO4 (0.00 %, 0.25 % and 0.50 %) and NaCl (2.5 % and 3.0 %) were added into goat meat, at the two different temperatures (11o C and 18o C) in order to investigate the emulsion properties in the model emulsion system. Emulsion capacity (EK), emulsion viscocity (EV), emulsion stability ratio (ES), the ratio of separated water (ESO) and oil (EYO) ratio from the emulsion, and the emulsion pH were determined. K2 HPO4 and NaCl levels and the oil temperatures have significant ...

  13. Variation of the Jahn-Teller distortion with pressure in the layered perovskite Rb2CuCl4: local and crystal compressibilities

    International Nuclear Information System (INIS)

    Aguado, F; RodrIguez, F; Valiente, R; Hanfland, M; Itie, J P

    2007-01-01

    This work investigates the effect of pressure on the Jahn-Teller distortion (JTD) associated with the axially elongated CuCl 6 octahedra in the A 2 CuCl 4 perovskite layer (A: Rb, CH 3 NH 3 , C 2 H 5 NH 3 , C 3 H 7 NH 3 ). The aim is to elucidate whether pressure favours disappearance of the JTD in the antiferrodistortive (AFD) structure exhibited by Cu 2+ within the layers or whether it induces tilts of the CuCl 6 octahedra preserving the molecular distortion associated with the JT effect. We have carried out x-ray absorption (XAS) and x-ray diffraction (XRD) experiments under pressure along the compound series, whose interlayer distances at ambient pressure vary from 7.77 to 12.33 A. The use of both XAS and XRD techniques allows us a complete local- and crystal-structure characterization in Rb 2 CuCl 4 as a function of pressure in the 0-16 GPa range. We show that pressure reduces the axial (long) and equatorial (short) Cu-Cl distances, R ax and R eq , as well as the intralayer and interlayer Cu-Cu distances, d Cu-Cu and d inter . Interestingly, the variation of R ax is an order of magnitude bigger than that of the corresponding R eq , yielding a reduction of the JTD. However, no evidence of JTD suppression has been observed below 16 GPa. Pressure-induced CuCl 6 tilting preserves the JTD in a wide pressure range. Estimates based on structural data suggest that JT suppression would occur at about 40 GPa

  14. Flexible electromagnetic wave sensor operating at GHz frequencies for instantaneous concentration measurements of NaCl, KCl, MnCl2 and CuCl solutions

    International Nuclear Information System (INIS)

    Korostynska, O; Ortoneda-Pedrola, M; Mason, A; Al-Shamma'a, A I

    2014-01-01

    A novel electromagnetic wave sensor operating at GHz frequencies for real-time chlorides concentration analysis is reported. The sensor response to deionized water, NaCl, KCl, MnCl 2  and CuCl solutions at various concentrations was tested. The sensing element, in the form of a silver pattern antenna that emits an electromagnetic field, was printed on a polyimide flexible laminate substrate to form a sensor to suit a broad range of applications, where a sensor could be placed in water reservoirs or fluid-carrying pipes for continuous analysis. The developed system confirmed the viability of using microwaves for real-time chloride solutions monitoring as the reflected signals represented by S 11  parameters were unique with clearly observed shifts in the resonant frequencies and amplitude changes when placed in direct contact with 20 µl of each solution. (paper)

  15. High 36Cl/Cl ratios in Chernobyl groundwater

    International Nuclear Information System (INIS)

    Roux, Céline; Le Gal La Salle, Corinne; Simonucci, Caroline; Van Meir, Nathalie; Fifield, L. Keith; Diez, Olivier; Bassot, Sylvain

    2014-01-01

    After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A 90 Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, 36 Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. 36 Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1–5 orders of magnitude higher than the theoretical natural 36 Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of 36 Cl, however other sources have to be involved to explain such contamination. 36 Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of 90 Sr, radionuclide which is impacted by retention and decay processes, 36 Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of 36 Cl from trench soil are better characterized. - Highlights: • High 36 Cl/Cl ratios measured in the Chernobyl Pilot Site groundwater. • Trench T22 acts as a modern source of groundwater contamination by 36 Cl but other sources are involved. • Contamination results from dilution of a contaminated “T22” soil water with rainwater. • Processes involved in the modern release need to be investigated

  16. Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

    International Nuclear Information System (INIS)

    Nemcsok, Denes; Kovacs, Attila; Szecsenyi, Katalin Meszaros; Leovac, Vukadin M.

    2006-01-01

    In the present paper we report a joint experimental and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and its complexes Co 2 L 2 Cl 4 , Cu 2 L 2 Cl 4 and Cu 2 L 2 Br 2 . DFT computations were used to model the structural and bonding properties of the title compounds as well as to derive a reliable force field for the normal coordinate analysis of L. The computations indicated the importance of hydrogen bonding interactions in stabilising the global minimum structures on the potential energy surfaces. In contrast to the S-bridged binuclear Cu 2 L 2 Br 2 complex found in the crystal, our computations predicted the formation of (CuLBr) 2 dimers in the isolated state stabilized by very strong (53 kJ/mol) N-H...Br hydrogen bonding interactions. On the basis of FT-IR and FT-Raman experiments and the DFT-derived scaled quantum mechanical force field we carried out a complete normal coordinate analysis of L. The FT-IR spectra of the three complexes were interpreted using the present assignment of L, literature data and computed results

  17. A Study on the Corrosion Behavior of Carbon Steel Exposed to a H2S-Containing NH4Cl Medium

    Science.gov (United States)

    Wang, Hai-bo; Li, Yun; Cheng, Guang-xu; Wu, Wei; Zhang, Yao-heng

    2018-04-01

    NH4Cl corrosion failure often occurs in the overhead systems of hydrotreaters, and this failure is always accompanied by the appearance of H2S. A combination of electrochemical and surface spectroscopic (SEM/EDS, AFM, XRD) techniques was used to investigate the effect of different factors, including the surface roughness, temperature, dissolved oxygen, pH and H2S concentration, on the corrosion behavior of carbon steel in an NH4Cl environment with the presence of H2S. The effect of H2S concentrations (at the ppm level) on the corrosion behavior of carbon steel was systematically revealed. The experimental results clearly indicated that the corrosion rate reached a minimum value at 10 ppm H2S. The steel surface was covered by a uniform corrosion product film in a 10 ppm H2S environment, and the corrosion product film was tight and protective. The ammonia from NH4Cl helped maintaining the protectiveness of the corrosion films in this environment. Dissolved oxygen mainly accelerated the cathodic reaction. The cathodic limiting current density increased with increasing temperature, and the anodic branch polarization curves were similar at different temperatures. The anodic current density decreased as the pH decreased, and the cathodic current density increased as the pH decreased. The absolute surface roughness (R a) of carbon steel increased from 132.856 nm at 72 h to 153.973 nm at 144 h, and the rougher surface resulted in a higher corrosion rate. The critical innovation in this research was that multiple influential factors were revealed in the NH4Cl environment with the presence of H2S.

  18. A Study on the Corrosion Behavior of Carbon Steel Exposed to a H2S-Containing NH4Cl Medium

    Science.gov (United States)

    Wang, Hai-bo; Li, Yun; Cheng, Guang-xu; Wu, Wei; Zhang, Yao-heng

    2018-05-01

    NH4Cl corrosion failure often occurs in the overhead systems of hydrotreaters, and this failure is always accompanied by the appearance of H2S. A combination of electrochemical and surface spectroscopic (SEM/EDS, AFM, XRD) techniques was used to investigate the effect of different factors, including the surface roughness, temperature, dissolved oxygen, pH and H2S concentration, on the corrosion behavior of carbon steel in an NH4Cl environment with the presence of H2S. The effect of H2S concentrations (at the ppm level) on the corrosion behavior of carbon steel was systematically revealed. The experimental results clearly indicated that the corrosion rate reached a minimum value at 10 ppm H2S. The steel surface was covered by a uniform corrosion product film in a 10 ppm H2S environment, and the corrosion product film was tight and protective. The ammonia from NH4Cl helped maintaining the protectiveness of the corrosion films in this environment. Dissolved oxygen mainly accelerated the cathodic reaction. The cathodic limiting current density increased with increasing temperature, and the anodic branch polarization curves were similar at different temperatures. The anodic current density decreased as the pH decreased, and the cathodic current density increased as the pH decreased. The absolute surface roughness ( R a) of carbon steel increased from 132.856 nm at 72 h to 153.973 nm at 144 h, and the rougher surface resulted in a higher corrosion rate. The critical innovation in this research was that multiple influential factors were revealed in the NH4Cl environment with the presence of H2S.

  19. Improved performance of dye-sensitized solar cell based on TiO{sub 2} photoanode with FTO glass and film both treated by TiCl{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jinlun [School of Materials and Energy, Guangdong University of Technology, Guangzhou Higher Education Mega Center 100#, Guangzhou, 510006 (China); Zhang, Haiyan, E-mail: hyzhang@gdut.edu.cn [School of Materials and Energy, Guangdong University of Technology, Guangzhou Higher Education Mega Center 100#, Guangzhou, 510006 (China); Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangzhou, 510006 (China); Wang, Wenguang, E-mail: wenguangwang2005@163.com [School of Materials and Energy, Guangdong University of Technology, Guangzhou Higher Education Mega Center 100#, Guangzhou, 510006 (China); Key Laboratory of Renewable Energy, Chinese Academy of Sciences, Guangzhou, 510640 (China); Qian, Yannan; Li, Zhenghui [School of Materials and Energy, Guangdong University of Technology, Guangzhou Higher Education Mega Center 100#, Guangzhou, 510006 (China)

    2016-11-01

    The dye-sensitized solar cell (DSSC) based on TiO{sub 2} photoanode with FTO glass and TiO{sub 2} film co-treated by TiCl{sub 4} were fabricated. The effects of TiCl{sub 4} treatment on the photovoltaic performance of the DSSCs were investigated. TiCl{sub 4} treatment of the FTO glass resulted in the formation of a compact TiO{sub 2} thin layer on its surface, which could increase the electron collection efficiency. Meanwhile, TiCl{sub 4} treatment of the TiO{sub 2} film could fill gaps between nanoparticles in the TiO{sub 2} film, leading to better electron transfer. These advantages make the DSSC exhibit a highest conversion efficiency of 3.34% under a simulated solar irradiation with an intensity of 100 mW/cm{sup 2} (1 sun), increased by 38% compared with that of the untreated DSSC.

  20. Determination of 36Cl/Cl ratio in ground water using the accelerator mass spectrometry technique

    International Nuclear Information System (INIS)

    Sharma, Suman; Deodhar, A.S.; Saravana Kumar, U.; Surendran, P.; Shrivastava, A.; Gupta, A.K.; Nair, J.P.; Yadav, M.L.; Hemalatha, M.; Sparrow, H.; Mahata, K.; Thomas, R.G.; Bhagwat, P.V.; Kailas, S.; Kale, R.M.

    2009-01-01

    The Accelerator Mass Spectrometry (AMS) programme using the 14 MV Pelletron Accelerator at Mumbai has been initiated with major emphasis on the determination of 36 Cl in water samples, of interest to hydrology and environment. In order to carry out the AMS measurement, a beam chopper to cut down beam intensity by a factor of 20 has been developed and commissioned. A multi-anode gas -si detector has been built to separate 36 Cl from the interfering 36 S. A new TPS system has been procured to operate the machine in the GVM mode. Standard and blank samples from Prime lab, Purdue have been employed in these measurements to standardise the technique for 36 Cl/Cl ratio determination. The detector was calibrated using the stable 35,37 Cl ions. The background 36 Cl in the system has been measured using the blank sample from Purdue and it was estimated that the ratio of 36 Cl/Cl was of the order of 10 -13 in the present setup. Ground water samples collected from South India were converted to AgCl and put in the SNICS ion source for the AMS measurements. These ground water samples, with 14 C content estimated to be in the range of 1 to 4 pMC indicate that the samples may be more than 35,000 years old. Using the AMS technique we have determined the 36 Cl/Cl ratio values for these ground water samples. They are found to range between 2 to 5 x 10 -12 . Additional measurements are planned to determine the age of the water samples and to understand the reasons for the observed high values of 36 Cl in these samples. (author)

  1. Electrochemical noise measurements of steel corrosion in the molten NaCl-K2SO4 system

    DEFF Research Database (Denmark)

    Cappeln, Frederik Vilhelm; Bjerrum, Niels; Petrushina, Irina

    2005-01-01

    -called active corrosion (i.e., the corrosion proceeds with no passivation due to the influence of chlorine), characterized by the formation of volatile metal chlorides as a primary corrosion product. It was found possible to obtain an empirical separation of general and intergranular corrosion using kurtosis (a......Electrochemical noise measurements have been carried out on AISI347, 10CrMo910, 15Mo3, and X20CrMoV121 steels in molten NaCl-K2SO4 at 630 degrees C. Different types of current noise have been identified for pitting, intergranular and peeling corrosion. The corrosion mechanism was the so...... statistical parameter calculated from the electrochemical noise data). It was found that average kurtosis values above 6 indicated intergranular corrosion and average values below 6 indicated general corrosion. The response time for localized corrosion detection in in-plant monitoring was approximately 90 min...

  2. Measurement of the spectral shift of the 3d→4p transitions in Ar+, Cl+ and S+ by means of collinear fast-beam laser spectroscopy

    International Nuclear Information System (INIS)

    Eichhorn, A.

    1981-01-01

    The spectral shift of the 3d→4p transitions in Ar + ( 36 Ar + and 40 Ar + ) Cl + ( 35 Cl + and 37 Cl + ) and S + ( 32 S + + 34 S + ) were measured by means of collinear fast-beam laser spectroscopy. Since the volume effect is neglectible only the normal and specific mass effect give contributions to the spectral shift. (BEF)

  3. Effect of the reaction time on the microstructure and porous texture of carbon materials obtained by chlorination of Ti(C{sub 5}H{sub 5})Cl{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Araujo-Pérez, D.J. [Centro de Investigación en Micro y Nanotecnología, Universidad Veracruzana, 94294, Boca del Río, Veracruz (Mexico); González-García, P., E-mail: pedro.gonzalez@cidesi.edu.mx [CONACYT Research Fellow – Centro de Ingeniería y Desarrollo Industrial, 76130, Querétaro, Querétaro (Mexico); Poisot, M. [Instituto de Química Aplicada, Universidad del Papaloapan, 68301, San Juan Bautista Tuxtepec, Oaxaca (Mexico); García-González, L. [Centro de Investigación en Micro y Nanotecnología, Universidad Veracruzana, 94294, Boca del Río, Veracruz (Mexico)

    2015-09-15

    Carbon materials have been obtained by the chlorination reaction of Ti(C{sub 5}H{sub 5})Cl{sub 2} at 900 °C, varying the reaction time at 30, 60, 90 and 120 min. The average microstructure, studied by X ray powder diffraction, suggest that these materials consist mainly of disordered carbon with low graphitization degree (from 13.5 to 16.5%). These results are in agreement with the Raman data since the D band (at ≈ 1350 cm{sup −1}) indicates that disordered carbon networks have appeared. The calculated in-plane correlation length increases from 4.04 to 4.70 nm as the chlorination time increases from 30 to 120 min. The textural analyses reveal adsorption isotherms type 1 with hysteresis H4, microporous areas as high as 855 m{sup 2}/g and pore volume of 0.55 cm{sup 3}/g. Additionally, an important contribution of mesoporosity, around 3.6 nm, was also detected. - Highlights: • Micro-mesoporous carbon materials were obtained by chlorination of Ti(C{sub 5}H{sub 5}){sub 2}Cl{sub 2} at 900 °C. • The effect of chlorination exposure time on the microstructure and textural properties was studied. • Microstructural analysis by XRD and Raman showed that carbon samples are mainly disordered. • N{sub 2} adsorption/desorption isotherms showed isotherms type 1 with hysteresis H4. • Micropore size increases at longer chlorination time; in contrast, pore volume decreases.

  4. Radiative forcing calculations for CH3Cl

    International Nuclear Information System (INIS)

    Grossman, A.S.; Grant, K.E.; Wuebbles, D.J.

    1994-06-01

    Methyl chloride, CH 3 Cl, is the major natural source of chlorine to the stratosphere. The production of CH 3 Cl is dominated by biological sources from the oceans and biomass burning. Production has a seasonal cycle which couples with the short lifetime of tropospheric CH 3 Cl to produce nonuniform global mixing. As an absorber of infrared radiation, CH 3 Cl is of interest for its potential affect on the tropospheric energy balance as well as for its chemical interactions. In this study, we estimate the radiative forcing and global warming potential (GWP) of CH 3 Cl. Our calculations use an infrared radiative transfer model based on the correlated k-distribution algorithm for band absorption. Global and annual average vertical profiles of temperature and trace gas concentration were assumed. The effects of clouds are modeled using three layers of global and annual average cloud optical properties. A radiative forcing value of 0.0053 W/m 2 ppbv was obtained for CH 3 Cl and is approximately linear in the background abundance. This value is about 2 percent of the forcing of CFC-11 and about 300 times the forcing of CO 2 , on a per molecule basis. The radiative forcing calculation for CH 3 Cl is used to estimate the global warming potential (GWP) of CH 3 Cl. The results give GWPs for CH 3 Cl of the order of 25 at a time of 20 years(CO 2 = 1). This result indicates that CH 3 Cl has the potential to be a major greenhouse gas if significant human related emissions were introduced into the atmosphere

  5. Synthesis of 4-aryl-3,4-dihydrocoumarin derivatives catalyzed by NbCl{sub 5}; Sintese de derivados 4-aril-3,4-di-hidrocuraminicos catalisada por NbCl{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Willian Henrique dos; Siqueira, Mayara de Souza; Silva-Filho, Luiz Carlos da, E-mail: lcsilva@fc.unesp.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Bauru, SP (Brazil). Faculdade de Ciencias

    2013-11-01

    Multicomponent reactions between phenols, {beta}-diesters and benzaldehydes for the synthesis of 4-aryl-3,4-dihydrocoumarin derivatives were carried out under mild conditions (room temperature) and presented moderate yields (38-88%) and reasonable reaction times (2-4 days), using niobium pentachloride as a catalyst. (author)

  6. EFFECT OF DIFFERENT K2 HPO4, NaCl LEVELS AND TWO DIFFERENT TEMPARATURES ON SOME EMULSION PROPERTIES OF GOAT MEAT

    Directory of Open Access Journals (Sweden)

    Mustafa KARAKAYA

    1996-03-01

    Full Text Available Different levels of K2 HPO4 (0.00 %, 0.25 % and 0.50 % and NaCl (2.5 % and 3.0 % were added into goat meat, at the two different temperatures (11o C and 18o C in order to investigate the emulsion properties in the model emulsion system. Emulsion capacity (EK, emulsion viscocity (EV, emulsion stability ratio (ES, the ratio of separated water (ESO and oil (EYO ratio from the emulsion, and the emulsion pH were determined. K2 HPO4 and NaCl levels and the oil temperatures have significant effect (p

  7. High (36)Cl/Cl ratios in Chernobyl groundwater.

    Science.gov (United States)

    Roux, Céline; Le Gal La Salle, Corinne; Simonucci, Caroline; Van Meir, Nathalie; Fifield, L Keith; Diez, Olivier; Bassot, Sylvain; Simler, Roland; Bugai, Dmitri; Kashparov, Valery; Lancelot, Joël

    2014-12-01

    After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A (90)Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, (36)Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. (36)Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1-5 orders of magnitude higher than the theoretical natural (36)Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of (36)Cl, however other sources have to be involved to explain such contamination. (36)Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of (90)Sr, radionuclide which is impacted by retention and decay processes, (36)Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of (36)Cl from trench soil are better characterized. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Electrochemical noise transient analysis for 316 and Duplex 2205 stainless steels in NaCl and FeCl; Analisis de los transitorios de ruido electroquimico para aceros inoxidables 316 Y - DUPLEX 2205 en NaCl Y FeCl

    Energy Technology Data Exchange (ETDEWEB)

    Almeraya-Calderaon, F.; Estupinan, F.; Zambrano, P.; Martinez-Villafane, A.; Borunda, A.; Colas, R.; Gaona-Tiburcio, C.

    2012-11-01

    This work shows the results obtained from electrochemical noise measurements for different materials exhibiting pitting corrosion. The transients presented in the potential and current time, correlates with the scanning electron microscopy (SEM) surface analysis. Electrochemical measurements were made at different exposure times to obtain the correlation. The materials used were stainless steel austenitic 316 and duplex 2205, immersed in ferric chloride (FeCl3) and sodium chloride (NaCl) electrolytes. SEM analysis shows that the transients observed in the time series, really correspond to the activity of pit nucleation developed over the surface of the electrodes. (Author) 31 refs.

  9. Effective Biotransformation of Ethyl 4-Chloro-3-Oxobutanoate into Ethyl (S)-4-Chloro-3-Hydroxybutanoate by Recombinant E. coli CCZU-T15 Whole Cells in [ChCl][Gly]-Water Media.

    Science.gov (United States)

    Dai, Yong; Huan, Bin; Zhang, Hai-Sheng; He, Yu-Cai

    2017-04-01

    To increase the biocatalytic activity of Escherichia coli CCZU-T15 whole cells, choline chloride/glycerol ([ChCl][Gly]) was firstly used as biocompatible solvent for the effective biotransformation of ethyl 4-chloro-3-oxobutanoate (COBE) into ethyl (S)-4-chloro-3-hydroxybutanoate [(S)-CHBE]. Furthermore, L-glutamine (150 mM) was added into [ChCl][Gly]-water ([ChCl][Gly] 12.5 vol%, pH 6.5) media instead of NAD + for increasing the biocatalytic efficiency. To further improve the biosynthesis of (S)-CHBE (>99 % e.e.) by E. coli CCZU-T15 whole cells, Tween-80 (7.5 mM) was also added into this reaction media, and (S)-CHBE (>9 % e.e.) could be effectively synthesized from 2000 and 3000 mM COBE in the yields of 100 and 93.0 % by whole cells of recombinant E. coli CCZU-T15, respectively. TEM image indicated that the cell membrane was permeabilized and lost its integrity and when the cell was exposed to [ChCl][Gly]-water media with Tween-80. Clearly, this bioprocess has high potential for the effective biosynthesis of (S)-CHBE (>99 % e.e.).

  10. 36Cl/Cl ratios in geothermal systems: preliminary measurements from the Coso Field

    International Nuclear Information System (INIS)

    Nimz, G.J.; Moore, J.N.; Kasameyer, P.W.

    1997-01-01

    The 36 Cl/Cl isotopic composition of chlorine in geothermal systems can be a useful diagnostic tool in characterizing hydrologic structure, in determining the origins and age of waters within the systems, and in differentiating the sources of chlorine (and other solutes) in the thermal waters. The 36 Cl/Cl values for several geothermal water samples and reservoir host rock samples from the Coso, California geothermal field have been measured for these purposes. The results indicate that most of the chlorine is not derived from the dominant granitoid that host the geothermal system. If the chlorine was originally input into the Coso subsurface through meteoric recharge, that input occurred at least 1-1.25 million years ago. The results suggest that the thermal waters could be connate waters derived from sedimentary formations, presumably underlying and adjacent top the granitic rocks, which have recently migrated into the host rocks. Alternatively, most of the chlorine but not the water, may have recently input into the system from magmatic sources. In either case, the results indicate that most of the chlorine in the thermal waters has existed within the granitoid host rocks for no more than about 100,00-200,00 years. this residence time for the chlorine is similar to residence times suggested by other researchers for chlorine in deep groundwaters of the Mono Basin north of the Coso field

  11. 36Cl/Cl ratios in geothermal systems: preliminary measurements from the Coso Field

    Energy Technology Data Exchange (ETDEWEB)

    Nimz, G.J.; Moore, J.N.; Kasameyer, P.W.

    1997-07-01

    The {sub 36}Cl/Cl isotopic composition of chlorine in geothermal systems can be a useful diagnostic tool in characterizing hydrologic structure, in determining the origins and age of waters within the systems, and in differentiating the sources of chlorine (and other solutes) in the thermal waters. The {sub 36}Cl/Cl values for several geothermal water samples and reservoir host rock samples from the Coso, California geothermal field have been measured for these purposes. The results indicate that most of the chlorine is not derived from the dominant granitoid that host the geothermal system. If the chlorine was originally input into the Coso subsurface through meteoric recharge, that input occurred at least 1-1.25 million years ago. The results suggest that the thermal waters could be connate waters derived from sedimentary formations, presumably underlying and adjacent top the granitic rocks, which have recently migrated into the host rocks. Alternatively, most of the chlorine but not the water, may have recently input into the system from magmatic sources. In either case, the results indicate that most of the chlorine in the thermal waters has existed within the granitoid host rocks for no more than about 100,00-200,00 years. this residence time for the chlorine is similar to residence times suggested by other researchers for chlorine in deep groundwaters of the Mono Basin north of the Coso field.

  12. TweetNaCl : a crypto library in 100 tweets

    NARCIS (Netherlands)

    Bernstein, D.J.; van Gastel, B.; Janssen, W.; Lange, T.; Schwabe, P.; Smetsers, S.; Aranha, D.F.; Menezes, A.

    2015-01-01

    This paper introduces TweetNaCl, a compact reimplementation of the NaCl library, including all 25 of the NaCl functions used by applications. TweetNaCl is published on Twitter and fits into just 100 tweets; the tweets are available from anywhere, any time, in an unsuspicious way. Distribution via

  13. Electrochemical behaviour of ThF4 in LiCl-KCl eutectic

    International Nuclear Information System (INIS)

    Agarwal, Renu; Mukerjee, S.K.; Ramakumar, K.L.

    2016-01-01

    Pyrochemical processing of nuclear fuels is an integral part of molten salt reactor technology. Thorium containing molten salt reactors are relevant for transmutation of minor actinides and utilizations of vast thorium resources. Understanding chemical and electrochemical behavior of actinide and lanthanide ions in chloride melts is an important task in this process. A eutectic of lithium and potassium chloride is found to be the most suitable salt for this study due to its low melting, high reduction potential and significant solubility of most of the actinide and lanthanide salts. However, electrochemistry of thorium in chloride melt is inconsistent due to dispute over the presence of Th(II) cation along with Th(IV). In the present experiments, cyclic-voltammograms of ThF 4 in LiCl-KCl eutectic salt were measured using three electrodes cell, where all the electrodes were 1 mm molybdenum wires and counter electrode wire was twisted into a spiral shape to increase surface area and was used for mixing the salts in molten state. Cyclic-voltammograms of pure eutectic melt and with ThF 4 were measured at scanning rates 50-300 mV/s, at 648 K and 723 K. Diffusion coefficient of Th 4+ was calculated using Delahay equation

  14. Enhancement of photocurrents due to the oxidation of water and organic compounds at BiZn2VO6 particulate thin film electrodes by treatment with a TiCl4 solution

    International Nuclear Information System (INIS)

    Liu Haimei; Imanishi, Akihito; Yang Wensheng; Nakato, Yoshihiro

    2010-01-01

    Photocurrents due to water oxidation at BiZn 2 VO 6 (E g 2.4 eV) particulate thin film electrodes were largely enhanced by pre-treatment with an aqueous TiCl 4 solution. Photocurrents for BiZn 2 VO 6 electrodes with no TiCl 4 treatment were also enhanced by the addition of organic compounds such as methanol and trimethyl amine to the aqueous electrolyte. Interestingly, such enhanced photocurrents by organic compounds were further enhanced by the TiCl 4 pre-treatment. EDAX and SEM investigations showed the formation of a flock-like TiO 2 overlayer on BiZn 2 VO 6 particles after the TiCl 4 treatment. The photocurrent enhancement by the TiCl 4 pre-treatment is thus mainly attributed to the necking effect of the flock-like TiO 2 overlayer, which facilitates the transport of photogenerated electrons within the BiZn 2 VO 6 particulate thin film electrode.

  15. Radiological assessment of {sup 36}Cl in the disposal of used CANDU fuel

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, L H; Goodwin, B W; Sheppard, S C; Tait, J C; Wuschke, D M; Davison, C C

    1995-06-01

    An assessment of the potential radiological impact of {sup 36}Cl in the disposal of used CANDU fuel has been performed. The assessment was based on new data on chlorine impurity levels in used fuel. Data bases for the vault, geosphere, and biosphere models used in the EIS postclosure assessment case study (Goodwin et al. 1994) were modified to include the necessary {sup 36}Cl data. The resulting safety analysis shows that estimated radiological risks from {sup 36}Cl are forty times lower than from {sup 129}I at 10{sup 4} a; this, incorporation of {sup 36}Cl into the models does not change the overall conclusions of the study of Goodwin et al. (1994a). For human intrusion scenarios, an analysis using the methodology of Wuschke (1992) showed that the maximum risk is unaffected by the inclusion of {sup 36}Cl. (author). 51 refs., 5 tabs., 15 figs.

  16. Electronic absorption bands of HoCl3 and SmCl3 complexes in alcohols

    International Nuclear Information System (INIS)

    Ramesh Babu, V.; Buddhudu, S.; Rangarajan, V.N.

    1987-01-01

    The normal absorption and second derivative spectra of ten alcoholic complexes of HoCl 3 and SmCl 3 were recorded. From the observed bands, energies and intensity values were measured. To fit in these measured values with the theoretical values, a set of spectroscopic parameters namely, Judd-Ofelt (T 2 , T 4 , T 6 ), intensity (Ω 2 , Ω 4 , Ω 6 ) had been computed. A good fit of intensities was obtained between the experimental and theoretical data. The environmental influences on the intensities of the hypersensitive transitions of Sm(III) and Ho(III) ions were found to be noteworthy. (author). 7 tables, 20 refs

  17. Electronic Structure and Magnetic Interactions in the Radical Salt [BEDT-TTF]2[CuCl4].

    Science.gov (United States)

    Calzado, Carmen J; Rodríguez-García, Bárbara; Galán Mascarós, José Ramón; Hernández, Norge Cruz

    2018-06-07

    The magnetic behavior and electric properties of the hybrid radical salt [BEDT-TTF] 2 [CuCl 4 ] have been revisited through extended experimental analyses and DDCI and periodic DFT plane waves calculations. Single crystal X-ray diffraction data have been collected at different temperatures, discovering a phase transition occurring in the 250-300 K range. The calculations indicate the presence of intradimer, interdimer, and organic-inorganic π-d interactions in the crystal, a magnetic pattern much more complex than the Bleaney-Bowers model initially assigned to this material. Although this simple model was good enough to reproduce the magnetic susceptibility data, our calculations demonstrate that the actual magnetic structure is significantly more intricate, with alternating antiferromagnetic 1D chains of the organic BEDT-TTF + radical, connected through weak antiferromagnetic interactions with the CuCl 4 2- ions. Combination of experiment and theory allowed us to unambiguously determine and quantify the leading magnetic interactions in the system. The density-of-states curves confirm the semiconductor nature of the system and the dominant organic contribution of the valence and conduction band edges. This general and combined approach appears to be fundamental in order to properly understand the magnetic structure of these complex materials, where experimental data can actually be fitted from a variety of models and parameters.

  18. Nano-TiCl4.SiO2: A Versatile and Efficient Catalyst for Synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes

    OpenAIRE

    B. F. Mirjalili; A. Bamoniri; L. Zamani

    2013-01-01

    Nano-silica supported titanium tetrachloride (TiCl4.SiO2) was prepared and used as an acid catalyst for the 14-aryl or alkyl-14H-dibenzo[a,,j]xanthenesreaction under solvent-free conditions. Compared to the classical 14-aryl or alkyl-14H-dibenzo[a,j]xanthenesreaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional groups and short reaction times.

  19. Mechanistic study on the fluorination of K[B(CN)4] with ClF enabling the high yield and large scale synthesis of K[B(CF3)4] and K[(CF3)3BCN].

    Science.gov (United States)

    Bernhardt, Eduard; Finze, Maik; Willner, Helge

    2011-10-17

    The fluorination of K[B(CN)(4)] with ClF is studied by millimolar test reactions in aHF and CH(2)Cl(2) solution and by subsequent identification of intermediates such as B-CF═NCl, B-CF(2)-NCl(2), and B-CF(3) species as well as NCl(3) by (19)F, (11)B NMR, and Raman spectroscopy, respectively. At first one cyano group of K[B(CN)(4)] is converted fast into a CF(3) group, and with increasing fluorination the reaction becomes slower and several intermediates could be observed. On the basis of these results, a synthesis was developed for K[B(CF(3))(4)] on a 0.2 molar scale by treatment of K[B(CN)(4)] diluted in aHF with ClF. The course of the reactions was followed by (i) monitoring the vapor pressure inside the reactor, (ii) observing the heat dissipation during ClF uptake, and (iii) measuring the volume of the released nitrogen gas. Since the fluorination of the last cyano group proceeds very slowly, the selective synthesis of K[(CF(3))(3)BCN] on a 0.2 molar scale is possible, as well. The analysis of the mechanisms, thermodynamics, and kinetics of the fluorination reactions is supported by density functional theory (DFT) calculations.

  20. The FI-SDW formation in (TMTSF)2ClO4 investigated in the infrared

    International Nuclear Information System (INIS)

    Gerrits, A.M.; Janssen, T.J.B.M.; Brooks, J.S.; Wittlin, A.; Perenboom, J.A.A.J.; Bentum, P.J.M. van

    1993-01-01

    From a magneto-optical study on (TMTSF) 2 ClO 4 we determine the SDW gap as a function of magnetic field and temperature. The transition temperatures found for the resolved FI-SDW subphases mimic the established phase diagram. Furthermore, the data confirm the existence of a collective excitation of the SDW condensate at relatively high frequency, which implies that this mode is pinned rather strongly to the lattice. In addition, we observed an interesting relaxation effect near the N=0 phase transition. (orig.)

  1. An efficient and green method for regio- and chemo-selective Friedel–Crafts acylations using a deep eutectic mixture ([CholineCl][ZnCl2]3)

    DEFF Research Database (Denmark)

    Hoang, Tran Phuong; Nguyen, Hai Truong; Hansen, Poul Erik

    2016-01-01

    [CholineCl][ZnCl2]3, a deep eutectic solvent between choline chloride and ZnCl2, has been used as a dual function catalyst and green solvent for the Friedel–Crafts acylation of aromatic compounds instead of using the moisture-sensitive Lewis acids and volatile organic solvents. The reactions...... are performed with high yields under microwave irradiation with short reaction times for the synthesis of ketones. Interestingly, indole derivatives are regioselectively acylated in the 3-position under mild conditions with high yields without NH protection. Three new ketone products are synthesized. [Choline......Cl][ZnCl2]3 is easily synthesized from choline chloride and zinc chloride at a low cost, with easy purification and environmentally benign compounds. [CholineCl][ZnCl2]3 can be reused up to five times without loss of catalytic activity, making it ideal in industrial processes....

  2. Effect of MgCl2 addition on the sintering behavior of MgAl2O4 spinel and formation of nano-particles

    Directory of Open Access Journals (Sweden)

    Mohammadi F.

    2014-01-01

    Full Text Available In this paper, the effect of MgCl2 addition on the sintering behavior of MgAl2O4 spinel produced via oxide mixture method was investigated. For this reason, the stoichiometric mixture of magnesite and calcined alumina as raw materials was calcined at 1100°C. The calcined mixture was milled, pressed and then, fired at 1300 and 1500°C after addition of various amounts of MgCl2. Besides, the physical properties, phase composition and microstructure of fired samples were investigated. The results showed that MgCl2 addition has great effect on the densification and particle size of spinel. Besides, MgCl2 addition increases the amount of spinel phase at all firing temperatures. Due to the decomposition of MgCl2 and then formation of ultra-fine MgO particles, the nano-sized spinel is formed on the surface of the larger spinel particles.

  3. Response of Eucalyptus occidentais to water stress induced by NaCl

    Energy Technology Data Exchange (ETDEWEB)

    Itai, C.

    1978-01-01

    Eucalyptus occidentalis plants were exposed to NaCl in their culture solution for various time. Determination of cytokinin, abscisic acid, /sup 14/C leucine incorporation of E. occidentalis, a xerophyte, does not differ from the response of mesophytes to such treatments. 13 references, 1 figure, 4 tables.

  4. Toxicity and carcinogenicity of acidogenic or alkalogenic diets in rats; effects of feeding NH4Cl, KHCO3 or KCl

    NARCIS (Netherlands)

    Lina, B.A.R.; Kuijpers, M.H.M.

    2004-01-01

    The effects of diet-induced acid-base disturbances were examined in 4-week, 13-week and 18-month toxicity studies, and in a 30-month carcinogenicity study. Rats were fed a natural ingredient diet (controls), supplemented with 2% or 4% KHCO3 (base-forming diets), or with 1% or 2.1% NH4Cl

  5. Oxidation of substituted alkyl radicals by IrCl62-, Fe(CN)63-, and MnO4- in aqueous solution. Electron transfer versus chlorine transfer from IrCl62-

    International Nuclear Information System (INIS)

    Steenken, S.; Neta, P.

    1982-01-01

    Alkyl radicals substituted at C/sub α/ by alkyl, carboxyl, hydroxyl, alkoxyl, and chlorine react in aqueous solutions with Ir/sup IV/Cl 6 2- to yield Ir(III) species. In the case of substitution by hydroxyl and alkoxyl, the rate constants are in the diffusion-controlled range ((4-6) x 10 9 M -1 s -1 ) and the reaction proceeds by electron transfer. In the case of ethyl, methyl, carboxymethyl, and chloromethyl radicals the rate constants range from 3.1 x 10 9 for ethyl to 2.8 x 10 7 M -1 s -1 for trichloromethyl and the reaction proceeds by chlorine transfer from IrCl 6 2- to the alkyl radical. With isopropyl and tert-butyll radicals the reaction proceeds by both electron and chlorine transfer. Alkyl radicals also react with Fe(CN) 6 3- . The rate constants increase strongly with increasing alkylation at C/sub α/ from 5 x 10 6 for methyl to 3.6 x 10 9 M -1 s -1 for tert-butyl, indicating that the transition state for the reaction is highly polar. Rate constants for reaction of MnO 4 - with alkyl radicals are of the order 10 9 M -1 s -1 . 4 figures, 1 table

  6. Synthesis of Fulvic Acid-Coated Magnetite (Fe3O4–FA and Its Application for the Reductive Adsorption of [AuCl4]–

    Directory of Open Access Journals (Sweden)

    Philip Anggo Krisbiantoro

    2017-11-01

    Full Text Available Fulvic acid-coated magnetite (Fe3O4–FA has been synthesized through coprecipitation method using NH4OH. Synthesis conducted by cheap and environmentally friendly preparation used iron salts and extracted fulvic acid (FA from Peat soil of Rawa Pening, Central Java, Indonesia. Characterization using FT–IR indicated that the coating of FA on Fe3O4 occurred through the formation of chemical bond between iron of Fe3O4 and carboxyl group of FA. The XRD measurement indicated that coated Fe3O4 successfully dispersed in smaller size than uncoated Fe3O4, i.e. from 16.67 to 14.84 nm for Fe3O4 and Fe3O4–FA, respectively. Synthesized Fe3O4–FA has pHPZC 6.37 and stable at pH > 3.0. The extracted FA has total acidity 866.61 cmol kg–1, –COOH content 229.77 cmol kg–1 and –OH content 636.84 cmol kg–1. Fe3O4–FA has total acidity 494.86 cmol kg–1, –COOH content 67.80 cmol kg–1 and –OH content 427.06 cmol kg–1. The adsorption rate constant (k of [AuCl4]– on Fe3O4–A according to the Ho kinetic model was 8006.53 g mol–1 min–1. The adsorption capacity (qmax according to Langmuir isotherm model was 1.24 × 10–4 mol g–1. The presence of reduction towards the adsorbed [AuCl4]– was shown by the appearance of peaks at 2θ: 37.41; 43.66; 64.25, and 76.67° in the XRD diffractogram.

  7. Determination of the Np(IV)-Np(III) normal potential in fused LiCl-CsCl (55-45%) by absorption spectrophotometry

    International Nuclear Information System (INIS)

    Lysy, R.; Duyckaerts, G.

    1977-01-01

    The following reaction Np 4+ + 1/2 H 2 + Cl - reversible Np 3+ + HCl has been studied quantitatively in fused LiCl-CsCl (55-45 mol %) in the temperature range of 450-600 0 C, by visible and near IR absorption spectrophotometry. At 450 deg C, the equilibrium constant equals K = 7.4 atmsup(1/2). The mean values of ΔH and ΔS in the temperature range of 450-600 deg C are: ΔH = (35.6+-10.3) kJ mol -1 , ΔS=(65.5+-13.0)J mol -1 K -1 [fr

  8. Highly Productive Application Development with ViennaCL for Accelerators

    Science.gov (United States)

    Rupp, K.; Weinbub, J.; Rudolf, F.

    2012-12-01

    The use of graphics processing units (GPUs) for the acceleration of general purpose computations has become very attractive over the last years, and accelerators based on many integrated CPU cores are about to hit the market. However, there are discussions about the benefit of GPU computing when comparing the reduction of execution times with the increased development effort [1]. To counter these concerns, our open-source linear algebra library ViennaCL [2,3] uses modern programming techniques such as generic programming in order to provide a convenient access layer for accelerator and GPU computing. Other GPU-accelerated libraries are primarily tuned for performance, but less tailored to productivity and portability: MAGMA [4] provides dense linear algebra operations via a LAPACK-comparable interface, but no dedicated matrix and vector types. Cusp [5] is closest in functionality to ViennaCL for sparse matrices, but is based on CUDA and thus restricted to devices from NVIDIA. However, no convenience layer for dense linear algebra is provided with Cusp. ViennaCL is written in C++ and uses OpenCL to access the resources of accelerators, GPUs and multi-core CPUs in a unified way. On the one hand, the library provides iterative solvers from the family of Krylov methods, including various preconditioners, for the solution of linear systems typically obtained from the discretization of partial differential equations. On the other hand, dense linear algebra operations are supported, including algorithms such as QR factorization and singular value decomposition. The user application interface of ViennaCL is compatible to uBLAS [6], which is part of the peer-reviewed Boost C++ libraries [7]. This allows to port existing applications based on uBLAS with a minimum of effort to ViennaCL. Conversely, the interface compatibility allows to use the iterative solvers from ViennaCL with uBLAS types directly, thus enabling code reuse beyond CPU-GPU boundaries. Out-of-the-box support

  9. Soft modes and phase transition at 74K in Rb2ZnCl4

    International Nuclear Information System (INIS)

    Mashiyama, Hiroyuki; Sugimoto, Kousirou; Oohara, Yasuaki; Yoshizawa, Hideki.

    1993-01-01

    The orthorhombic to monoclinic transition at T m = 73.5K in Rb 2 ZnCl 4 is investigated by means of neutron scattering at JRR-3M. The superlattice reflections observed below T m increases as (T m - T) 2β with β = 0.38. The dispersion relations of low energy are determined both above and below T m . The softening of phonon frequency is observed around the Brillouin zone-boundary. The square of the energy transfer of the soft phonon obeys a linear relation on temperature. (author)

  10. Nano-TiCl4.SiO2: A Versatile and Efficient Catalyst for Synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes

    Directory of Open Access Journals (Sweden)

    B. F. Mirjalili

    2013-12-01

    Full Text Available Nano-silica supported titanium tetrachloride (TiCl4.SiO2 was prepared and used as an acid catalyst for the 14-aryl or alkyl-14H-dibenzo[a,,j]xanthenesreaction under solvent-free conditions. Compared to the classical 14-aryl or alkyl-14H-dibenzo[a,j]xanthenesreaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional groups and short reaction times.

  11. Inhibition effect of 4-amino-antipyrine on the corrosion of copper in 3 wt.% NaCl solution

    Energy Technology Data Exchange (ETDEWEB)

    Hong Song; Chen Wen; Luo Hongqun [Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Li Nianbing, E-mail: linb@swu.edu.cn [Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer 4-Amino-antipyrine (AAP) has inhibition behaviour for copper corrosion in 3.0 wt.% NaCl. Black-Right-Pointing-Pointer AAP acted as a mixed-type inhibitor with anodic predominance. Black-Right-Pointing-Pointer Adsorption of AAP on the copper surface obeys the Langmuir isotherm. Black-Right-Pointing-Pointer Quantum chemical calculations were applied to explain the experimental results. - Abstract: The effect of 4-amino-antipyrine (AAP) on the corrosion of copper in 3.0 wt.% NaCl was investigated using weight loss, potentiodynamic polarisation, and electrochemical impedance spectroscopy. The results revealed that AAP acts as a mixed-type inhibitor with more pronounced effect on anodic domain and the inhibition efficiency decreases with increasing the temperature. The adsorption of AAP was found to obey the Langmuir isotherm. Surface characterisation was performed using scanning electron microscope and Fourier transform infrared spectrometer. Quantum chemical calculations show that AAP has large negative charge in nitrogen and oxygen atoms, which facilitates the adsorption of AAP on the copper surface.

  12. Production of barium molybdate and tungstate on the base of ternary reciprocal Na, Ba long Cl, EhO4 (Eh - Mo, W) systems

    International Nuclear Information System (INIS)

    Garkushin, I.K.; Sechnoj, A.I.; Dibirov, M.A.; Trunin, A.S.

    1984-01-01

    Possibilities of the syntnesis of barium molybdate and tungstate on the base of ternary reciprocal Na, Ba parallel Cl, EhO 4 (Eh=Mo, W) system state diagrams are under study. It is shown that on the basis of these reciprocal state diagrams syntnesis of not only BaO 4 but also of other suhstances is possible. Purity of obtained chemical agents is basically dependent on qualification of initial components. Synthesis temperature is decreased and time is reduced as compared to other known methods. For substance synthesis, state diagrams examination (reaction type confirmation and component crystallization fields separation from compound crystallization fields) is necessary along with the calculation of the conventional thermochemical effect

  13. Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis

    KAUST Repository

    Credendino, Raffaele

    2017-09-18

    Adducts of TiCl4 with Lewis bases used as internal or external donors in heterogeneous Ziegler-Natta (ZN) catalysis represents a fundamental interaction contributing to the final composition of MgCl2 supported ZN-catalysts. This study presents the accurate experimental evaluation, from titration calorimetry, of the formation enthalpy of TiCl4 adducts with 15 Lewis bases of industrial interests. In addition, we report accurate energies of association of TiCl4 with the same Lewis bases from calculations at the DLPNO-CCSD(T) level of theory. These accurate experimental and theoretical association values are compared with selected methods based on density functional theory (DFT) in combination with popular continuum solvation models. Calculations suggest that the PBE-D3, and M06 functionals in combination with a triple-ζ plus polarization quality basis set provide the best performance when the basis set superposition error (BSSE) is not removed from the association energies. Cleaning the association energies by the BSSE with the counterpoise protocol suggests the B3LYP-D3, TPSS-D3 and M06L as the best performing functionals. Introducing solvent effects with the PCM and SMD continuum solvation models allows comparing the DFT based association enthalpies with the experimental values obtained from titration calorimetry. Both solvation models in combination with the PBE-D3, PBE0-D3, B3LYP-D3, TPSS-D3, M06L, and M06 functionals provide association enthalpies close to the experimental values with MUEs in range 10 – 15 kJ/mol.

  14. Two ternary mixed-anion chlorides with divalent europium: Eu{sub 2}H{sub 3}Cl and Eu{sub 7}F{sub 12}Cl{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Reckeweg, Olaf [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); DiSalvo, Francis J. [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Wolf, Sarah; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

    2014-06-15

    Dark ruby-red, transparent, triangular plate-shaped single crystals of Eu{sub 2}H{sub 3}Cl and colorless, transparent, needle-shaped single crystals of Eu{sub 7}F{sub 12}Cl{sub 2} were obtained by solid-state reactions of Eu, NaH, NaCl, and Na (2:4:1:2 molar ratio) or Eu, EuCl{sub 3}, and LiF (1:1:4 molar ratio), respectively, in silica-jacketed tantalum ampoules at 900 C for 13 h. Eu{sub 2}H{sub 3}Cl crystallizes isotypically to Ba{sub 2}H{sub 3}X (X = Cl, Br, I) in the trigonal space group P anti 3m1 (no. 164) with lattice parameters a = 409.67(4) and c = 696.18(7) pm, whereas Eu{sub 7}F{sub 12}Cl{sub 2} crystallizes isotypically to Ba{sub 7}F{sub 12}Cl{sub 2} or Sr{sub 7}H{sub 12}Cl{sub 2} in the hexagonal space group P anti 6 (no. 174) with lattice parameters a = 1002.31(5) and c = 392.54(2) pm. Both compounds contain Eu{sup 2+} cations with coordination numbers as high as nine (Eu{sub 7}F{sub 12}Cl{sub 2}) and ten (Eu{sub 2}H{sub 3}Cl) with respect to the halide anions (F{sup -} or H{sup -} and Cl{sup -}). The structural results are corroborated by EUTAX and MAPLE calculations on both ternary mixed-anion europium(II) chlorides in comparison to these for related binary and ternary compounds with divalent europium. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Chemical effects of nuclear transformations in mixed crystals. 7. Chemical effects of the 35Cl(n,γ)36Cl nuclear reaction in K2ReCl6-K2ReBr6 mixed crystals

    International Nuclear Information System (INIS)

    Mueller, H.; Diefallah, E.H.M.; Martin, S.

    1981-01-01

    The solid-state reactions occurring during the moderation of recoiling 36 Cl, produced by the (n,γ) reaction, have been studied in K 2 ReCl 6 -K 2 ReBr 6 mixed crystals. The main reaction products are Re 36 ClCl 5 2- , Re 36 ClBr 5 2- , and 36 Cl - , but the more intimately mixed species Re 36 ClCl/sub n/Br/sub 5-n/ 2- (n = 1, 2, 3, 4) are found in significant amounts. The production of the different recoil-labeled species can be explained by elementary impact models: 6% of the recoils do not leave their original lattice site (primary retetion); between 6% and 23%, dependent upon the mixed-crystal composition, appear as interstitials; 31 to 48% give rise to direct displacement reactions of one halide ligand; and 40% produce larger disruption by substitution of at least two halide ligands. The results have been compared with Roessler's 38 Cl recoil experiments

  16. Esplacnología clínica

    OpenAIRE

    Sánchez Hernández, Fernando; Santos del Rey, Fernando

    2008-01-01

    Materiales de clase: 1.Tema 1.Asistencia 1; 2.Tema 2: Asistencia 2; 3. Tema 3: Reanimación cardiopulmonar; 4. Tema 4: Manejo C. RCP. Cohibir-fluidos-shock. Lesiones con riesgo inminente de muerte; 5. Tema 5: Manejo D. Exploración neurológica. Escala de Glasgow; 6. Tema 6: Ejercicio de Triage; 7. Tema 7: Casos clínicos reales; 8. Tema 8: Material de emergencias en atención primaria. Esta asignatura tiene como objetivo aplicar, mediante casos clínicos enfocados hacia Enfermería, criterios y ...

  17. Comparison of effects of ATP-MgCl2 and adenosine-MgCl2 on renal function following ischemia

    International Nuclear Information System (INIS)

    Sumpio, B.E.; Hull, M.J.; Baue, A.E.; Chaudry, I.H.

    1987-01-01

    ATO-MgCl 2 administration had been shown to accelerate the recovery of renal function following warm ischemia. However, since the major breakdown product of ATP is adenosine, the relative contribution of ATP vs. adenosine in improving renal function following ischemia remains to be determined. To study this, kidneys were subjected to 45 min of normothermic ischemia and then perfused at 100 mmHg with oxygenated Krebs-HCO 3 buffer containing albumin, [ 3 H]inulin, substrates, and either 0.3 mM ATP-MgCl 2 or adenosine-MgCl 2 for 110 min. Perfusate and timed urine samples were collected and analyzed for radioactivity and [Na + ]. The functional parameters indicated that although adenosine-MgCl 2 treatment provided a transient improvement, it failed to provided a sustained improvement in renal function or attain control valued compared with ATP-MgCl 2 treatment. Thus, the salutary effects of ATP-MgCl 2 following warm ischemia in the kidney are not mediated by adenosine

  18. Demonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO4-)

    Energy Technology Data Exchange (ETDEWEB)

    Hatzinger, Paul B. [Shaw Environmental, Inc., Lawrenceville, NJ (United States); Eres, Gyula [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Gu, Baohua [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jubb, Aaron M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-03-01

    Costs for environmental analysis and monitoring are increasing at a rapid rate and represent a significant percentage of the total and future remedial expenses at many U.S. Department of Defense (DoD) contaminated sites. It has been reported that about 30 to 40% of the remediation budget is usually spent on long-term monitoring (LTM), of which a large percentage represents laboratory analytical costs. Energetics such as perchlorate (ClO4-) are among the most frequently detected contaminants in groundwater and surface water at or near military installations due to their persistence and mobility. Currently, the standard protocol entails collecting samples in the field, packaging them, and shipping them overnight to a designated laboratory for analysis. This process requires significant sample preparation and handling, and analytical results may not be available for several days to weeks. In this project, we developed and demonstrated a portable Raman sensor based on surface enhanced Raman scattering (SERS) technology to detect ClO4- in contaminated water. We summarize major accomplishments as follows: • A SERS sensor based on elevated gold (Au) nano-ellipse dimer architectures was designed and developed for ClO4- with a detection limit of ~10-6 M (or 100 μg/L); The performance of these sensors was evaluated and optimized through variation of their geometric characteristics (i.e., dimer aspect ratio, dimer separation, etc.). • Large-scale commercial production of SERS substrate sensors via nanoimprinting by Nanova Inc. and Nanoimprint lithography (NIL) technology was successfully demonstrated. This is a substantial step forward toward the commercialization of the SERS sensors and may potentially lead to significantly reduced fabrication costs of SERS substrates. • Commercially produced SERS sensors were demonstrated to detect ClO4- at levels above 10-6

  19. Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O.

    Science.gov (United States)

    Babić-Ivancić, Vesna; Kontrec, Jasminka; Brecević, Ljerka; Kralj, Damir

    2006-10-01

    The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.

  20. Radiative transitions for the Cs2NaErCl6 elpasolite crystal. II.- Vibronic intensities for the emissions |(4S3/2Γ8]→4I15/2Γ] in the Cs2NaErCl6

    International Nuclear Information System (INIS)

    Acevedo, R.; Escudero, M; Navarro, G; Meruane, T

    2002-01-01

    We have recently reported explicit vibronic intensity calculations for the emissions |( 4 I 15/ ) Γ k ]→|( 4 I 13/2 )Γ l ] of Er 3+ in the Cs 2 NaErCl 6 elpasolite system. The experimental evidence indicates than over an energy range of about 400cm -1 , a substantial number of transitions take place (about one hundred excitations; twenty five of them are magnetic dipole allowed whereas the remaining seventy five are vibronically allowed in character). The spectrum is very complex indeed and the superposition of various spectral features is most likely to occur and this represents a serious challenge to theoreticians. For this system, there is solid evidence which indicates that for the |( 4 S 3/2 )Γ 8 ]→|( 4 I 15/2 )Γ] transitions, where Γ=Γ 6 , Γ 7 , Γ 8 a , Γ 8 b , Γ 8 c , the most intense features of the spectrum are assigned to one photon electric-dipole vibronic excitations, involving the v 3 (stretching; τ 1u ), v 4 (bending; τ 1u ) and v 6 (bending; τ 2u ) moiety modes of the ErCl 3- 6 clusters in the crystal. It is the aim of this paper to explain on both a qualitative and a quantitative basis the rather unexpected high intensity with these type of transitions for which the static selection rule ΔJ=6 is operative. To achieve our goals, we introduce an intensity path and/or mechanism, according to the following radiative decay cascade: |( S 3/2 )Γ 8 ]→|( 4 I 11/2 )Γ']→|( 4 I 15/2 )]. It is shown that when this mechanism is adopted, then the calculated overall spectral intensity due to the three false origins (v 3 , v 4 , v 6 ) is in a fairly good agreement with experiment (author)

  1. The assessment of the energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-Hexaazaisowurtzitane (CL-20) degradability in soil

    International Nuclear Information System (INIS)

    Strigul, Nikolay; Braida, Washington; Christodoulatos, Christos; Balas, Wendy; Nicolich, Steven

    2006-01-01

    CL-20 is a relatively new energetic compound with applications in explosive and propellant formulations. Currently, information about the fate of CL-20 in ecological systems is scarce. The aim of this study is to evaluate the biodegradability of CL-20 in soil environments. Four soils were used where initial CL-20 concentrations (above water solubility) ranged from 125 to 1500 mg of CL-20 per kg dry soil (corresponding to the concentrations derived from unexploded ordnance, low order detonation, or manufacturing spills). CL-20 appears to be biodegradable in soil under anaerobic conditions, and additions of organic substrates can substantially accelerate this process. However, CL-20 is not degraded in soil under aerobic conditions kept in the dark at temperatures up to 30 deg. C without organic amendments. Additions of starch or cellulose promote the biodegradation of CL-20 under aerobic conditions. Soil microbial community mediated biodegradation and plant uptake appears to enhance CL-20 biodegradation, the latter suggesting a possible route for CL-20 to entry in the food chain. - Biodegradation and plant uptake suggest possible entry of CL-20 into food chain

  2. Metal-ligand delocalization and spin density in the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} molecules: Some insights from wave function theory

    Energy Technology Data Exchange (ETDEWEB)

    Giner, Emmanuel, E-mail: gnrmnl@unife.it; Angeli, Celestino, E-mail: anc@unife.it [Dipartimento di Scienze Chimiche e Famaceutiche, Universita di Ferrara, Via Fossato di Mortara 17, I-44121 Ferrara (Italy)

    2015-09-28

    The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that each valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.

  3. Luminescence of the SrCl2:Pr crystals under high-energy excitation

    International Nuclear Information System (INIS)

    Antonyak, O.T.; Voloshinovskii, A.S.; Vistovskyy, V.V.; Stryganyuk, G.B.; Kregel, O.P.

    2014-01-01

    The present research was carried out in order to elucidate the mechanisms of energy transfer from the crystal lattice to Pr 3+ ions in SrCl 2 . The luminescence excitation and emission spectra as well as luminescence kinetics of the SrCl 2 :Pr single crystals containing 0.2 mol% Pr were investigated at 300 and 10 K using the vacuum ultraviolet (VUV) synchrotron radiation. The X-ray excited luminescence spectra of the SrCl 2 :Pr (C Pr =0.2 and 0.5 mol%) and SrCl 2 :Pr, K (C Pr =1.5 mol%; C K =1.5 mol%) crystals were studied at 294 and 80 K. Under optical excitation of the samples in the Pr 3+ absorption bands, there were observed five fast ultraviolet emissions assigned to the 4f 1 5d→4f 2 transitions, and two long-wave bands corresponding to the f–f transitions. Furthermore, the intrinsic emission bands of SrCl 2 were observed at 10 K. The X-ray excited luminescence spectrum of the SrCl 2 :Pr crystal containing 0.2 mol% Pr, besides intrinsic emission band near 400 nm, has got a long-wave band at about 490 nm of the Pr 3+ centers. There were not observed any emission bands of the Pr 3+ centers corresponding to the 4f 1 5d–4f 2 transitions in the X-ray excited luminescence spectrum of the SrCl 2 :Pr crystal. The possible mechanisms of energy transfer from the SrCl 2 matrix to the Pr 3+ centers are discussed. -- Highlights: • Spectral-luminescent properties of SrCl 2 :Pr have been investigated. • The identification of emission 4f–4f and 5d–4f bands of Pr 3+ ions was performed. • Adding of potassium prevents clustering of the Pr 3+ centers in the SrCl 2 :Pr, K crystals. • Under X-ray excitation at 80–300 K only Pr 3+ 4f–4f and intrinsic emission is observed

  4. Acrylamide and 5-hydroxymethylfurfural formation during baking of biscuits: NaCl and temperature-time profile effects and kinetics

    NARCIS (Netherlands)

    Fels, van der H.J.; Capuano, E.; Nguyen, H.T.; Mogol, B.A.; Kocadagli, T.; Goncuoglu Tas, N.; Hamzalioglu, A.; Boekel, van M.A.J.S.; Gokmen, V.

    2014-01-01

    The present study aimed to investigate the effect of recipe and temperature–time on the formation of acrylamide and 5-hydroxymethylfurfural (HMF) during biscuit baking. Baking experiments were performed with biscuits of two different recipes, with and without NaCl, at 180 °C, 190 °C and 200 °C.

  5. Cl- channels in apoptosis

    DEFF Research Database (Denmark)

    Wanitchakool, Podchanart; Ousingsawat, Jiraporn; Sirianant, Lalida

    2016-01-01

    A remarkable feature of apoptosis is the initial massive cell shrinkage, which requires opening of ion channels to allow release of K(+), Cl(-), and organic osmolytes to drive osmotic water movement and cell shrinkage. This article focuses on the role of the Cl(-) channels LRRC8, TMEM16/anoctamin......, and cystic fibrosis transmembrane conductance regulator (CFTR) in cellular apoptosis. LRRC8A-E has been identified as a volume-regulated anion channel expressed in many cell types. It was shown to be required for regulatory and apoptotic volume decrease (RVD, AVD) in cultured cell lines. Its presence also......(-) channels or as regulators of other apoptotic Cl(-) channels, such as LRRC8. CFTR has been known for its proapoptotic effects for some time, and this effect may be based on glutathione release from the cell and increase in cytosolic reactive oxygen species (ROS). Although we find that CFTR is activated...

  6. High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

    Science.gov (United States)

    Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

    2016-07-21

    In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

  7. Rationally designed chimeric peptide of met-enkephalin and FMRFa-[D-Ala2,p-Cl-Phe4]YFa induce multiple opioid receptors mediated antinociception and up-regulate their expression.

    Science.gov (United States)

    Vats, Ishwar Dutt; Chaudhary, Snehlata; Sharma, Ahuti; Nath, Mahendra; Pasha, Santosh

    2010-07-25

    The physiological role of NPFF/FMRFa family of peptides appears to be complex and exact mechanism of action of these peptides is not yet completely understood. In same line of scrutiny, another analog of YGGFMKKKFMRFamide (YFa), a chimeric peptide of met-enkephalin and FMRFamide, was rationally designed and synthesized which contain D-alanine and p-Cl-phenylalanine residues at 2nd and 4th positions, respectively i.e., Y-(D-Ala)-G-(p-Cl-Phe)-MKKKFMRFamide ([D-Ala(2), p-Cl-Phe(4)]YFa) in order to achieve improved bioavailability and blood brain barrier penetration. Therefore, present study investigates the possible antinociceptive effect of [D-Ala(2), p-Cl-Phe(4)]YFa on intra-peritoneal (i.p.) administration using tail-flick test in rats followed by its opioid receptor(s) specificity using mu, delta and kappa receptor antagonists. Further, its antinociceptive effect was examined during 6 days of chronic i.p. treatment and assessed effect of this treatment on differential expression of opioid receptors. [D-Ala(2), p-Cl-Phe(4)]YFa in comparison to parent peptide YFa, induce significantly higher dose dependent antinociception in rats which was mediated by all three opioid receptors (mu, delta and kappa). Importantly, it induced comparable antinociception in rats throughout the chronic i.p. treatment and significantly up-regulated the overall expression (mRNA and protein) of mu, delta and kappa opioid receptors. Therefore, pharmacological and molecular behavior of [D-Ala(2), p-Cl-Phe(4)]YFa demonstrate that incorporation of D-alanine and p-Cl-phenylalanine residues at appropriate positions in chimeric peptide leads to altered opioid receptor selectivity and enhanced antinociceptive potency, relative to parent peptide. (c) 2010 Elsevier B.V. All rights reserved.

  8. Dosimetric characteristics and radiation monitoring with CaSO4(Dy):NaCl pellets

    International Nuclear Information System (INIS)

    Kathuria, S.P.; Campos, L.L.; Gordon, A.M.P.L.

    1981-06-01

    CaSO 4 (Dy):NaCl Tl dosimeters, in the form of pellets, are used in the field for a period of one month. Before using these pellets for environmental and personnel radiation monitoring some of the important dosimetric characteristics like fading reusability and effect of ambient light are investigated and described. The pellets are used with plastic and lead filters for personnel and environmental radiation monitoring and the results obtained with the lead filters are in good agreement with those of the energy independent LiF dosimeters. A new combination of plastic, aluminium and lead filters is suggested for dose measurements in a mixed field of X, gamma and beta radiations. (Author) [pt

  9. Separation of CsCl and SrCl_2 from a ternary CsCl-SrCl_2-LiCl via a zone refining process for waste salt minimization of pyroprocessing

    International Nuclear Information System (INIS)

    Shim, Moonsoo; Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon; Lee, Jong Hyeon

    2016-01-01

    The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl_2 salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The k_e_f_f of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively. - Highlights: • The LiCl-CsCl-SrCl_2 salt ingot was purified by zone refining technique to minimize waste salt. • The concentration distribution of Cs and Sr were analyzed by mass transfer equation. • The decontamination factors of Cs and Sr were 1600 and 450 respectively in case of 60% of recovery yield.

  10. Comment on 'Effects of hydrogen dilution on deposition process of nano-crystalline silicon film by SiCl4/H2 plasma'

    International Nuclear Information System (INIS)

    Tanarro, Isabel

    2007-01-01

    In a recent paper, Wang et al (2006 J. Phys. D: Appl. Phys. 39 3030) have reported the effects of hydrogen dilution ratio on the relative densities of SiCl n (n = 0-2) radicals in a SiCl 4 /H 2 plasma generated in a RF low pressure discharge. This comment argues that the radical detection method proposed and used by Wang et al is not appropriate to estimate radical concentrations and that the experimental results obtained with it consequently seem to be unreliable. (comment)

  11. 36Cl in shallow, perched aquifers from central Indiana

    Science.gov (United States)

    Vogt, S.; Elmore, D.; Fritz, S. J.

    1994-06-01

    36Cl/Cl ratios and chloride concentrations were measured in several shallow, perched aquifers situated within glacial till in west-central Indiana (USA). Most of these aquifers show 36Cl/Cl ratios which have to be attributed to admixed 36Cl from nuclear weapons tests in the 1950s and 1960s. Two wells from Purdue's Horticultural Farm tap perched aquifers uninfluenced by anthropogenic sources of chloride, and their 36Cl/Cl ratios are comparable with ratios measured in modern, local precipitation. As such, the chloride contents of these wells (1 to 3 ppm) reflect evaporative concentration of the precipitation's chloride contents (averaging 0.17 ppm) in the vadose zone. Since one of these two wells (HA-2a) does not contain any detectable tritium, we conclude that recent pre-bomb 36Cl/Cl ratios and 36Cl deposition in precipitation are quite similar to those in modern precipitation. We attribute the slight 36Cl excess of about 20% in both of these wells largely to 36Cl deposition associated with dry fall-out. As much as 2 × 10 4 at. 36Cl/cm 2 might reach the surface via dry fall-out annually.

  12. Electrical properties and conduction mechanism of [C2H5NH3]2CuCl4 compound

    Science.gov (United States)

    Mohamed, C. Ben; Karoui, K.; Jomni, F.; Guidara, K.; Rhaiem, A. Ben

    2015-02-01

    The [(C2H5)NH3]2CuCl4 compound was prepared and characterized by several technique: the X-ray powder diffraction confirms the purity of the synthetized compound, the differential scanning calorimetric show several phase transitions at 236 K, 330 K, 357 K and 371 K, the dialectical properties confirms the ferroelectric-paraelectric phase transition at 238 K, which is reported by V. Kapustianyk et al. (2007) [1]. The two semi-circles observed in the complex impedance identify the presence of the grain interior and grain boundary contributions to the electrical response in this material. The equivalent circuit is modeled by a combination series of two parallel RP-CPE circuits. The temperature dependence of the alternative current conductivity (σg) and direct current conductivity (σdc) confirm the observed transitions in the calorimetric study. The (AC) electrical conduction in [(C2H5)NH3]2CuCl4 was studied by two processes that can be attributed to a hopping transport mechanism: the non-overlapping small polaron tunneling (NSPT) model in phase III and the correlated barrier hopping (CBH) model in phases I, II, IV, V and VI.

  13. Adjustment of Conduction Band Edge of Compact TiO2 Layer in Perovskite Solar Cells Through TiCl4 Treatment.

    Science.gov (United States)

    Murakami, Takurou N; Miyadera, Tetsuhiko; Funaki, Takashi; Cojocaru, Ludmila; Kazaoui, Said; Chikamatsu, Masayuki; Segawa, Hiroshi

    2017-10-25

    Perovskite solar cells (PSCs) without a mesoporous TiO 2 layer, that is, planar-type PSCs exhibit poorer cell performance as compared to PSCs with a porous TiO 2 layer, owing to inefficient electron transfer from the perovskite layer to the compact TiO 2 layer in the former case. The matching of the conduction band levels of perovskite and the compact TiO 2 layer is thus essential for enhancing PSC performance. In this study, we demonstrate the shifting of the conduction band edge (CBE) of the compact TiO 2 layer through a TiCl 4 treatment, with the aim of improving PSC performance. The CBE of the compact TiO 2 layer was shifted to a higher level through the TiCl 4 treatment and then shifted in the opposite direction, that is, to a lower level, through a subsequent heat treatment. These shifts in the CBE were reflected in the PSC performance. The TiCl 4 -treated PSC showed an increase in the open-circuit voltage of more than 150 mV, as well as a decrease of 100 mV after being heated at 450 °C. On the other hand, the short-circuit current decreased after the treatment but increased after heating at temperatures higher than 300 °C. The treated PSC subjected to subsequent heating at 300 °C exhibited the best performance, with the power conversion efficiency of the PSC being 17% under optimized conditions.

  14. Role of the d -d interaction in the antiferromagnetic phase of λ -(BEDT-STF ) 2FeCl4

    Science.gov (United States)

    Minamidate, Takaaki; Shindo, Hironori; Ihara, Yoshihiko; Kawamoto, Atsushi; Matsunaga, Noriaki; Nomura, Kazushige

    2018-03-01

    Magnetic susceptibility and proton nuclear magnetic resonance (1H-NMR ) measurements were performed for the quasi-two-dimensional π -d interacting system λ -(BEDT-STF ) 2FeCl4 at ambient pressure. Magnetic susceptibility arising from the 3 d spins of the FeCl4 anion show an anisotropy at low temperature and its temperature dependence for the external field parallel to the c axis is described as a broad peak structure at 8 K. A sharp peak in the temperature dependence of T1-1 associated with the antiferromagnetic (AF) transition is observed at TAF=16 K, together with the drastic splitting of the NMR spectrum below TAF. The relation between the static susceptibility and the splitting of the NMR shift suggests the existence of the relatively strong d -d AF interaction. These results can be explained by the model considering the AF-coupled d -spin system in the AF long-range-ordered π -spin system. We find that the AF phases in λ -type salts can be universally explained by this model.

  15. Primary retention following nuclear recoil in β-decay: Proposed synthesis of a metastable rare gas oxide ((38)ArO4) from ((38)ClO4(-)) and the evolution of chemical bonding over the nuclear transmutation reaction path.

    Science.gov (United States)

    Timm, Matthew J; Matta, Chérif F

    2014-12-01

    Argon tetroxide (ArO4) is the last member of the N=50 e(-) isoelectronic and isosteric series of ions: SiO4(4-), PO4(3-), SO4(2-), and ClO4(-). A high level computational study demonstrated that while ArO4 is kinetically stable it has a considerable positive enthalpy of formation (of ~298kcal/mol) (Lindh et al., 1999. J. Phys. Chem. A 103, pp. 8295-8302) confirming earlier predictions by Pyykkö (1990. Phys. Scr. 33, pp. 52-53). ArO4 can be expected to be difficult to synthesize by traditional chemistry due to its metastability and has not yet been synthesized at the time of writing. A computational investigation of the changes in the chemical bonding of chlorate (ClO4(-)) when the central chlorine atom undergoes a nuclear transmutation from the unstable artificial chlorine isotope (38)Cl to the stable rare argon isotope (38)Ar through β-decay, hence potentially leading to the formation of ArO4, is reported. A mathematical model is presented that allows for the prediction of yields following the recoil of a nucleus upon ejecting a β-electron. It is demonstrated that below a critical angle between the ejected β-electron and that of the accompanying antineutrino their respective linear momentums can cancel to such an extent as imparting a recoil to the daughter atom insufficient for breaking the Ar-O bond. As a result, a primary retention yield of ~1% of ArO4 is predicted following the nuclear disintegration. The study is conducted at the quadratic configuration interaction with single and double excitations [QCISD/6-311+G(3df)] level of theory followed by an analysis of the electron density by the quantum theory of atoms in molecules (QTAIM). Crossed potential energy surfaces (PES) were used to construct a PES from the metastable ArO4 ground singlet state to the Ar-O bond dissociation product ArO3+O((3)P) from which the predicted barrier to dissociation is ca. 22kcal/mol and the exothermic reaction energy is ca. 28kcal/mol [(U)MP2/6-311+G(d)]. Copyright © 2014

  16. Use of thermodynamic calculation for investigating phase diagram of the ternary system NaCl-PbCl2-NdCl3

    International Nuclear Information System (INIS)

    Kostygov, V.I.; Potemin, S.S.

    1984-01-01

    Thermodynamic calculation of meltability diagram of ternary system NaCl-PbCl 2 -NdCl 3 with the use of literature and experimental data on meltability diagrams of binary systems forming it, as well as data on crystallization heats of the components, has been carried out. Equations are derived under condition of pseudoperfection of the ternary system. 64 mol.% PbCl 2 , 26 mol.% NaCl, 10 mol.% NdCl 3 and average temperature of crystallization 391 deg C correspond to the calculated composition of the ternary eutectics, 49 mol.% PbCl 2 , 35 mol.% NaCl, 16 mol.% NdCl 3 and average temperature of peritectic transformation 416 deg C - to the composition of the ternary peritectic. The results obtained agree well with the experimental data

  17. Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO{sub 4} for lithium ion battery application

    Energy Technology Data Exchange (ETDEWEB)

    Nurhadini,, E-mail: nur-chem@yahoo.co.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Inorganic and Physical Chemistry Research Division, Faculty of Mathematics and Natural Sciences, Institiut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132 (Indonesia)

    2015-09-30

    This study was conducted to determine the effect of cellulose acetate on poly(ethylene oxide)-LiClO{sub 4} membranes as the polymer electrolyte. Cellulose acetate is used as an additive to increase ionic conductivity and mechanical property of polymer electrolyte membranes. The increase the percentage of cellulose acetate in membranes do not directly effect on the ionic conductivity, and the highest ionic conductivity of membranes about 5,7 × 10{sup −4} S/cm was observed in SA/PEO/LiClO{sub 4} membrane with cellulose ratio of 10-25% (w/w). Cellulose acetate in membranes increases mechanical strength of polymer electrolyte membranes. Based on TGA analysis, this polymer electrolyte thermally is stable until 270 °C. The polymer electrolyte membrane prepared by blending the cellulose acetate, poly(ethylene oxide), and lithium chlorate could be potentially used as a polymer electrolyte for lithium ion battery application.

  18. A new 36Cl hydrological model and 36Cl systematics in the Jordan River/Dead Sea system

    International Nuclear Information System (INIS)

    Paul, M.; Fink, D.; Meirav, O.; Kaim, R.

    1986-01-01

    Accelerator mass spectrometry results of 36 Cl for the Jordan River/Dead Sea system show that the amount of chloride leached from rocks ranges from approx. 70% in source springs to >90% in water bodies downstream. Furthermore, the amount of water left after evaporation decreases from approx. 50% in the source springs to 20% in the intermediate Lake Kinneret. In the terminal Dead Sea, 99% of the stable chloride originates from ancient rocks and evaporite formations while approx. 80% of its 36 Cl content is of meteoric origin. Using 36 Cl measurements, the accumulation time of the Dead Sea salt is estimated to be 19,000-25,000 yr. (author)

  19. Studies of the electronic structure and biological activity of chosen 1,4-benzodiazepines by {sup 35}Cl NQR spectroscopy and DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Bronisz, K. [Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan (Poland); Ostafin, M. [Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan (Poland)], E-mail: ostifnqr@amu.edu.pl; Poleshchuk, O. Kh. [Department of Chemistry, Tomsk Pedagogical University, Komsomolskii 75, 634041 Tomsk (Russian Federation); Mielcarek, J. [Faculty of Pharmacy, University of Medical Sciences, Grunwaldzka 6, 60-780 Poznan (Poland); Nogaj, B. [Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan (Poland)

    2006-11-08

    Selected derivatives of 1,4-benzodiazepine: lorazepam, lormetazepam, oxazepam and temazepam, used as active substances in anxiolytic drugs, have been studied by {sup 35}Cl NQR method in order to find the correlation between electronic structure and biological activity. The {sup 35}Cl NQR resonance frequencies ({nu} {sub Q}) measured at 77 K have been correlated with the following parameters characterising their biological activity: biological half-life period (t {sub 0.5}), affinity to benzodiazepine receptor (IC{sub 50}) and mean dose equivalent. The results of experimental study of some benzodiazepine derivatives by nuclear quadrupole resonance of {sup 35}Cl nuclei are compared with theoretical results based on DFT calculations which were carried out by means of Gaussian'98 W software.

  20. SO 2 Phototriggered Crystalline Nanomechanical Transduction of Aromatic Rotors in Tosylates: Rationalization via Photocrystallography of [Ru(NH 3 ) 4 SO 2 X]tosylate 2 (X = pyridine, 3-Cl-pyridine, 4-Cl-pyridine)

    Energy Technology Data Exchange (ETDEWEB)

    Sylvester, Sven O.; Cole, Jacqueline M.; Waddell, Paul G.; Nowell, Harriott; Wilson, Claire

    2014-07-24

    Thermally-reversible solid-state linkage SO2 photoisomers of three complexes in the [Ru(NH3)4SO2X]tosylate2 family are captured in their metastable states using photocrystallography, where X = pyridine (1), 3-Cl-pyridine (2) and 4-Cl-pyridine (3). This photoisomerism only exists in the single-crystal form; accordingly, the nature of the crystalline environment surrounding the photo-active species controls its properties. In particular, the structural role of the tosylate anion needs to be understood against possible chemical influences due to varying the trans ligand, X. The photo-excited geometries, photoconversion levels and thermal stabilities of the photoisomers that form in 1-3 are therefore studied. 1 and 2 yield two photo-isomers at 100 K: the O-bound end-on n1-SO2 Page 1 of 32 ACS Paragon Plus Environment The Journal of Physical Chemistry (MS1) configuration and the side-bound n2-SO2 (MS2), while 3 only exhibits the more thermally stable MS2 geometry. The decay kinetics of the MS2 geometry for 1-3 demonstrate that the greater the free volume of the GS SO2 ligand for a given counterion, the greater the MS2 thermal stability. Furthermore, a rationalization is sought for the SO2 phototriggered molecular rotation of the phenyl ring in the tosylate anion; this is selectively observed in 2, manifesting as nanomechanical molecular transduction. This molecular transduction was not observed in 1, despite the presence of the MS1 geometry due to the close intermolecular interactions between the MS1 SO2 and the neighbouring tosylate ion. The decay of this anionic molecular rotor in 2, however, follows a non-traditional decay pathway, as determined by time-resolved crystallographic analysis; this contrasts with the well-behaved first-order kinetic decay of its MS1 SO2 phototrigger.

  1. Crystallographic characterization of cement pastes hydrated with NaCl; Caracterizacao cristalografica de pastas de cimento hidratadas com NaCl

    Energy Technology Data Exchange (ETDEWEB)

    Melo, Carina Gabriela de Melo e; Martinelli, Antonio Eduardo; Melo, Dulce Maria Araujo; Melo, Marcus Antonio de Freitas; Melo, Vitor Rodrigo de Melo e [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil)

    2012-07-01

    One of the major current challenges faced by oil companies is the exploration of pre salt basins. Salt layers deposited upon the evaporation of ocean water and continental separation are mainly formed by NaCl and isolate immense oil reservoirs. The mechanical stability and zonal isolation of oil wells that run through salt layers must be fulfilled by cement sheaths saturated with NaCl to assure chemical compatibility between cement and salt layer. The present study aimed at evaluating the effect of NaCl addition on the hydration of oil well cement slurries as well as identifying the nature of crystalline phases present in the hardened cement. To that end, cement slurries containing NaCl were mixed, hardened and characterized by X-ray diffraction. The results revealed that the presence of NaCl affects the formation of hydration products by the presence of Friedel's salt. The intensity of the corresponding peaks increase as the contents of NaCl in the slurry increase. High concentrations of NaCl in Portland slurries increase the setting time of cement and the presence of Friedel's salt decreases the strength of the hardened cement. (author)

  2. Variation of the Jahn-Teller distortion with pressure in the layered perovskite Rb{sub 2}CuCl{sub 4}: local and crystal compressibilities

    Energy Technology Data Exchange (ETDEWEB)

    Aguado, F [DCITIMAC, Facultad de Ciencias, Universidad de Cantabria, Santander 39005 (Spain); RodrIguez, F [DCITIMAC, Facultad de Ciencias, Universidad de Cantabria, Santander 39005 (Spain); Valiente, R [Departamento de Fisica Aplicada, Universidad de Cantabria, Santander 39005 (Spain); Hanfland, M [ESRF, BP220, 156 rue des Martires, 38043 Grenoble Cedex (France); Itie, J P [Universite Pierre et Marie Curie, B77 4 Place Jussieu 75252 Paris Cedex 05 (France)

    2007-08-29

    This work investigates the effect of pressure on the Jahn-Teller distortion (JTD) associated with the axially elongated CuCl{sub 6} octahedra in the A{sub 2}CuCl{sub 4} perovskite layer (A: Rb, CH{sub 3}NH{sub 3}, C{sub 2}H{sub 5}NH{sub 3}, C{sub 3}H{sub 7}NH{sub 3}). The aim is to elucidate whether pressure favours disappearance of the JTD in the antiferrodistortive (AFD) structure exhibited by Cu{sup 2+} within the layers or whether it induces tilts of the CuCl{sub 6} octahedra preserving the molecular distortion associated with the JT effect. We have carried out x-ray absorption (XAS) and x-ray diffraction (XRD) experiments under pressure along the compound series, whose interlayer distances at ambient pressure vary from 7.77 to 12.33 A. The use of both XAS and XRD techniques allows us a complete local- and crystal-structure characterization in Rb{sub 2}CuCl{sub 4} as a function of pressure in the 0-16 GPa range. We show that pressure reduces the axial (long) and equatorial (short) Cu-Cl distances, R{sub ax} and R{sub eq}, as well as the intralayer and interlayer Cu-Cu distances, d{sub Cu-Cu} and d{sub inter}. Interestingly, the variation of R{sub ax} is an order of magnitude bigger than that of the corresponding R{sub eq}, yielding a reduction of the JTD. However, no evidence of JTD suppression has been observed below 16 GPa. Pressure-induced CuCl{sub 6} tilting preserves the JTD in a wide pressure range. Estimates based on structural data suggest that JT suppression would occur at about 40 GPa.

  3. Analytical investigation of AlCl[3]/SO[2]Cl[2] catholyte materials for secondary fuze reserve batteries.

    Energy Technology Data Exchange (ETDEWEB)

    Butler, Paul Charles; Rodriguez, Mark Andrew; Segall, Judith M.; Malizia, Louis A., Jr.; Cherry, Brian Ray; Andrews, Nicholas L.; Clark, Nancy H.; Alam, Todd Michael; Ingersoll, David T.; Tallant, David Robert; Simpson, Regina Lynn; Boyle, Timothy J.; Garcia, Manuel Joseph

    2004-05-01

    Exploration of the fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system for the ARDEC Self-Destruct Fuze Reserve Battery Project under accelerated aging conditions was completed using a variety of analytical tools. Four different molecular species were identified in this solution, three of which are major. The relative concentrations of the molecular species formed were found to depend on aging time, initial concentrations, and storage temperature, with each variable affecting the kinetics and thermodynamics of this complex reaction system. We also evaluated the effect of water on the system, and determined that it does not play a role in dictating the observed molecular species present in solution. The first Al-containing species formed was identified as the dimer [Al({mu}-Cl)Cl{sub 2}]{sub 2}, and was found to be in equilibrium with the monomer, AlCl{sub 3}. The second species formed in the reaction scheme was identified by single crystal X-ray diffraction studies as [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (I), a scrambled AlCl{sub 3}{center_dot}SO{sub 2} adduct. The SO{sub 2}(g) present, as well as CL{sub 2}(g), was formed through decomposition of SO{sub 2}CL{sub 2}. The SO{sub 2}(g) generated was readily consumed by AlCl{sub 3} to form the adduct 1 which was experimentally verified when 1 was also isolated from the reaction of SO{sub 2}(g) and AlCl {sub 3}. The third species found was tentatively identified as a compound having the general formula {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. This was based on {sup 27}Al NMR data that revealed a species with tetrahedrally coordinated Al metal centers with increased oxygen coordination and the fact that the precipitate, or gel, that forms over time was shown by Raman spectroscopic studies to possess a component that is consistent with SOCl{sub 2}. The precursor to the precipitate should have similar constituents, thus the assignment of {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2

  4. In vitro studies of theophylline-induced changes in Na, K and Cl transport in hen (Gallus domesticus) colon suggesting bidirectional, basolateral NaK2Cl cotransport

    DEFF Research Database (Denmark)

    Andersen, Vibeke; Munck, B G; Munck, L K

    1990-01-01

    1. In isolated mucosa from a NaCl-loaded hen theophylline stimulates both unidirectional chloride fluxes (JmsCl and JsmCl). Conductive and electroneutral exchange processes, besides a bumetanide-sensitive, rheogenic process contribute. 2. The bumetanide-sensitive fraction of the theophylline......-induced delta JcmCl is sodium-dependent. 3. Incubation in nominally K(+)-free solutions reduces the bumetanide-sensitive fraction delta JsmCl more than treatment with ouabain. 4. With respect to chloride the bumetanide-sensitive fraction of delta JsmCl has a Hill coefficient of 1.93 +/- 0.03, a Jmax of 12...

  5. Separation of CsCl and SrCl{sub 2} from a ternary CsCl-SrCl{sub 2}-LiCl via a zone refining process for waste salt minimization of pyroprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Shim, Moonsoo [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon [Graduate School of Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Graduate School of Department of Advanced Materials Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Rapid Solidified Materials Research Center, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of)

    2016-11-15

    The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl{sub 2} salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The k{sub eff} of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively. - Highlights: • The LiCl-CsCl-SrCl{sub 2} salt ingot was purified by zone refining technique to minimize waste salt. • The concentration distribution of Cs and Sr were analyzed by mass transfer equation. • The decontamination factors of Cs and Sr were 1600 and 450 respectively in case of 60% of recovery yield.

  6. Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

    KAUST Repository

    Nolan, Steven Patrick; Izquierdo, Frederic; Zinser, Caroline; Minenkov, Yury; Cordes, David; Slawin, Alexandra; Cavallo, Luigi; Nahra, Fady; Cazin, Catherine

    2017-01-01

    The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After

  7. Sodium bicarbonate improves 4 km time trial cycling performance when individualised to time to peak blood bicarbonate in trained male cyclists.

    Science.gov (United States)

    Gough, Lewis A; Deb, Sanjoy K; Sparks, S Andy; McNaughton, Lars R

    2018-08-01

    The aim of this study was to investigate the effects of sodium bicarbonate (NaHCO 3 ) on 4 km cycling time trial (TT) performance when individualised to a predetermined time to peak blood bicarbonate (HCO 3 - ). Eleven male trained cyclists volunteered for this study (height 1.82 ± 0.80 m, body mass (BM) 86.4 ± 12.9 kg, age 32 ± 9 years, peak power output (PPO) 382 ± 22 W). Two trials were initially conducted to identify time to peak HCO 3 - following both 0.2 g . kg -1 BM (SBC2) and 0.3 g . kg -1 BM (SBC3) NaHCO 3 . Thereafter, on three separate occasions using a randomised, double-blind, crossover design, participants completed a 4 km TT following ingestion of either SBC2, SBC3, or a taste-matched placebo (PLA) containing 0.07 g . kg -1 BM sodium chloride (NaCl) at the predetermined individual time to peak HCO 3 - . Both SBC2 (-8.3 ± 3.5 s; p < 0.001, d = 0.64) and SBC3 (-8.6 ± 5.4 s; p = 0.003, d = 0.66) reduced the time to complete the 4 km TT, with no difference between SBC conditions (mean difference = 0.2 ± 0.2 s; p = 0.87, d = 0.02). These findings suggest trained cyclists may benefit from individualising NaHCO 3 ingestion to time to peak HCO 3 - to enhance 4 km TT performance.

  8. Spectroscopic and quantum-chemical investigation of association of ions in acetonitrile - LiX (X=I, ClO4, NCS) systems

    International Nuclear Information System (INIS)

    Semenov, S.G.; Solov'eva, L.A.; Akopyan, S.Kh.

    1995-01-01

    Data on association constants of ions in acetonitrile-salt binary systems, obtained from the data on intensity of IR absorption bands of acetonitrile (Acn) molecules contained in solvate shells of Li + cations, have been analyzed. Using the CCP MO LCAO semiempirical method in the PPDP approximation, electronic structure of acetonitrile molecule and Acn k Li + and Acn m Li + X - complexes has been studied. It is ascertained that relative stability of ionic pairs Acn 3 Li + X - , estimated by the squares of their dipole momenta (characterizing solvation energy) increases in the series X=I, ClO 4 , NCS in agreement with data of spectroscopic experiment, according to which the constant of ion association for LiNCS solution in acetonitrile is much higher than for the systems CH 3 CN-LiI and CH 3 CN-LiClO 4 . 13 refs.,2 figs., 2 tabs.64

  9. Action mechanism of hydrogen gas on deposition of HfC coating using HfCl{sub 4}-CH{sub 4}-H{sub 2}-Ar system

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yalei, E-mail: yaleipm@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); School of Metallurgy and Environment, Central South University, Changsha, 410083 (China); Li, Zehao [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); Xiong, Xiang, E-mail: xiongx@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China); Li, Xiaobin [School of Metallurgy and Environment, Central South University, Changsha, 410083 (China); Chen, Zhaoke; Sun, Wei [State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 (China)

    2016-12-30

    Highlights: • HfC coatings were deposited on C/C composites by LPCVD using HfCl4-CH4-H2-Ar system. • Action mechanism of H2 on structure and growth behavior of HfC coating was studied. • Increased H2 concentration leads to transformation in growth mechanism of coating. - Abstract: Hafnium carbide coatings were deposited on carbon/carbon composites by low pressure chemical vapor deposition using HfCl{sub 4}-CH{sub 4}-H{sub 2}-Ar system. The microstructure, mechanical and ablation resistance performance of HfC coatings deposited with various H{sub 2} concentrations were investigated. The effect of hydrogen gas on the deposition of HfC coating was also discussed. Results show that all of the deposited coatings are composed of single cubic HfC phase, the hydrogen gas acted as a crucial role in determining the preferred orientation, microstructure and growth behavior of HfC coatings. During the deposition process, the gas phase supersaturation of the reaction species can be controlled by adjusting the hydrogen gas concentration. When deposited with low hydrogen gas concentration, the coating growth was dominated by the nucleation of HfC, which results in the particle-stacked structure of HfC coating. Otherwise, the coating growth was dominated by the crystal growth at high hydrogen gas concentration, which leads to the column-arranged structure of HfC coating. Under the ablation environment, the coating C2 exhibits better configurational stability and ablation resistance. The coating structure has a significant influence on the mechanical and ablation resistance properties of HfC coating.

  10. Modeling L2,3-Edge X-ray Absorption Spectroscopy with Real-Time Exact Two-Component Relativistic Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Kasper, Joseph M; Lestrange, Patrick J; Stetina, Torin F; Li, Xiaosong

    2018-04-10

    X-ray absorption spectroscopy is a powerful technique to probe local electronic and nuclear structure. There has been extensive theoretical work modeling K-edge spectra from first principles. However, modeling L-edge spectra directly with density functional theory poses a unique challenge requiring further study. Spin-orbit coupling must be included in the model, and a noncollinear density functional theory is required. Using the real-time exact two-component method, we are able to variationally include one-electron spin-orbit coupling terms when calculating the absorption spectrum. The abilities of different basis sets and density functionals to model spectra for both closed- and open-shell systems are investigated using SiCl 4 and three transition metal complexes, TiCl 4 , CrO 2 Cl 2 , and [FeCl 6 ] 3- . Although we are working in the real-time framework, individual molecular orbital transitions can still be recovered by projecting the density onto the ground state molecular orbital space and separating contributions to the time evolving dipole moment.

  11. Growth and luminescent properties of the Ce, Pr doped NaCl single crystals grown by the modified micro-pulling-down method

    International Nuclear Information System (INIS)

    Yokota, Yuui; Yanagida, Takayuki; Fujimoto, Yutaka; Nikl, Martin; Yoshikawa, Akira

    2010-01-01

    We have investigated luminescent properties of nondope, Ce and Pr doped NaCl [nondope NaCl, Ce:NaCl, Pr:NaCl] single crystals grown by a modified micro-pulling-down method with a removable chamber system. Nondope, Ce 1% and Pr 1% doped NaCl crystals with a single phase of NaCl structure were obtained and the crystals indicated general crystal quality by the X-ray rocking curve measurement. For the nondope NaCl and Pr:NaCl crystals, the transmittance spectra indicated almost more than 60% in the wavelength from 200 to 800 nm and an absorption of Ce 3+ ion was observed in the transmittance spectrum of Ce:NaCl crystal. The emission spectrum originated from Ce 3+ 5d-4f transition appeared around 300 nm in the photoluminescence spectrum and the decay time was 19.7 ns.

  12. Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

    International Nuclear Information System (INIS)

    Henglein, A.

    1979-01-01

    (CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 Cl 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and the possible role of adsorbed hydrogen atoms. Colloidal silver and organic radicals were radiolytically produced. 7 figures

  13. Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

    International Nuclear Information System (INIS)

    Henglein, A.

    1979-01-01

    (CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 CL 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and tha materials handling point of view, are being determined

  14. Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

    Science.gov (United States)

    Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

    2015-02-25

    Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

  15. Time-dependent EQPET analysis of TSC

    International Nuclear Information System (INIS)

    Takahashi, Akito

    2006-01-01

    Time-dependent fusion rates for 2D and 4D reactions are calculated for squeezing of tetrahedral symmetric condensate (TSC) from about 100 pm size to its minimum size (about 10 fm), within about 75 fs squeezing motion. Life time of the minimum TSC state is yet to be studied. Time-averaged fusion rates are given by assuming the life time of minimum TSC state is negligible. Time-averaged 2D fusion rate was given as 2.9x10 -25 f/s/pair, and time-averaged 4D fusion rate was 5.5x10 -8 f/s/cl. These values are compared with 1.0x10 -20 f/s/pair for 2D and 1.0x10 -9 f/s/cl for 4D, respectively, of previously estimated values by electronic quasi-particle expansion theory/TSC models. Effective fusion time by the TSC squeezing motion was estimated as 0.014 fs: namely fusions may happen in very short time interval. (author)

  16. An empirical, quantitative approach to predict the reactivity of some substituted aromatic compounds towards reactive radical species (Cl2-*, Br2-*, *NO2, SO3-*, SO4-*) in aqueous solution.

    Science.gov (United States)

    Minero, Claudio; Maurino, Valter; Pelizzetti, Ezio; Vione, Davide

    2006-07-01

    The Hammett approach, applied to the reaction of various classes of aromatic compounds with the radicals Cl2-*, Br2-*, *NO2, SO3-*, and SO4-* yielded good predictive models, supported by high values of the correlation coefficient r2 in the case of phenols with Cl2-* and of phenolates with *NO2 and SO3-*. Lower but statistically significant correlation coefficients could be obtained for benzoates with Cl2-*, phenolates with Br2-*, and benzoates and anisoles with SO4-*.

  17. Square-lattice magnetism of diaboleite Pb2Cu(OH)4Cl2

    Science.gov (United States)

    Tsirlin, Alexander A.; Janson, Oleg; Lebernegg, Stefan; Rosner, Helge

    2013-02-01

    We report on the quasi-two-dimensional magnetism of the natural mineral diaboleite Pb2Cu(OH)4Cl2 with a tetragonal crystal structure, which is closely related to that of the frustrated spin-(1)/(2) magnet PbVO3. Magnetic susceptibility of diaboleite is well described by a Heisenberg spin model on a diluted square lattice with the nearest-neighbor exchange of J≃35 K and about 5% of nonmagnetic impurities. The dilution of the spin lattice reflects the formation of Cu vacancies that are tolerated by the crystal structure of diaboleite. The weak coupling between the magnetic planes triggers the long-range antiferromagnetic order below TN≃11 K. No evidence of magnetic frustration is found. We also analyze the signatures of the long-range order in heat-capacity data, and discuss the capability of identifying magnetic transitions with heat-capacity measurements.

  18. Preparation of compounds AWCl6 from WCl6 in Cl--containing solvents

    International Nuclear Information System (INIS)

    Seifert, H.J.; Kiewisch, B.; Wuesteneck, A.

    1977-01-01

    In Glyme, ACN or CH 2 Cl 2 WCl 6 is reduced by Cl - to WCl 6 - . From those solutions compounds AWCl 6 can be isolated with A = Cs (Glyme, ACN), A = Rb, K, NH 4 (ACN) and A = N(C 2 H 5 ) 4 (CH 2 Cl 2 ). By concentrating of glyme-solutions a precipitate of A 2 WCl 6 is formed by disproportionation. In methanol/HCl also solvolysis to oxo-compounds of W 6+ takes place as function of the H + -concentration. With N(C 2 H 5 ) 4 Cl not only chlorotungstates but also methoxy- and oxo-spezies of W 5+ can be isolated. (author)

  19. Intermolecular C-H···O, Cl···Cl and π-π interactions in the 2-dichloromethyl derivative of vitamin K3.

    Science.gov (United States)

    Soave, Raffaella; Colombo, Pietro

    2013-12-15

    The title 1,4-naphthoquinone, 2-dichloromethyl-3-methyl-1,4-dihydronaphthalene-1,4-dione, C12H8Cl2O2, is a chlorinated derivative of vitamin K3, which is a synthetic compound also known as menadione. Molecules of (I) are planar and lie on a crystallographic mirror plane (Z' = 0.5) in the space group Pnma. They are connected to each other by C-H···O hydrogen bonds, forming two-dimensional layers parallel to the ac plane. In addition, Cl···Cl and π-π interactions link adjacent molecules in different layers, thus forming zigzag ribbons along the b axis, such that a three-dimensional architecture is generated.

  20. Efficient and Selective Reduction of Aromatic Nitro Compounds to Aromatic Amines by NbCl{sub 5}/Indium System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Kim, Duckil; Kim, Hyung Min; Kang, Sung Ho [Korea Univ., Seoul (Korea, Republic of)

    2012-09-15

    Aromatic amines find applicability in diverse fields including dyes, pharmaceuticals, agrochemicals, and photographic materials. To date, there are a variety of methods, which can be used to convert aromatic nitro compounds to their corresponding amines. Some of them include Cp{sub 2}TiCl{sub 2}/In, Al/NH{sub 4}Cl, (NH{sub 4}){sub 2}SO{sub 4}/NaBH{sub 4}, NiCl{sub 2}6H{sub 2}O/In, HI, Sm/I{sub 2}, In/NH{sub 4}Cl, B{sub 4}H{sub 10}/Pd/C, Co{sub 2}(CO){sub 8}/H{sub 2}O and In/HCl. However, most methods still lack the desired chemo-selectivity when other reducible functional groups are present in the nitroarene and often require long reaction times, or harsh reaction conditions. Consequently, efficient and selective methods for the reduction of aromatic nitro compounds continue to be developed. It has been reported that NbCl{sub 5}/Zn system is used as a reagent for reducing sulfoxides, epoxides, and amine N-oxides.12 Because of the close resemblance of indium to zinc in several respects, including first ionization potential, we considered that NbCl{sub 5}/In system can be an efficient reducing agent for the conversion of aromatic nitro compounds to the corresponding amines. Recently, indium metal has attracted much attention for its unique properties such as low toxicity and high stability in water and air compared with other metals. In continuation of our interest in exploring the utility of metal-metal salt system in organic synthesis, we would like to report an efficient and chemo-selective method for the reduction of various aromatic nitro compounds to the corresponding amines by treatment with NbCl{sub 5}/In system (eq. 1). The new reduction system was generated by the addition of indium powder to a stirred solution of niobium(V) chloride in THF under sonication. The generation of low-valent niobium species was examined at room temperature with an excess of indium metal. The observations suggest that this procedure can be applied for the chemo

  1. NaCl leached sustainable porous flexible Fe3O4 decorated RGO-polyaniline/PVDF composite for durable application against electromagnetic pollution

    Directory of Open Access Journals (Sweden)

    R. Bera

    2017-05-01

    Full Text Available To avoid the interference of electromagnetic radiation from other devices, an electronic device needs to be fabricated with flexible and light weight electromagnetic interference (EMI shielding materials with high efficiency. According, highly flexible porous poly(vinylidene fluoride (PVDF/PFR (Fe3O4 decorated polyaniline/RGO composite composite was prepared through solution blending of PVDF with pre-synthesized PFR conductive composite that involves in-situ oxidative polymerization of aniline in the presence of reduced graphene oxide (RGO using FeCl3 as oxidant. The porous morphology of the composite was created by leaching out of mixed NaCl from the composite. Polyaniline and RGO were mutually decorated by chemically in-situ synthesized ferrosoferric oxide (Fe3O4 using the Fe source of FeCl3. A homogeneous dispersion of PFR in insulated PVDF matrix resulted in a highly electrical conductive composite (PVDF-PFR material through formation of three dimensional continuous conductive networks of polyaniline-RGO in the matrix phase. The composite shows an outstanding EMI shielding effectiveness (EMI SE property due to the porous structure and the presence of conductive network and ferromagnetic Fe3O4 nanoparticles. The PVDF-PFR composite (0.5 mm thickness depicts a great permittivity and permeability value and achieve high EMI SE value (≈–28.18 dB and conductivity value of ≈1.10·10–1 S·cm–1 at very low loading (5 wt% of RGO.

  2. Energy levels of Ho3+ in HoCl63-

    International Nuclear Information System (INIS)

    Tanner, P.A.

    1987-01-01

    The 5 S 2 , 5 F 4 , 5 F 2 , 3 K 8 , 5 G 6 , 5 F 1 , 5 G 5 5 I 8 absorption spectra of Cs 2 NaHoCl 6 have been recorded at temperatures down to that of liquid helium and new assignments are made for the 5 S 2 , 5 F 4 , 3 K 8 and 5 G 5 terms of HoCl 6 3- . The 5 F 3 → 5 I 8 , 5 F 4 , 5 S 2 → 5 I 7 , 5 I 8 and 5 F 5 → 5 I 7 luminescence transitions of HoCl 6 3- in various elpasolite lattices are reported and assigned, together with luminescence decay measurements. Including the previously reported data, these results enable 57 of the first 60 crystal-field levels of HoCl 6 3- , comprising 14 Lsub(j) terms, to be firmly assigned and tentative assignments are made for the remaining three levels. The agreement between the calculated and observed crystal-field splittings is reasonable. (author)

  3. Urinary excretion of furosemide in rats with HgCl sub 2 -induced acute renal damage

    Energy Technology Data Exchange (ETDEWEB)

    Fujimura, Akio; Sudoh, Toshiaki; Ohashi, Kyoichi; Ebihara, Akio (Jichi Medical School, Tochigi (Japan))

    1992-01-01

    To examine the influence of mercuric chloride (HgCl{sub 2})-induced acute renal damage on urinary excretion of furosemide, HgCl{sub 2} or its vehicle along was given intraperitoneally to Wistar rats. The following two experiments were done. Study 1: three percent body weight (b.w.) of 1% NaCl solution or furosemide in 3% b.w. of 1% NaCl solution was given orally before and after HgCl{sub 2} treatment, and an 8-hour urine was collected. Study 2: furosemide was given orally, and blood samples were obtained at 1, 2, 3, 4, 6 and 8 hours after administration. Urinary excretion of N-acetyl-{beta}-D-glucosaminidase increased, and urine volume and urinary excretions of furosemide and sodium decreased in the HgCl{sub 2}-treated rats. There were significant correlations between the urinary furosemide and its diuretic effects. Regression lines after HgCl{sub 2} were significantly different from those before treatment. The values of absorption as well as elimination rate constant were smaller, while the time to maximum concentration and the elimination half-life were longer in the HgCl{sub 2}-treated rats compared to vehicle-treated animals. These results suggest that the urinary excretion of furosemide and the responsiveness of renal tubular cells to this agent are impaired in rats with HgCl{sub 2}-induced acute renal damage.

  4. Oxidation of cyclic amines by molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br

    Directory of Open Access Journals (Sweden)

    H.M. Mbuvi

    2013-05-01

    Full Text Available The molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br react with a large excess of the nitrogen bases, 1-methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine and 2-ethylpiperidine to give aminecarbonyl complexes of the type M(CO3L3 (L= alkylamine. Excess piperidine reacts with the tungsten halocarbonyls, [W(CO4X2]2 (X = Cl, Br, to give the trans isomer of the complex, W(CO3(C5H11N3. The halogens were recovered as the amminium salts, amine, HX. The oxidized amine dimerized to form a yellow product which was recovered as an oily liquid but in very small amounts. However, in the reaction between Mo(CO4Br2 and 1-ethylpiperidine, a yellow crystalline solid, with a melting point of 224 oC was recovered in sufficient amounts for elemental analysis, melting point and spectral data. Its mass spectrum showed a molecular ion peak at m+/z = 222, a clear evidence that the oxidized amine dimerizes. The cyclic dibasic amine piperazine, C4H10N2 is not, however, oxidized by these halocarbonyls but rather it reacts by substituting some CO groups to form products of the type, M(CO3(C4H10N22X2 (M = Mo, W; X = Cl, Br. Products were characterized by elemental analysis, IR, UV, 1H NMR and mass spectrometry.

  5. Evaluation of the OpenCL AES Kernel using the Intel FPGA SDK for OpenCL

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Zheming [Argonne National Lab. (ANL), Argonne, IL (United States); Yoshii, Kazutomo [Argonne National Lab. (ANL), Argonne, IL (United States); Finkel, Hal [Argonne National Lab. (ANL), Argonne, IL (United States); Cappello, Franck [Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-04-20

    The OpenCL standard is an open programming model for accelerating algorithms on heterogeneous computing system. OpenCL extends the C-based programming language for developing portable codes on different platforms such as CPU, Graphics processing units (GPUs), Digital Signal Processors (DSPs) and Field Programmable Gate Arrays (FPGAs). The Intel FPGA SDK for OpenCL is a suite of tools that allows developers to abstract away the complex FPGA-based development flow for a high-level software development flow. Users can focus on the design of hardware-accelerated kernel functions in OpenCL and then direct the tools to generate the low-level FPGA implementations. The approach makes the FPGA-based development more accessible to software users as the needs for hybrid computing using CPUs and FPGAs are increasing. It can also significantly reduce the hardware development time as users can evaluate different ideas with high-level language without deep FPGA domain knowledge. In this report, we evaluate the performance of the kernel using the Intel FPGA SDK for OpenCL and Nallatech 385A FPGA board. Compared to the M506 module, the board provides more hardware resources for a larger design exploration space. The kernel performance is measured with the compute kernel throughput, an upper bound to the FPGA throughput. The report presents the experimental results in details. The Appendix lists the kernel source code.

  6. A possible NaCl pathway in the bioregenerative human life support system

    Science.gov (United States)

    Polonskiy, V. I.; Gribovskaya, I. V.

    One of the ways to involve NaCl in the mass exchange of the bioregenerative human life support system (BLSS) is to grow some vegetables and leafy greens that can accumulate sodium chloride at high concentrations in their edible biomass. Lettuce, celery cabbage, chard, dill and radish plants were grown hydroponically in Knop's nutrient solution. In the first series of experiments, at the end of the growth period the plants were grown on solutions containing 2-14 g/L of NaCl for 1-5 days. It was found that the amount of sodium in edible biomass of the plants increased with NaCl concentration in the solution and with the time plants were irrigated with that solution. The content of NaCl in the biomass of leaves and edible roots was considerable—up to 10% dry matter. At the same time, the amount of water in the leaves decreased and productivity of the treatment plants was 14-28% lower than that of the control ones, grown on Knop's solution. The treatment plants contained less than half of the amount of nitrates recorded in the control ones. Expert evaluation showed that the taste of the vegetables and leafy greens of the treatment group were not inferior to the taste of the control plants. In the second series of experiments, prior to being grown on the NaCl solution, the plants were irrigated with water for 2, 4 or 6 days. It was found that lower salt status of the plants was not favorable for increased salt accumulation in their biomass. If a human consumes 30 g salad vegetables and follows a low-sodium diet (3 g/d of table salt), it may be feasible to recycle NaCl in the BLSS using vegetables and leafy greens.

  7. Virus purification by CsCl density gradient using general centrifugation.

    Science.gov (United States)

    Nasukawa, Tadahiro; Uchiyama, Jumpei; Taharaguchi, Satoshi; Ota, Sumire; Ujihara, Takako; Matsuzaki, Shigenobu; Murakami, Hironobu; Mizukami, Keijirou; Sakaguchi, Masahiro

    2017-11-01

    Virus purification by cesium chloride (CsCl) density gradient, which generally requires an expensive ultracentrifuge, is an essential technique in virology. Here, we optimized virus purification by CsCl density gradient using general centrifugation (40,000 × g, 2 h, 4 °C), which showed almost the same purification ability as conventional CsCl density gradient ultracentrifugation (100,000 × g, 1 h, 4 °C) using phages S13' and φEF24C. Moreover, adenovirus strain JM1/1 was also successfully purified by this method. We suggest that general centrifugation can become a less costly alternative to ultracentrifugation for virus purification by CsCl densiy gradient and will thus encourage research in virology.

  8. Dissociation of deep-core-excited CH{sub 3}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, D.L.; Martin, R.; Vanderford, B. [Univ. of Nevada, Las Vegas, NV (United States)] [and others

    1997-04-01

    Using x-rays from B.L. 9.3.1, a space-focused time-of-flight (TOF) was used to study photofragmentation of CH{sub 3}Cl following excitation in the neighborhood of the Cl K-shell threshold ({approximately} 2.8 keV). Multi-ion coincidence measurements were used to search for selective dissociation of specific bonds in the molecule. Such selectivity has been observed for excitation near outer-core-level thresholds (e.g., Cl 2p), but this is the first study in deep core levels, where very-short core-hole lifetimes and Auger cascade effects may influence fragmentation. Both high-resolution time-of-flight spectroscopy and multi-coincidence photoelectron-photoion-photoion (PE-PIPICO), as well as photoelectron-photoion-photoion-photoion (PE3PICO) measurements were performed. Dramatic changes in the line shapes for different fragment ions are observed as a function of the excitation energy, and are attributed to selective dissociation of the CH{sub 3}Cl molecule along the C-Cl bond. In addition, pronounced angular distributions of the ejected ions are observed on resonance.

  9. Eu2+-doped Ba2GaB4O9Cl blue-emitting phosphor with high color purity for near-UV-pumped white light-emitting diodes

    Science.gov (United States)

    Gao, Zhiwen; Deng, Huajuan; Xue, Na; Jeong, Jung Hyun; Yu, Ruijin

    2018-01-01

    Eu2+-doped borate fluoride Ba2GaB4O9Cl was synthesized by the conventional high-temperature solid-state reaction. The crystal structure and luminescence properties of the phosphors, as well as their thermal luminescence quenching capabilities and CIE chromaticity coordinates were systematically investigated. Under the excitation at 340 nm, the phosphor exhibited an asymmetric broad-band blue emission with a peak at 445 nm, which is ascribed to the 4f-5d transition of Eu2+. It was further proved that energy transfer among the nearest neighbor ions is the major mechanism for concentration quenching of Eu2+ in Ba2-xGaB4O9Cl:xEu2+ phosphors. The luminescence quenching temperature is 432 K. The CIE color coordinates are very close to those of BaMgAl10O17:Eu2+ (BAM). All the properties indicated that the blue-emitting Ba2GaB4O9Cl:Eu2+ phosphor has potential application in white LEDs.

  10. Analysis of X-ray adsorption edges: L2,3 edge of FeCl4-

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Department of Chemistry, University of North Texas, Denton, Texas 76203-5017, USA; Nelin, Connie J. [Consultant, Austin, Texas 78730, USA; Ilton, Eugene S. [Pacific Northwest National Laboratory, Richland, Washington 99352, USA; Sassi, Michel J. [Pacific Northwest National Laboratory, Richland, Washington 99352, USA; Rosso, Kevin M. [Pacific Northwest National Laboratory, Richland, Washington 99352, USA

    2017-12-14

    We describe a detailed analysis of the features of the X-ray adsorption spectra at the Fe L2,3 edge of FeCl4. The objective of this analysis is to explain the origin of the complex features in relation to properties of the wavefunctions, especially for the excited states. These properties include spin-orbit and ligand field splittings where a novel aspect of the dipole selection rules is applied to understand the influence of these splittings on the spectra. We also explicitly take account of the intermediate coupling of the open core and valence shell electrons. Our analysis also includes comparison of theory and experiment for the Fe L2,3 edge and comparison of theoretical predictions for the Fe3+ cation and FeCl4-. The electronic structure is obtained from theoretical wavefunctions for the ground and excited states.

  11. Growth and luminescent properties of the Ce, Pr doped NaCl single crystals grown by the modified micro-pulling-down method

    Energy Technology Data Exchange (ETDEWEB)

    Yokota, Yuui, E-mail: y-yokota@tagen.tohoku.ac.j [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University/2-1-1, Katahira, Aoba-ku, Sendai (Japan); Yanagida, Takayuki; Fujimoto, Yutaka [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University/2-1-1, Katahira, Aoba-ku, Sendai (Japan); Nikl, Martin [Institute of Physics, Academy of Sciences of the Czech Republic/6253, Prague (Czech Republic); Yoshikawa, Akira [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University/2-1-1, Katahira, Aoba-ku, Sendai (Japan); New Industry Creation Hatchery Center (NICHe), Tohoku University/2-1-1, Katahira, Aoba-ku, Sendai (Japan)

    2010-03-15

    We have investigated luminescent properties of nondope, Ce and Pr doped NaCl [nondope NaCl, Ce:NaCl, Pr:NaCl] single crystals grown by a modified micro-pulling-down method with a removable chamber system. Nondope, Ce 1% and Pr 1% doped NaCl crystals with a single phase of NaCl structure were obtained and the crystals indicated general crystal quality by the X-ray rocking curve measurement. For the nondope NaCl and Pr:NaCl crystals, the transmittance spectra indicated almost more than 60% in the wavelength from 200 to 800 nm and an absorption of Ce{sup 3+} ion was observed in the transmittance spectrum of Ce:NaCl crystal. The emission spectrum originated from Ce{sup 3+} 5d-4f transition appeared around 300 nm in the photoluminescence spectrum and the decay time was 19.7 ns.

  12. Proton-stimulated Cl-HCO3 antiport by basolateral membrane vesicles of lobster hepatopancreas

    International Nuclear Information System (INIS)

    Ahearn, G.A.; Grover, M.L.; Tsuji, R.T.; Clay, L.P.

    1987-01-01

    Purified epithelial basolateral membrane vesicles were prepared from lobster hepatopancreas by sorbitol gradient centrifugation. Na+-K+-adenosinetriphosphatase, alkaline phosphatase, and cytochrome-c oxidase enzyme activities in the final membrane preparation were enriched 9.6-, 1.4-, and 0.4-fold, respectively, compared with their activities in the original tissue homogenate. Vesicle osmotic reactivity was demonstrated using 60-min equilibrium 36 Cl uptake experiments at a variety of transmembrane osmotic gradients. 36 Cl uptake into vesicles preloaded with HCO 3 was significantly greater than into vesicles lacking HCO 3 . This exchange process was stimulated by a transmembrane proton gradient (internal pH greater than external pH). Proton-gradient-dependent Cl-HCO 3 exchange was potential sensitive and stimulated by an electrically negative vesicle interior. 36 Cl influx (4-s exposures) into HCO 3 -loaded vesicles occurred by the combination of 4-acetamido-4'-isothiocyanatostilbene-2,2'-disulfonic acid sensitive, carrier-mediated transfer and apparent diffusion. 36 Cl influx was a hyperbolic function of both internal [HCO 3 ] and internal [Cl]. The two internal anions displayed a 100-fold difference in apparent affinity constants with HCO 3 being strongly preferred. 36 Cl influx was stimulated more by preloaded monovalent than by divalent anions. Na was an inhibitor of proton-dependent anion antiport, whereas K had no effect. A model for HCl-HCO 3 antiport is suggested that employs combined transmembrane concentration gradients of Cl and HCO 3 to power anion exchange and transfer protons against a concentration gradient

  13. Formation of new halogenothiocarbonylsulfenyl halides, XC(S)SY, through photochemical matrix reactions starting from CS2 and a dihalogen molecule XY (XY=Cl2, Br2, or BrCl).

    Science.gov (United States)

    Tobón, Yeny A; Romano, Rosana M; Védova, Carlos O Della; Downs, Anthony J

    2007-05-28

    Isolation of a dihalogen molecule XY (XY=Cl2, Br2, or BrCl) with CS2 in a solid Ar matrix at about 15 K leads, by broad-band UV-vis photolysis (200ClCS*, Cl*...SCS, CCl4, *CCl3, :CCl2, SCl2, SCBr2, CBr4, *CBr3, BrC(S)Cl, BrCCl3, and :CBrCl, the following new molecules have also been identified as products of the various photoreactions: syn-ClC(S)SCl, anti-ClC(S)SCl, syn-BrC(S)SBr, anti-BrC(S)SBr, syn-ClC(S)SBr, anti-ClC(S)SBr, syn-BrC(S)SCl, anti-BrC(S)SCl, ClC(S)S*, BrCS*, and Br*...SCS. The IR spectra of these hitherto unknown species have been interpreted with reference to the predictions of ab initio (HF and MP2) and density functional theory (DFT) calculations. The results are analyzed in relation to the reaction pathways accessed by matrix photolysis.

  14. Constants of hyperfine interaction of lanthanoid-phosphorus for [LnCl2Hmpa4]BPh4 composition compounds from data on 1H and 31P NMR

    International Nuclear Information System (INIS)

    Skopenko, V.V.; Amirkhanov, V.M.; Turov, A.V.; Trachevskij, V.V.

    1991-01-01

    By the method of 1 H and 31 P NMR at 233 and 298 K acetone solutions of lanthanide complexes of the composition [LnCl 2 Hmpa 4 ]BPh 4 (Hmpa=OP[N(CH 3 ) 2 ] 3 , Ln=La, Ce-Lu) have been considered. Two series of complexes having similar structure of coordination sphere (Ln=Pr-Ho and Ln=Er-Yb) are revealed and for each series the values of hyperfine interaction constants, which are 0.49 and 0.28 MHz respectively, have been determined

  15. Low Temperature Growth of In2O3and InN Nanocrystals on Si(111 via Chemical Vapour Deposition Based on the Sublimation of NH4Cl in In

    Directory of Open Access Journals (Sweden)

    Tsokkou Demetra

    2009-01-01

    Full Text Available Abstract Indium oxide (In2O3 nanocrystals (NCs have been obtained via atmospheric pressure, chemical vapour deposition (APCVD on Si(111 via the direct oxidation of In with Ar:10% O2at 1000 °C but also at temperatures as low as 500 °C by the sublimation of ammonium chloride (NH4Cl which is incorporated into the In under a gas flow of nitrogen (N2. Similarly InN NCs have also been obtained using sublimation of NH4Cl in a gas flow of NH3. During oxidation of In under a flow of O2the transfer of In into the gas stream is inhibited by the formation of In2O3around the In powder which breaks up only at high temperatures, i.e.T > 900 °C, thereby releasing In into the gas stream which can then react with O2leading to a high yield formation of isolated 500 nm In2O3octahedrons but also chains of these nanostructures. No such NCs were obtained by direct oxidation forT G < 900 °C. The incorporation of NH4Cl in the In leads to the sublimation of NH4Cl into NH3and HCl at around 338 °C which in turn produces an efficient dispersion and transfer of the whole In into the gas stream of N2where it reacts with HCl forming primarily InCl. The latter adsorbs onto the Si(111 where it reacts with H2O and O2leading to the formation of In2O3nanopyramids on Si(111. The rest of the InCl is carried downstream, where it solidifies at lower temperatures, and rapidly breaks down into metallic In upon exposure to H2O in the air. Upon carrying out the reaction of In with NH4Cl at 600 °C under NH3as opposed to N2, we obtain InN nanoparticles on Si(111 with an average diameter of 300 nm.

  16. Metabolism and disposition of a novel antineoplastic JS-38 (Benzamide, N-[4-(2,4-dimethoxyphenyl)-4,5-dihydro-5-oxo-1,2-dithiolo[4,3-b]pyrrol-6-yl]-3,5-bis (trifluoromethyl)-(9Cl)) in rats.

    Science.gov (United States)

    Zhang, Hong; Liu, Quanhai; Fan, Tingting; Fang, Yu; Li, Ying; Wang, Guoping

    2012-03-01

    The metabolism and catabolism of a novel antineoplastic (ID code JS-38),Benzamide, N-[4-(2,4-dimethoxyphenyl)-4,5-dihydro-5-oxo-1,2-dithiolo[4,3-b]pyrrol-6-yl]-3,5-bis (trifluoromethyl)-(9Cl), were investigated in Wistar rats (3 female, 3 male). LC/UV, LC/MS, LC/MS/MS, NMR and acid hydrolysis methods showed that the metabolic process of JS-38 consists of a series of acetylation and glucoronation that form a metabolic product with a unique pharmacologic property of accelerating bone-marrow cell formation, and also showed a novel metabolic pathway of being acetylated and glucuronated in series.

  17. Hyperfine-resolved transition frequency list of fundamental vibration bands of H35Cl and H37Cl

    Science.gov (United States)

    Iwakuni, Kana; Sera, Hideyuki; Abe, Masashi; Sasada, Hiroyuki

    2014-12-01

    Sub-Doppler resolution spectroscopy of the fundamental vibration bands of H35Cl and H37Cl has been carried out from 87.1 to 89.9 THz. We have determined the absolute transition frequencies of the hyperfine-resolved R(0) to R(4) transitions with a typical uncertainty of 10 kHz. We have also yielded six molecular constants for each isotopomer in the vibrational excited state, which reproduce the determined frequencies with a standard deviation of about 10 kHz.

  18. Solubility relations in the ternary system NaCl-CsCl-H2O at 1 atm. 1. Solubilities of halite from 20 to 100 °C

    Science.gov (United States)

    Chou, I.-Ming; Lee, R.D.

    1983-01-01

    Solubilities of halite in the ternary system NaCl-CsCl-H2O have been determined by the visual polythermal method at 1 atm from 20 to 100??C along five constant CsCl/(CsCl + H2O) weight ratio lines. These five constant weight ratios are 0.1, 0.2, 0.3, 0.4, and 0.5. The maximum uncertainties in these measurements are ??0.02 wt % NaCl and ??0.15??C. The data along each constant CsCl/(CsCl + H2O) weight ratio line were regressed to a smooth curve. The maximum deviation of the measured solubilities from the smooth curves is 0.06 wt % NaCl. Isothermal solubilities of halite were calculated from smoothed curves at 25, 50, and 75??C.

  19. Characterization of CuCl quantum dots grown in NaCl single crystals via optical measurements, X-ray diffraction, and transmission electron microscopy

    Science.gov (United States)

    Miyajima, Kensuke; Akatsu, Tatsuro; Itoh, Ken

    2018-05-01

    We evaluated the crystal size, shape, and alignment of the lattice planes of CuCl quantum dots (QDs) embedded in NaCl single crystals by optical measurements, X-ray diffraction (XRD) patterns, and transmission electron microscopy (TEM). We obtained, for the first time, an XRD pattern and TEM images for CuCl QDs in NaCl crystals. The XRD pattern showed that the lattice planes of the CuCl QDs were parallel to those of the NaCl crystals. In addition, the size of the QDs was estimated from the diffraction width. It was apparent from the TEM images that almost all CuCl QDs were polygonal, although some cubic QDs were present. The mean size and size distribution of the QDs were also obtained. The dot size obtained from optical measurements, XRD, and TEM image were almost consistent. Our new findings can help to reveal the growth mechanism of semiconductor QDs embedded in a crystallite matrix. In addition, this work will play an important role in progressing the study of optical phenomena originating from assembled semiconductor QDs.

  20. The first quinary rare earth thiophosphates. Cs{sub 5}Ln{sub 3}X{sub 3}(P{sub 2}S{sub 6}){sub 2}(PS{sub 4}) (Ln = La, Ce, X = Br, Cl) and the quasi-quaternary Cs{sub 10}Y{sub 4}Cl{sub 10}(P{sub 2}S{sub 6}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Schoop, Leslie Mareike; Eger, Roland; Nuss, Juergen; Pielnhofer, Florian [Max Planck Institute for Solid State Research, Stuttgart (Germany); Lotsch, Bettina Valeska [Max Planck Institute for Solid State Research, Stuttgart (Germany); Nanosystems Initiative Munich (NIM) and Center for Nanoscience, Muenchen (Germany)

    2017-12-13

    We report the first examples of quinary rare earth thiophosphates with a fully ordered cation and anion distribution, Cs{sub 5}Ln{sub 3}X{sub 3}(P{sub 2}S{sub 6}){sub 2}(PS{sub 4}), (Ln = La, Ce and X = Br, Cl) as well as the quasi-quaternary Cs{sub 10}Y{sub 4}Cl{sub 10}(P{sub 2}S{sub 6}){sub 3}. These four new compounds crystallize in three different, unknown structure types. The yellowish, transparent, brittle Cs{sub 5}Ce{sub 3}Br{sub 3}(P{sub 2}S{sub 6}){sub 2}(PS{sub 4}) crystallizes in the orthorhombic space group Pnma (no. 62) with a = 13.276(3), b = 14.891(3), c = 19.593(4) Aa, and V = 3873(1) Aa{sup 3} in a novel structure type. Colorless crystals of Cs{sub 5}La{sub 3}Br{sub 3}(P{sub 2}S{sub 6}){sub 2}(PS{sub 4}) and Cs{sub 5}La{sub 3}Cl{sub 3}(P{sub 2}S{sub 6}){sub 2}(PS{sub 4}) are isotypic and were obtained in the monoclinic space group P2{sub 1}/m (no. 11) with a = 9.715(2), b = 14.310(3), c = 13.685(3) Aa, β = 100.16(3) and V = 1873(1) Aa{sup 3} and a = 9.513(2), b = 14.182(3), c = 13.699(3) Aa, β = 99.39(3) and V = 1823(1) Aa{sup 3}, respectively. Both structures contain isolated hexathiohypodiphosphate(IV) [P{sub 2}S{sub 6}]{sup 4-} and thiophosphate [PS{sub 4}]{sup 3-} units that are arranged alternately in layers. Cs{sub 10}Y{sub 4}Cl{sub 10}(P{sub 2}S{sub 6}){sub 3} crystallizes in colorless transparent platelets in the orthorhombic space group Pnnm (no. 58) with a = 13.153(3), b = 28.964(6), c = 7.780(2) Aa, and V = 2964(1) Aa{sup 3}. The structure is composed of isolated [P{sub 4/2}S{sub 6}]{sup 4-} octahedra containing four half occupied P positions surrounded octahedrally by sulfur. We show with Raman scattering that this disordered thiophosphate anion shows a Raman spectrum that is distinct from spectra published for other literature-known thiophosphate anions. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Ethanol enhances GABA-induced 36Cl-influx in primary spinal cord cultured neurons

    International Nuclear Information System (INIS)

    Ticku, M.K.; Lowrimore, P.; Lehoullier, P.

    1986-01-01

    Ethanol has a pharmacological profile similar to other centrally acting drugs, which facilitate GABAergic transmission. GABA is known to produce its effects by increasing the conductance to Cl- ions. In this study, we have examined the effect of ethanol on GABA-induced 36Cl-influx in primary spinal cord cultured neurons. GABA produces a concentration-dependent, and saturable effect on 36Cl-influx in these neurons. Ethanol potentiates the effect of GABA on 36Cl-influx in these neurons. GABA (20 microM) increased the 36Cl-influx by 75% over the basal value, and in the presence of 50 mM ethanol, the observed increase was 142%. Eadie-Hoffstee analysis of the saturation curves indicated that ethanol decreases the Km value of GABA (10.6 microM to 4.2 microM), and also increases the Vmax. Besides potentiating the effect of GABA, ethanol also appears to have a direct effect in the absence of added GABA. These results suggest that ethanol enhances GABA-induced 36Cl-influx and indicate a role of GABAergic system in the actions of ethanol. These results also support the behavioral and electrophysiological studies, which have implicated GABA systems in the actions of ethanol. The potential mechanism(s) and the role of direct effect of ethanol is not clear at this time, but is currently being investigated

  2. Design and Fabrication of a 200N Thrust Rocket Motor Based on NH4ClO4+Al+HTPB as Solid Propellant

    Science.gov (United States)

    Wahid, Mastura Ab; Ali, Wan Khairuddin Wan

    2010-06-01

    The development of rocket motor using potassium nitrate, carbon and sulphur mixture has successfully been developed by researchers and students from UTM and recently a new combination for solid propellant is being created. The new solid propellant will combine a composition of Ammonium perchlorate, NH4ClO4 with aluminium, Al and Hydroxyl Terminated Polybutadiene, HTPB as the binder. It is the aim of this research to design and fabricate a new rocket motor that will produce a thrust of 200N by using this new solid propellant. A static test is done to obtain the thrust produced by the rocket motor and analyses by observation and also calculation will be done. The experiment for the rocket motor is successful but the thrust did not achieve its required thrust.

  3. Time to and Predictors of CD4+ T-Lymphocytes Recovery in HIV-Infected Children Initiating Highly Active Antiretroviral Therapy in Ghana

    Directory of Open Access Journals (Sweden)

    Lorna Renner

    2011-01-01

    Full Text Available Background. CD4+ T-lymphocyte monitoring is not routinely available in most resource-limited settings. We investigated predictors of time to CD4+ T-lymphocyte recovery in HIV-infected children on highly active antiretroviral (HAART at Korle-Bu Teaching Hospital, Ghana. Methods. Time to CD4+ T-lymphocyte recovery was defined as achieving percent CD4+ T-lymphocytes of 25%. We used Cox proportional hazard models for identifying significant predictor variables. Results. Of the 233 children with complete CD4+ T-lymphocyte data, the mean age at HAART initiation was 5.5 (SD=3.1 years. The median recovery time was 60 weeks (95% CL: 55–65. Evidence at baseline of severe suppression in CD4+ T-lymphocyte count adjusted for age, age at HAART initiation, gender, and having parents alive were statistically significant in predicting time to CD4+ T-lymphocyte recovery. Conclusions. A targeted approach based on predictors of CD4+ T-lymphocyte recovery can be a viable and cost-effective way of monitoring HAART in HIV-infected children in resource-limited settings.

  4. Thermodynamic properties of thulium and ytterbium in fused NaCl-KCl-CsCl eutectic

    Energy Technology Data Exchange (ETDEWEB)

    Novoselova, A., E-mail: A.Novoselova@ihte.uran.ru [Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Science, S. Kovalevskaya Str., 22, Ekaterinburg 620990 (Russian Federation); Smolenski, V. [Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Science, S. Kovalevskaya Str., 22, Ekaterinburg 620990 (Russian Federation)

    2011-07-15

    Research highlights: > Tm and Yb chloride compounds as fission products. > The investigation of electrochemical properties of lanthanides. > Determination of the apparent standard redox potentials of the couple Ln(III)/Ln(II) in fused NaCl-KCl-CsCl eutectic at (823 to 973) K. > The calculation of the basic thermodynamic properties of redox reaction in molten salt. - Abstract: This work presents the results of a study of the Tm{sup 3+}/Tm{sup 2+} and Yb{sup 3+}/Yb{sup 2+} couple redox potentials vs. Cl{sup -}/Cl{sub 2} reference electrode at the temperature range (823 to 973) K in fused NaCl-KCl-CsCl eutectic by direct potentiometric method. Initial concentrations of TmCl{sub 3} and YbCl{sub 3} in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TmCl{sub 2(l)} + 1/2 Cl{sub 2(g)} {r_reversible} TmCl{sub 3(l)} and YbCl{sub 2(l)} + 1/2 Cl{sub 2(g)} {r_reversible} YbCl{sub 3(l)} were calculated using the temperature dependencies of apparent standard potentials of the couples E{sub Tm{sup 3+}/Tm{sup 2+*}} and E{sub Yb{sup 3+}/Yb{sup 2+*}}.

  5. cl-Supercontinuous Functions

    Directory of Open Access Journals (Sweden)

    D. Singh

    2007-10-01

    Full Text Available Basic properties of cl-supercontinuity, a strong variant of continuity, due to Reilly and Vamanamurthy [Indian J. Pure Appl. Math., 14 (1983, 767–772], who call such maps clopen continuous, are studied. Sufficient conditions on domain or range for a continuous function to be cl-supercontinuous are observed. Direct and inverse transfer of certain topological properties under cl-supercontinuous functions are studied and existence or nonexistence of certain cl-supercontinuous function with specified domain or range is outlined.

  6. Synthesis and characterization of [Ru(η6-C6Me6)Cl2(CNPy)] and [Cl2(η6-C6Me6)Ru-(μ-CNPy)-Ru(η6-C6Me6)Cl2] and reactivity of [Ru(η6-C6Me6)Cl2(CNPy)] with various bases

    International Nuclear Information System (INIS)

    Pandey, D.S.; Sahay, A.N.; Agarwala, U.C.

    1996-01-01

    Reactions of [(Ru(η 6 -C 6 Me 6 )Cl 2 ) 2 ] with 4-cyanopyridine leads to the formation of neutral mono and dimeric complexes viz., [Ru(η 6 C 6 Me 6 )Cl 2 (CNPy)] (I) and [Cl 2 (η 6 -C 6 Me 6 ) Ru-(μ-CNPy)-Ru(η 6 -C 6 Me 6 )Cl 2 ] (II). Complex (I) undergoes metathetical reactions with EPh 3 (E=P, As and Sb) and N-donor heterocyclic bases yielding corresponding substitutional products which have been characterized by elemental analyses and spectroscopic: (IR, UV/vis, 1 H and 13 C NMR) studies. (author). 21 refs., 1 tab

  7. Development of a Cl-impregnated activated carbon for entrained-flow capture of elemental mercury.

    Science.gov (United States)

    Ghorishi, S Behrooz; Keeney, Robert M; Serre, Shannon D; Gullett, Brian K; Jozewicz, Wojciech S

    2002-10-15

    Efforts to discern the role of an activated carbon's surface functional groups on the adsorption of elemental mercury (Hg0) and mercuric chloride demonstrated that chlorine (Cl) impregnation of a virgin activated carbon using dilute solutions of hydrogen chloride leads to increases (by a factor of 2-3) in fixed-bed capture of these mercury species. A commercially available activated carbon (DARCO FGD, NORITAmericas Inc. [FGD])was Cl-impregnated (Cl-FGD) [5 lb (2.3 kg) per batch] and tested for entrained-flow, short-time-scale capture of Hg0. In an entrained flow reactor, the Cl-FGD was introduced in Hg0-laden flue gases (86 ppb of Hg0) of varied compositions with gas/solid contact times of about 3-4 s, resulting in significant Hg0 removal (80-90%), compared to virgin FGD (10-15%). These levels of Hg0 removal were observed across a wide range of very low carbon-to-mercury weight ratios (1000-5000). Variation of the natural gas combustion flue gas composition, by doping with nitrogen oxides and sulfur dioxide, and the flow reactor temperature (100-200 degrees C) had minimal effects on Hg0 removal bythe Cl-FGD in these carbon-to-mercury weight ratios. These results demonstrate significant enhancement of activated carbon reactivity with minimal treatment and are applicable to combustion facilities equipped with downstream particulate matter removal such as an electrostatic precipitator.

  8. 20 years of ClO measurements in the Antarctic lower stratosphere

    Science.gov (United States)

    Nedoluha, Gerald E.; Connor, Brian J.; Mooney, Thomas; Barrett, James W.; Parrish, Alan; Gomez, R. Michael; Boyd, Ian; Allen, Douglas R.; Kotkamp, Michael; Kremser, Stefanie; Deshler, Terry; Newman, Paul; Santee, Michelle L.

    2016-08-01

    We present 20 years (1996-2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOE1) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004-2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly = HCl + ClONO2 + HOCl + 2 × Cl2 + 2 × Cl2O2 + ClO + Cl). The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be -0.5 ± 0.2, -1.4 ± 0.9, and -0.6 ± 0.4 % year-1, for zonal MLS, Scott Base MLS (both 2004-2015), and ChlOE (1996-2015) respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

  9. Quasi-static tensile properties of the Cranial Cruciate Ligament (CrCL) in adult cattle: towards the design of a prosthetic CrCL.

    Science.gov (United States)

    Diotalevi, Lucien; Petit, Yvan; Brailovski, Vladimir; Nichols, Sylvain; Marchionatti, Emma; Wagnac, Éric

    2018-03-01

    Mechanical properties of the Cranial Cruciate Ligament (CrCL) in adult cattle are not well documented and protocols used in the literature focus on testing a full femur-CrCL-tibia complex rather than an isolated CrCL. The aim of this study was to assess a wider range of tensile properties of the CrCL along its anatomic axis with experimental measurements of the global elongation, displacement and strain fields, in order to provide guidelines for the design of CrCL prosthetic surrogates. Fourteen bovine CrCL were harvested from seven mature cows (5.1 ± 1.3 years) weighing 631 ± 90kg. The mean CrCL length was 41.4 ± 1.5mm and its mean cross-section was 103.9 ± 23.8mm 2 . Pre-conditioning was achieved with 30 cycles of loading from 30 to 200N at a strain rate of 0.02s -1 . Specimens were then loaded to failure at the same strain rate. The following results were obtained: the mean ultimate tensile load (UTL) 4372 ± 1485N and the median [quartiles] maximal global elongation 19.3 [17.8; 21.4] %. At first physical signs of tearing, the mean load was 3315 ± 1336N and mean elongation 13.5 ± 4.9%. The mean absorbed energy at failure was 5.23 ± 2.08 MJ.mm -3 and the mean stiffness at various levels of elongation was: 220 ± 195N.% -1 (5%), 285 ± 162N.% -1 (10%), 239 ± 200N.% -1 (15%), 146 ± 59N.% -1 (20%), 153 ± 136N.% -1 (25%). None of these properties were related to the bovine weight, age and side of the body (p > 0.05). An ideal prosthetic surrogate should then follow these sets of properties and the experimental data suggest that the in-vivo maximal elongation is below 13.5%. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Effects of KOH:ZnCl2 mole ratio on the phase formation, morphological and inhibitive properties of potassium zinc phosphate (PZP) pigments

    International Nuclear Information System (INIS)

    Askari, F.; Ghasemi, E.; Ramezanzadeh, B.; Mahdavian, M.

    2015-01-01

    Graphical abstract: This figure illustrates the inhibition mechanism. The film precipitation on the anodic and cathodic regions of the metal surface causes a drop in dissolution rate of steel. - Highlights: • We synthesized the ZP pigments via coprecipitation method. • Effect of KOH:ZnCl 2 on phase formation, morphology and inhibitive performance of pigment. • KOH:ZnCl 2 ratio is effective on phase formation and morphology of ZP pigments. • KZn 2 H(PO 4 ) 2 phase showed superior corrosion inhibition behavior than KZnPO 4 . - Abstract: Different types of potassium zinc phosphate (PZP) pigments were synthesized by a co-precipitation method. The PZPs were obtained through changing KOH:ZnCl 2 mole ratio. The chemical composition of the pigments was studied by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). Then, the extracts of the PZPs were prepared in 3.5% (w/w) NaCl solution. The inhibitive performance of the pigments was investigated by polarization technique and SEM surface analysis through dipping mild steel panels in the pigment extracts for different immersion times. Results showed that changing ZnCl 2 /KOH mole ratio could influence formation of KZn 2 H(PO 4 ) 2 and KZnPO 4 phases. It was known that the KZn 2 H(PO 4 ) 2 phase has a superior corrosion inhibition behavior in 3.5% NaCl solution than KZnPO 4 phase

  11. Site and local structure of activator Eu{sup 2+} in phosphor Ca{sub 10−x}(PO{sub 4}){sub 6}Cl{sub 2}:xEu{sup 2+}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chun-Hai, E-mail: chwang81@gmail.com [National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, Mianyang 621900 (China); Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); School of Physics, Peking University, Beijing 100871 (China); Gui, Dong-Yun; Qin, Rui [National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, Mianyang 621900 (China); Yang, Feng-Li [Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Jing, Xi-Ping, E-mail: xpjing@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Tian, Guang-Shan [School of Physics, Peking University, Beijing 100871 (China); Zhu, Wenjun [National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, Mianyang 621900 (China)

    2013-10-15

    The site and local structure of activator Eu{sup 2+} in phosphor Ca{sub 10−x}(PO{sub 4}){sub 6}Cl{sub 2}:xEu{sup 2+} is investigated by experiment measurements, first-principle calculations and XAFS simulations. From first-principle calculations, the “local” structure [bond length L(M–O)≤R(M{sup 2+})+R(O{sup 2−})] of host shows a significant deformation (expansion) when Ca{sup 2+} is substituted by Eu{sup 2+}, and Eu{sup 2+} should prefer 6h site to 4f site in the host. The d→f emission of Eu{sup 2+} at 4f site should show a longer wavelength than that of Eu{sup 2+} at 6h site. The XAFS measurement and simulations suggest that the Eu{sup 2+} in our Ca{sub 9.9}(PO{sub 4}){sub 6}Cl{sub 2}:0.1Eu{sup 2+} sample mainly locates at 6h site. In the emission spectrum, two emission profiles of Ca{sub 9.9}(PO{sub 4}){sub 6}Cl{sub 2}:0.1Eu{sup 2+} sample are obtained and assigned. The major one (2.71 eV≈456 nm) should be the emission of Eu{sup 2+} at 6h site. The minor one (2.61 eV≈465 nm) should be that of Eu{sup 2+} at 4f site. - Graphical abstract: The d→f emission of Eu{sup 2+} in Ca{sub 9.9}(PO{sub 4}){sub 6}Cl{sub 2}:0.1Eu{sup 2+} can be assigned as: emission profile at 2.71 eV and 2.61 eV are Eu{sup 2+} at 6h and 4f site, respectively. Display Omitted - Highlights: • Eu{sup 2+} in Ca{sub 10−x}(PO{sub 4}){sub 6}Cl{sub 2}:xEu{sup 2+} causes deformation to “local” structure. • Eu{sup 2+} should prefer 6h site to 4f site in the host from energy aspect. • Emission at 2.71 eV and 2.61 eV should be Eu{sup 2+} at 6h and 4f site.

  12. Probing the pre-reactive a Cl (2P) + H2(D2) Van der Waals well through the photodetachment spectroscopy of Cl- H2(D2). CP-31

    International Nuclear Information System (INIS)

    Ghosal, Subhas; Mahapatra, Susanta

    2004-01-01

    The photodetachment spectrum of ClH 2 - and ClD 2 , probing the van der Waals well region of the reactive Cl( 2 P) + H 2 (D 2 ) potential energy surface, is theoretically calculated and compared with the experiment. A time-dependent wave packet approach is employed using the Capecchi-Werner coupled multi-sheeted ab initio potential energy surfaces of neutral ClH 2 for this purpose

  13. 16 CFR 4.3 - Time.

    Science.gov (United States)

    2010-01-01

    ... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Time. 4.3 Section 4.3 Commercial Practices FEDERAL TRADE COMMISSION ORGANIZATION, PROCEDURES AND RULES OF PRACTICE MISCELLANEOUS RULES § 4.3 Time. (a) Computation. Computation of any period of time prescribed or allowed by the rules in this chapter, by order of...

  14. Cl-36 in polar ice, rainwater and seawater

    Science.gov (United States)

    Finkel, R. C.; Nishiizumi, K.; Elmore, D.; Ferraro, R. D.; Gove, H. E.

    1980-01-01

    Concentrations of the cosmogenic radioisotope Cl-36 in Antarctic ice, rain, and an upper limit of the seawater value are determined using van de Graaff accelerator high energy mass spectrometry. Cl-36 concentrations in Antarctic ice range between 2.5 to 8.7 x 10 to the 6th atoms Cl-36/kg, while those concentrations in samples collected at the Alan Hills ice field locations where meteorites have been brought to the surface by glacial flow and ablation are found to vary by more than a factor of three. This variation is attributed either to the effects of atmospheric mixing and scavenging or to radioactive decay in old ice. The Cl-36 concentration found in a present sample of rainwater is much lower than that reported in samples collected in the early 1960's, suggesting the occurrence of a decrease in the concentration of atmospheric Cl-36 derived from nuclear weapons tests over this time period.

  15. Design, synthesis, and pharmacology of a highly subtype-selective GluR1/2 agonist, (RS)-2-amino-3-(4-chloro-3-hydroxy-5-isoxazolyl)propionic acid (Cl-HIBO)

    DEFF Research Database (Denmark)

    Bjerrum, Esben J; Kristensen, Anders S; Pickering, Darryl S

    2003-01-01

    On the basis of structural studies, chloro-homoibotenic acid (Cl-HIBO) was designed and synthesized. Cl-HIBO was characterized in binding and electrophysiology experiments on native and cloned subtypes of GluRs. Electrophysiological selectivities ranged from 275 to 1600 for GluR1/2 over GluR3/4. ...

  16. Cyclic voltammetric study of the reduction of U(III) to uranium metal in molten LiCl-NaCl-CaCl2-BaCl2-UCl3

    International Nuclear Information System (INIS)

    Poa, D.S.; Tomczuk, Z.; Steunenberg, R.K.

    1986-01-01

    Cyclic voltammetry was used to investigate the electrochemistry of the reduction of UCl 3 to uranium metal in molten LiCl-NaCl-CaCl 2 -BaCl 2 (49.7-8.0-26.5-15.8 mol %) containing dissolved UCl 3 . The purpose of the study was to obtain information on the kinetics of the reaction, which will be used in the design of electrorefining equipment for the reprocessing of core and blanket fuel discharged from the Integral Fast Reactor (IFR). The electrorefining operation employs the above salt as the electrolyte and a liquid cadmium pool as the anode

  17. Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

    Science.gov (United States)

    Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

    2009-06-22

    Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand

  18. Preparation and Characterization of TiO2 Nanostructure by TiCl4 Hydrolysis with Additive NaOH

    Directory of Open Access Journals (Sweden)

    Rashed Taleb Rasheed

    2018-04-01

    Full Text Available Titanium dioxide (TiO2 nanostructures were synthesized via the hydrolysis of TiCl4 in alcohol / water solution/with sodium hydroxide solution in the ice-bath (0-5 ◦C. The particles were char-acterized by using X-ray diffraction technique (XRD, spectroscopy of Ultra Violet-Visible (UV / Visible and infrared (FT-IR, atomic force microscope (AFM and scanning electron micro-scope (SEM analysis were used in order to gain information about the material, morphology, size and the shape of the particles

  19. 37Cl/35Cl isotope ratio analysis in perchlorate by ion chromatography/multi collector -ICPMS: Analytical performance and implication for biodegradation studies.

    Science.gov (United States)

    Zakon, Yevgeni; Ronen, Zeev; Halicz, Ludwik; Gelman, Faina

    2017-10-01

    In the present study we propose a new analytical method for 37 Cl/ 35 Cl analysis in perchlorate by Ion Chromatography(IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). The accuracy of the analytical method was validated by analysis of international perchlorate standard materials USGS-37 and USGS -38; analytical precision better than ±0.4‰ was achieved. 37 Cl/ 35 Cl isotope ratio analysis in perchlorate during laboratory biodegradation experiment with microbial cultures enriched from the contaminated soil in Israel resulted in isotope enrichment factor ε 37 Cl = -13.3 ± 1‰, which falls in the range reported previously for perchlorate biodegradation by pure microbial cultures. The proposed analytical method may significantly simplify the procedure for isotope analysis of perchlorate which is currently applied in environmental studies. Copyright © 2017. Published by Elsevier Ltd.

  20. The importance of dye chemistry and TiCl4 surface treatment in the behavior of Al2O3 recombination barrier layers deposited by atomic layer deposition in solid-state dye-sensitized solar cells

    KAUST Repository

    Brennan, Thomas P.

    2012-01-01

    Atomic layer deposition (ALD) was used to fabricate Al 2O 3 recombination barriers in solid-state dye-sensitized solar cells (ss-DSSCs) employing an organic hole transport material (HTM) for the first time. Al 2O 3 recombination barriers of varying thickness were incorporated into efficient ss-DSSCs utilizing the Z907 dye adsorbed onto a 2 μm-thick nanoporous TiO 2 active layer and the HTM spiro-OMeTAD. The impact of Al 2O 3 barriers was also studied in devices employing different dyes, with increased active layer thicknesses, and with substrates that did not undergo the TiCl 4 surface treatment. In all instances, electron lifetimes (as determined by transient photovoltage measurements) increased and dark current was suppressed after Al 2O 3 deposition. However, only when the TiCl 4 treatment was eliminated did device efficiency increase; in all other instances efficiency decreased due to a drop in short-circuit current. These results are attributed in the former case to the similar effects of Al 2O 3 ALD and the TiCl 4 surface treatment whereas the insulating properties of Al 2O 3 hinder charge injection and lead to current loss in TiCl 4-treated devices. The impact of Al 2O 3 barrier layers was unaffected by doubling the active layer thickness or using an alternative ruthenium dye, but a metal-free donor-π-acceptor dye exhibited a much smaller decrease in current due to its higher excited state energy. We develop a model employing prior research on Al 2O 3 growth and dye kinetics that successfully predicts the reduction in device current as a function of ALD cycles and is extendable to different dye-barrier systems. © This journal is the Owner Societies 2012.

  1. Study on treatment of distilled ammonia waste water from coke plant with activated carbon-NaClO catalytic oxidation method

    Energy Technology Data Exchange (ETDEWEB)

    Luo, D.; Yi, P.; Liu, J.; Chen, A. [Xiangtan Polytechnic University, Xiangtan (China). Dept. of Chemical Enginering

    2001-12-01

    Catalytic oxidation method for the treatment of distilled ammonia waste water from coke plant was investigated using activated carbon as catalyst and NaClO as oxidant. The influences of main factors, such as NaClO, activated carbon, pH and reactionary time were discussed. The results showed that under the conditions of 25{degree}C, NaClO/CODO=1.5, carbon/NaClO=0.6 and pH=3.0, the reaction completed within 120 minutes with 99.5% of phenol removal and 75.8% of COD removal when the distilled ammonia waste water from coke plant which containing phenol 510 mg/L and CODO 8420 mg/L was treated. 13 refs., 4 figs.

  2. Intermediate-range chemical ordering of cations in molten RbCl-AgCl

    Energy Technology Data Exchange (ETDEWEB)

    Tahara, S. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Kawakita, Y. [J-PARC Center, Japan Atomic Energy Agency (JAEA), Ibaraki 319-1195 (Japan); Shimakura, H. [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Sciences, Niigata 956-8603 (Japan); Ohara, K. [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Fukami, T. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Takeda, S. [Department of Physics, Faculty of Sciences, Kyushu University, Fukuoka 812-8581 (Japan)

    2015-07-28

    A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S{sub AgAg}(Q) and S{sub RbRb}(Q), show a positive contribution to the FSDP, while S{sub AgRb}(Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM.

  3. Intermediate-range chemical ordering of cations in molten RbCl-AgCl

    International Nuclear Information System (INIS)

    Tahara, S.; Kawakita, Y.; Shimakura, H.; Ohara, K.; Fukami, T.; Takeda, S.

    2015-01-01

    A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S AgAg (Q) and S RbRb (Q), show a positive contribution to the FSDP, while S AgRb (Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM

  4. Preparation and calibration by liquid scintillation of a sample of Cl 36. Preparacion y calibracion por centelleo liquido de una muestra de Cl 36

    Energy Technology Data Exchange (ETDEWEB)

    Grau Malonda, A; Los Arcos, J M; Rodriguez Barquero, L; Suarez, C [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Madrid (Spain)

    1989-01-01

    A procedure to prepare a sample of Clorine 36, as Li{sup 36}Cl, able to be measured by liquid scintillation counting, is described. The sample is chemically stable, with no variation of the quenching parameter up to 4 mg of LiCl per 15 ml of scintillator, keeps constant the counting efficiency for concentration higher than 40 {mu}g of Li{sup 36}Cl in that volume, and shows no deterioration over a 3 weed period. The Li{sup 36}Cl solution has been standarized using the free parameter method with different volumes of toluene, PCS and Instagel, to an uncertainty of 0,3% (Author).

  5. A data base for thermodynamic modeling of +III actinide solubility in concentrated Na-Cl-SO4-CO3-PO4 electrolytes

    International Nuclear Information System (INIS)

    Novak, C.F.; Crafts, C.C.; Dhooge, N.J.

    1995-01-01

    The literature contains thermodynamic parameters for describing the chemical behavior of the following: Am(III) in dilute NaHCO 3 media; Nd(III) in dilute to concentrated Na 2 CO 3 and NaHCO 3 media; Pu(III) in dilute to concentrated NaCl media; Nd(III)/Am(III) in dilute to concentrated Na 2 SO 4 media; and Am(III) in NaH 2 PO 4 media. We have combined this information into a thermodynamic data base for the general +III actinide, An(III), using the analogy for chemical behavior of f-elements in the same oxidation state. This internally consistent data base is based on equilibrium thermodynamics and the specific ion interaction activity coefficient formalism of Pitzer. This data base forms the basis for the prediction of potential Am(III) and Pu(III) dissolved concentrations in the concentrated natural brines associated with the Waste Isolation Pilot Plant (WIPP) in Southeastern New Mexico, USA

  6. Electrochemical performance of all-solid-state lithium batteries using inorganic lithium garnets particulate reinforced PEO/LiClO4 electrolyte

    International Nuclear Information System (INIS)

    Cheng, Samson Ho-Sum; He, Kang-Qiang; Liu, Ying; Zha, Jun-Wei; Kamruzzaman, Md; Ma, Robin Lok-Wang; Dang, Zhi-Min; Li, Robert K.Y.; Chung, C.Y.

    2017-01-01

    All-solid-state batteries are proposed to have ultimate safety and higher power and energy densities over conventional lithium ion batteries with liquid electrolytes. The Li ion conductivity and interfacial resistance between electrolyte and electrodes are the major bottleneck of the development of all-solid-state batteries for practical uses. Here, we reported a novel composite electrolyte which is composed of uniform distributed Li ion conducting Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) fillers in PEO/LiClO 4 matrix. The EO:Li + ratio of 15:1 is being used to achieve lower interfacial resistance between electrolyte and electrodes through the melting process. The composite electrolyte is fabricated by simple solution casting method, which is more advantageous comparing with high temperature sintering or sol-gel method used in the fabrication of ceramic electrolytes. The composite electrolyte exhibits good Li ion conductivity of 4.8 × 10 −4 Scm −1 at 60 °C and excellent interfacial stability against Li metal. The all-solid-state lithium battery using this composite electrolyte shows a specific capacity of 140mAhg −1 and an unprecedentedly high capacity retention of 83% after 500 cycles at 60 °C and the rate of 1C. It is concluded that good electrode/electrolyte interfacial stability and contact as well as fast Li ion conductivity obtained by the addition of active garnet particulates to PEO/LiClO 4 matrix are essential criteria for good charge/discharge performance of all-solid-state lithium batteries.

  7. Effect of Al2O3 nanoparticles in plasticized PMMA-LiClO4 based solid polymer electrolyte

    Science.gov (United States)

    Pal, P.; Ghosh, A.

    2017-05-01

    We have studied the broadband complex conductivity spectra covering a 0.01 Hz-3 GHz frequency range for plasticized PMMA-LiClO4 based solid polymer electrolyte embedded with Al2O3 nanoparticle. We have analyzed the conductivity spectra using the random free-energy barrier model (RBM) coupled with electrode polarization contribution in the low frequency region and at high temperatures. The temperature dependence of the ionic conductivity obtained from the analysis has been analyzed using Vogel-Tammann-Fulcher equation. The maximum ionic conductivity ˜ 1.93×10-4 S/cm has been obtained for 1 wt% Al2O3 nanoparticle.

  8. Charge carrier dynamics in PMMA-LiClO4 based polymer electrolytes plasticized with different plasticizers

    Science.gov (United States)

    Pal, P.; Ghosh, A.

    2017-07-01

    We have studied the charge carrier dynamics in poly(methylmethacrylate)-LiClO4 polymer electrolytes plasticized with different plasticizers such as ethylene carbonate (EC), propylene carbonate (PC), polyethylene glycol (PEG), and dimethyl carbonate (DMC). We have measured the broadband complex conductivity spectra of these electrolytes in the frequency range of 0.01 Hz-3 GHz and in the temperature range of 203 K-363 K and analyzed the conductivity spectra in the framework of the random barrier model by taking into account the contribution of the electrode polarization observed at low frequencies and/or at high temperatures. It is observed that the temperature dependences of the ionic conductivity and relaxation time follow the Vogel-Tammann-Fulcher relation for all plasticized electrolytes. We have also performed the scaling of the conductivity spectra, which indicates that the charge carrier dynamics is almost independent of temperature and plasticizers in a limited frequency range. The existence of nearly constant loss in these electrolytes has been observed at low temperatures and/or high frequencies. We have studied the dielectric relaxation in these electrolytes using electric modulus formalism and obtained the stretched exponent and the decay function. We have observed less cooperative ion dynamics in electrolytes plasticized with DMC compared to electrolytes plasticized with EC, PC, and PEG.

  9. Pressure-dependent ground states and fermiology in β- ( BDA-TTP ) 2 M Cl4 ( M=Fe,Ga )

    Science.gov (United States)

    Choi, E. S.; Graf, D.; Brooks, J. S.; Yamada, J.; Akutsu, H.; Kikuchi, K.; Tokumoto, M.

    2004-07-01

    We have investigated pressure- and magnetic-field-dependent electrical transport properties in the charge transfer salts β-(BDA-TTP)2MCl4(M=Fe,Ga) , both of which show a metal-insulator (MI) transition around 120K at ambient pressure. The zero field temperature-pressure phase diagrams of the two compounds are quite similar; the MI transition temperature decreases with pressure, and superconductivity is observed in both the magnetic and non-magnetic compounds above ˜4.5kbar . Likewise, Shubnikov-de Haas effect measurements show nearly identical Fermi surfaces. These similarities suggest that the magnetic interaction J between the conduction electrons and the magnetic moments in β-(BDA-TTP)2FeCl4 is small. Nevertheless, magnetoresistance measurements show remarkable differences and reveal that magnetic interactions with the conduction electrons are still effective in M=Fe compounds.

  10. Synthesis, characterisation and antibacterial activity of [(p-cym)RuX(L)](+/2+) (X = Cl, H2O; L = bpmo, bpms) complexes.

    Science.gov (United States)

    Tripathy, Suman Kumar; Taviti, Ashoka Chary; Dehury, Niranjan; Sahoo, Anupam; Pal, Satyanaryan; Beuria, Tushar Kant; Patra, Srikanta

    2015-03-21

    Mononuclear half-sandwiched complexes [(p-cym)RuCl(bpmo)](ClO4) {[1](ClO4)} and [(p-cym)RuCl(bpms)](PF6) {[2](PF6)} have been prepared by reacting heteroscorpionate ligands bpmo = 2-methoxyphenyl-bis(3,5-dimethylpyrazol-1-yl)methane and bpms = 2-methylthiophenyl-bis(3,5-dimethylpyrazol-1-yl)methane, respectively, with a dimeric precursor complex [(p-cym)RuCl(μ-Cl)]2 (p-cym = 1-isopropyl-4-methylbenzene) in methanol. The corresponding aqua derivatives [(p-cym)Ru(H2O)(bpmo)](ClO4)2 {[3](ClO4)2} and [(p-cym)Ru(H2O)(bpms)](PF6)2 {[4](PF6)2} are obtained from {[1](ClO4)} and {[2](PF6)}, respectively, via Cl(-)/H2O exchange process in the presence of appropriate equivalents of AgClO4/AgNO3 + KPF6 in a methanol-water mixture. The molecular structures of the complexes {[1]Cl, [3](ClO4)2 and [4](PF6)(NO3)} are authenticated by their single crystal X-ray structures. The complexes show the expected piano-stool geometry with p-cym in the η(6) binding mode. The aqua complexes [3](ClO4)2 and [4](PF6)2 show significantly good antibacterial activity towards E. coli (gram negative) and B. subtilis (gram positive) strains, while chloro derivatives ({[1](ClO4)} and {[2](PF6)} are found to be virtually inactive. The order of antibacterial activity of the complexes according to their MIC values is [1](ClO4) (both 1000 μg mL(-1)) < [2](PF6) (580 μg mL(-1) and 750 μg mL(-1)) < [3](ClO4)2 (both 100 μg mL(-1)) < [4](PF6)2 (30 μg mL(-1) and 60 μg mL(-1)) for E. coli and B. subtilis strains, respectively. Further, the aqua complexes [3](ClO4)2 and [4](PF6)2 show clear zones of inhibition against kanamycin, ampicillin and chloramphenicol resistant E. coli strains. The detailed mechanistic aspects of the aforesaid active aqua complexes [3](ClO4)2 and [4](PF6)2 have been explored, and it reveals that both the complexes inhibit the number of nucleoids per cell in vivo and bind to DNA in vitro. The results indeed demonstrate that both [3](ClO4)2 and [4](PF6)2 facilitate the inhibition of

  11. Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

    DEFF Research Database (Denmark)

    Joelsson, Lars Magnus Torvald; Forecast, Roslyn; Schmidt, Johan Albrecht

    2014-01-01

    The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D is found to be 1.60 ± 0.04. In addition, a quantum chemistry/transition state theory model with tunneling...

  12. 20 years of ClO measurements in the Antarctic lower stratosphere

    Directory of Open Access Journals (Sweden)

    G. E. Nedoluha

    2016-08-01

    Full Text Available We present 20 years (1996–2015 of austral springtime measurements of chlorine monoxide (ClO over Antarctica from the Chlorine Oxide Experiment (ChlOE1 ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004–2015 of ClO measurements from the Aura Microwave Limb Sounder (MLS. From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly  =  HCl + ClONO2 + HOCl + 2  ×  Cl2 + 2  ×  Cl2O2 + ClO + Cl. The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be −0.5 ± 0.2, −1.4 ± 0.9, and −0.6 ± 0.4 % year−1, for zonal MLS, Scott Base MLS (both 2004–2015, and ChlOE (1996–2015 respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

  13. Evidence of parity violation in 118Sn and 36Cl

    International Nuclear Information System (INIS)

    Benkoula, H.

    1978-01-01

    Parity violation in nuclear systems was studied by forward-backward asymmetry measurement methods in radiative capture of polarized neutrons in the reactions 117 Sn(n,γ) 118 Sn and 35 Cl(n,γ) 36 Cl. The experimental set ups used two INa detectors situated at left and right sides of the beam and parallel to polarisation direction, and an electronic system adapted to high-counting rate. The asymmetry measurement, A=(4.56+-0.6)x10 -4 in the 9.328 MeV Ml transition demonstrates the existence of parity violation effects. The 8.58 MeV (M1+E2) transition in 36 Cl was also studied and the asymmetry value is A=(1.11+-0.35)x10 -4 . Several beam and electronic tests have shown that there was no spurious asymmetry in the measurement due to the equipment [fr

  14. Modeling electronic defects in La2CuO4 and LiCl using embedded quantum cluster methodology

    International Nuclear Information System (INIS)

    Grimes, R.W.; Shluger, A.L.; Baetzold, R.; Catlow, C.R.A.

    1991-01-01

    By exploiting recent developments in computer simulation methods the authors modeled the behavior of hole states in La 2 CuO 4 and excited state defects such as the exciton in LiCl. The authors methodology employs a Hartree-Fock cluster embedded in a classical surround. Although the method is discussed with respect to the hole and exciton defects in particular, the scope of the talk includes other material problems currently being investigated by this method. Thus, the types of problems for which the method are appropriate are illustrated and the present limitations are discussed

  15. OpenCL programming guide

    CERN Document Server

    Munshi, Aaftab; Mattson, Timothy G; Fung, James; Ginsburg, Dan

    2011-01-01

    Using the new OpenCL (Open Computing Language) standard, you can write applications that access all available programming resources: CPUs, GPUs, and other processors such as DSPs and the Cell/B.E. processor. Already implemented by Apple, AMD, Intel, IBM, NVIDIA, and other leaders, OpenCL has outstanding potential for PCs, servers, handheld/embedded devices, high performance computing, and even cloud systems. This is the first comprehensive, authoritative, and practical guide to OpenCL 1.1 specifically for working developers and software architects. Written by five leading OpenCL authorities, OpenCL Programming Guide covers the entire specification. It reviews key use cases, shows how OpenCL can express a wide range of parallel algorithms, and offers complete reference material on both the API and OpenCL C programming language. Through complete case studies and downloadable code examples, the authors show how to write complex parallel programs that decompose workloads across many different devices. They...

  16. Spectrophotometric determination of Tl carrier in 201Tl-TlCl injection

    International Nuclear Information System (INIS)

    Gong Quansheng; Jing Lie

    1997-01-01

    A simple and sensitive method for the spectrophotometric determination of carrier content (Thallium) in 201 Tl-TlCl injection is described. Thallium (I) is oxidised to Thallium (III) by aqueous bromine, then excess bromine is removed by adding sulfosalicylic acid. In buffer solution (NH 4 Cl-NH 4 OH) at pH 11.7 with the presence of emulsifier OP, thallium (III) and cadion form a complex having an absorption maximum at 469 nm with a molar absorptivity of 1.37 x 10 4 m 2 /mol. Beer's law is obeyed in the concentration range of 0-7 μg/5 mL. The effect of impurity elements in 201 Tl-TlCl injection is examined. It is an ideal method for the analysis of radioactive solution

  17. Platelet-derived growth factor regulates K-Cl cotransport in vascular smooth muscle cells.

    Science.gov (United States)

    Zhang, Jing; Lauf, Peter K; Adragna, Norma C

    2003-03-01

    Platelet-derived growth factor (PDGF), a potent serum mitogen for vascular smooth muscle cells (VSMCs), plays an important role in membrane transport regulation and in atherosclerosis. K-Cl cotransport (K-Cl COT/KCC), the coupled-movement of K and Cl, is involved in ion homeostasis. VSMCs possess K-Cl COT activity and the KCC1 and KCC3 isoforms. Here, we report on the effect of PDGF on K-Cl COT activity and mRNA expression in primary cultures of rat VSMCs. K-Cl COT was determined as the Cl-dependent Rb influx and mRNA expression by semiquantitative RT-PCR. Twenty four-hour serum deprivation inhibited basal K-Cl COT activity. Addition of PDGF increased total protein content and K-Cl COT activity in a time-dependent manner. PDGF activated K-Cl COT in a dose-dependent manner, both acutely (10 min) and chronically (12 h). AG-1296, a selective inhibitor of the PDGF receptor tyrosine kinase, abolished these effects. Actinomycin D and cycloheximide had no effect on the acute PDGF activation of K-Cl COT, suggesting posttranslational regulation by the drug. Furthermore, PDGF increased KCC1 and decreased KCC3 mRNA expression in a time-dependent manner. These results indicate that chronic activation of K-Cl COT activity by PDGF may involve regulation of the two KCC mRNA isoforms, with KCC1 playing a dominant role in the mechanism of PDGF-mediated activation.

  18. Resonant x-ray emission from gas-phase TiCl4

    International Nuclear Information System (INIS)

    Hague, C.F.; Tronc, M.; De Groot, F.

    1997-01-01

    Resonant x-ray emission spectroscopy (RXES) has proved to be a powerful tool for studying the electronic structure of condensed matter. Over the past few years it has been used mainly for studying the valence bands of solids and condensed molecules. Very recently the advent of high brightness photon beams provided by third generation synchrotron radiation source undulators, associated with efficient x-ray emission spectrometers has made it possible to perform experiments on free diatomic molecular systems. RXE spectra of free molecules are of prime importance to gain insight into their electronic structure and bonding as they reflect the symmetry of orbitals engaged in the two-electron, two-step process with the l = 0, ±2 parity-conserving selection rule, and are free from solid state effects which can introduce difficulties in the interpretation. They provide information (more so than XAS) on the core excited states, and, when performed at fixed incident photon energy as a function of the emitted photon energy, on the electronic excitation (charge transfer, multiplet states). Moreover the anisotropy of the angular distribution of resonant x-ray emission affects the relative intensity of the emission peaks and provides information concerning the symmetries of final states. This is a preliminary report on what are the first RXE spectra of a 3d transition metal complex in the gas phase. The experiment concerns the Ti 3d →2p emission spectrum of TiCl 4 over the 450 to 470 eV region

  19. Ordered distribution of I and Cl in the low-temperature crystal structure of mutnovskite, Pb4As2S6ICl: An X-ray single-crystal study

    International Nuclear Information System (INIS)

    Bindi, Luca; Garavelli, Anna; Pinto, Daniela; Pratesi, Giovanni; Vurro, Filippo

    2008-01-01

    To study the temperature-dependent structural changes and to analyze the crystal chemical behavior of the halogens as a function of temperature, a crystal of the recently discovered mineral mutnovskite, ideally Pb 2 AsS 3 (I,Cl,Br), has been investigated by X-ray single-crystal diffraction methods at 300 and 110 K. At room temperature (RT) mutnovskite was confirmed to possess a centrosymmetric structure-type, space group Pnma, while at low temperature (110 K) it adopts a non-centrosymmetric orthorhombic structure-type, space group Pnm2 1 , with a=11.5394(9) A, b=6.6732(5) A, c=9.3454(7) A, V=719.64(9) A 3 and Z=2. Mutnovskite reconverts to the centrosymmetric-type upon returning to RT thus indicating that the phase transition is completely reversible in character. The refinement of the LT-structure leads to a residual factor R=0.0336 for 1827 independent observed reflections [F o >4σ(F o )] and 80 variables. The crystal structure of cooled mutnovskite is topologically identical to that observed at RT and the slight structural changes occurring during the phase transition Pnma→Pnm2 1 are mainly restricted to the coordination polyhedra around Pb. The structure solution revealed that I and Cl are ordered into two specific sites. Indeed, the unique mixed (I,Cl) position in the RT-structure (Wyckoff position 4c) transforms into two 2a Wyckoff positions in the LT-structure hosting I and Cl, respectively. - Graphical abstract: In the crystal structure of mutnovskite at 110 K the two halogens I and Cl are ordered into two specific sites and only slight changes in the coordination environment around Pb atoms occur during the phase transition Pnma→Pnm2 1 from the RT-structure to the LT-structure. Two kinds of layers alternating along a are present in the LT-structure: Layer I contains Cl atoms and [001] columns of Pb1 and Pb4 prisms, layer II contains I atoms and [001] columns of Pb2 and Pb3 prisms

  20. Three-site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2-supported Ziegler-Natta catalyst

    NARCIS (Netherlands)

    Shimizu, Fumihiko; Pater, J.T.M.; Weickert, G.

    2001-01-01

    This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl2-supported catalyst is used in a liquid pool polymerization at constant H2 concentration and temperature. To track the

  1. Density of molten salt Mixtures of eutectic LiCl-KCl containing UCl{sub 3}, CeCl{sub 3}, or LaCl{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C.; Simpson, M. F. [Dept. of Metallurgical Engineering, University of Utah, Salt Lake City (United States)

    2017-06-15

    Densities of molten salt mixtures of eutectic LiCl-KCl with UCl{sub 3}, CeCl{sub 3}, or LaCl{sub 3} at various concentrations (up to 13 wt%) were measured using a liquid surface displacement probe. Linear relationships between the mixture density and the concentration of the added salt were observed. For LaCl{sub 3} and CeCl{sub 3}, the measured densities were signifcantly higher than those previously reported from Archimedes’ method. In the case of LiCl-KCl-UCl{sub 3}, the data ft the ideal mixture density model very well. For the other salts, the measured densities exceeded the ideal model prediction by about 2%.

  2. Cyclotron resonance and De Haas-Van Alphen effect in (BEDT-TTF) sub 8 Hg sub 4 Cl sub 1 sub 2 (C sub 6 H sub 5 Cl) sub 2 organic conductor

    CERN Document Server

    Voskobojnikov, I B; Samarin, N A; Cluchanko, N E; Lyubovskaya, R N; Moshchalkov, V V

    2002-01-01

    Within 0.33-1.44 K temperature range at B <= 50 T magnetic field values one measured the De Haas-Van Alphen effect for (BEDT-TTF) sub 8 Hg sub 4 Cl sub 1 sub 2 (C sub 6 H sub 5 Cl) sub 2 organic quasi-two-dimensional conductor. Analysis of quantum oscillations with regard to data on cyclotron resonance derived for 40-120 GHz frequency interval enabled to determine that a complex spectrum of quantum oscillations was formed by alpha approx 256 T and beta approx 670-610 T fundamental frequencies as well as, by combination and multiple frequencies. It is shown that nature of temperature rearrangement of oscillation spectrum may be interpreted in terms of model taking account of occurrence of magnetic phase transition at T sub c approx 0.9 K and proximity of a fundamental frequency with m* = 1.48m sub 0 efficient mass to the spin dumping condition

  3. On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

    Science.gov (United States)

    Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

    2013-10-01

    The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH3)4][IrCl6] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.

  4. On formation mechanism of Pd–Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

    International Nuclear Information System (INIS)

    Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

    2013-01-01

    The formation mechanism of Pd–Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH 3 ) 4 ][IrCl 6 ] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd–Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10–200 nm) and dendrite Ir-rich (10–50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd–Ir nanoparticles, were found to occur.Graphical Abstract

  5. Effects of the new imidazopyridine CL 86-02-01 on isolated papillary muscle of guinea-pig hearts.

    Science.gov (United States)

    Studenik, C; Lemmens-Gruber, R; Heistracher, P

    1998-06-01

    Inotropic activity and the effect of CL 86-02-01 (2-(3-methoxy-5-methylsulfinyl-2-thienyl)-1H-imidazo[4,5-c]pyridine hydrochloride, CAS 109 792-24-7) on membrane resting and action potentials were studied in isolated guinea-pig papillary muscles. Membrane resting potential and action potential parameters were not significantly changed, while CL 86-02-01 exerted a concentration-dependent inotropic effect by increasing the maximum rate of force development and maximum rate of force relaxation. Time to peak force, relaxation time and total contraction time were reduced. These effects are similar to those of beta-adrenergic drugs and phosphodiesterase inhibitors, but markedly differ from those described for other positive inotropic agents like cardiac glycosides, calcium agonists, alpha-adrenergic drugs or increased extracellular calcium concentration.

  6. Virtual screening of cocrystal formers for CL-20

    Science.gov (United States)

    Zhou, Jun-Hong; Chen, Min-Bo; Chen, Wei-Ming; Shi, Liang-Wei; Zhang, Chao-Yang; Li, Hong-Zhen

    2014-08-01

    According to the structure characteristics of 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) and the kinetic mechanism of the cocrystal formation, the method of virtual screening CL-20 cocrystal formers by the criterion of the strongest intermolecular site pairing energy (ISPE) was proposed. In this method the strongest ISPE was thought to determine the first step of the cocrystal formation. The prediction results for four sets of common drug molecule cocrystals by this method were compared with those by the total ISPE method from the reference (Musumeci et al., 2011), and the experimental results. This method was then applied to virtually screen the CL-20 cocrystal formers, and the prediction results were compared with the experimental results.

  7. Electrodeposition of Al-Ta alloys in NaCl-KCl-AlCl{sub 3} molten salt containing TaCl{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Kazuki; Matsushima, Hisayoshi; Ueda, Mikito, E-mail: mikito@eng.hokudai.ac.jp

    2016-12-01

    Highlights: • Electrodeposition of Al-Ta alloys in an AlCl{sub 3}-NaCl-KCl-TaCl{sub 5} melt was carried out. • We were obtained 72 at% Ta-Al alloy at 0.3 V. • Amorphous Ta-Al was formed in high Ta concentration. - Abstract: To form Al-Ta alloys for high temperature oxidation resistance components, molten salt electrolysis was carried out in an AlCl{sub 3}-NaCl-KCl melt containing TaCl{sub 5} at 423 K. The voltammogram showed two cathodic waves at 0.45 V and 0.7 V vs. Al/Al(III), which may correspond to reduction from Ta(V) to Ta(III) and from Ta(III) to tantalum metal, respectively. Electrodeposits of Al and Ta were obtained in the range from −0.05 to 0.3 V and the highest concentration of Ta in the electrodeposit was 72 at% at 0.3 V. With increasing Ta content in the alloy, the morphology of the electrodeposits became powdery and the particle size smaller.

  8. Coagulation of landfill leachate by FeCl3: process optimization using Box-Behnken design (RSM)

    Science.gov (United States)

    Kumar, Smita S.; Bishnoi, Narsi R.

    2017-07-01

    FeCl3 coagulation was used to achieve maximum reduction of COD, phosphate, sulfate and color and process optimization (FeCl3 dosage, pH, reaction time) was done by BBD-RSM. Responses were recorded in terms of EC, COD, phosphate, color and sulfate removal. Variables A (pH) and B (reaction time) were negatively related to removal of COD and phosphate, whereas, C (FeCl3 dosage) was positive in case of COD removal and negative for phosphate removal. pH and coagulant dosage had negative relationship with color removal; however, reaction time showed positive relationship. In case of percent sulfate removal, variable A (pH) demonstrated negative relationship whereas B (reaction time) and C (FeCl3 dosage) were found to be positively related. Numerical optimization of the model revealed a maximum reduction of 71, 93, 86 and 99.6 % COD, phosphate, color and sulfate at optimal FeCl3 dosage = 3 g/l, pH 8, and reaction time = 95 min.

  9. The collectins CL-L1, CL-K1 and CL-P1, and their roles in complement and innate immunity

    DEFF Research Database (Denmark)

    Hansen, Soren W K; Ohtani, Katsuki; Roy, Nitai

    2016-01-01

    as CL-LK) and its activation of the lectin pathway via MASPs, drew new attention in the complement biology, which was further strengthened by the observed interactions between CL-P1 and CRP-C1q-factor H or properdin. Deficiency of either CL-K1 or MASP-3 has been demonstrated in 3MC syndrome patients...

  10. Structural and optical properties of AgCl-sensitized TiO2 (TiO2 @AgCl prepared by a reflux technique under alkaline condition

    Directory of Open Access Journals (Sweden)

    V. A. Mu’izayanti

    Full Text Available Abstract The AgCl-sensitized TiO2 (TiO2@AgCl has been prepared from the precursor of TiO2-rutile type which on its surface adsorb chloride anion (Cl- and various amounts of silver using AgNO3 as starting material: AgNO3/(AgNO3+TiO2 mass ratio of 0.00, 1.14, 3.25, 6.38 and 10.32%. Reflux under alkaline condition was the employed technique. All samples were characterized by X-ray diffraction (XRD and diffuse reflectance UV-vis spectroscopy. The sample without the addition of AgNO3 was analyzed by scanning electron microscope and surface area analyzer. The morphology of the sample showed a distribution of microspheres of approximately 0.5 to 1.0 µm and the specific surface area was 68 m2/g. XRD patterns indicated that the sample without the addition of AgNO3 contained two types of TiO2: rutile (major and anatase (minor, whereas the samples with the addition of AgNO3 consisted of one phase of AgCl and two types of TiO2: rutile and anatase. The bandgaps of the samples were in the range of 2.97 to 3.24 eV, which were very close to the bandgap of intrinsic TiO2 powder. The presence of 0.8, 2.6 and 4.4 wt% of AgCl in each sample resulted in an additional bandgap in visible light region of 1.90, 1.94 and 2.26 eV, respectively, whereas the presence of 9.4 wt% of AgCl in the sample resulted in two bandgaps in visible light region of 1.98 and 1.88 eV.

  11. Synthesis of 2-Isopropyl Naphthalene Catalyzed by Et3NHCl-AlCl3 Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    Li Chenmin; Qi Xin; Tang Xiangyang

    2014-01-01

    In this paper, 2-isopropyl naphthalene has been synthesized by the reaction of naphthalene and isopropyl bromide, using triethylamine hydrochloride-aluminum chloride ionic liquid as the catalyst. The effect of the catalyst composition, the reaction time, the reaction temperature, the ionic liquid dosage, as well as the molar ratio of the reagents on the 2-isopropyl naphthalene yield was systematically investigated. The optimal reaction conditions cover:an AlCl3 to Et3NHCl ratio of 2.0, a reaction time of 3 h, a reaction temperature of 15.0℃, a volume fraction of ionic liquid to the mixture (isopropyl bromide, n-dodecane and n-hexane) of 9%, and a naphthalene/isopropyl bromide molar ratio of 4.0. Under the optimal reaction condi-tions, the conversion of isopropyl bromide reached 98%and the selectivity of 2-isopropyl naphthalene was equal to 80%. The test results veriifed good catalytic activity upon using Et3NHCl-AlCl3 ionic liquid as the catalyst for alkylation of naph-thalene with isopropyl bromide. The activity of the ionic liquid remains unchanged after it has been recycled for 4 times.

  12. Reactions of the dirhenium(II) complexes Re2X4(dppm)2 (X = Cl, Br; dppm = Ph2PCH2PPh2) with isocyanides. 5. Mixed carbonyl-isocyanide and carbonyl-isocyanide-nitrile complexes of stoichiometry (Re2Cl3(dppm)2(CO)(CNR)(L))PF6 (R = t-Bu, xyl (Xylyl); L = t-BuNC, xylNC, MeCN, EtCN). Structural characterization of the cation (Cl2(CO)Re(μ-dppm)2ReCl (CN-t-Bu)2)+

    International Nuclear Information System (INIS)

    Fanwick, P.E.; Price, A.C.; Walton, R.A.

    1988-01-01

    Several dirhenium (II) species that contain mixed sets of carbonyl, isocyanide, and/or nitrile ligands have been prepared from the reactions between Re 2 Cl 4 (dppm) 2 (CO)(CNR) (dppm = Ph 2 PCHPPh 2 ; R = t-Bu, xyl (xylyl)), and the appropriate ligands in the presence of TlPF 6 . The crystal structures of these compounds are reported. The terminally-bound ligand noted in the complexes (Re 2 Cl 3 (dppm) 2 (CO)(CN-t-Bu) 2 )PF 6 and (Re 2 CL 3 (dppm) 2 (CO)(CN-t-Bu)(CNxyl))PF 6 indicates structures that have not been previously reported. Complexes in which there are mixed sets of carbonyl, isocyanide, and nitrile ligands, viz. (Re 2 Cl 3 (dppm) 2 (CO)(CNR)(CNR'))PF 6 are also reported. 20 refs., 1 fig., 5 tabs

  13. Effects of KOH:ZnCl{sub 2} mole ratio on the phase formation, morphological and inhibitive properties of potassium zinc phosphate (PZP) pigments

    Energy Technology Data Exchange (ETDEWEB)

    Askari, F. [Inorganic Pigment and Glazes Department, Institute for Color Science and Technology, Tehran 1668814811 (Iran, Islamic Republic of); Surface Coatings and Corrosion Department, Institute for Color Science and Technology, Tehran 1668814811 (Iran, Islamic Republic of); Ghasemi, E., E-mail: eghasemi@iust.ac.ir [Inorganic Pigment and Glazes Department, Institute for Color Science and Technology, Tehran 1668814811 (Iran, Islamic Republic of); Ramezanzadeh, B.; Mahdavian, M. [Surface Coatings and Corrosion Department, Institute for Color Science and Technology, Tehran 1668814811 (Iran, Islamic Republic of)

    2015-05-15

    Graphical abstract: This figure illustrates the inhibition mechanism. The film precipitation on the anodic and cathodic regions of the metal surface causes a drop in dissolution rate of steel. - Highlights: • We synthesized the ZP pigments via coprecipitation method. • Effect of KOH:ZnCl{sub 2} on phase formation, morphology and inhibitive performance of pigment. • KOH:ZnCl{sub 2} ratio is effective on phase formation and morphology of ZP pigments. • KZn{sub 2}H(PO{sub 4}){sub 2} phase showed superior corrosion inhibition behavior than KZnPO{sub 4}. - Abstract: Different types of potassium zinc phosphate (PZP) pigments were synthesized by a co-precipitation method. The PZPs were obtained through changing KOH:ZnCl{sub 2} mole ratio. The chemical composition of the pigments was studied by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). Then, the extracts of the PZPs were prepared in 3.5% (w/w) NaCl solution. The inhibitive performance of the pigments was investigated by polarization technique and SEM surface analysis through dipping mild steel panels in the pigment extracts for different immersion times. Results showed that changing ZnCl{sub 2}/KOH mole ratio could influence formation of KZn{sub 2}H(PO{sub 4}){sub 2} and KZnPO{sub 4} phases. It was known that the KZn{sub 2}H(PO{sub 4}){sub 2} phase has a superior corrosion inhibition behavior in 3.5% NaCl solution than KZnPO{sub 4} phase.

  14. Simultaneous voltammetric determination of dopamine and ascorbic acid using multivariate calibration methodology performed on a carbon paste electrode modified by a mer-[RuCl3(dppb)(4-pic)] complex

    International Nuclear Information System (INIS)

    Santos, Poliana M.; Sandrino, Bianca; Moreira, Tiago F.; Wohnrath, Karen; Nagata, Noemi; Pessoa, Christiana A.

    2007-01-01

    The preparation and electrochemical characterization of a carbon paste electrode (CPE) modified with mer-[Ru0Cl 3 (dppb)(4-pic)] (dppb=Ph 2 P(CH 2 ) 4 PPh 2 , 4-pic=CH 3 C 5 H 4 N), referred to as Rupic, were investigated. The CPE/Rupic system displayed only one pair of redox peaks, with a midpoint potential at 0.28 V vs. Ag/AgCl, which were ascribed to Ru III /Ru II charge transfer. This modified electrode presented the property of electrocatalysing the oxidation of dopamine (DA) and ascorbic acid (AA) at 0.35 V and 0.30 V vs. Ag/AgCl, respectively. Because the oxidation for both AA and DA practically occurred at the same potential, distinguishing between them was difficult with cyclic voltammetry. This limitation was overcome using Partial Least Square Regression (PLSR), which allowed us, with the optimised models, to determine four synthetic samples with prediction errors (RMSEP) of 5.55 X 10 -5 mol L -1 and 7.48 X 10 -6 mol L -1 for DA and AA, respectively. (author)

  15. Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

    KAUST Repository

    Nolan, Steven Patrick

    2017-09-06

    The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After determining electronic and steric properties of these ligands, their properties were compared to those of [Pd(IPr)(cin)Cl]. The three palladium complexes were studied using DFT calculations to delineate their behaviour in the activation step leading to the putative 12-electron active catalyst. Experimentally, their catalytic activity in the Suzuki-Miyaura reaction involving a wide range of coupling partners (30 entries) at low catalyst loading was studied.

  16. Single-molecule magnets: structure and properties of [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 with spin S = 13.

    Science.gov (United States)

    Brechin, E K; Sañudo, E C; Wernsdorfer, W; Boskovic, C; Yoo, J; Hendrickson, D N; Yamaguchi, A; Ishimoto, H; Concolino, T E; Rheingold, A L; Christou, G

    2005-02-07

    The reaction of 2-(hydroxyethyl)pyridine (hepH) with a 2:1 molar mixture of [Mn3O(O2CMe)6(py)3]ClO4 and [Mn3O(O2CMe)6(py)3] in MeCN afforded the new mixed-valent (16Mn(III), 2Mn(II)), octadecanuclear complex [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 (1) in 20% yield. Complex 1 crystallizes in the triclinic space group P. Direct current magnetic susceptibility studies in a 1.0 T field in the 5.0-300 K range, and variable-temperature variable-field dc magnetization studies in the 2.0-4.0 K and 2.0-5.0 T ranges were obtained on polycrystalline samples. Fitting of magnetization data established that complex 1 possesses a ground-state spin of S = 13 and D = -0.18 K. This was confirmed by the value of the in-phase ac magnetic susceptibility signal. Below 3 K, the complex exhibits a frequency-dependent drop in the in-phase signal, and a concomitant increase in the out-of-phase signal, consistent with slow magnetization relaxation on the ac time scale. This suggests the complex is a single-molecule magnet (SMM), and this was confirmed by hysteresis loops below 1 K in magnetization versus dc field sweeps on a single crystal. Alternating current and direct current magnetization data were combined to yield an Arrhenius plot from which was obtained the effective barrier (U(eff)) for magnetization reversal of 21.3 K. Below 0.2 K, the relaxation becomes temperature-independent, consistent with relaxation only by quantum tunneling of the magnetization (QTM) through the anisotropy barrier via the lowest-energy MS = +/-13 levels of the S = 13 spin manifold. Complex 1 is thus the SMM with the largest ground-state spin to display QTM.

  17. The effect of NaCl substitution by KCl on telemea cheese properties

    Directory of Open Access Journals (Sweden)

    Mihai ANGHELOIU

    2016-12-01

    Full Text Available The effect of partial or total substitution of sodium chloride by potassium chloride on the chemical composition, texture profile and sensory properties of Telemea cheese during 28 days of ripening at 4°C was evaluated in the current study. Telemea cheese was ripened in 4 different brine solutions (20%, wt/wt made from different NaCl:KCl ratios as follows: (NaCl (A, KCl (B, 1NaCl:1KCl (C and 1NaCl:2KCl (D. The physicochemical properties of Telemea cheese (dry matter, fat, protein, ash, pH, total nitrogen (TN, water soluble nitrogen (WSN and ripening degree values were determined after 1, 7, 14, 21 and 28 days of ripening. Dry matter, pH and ripening degree values were significantly (p < 0.05 affected during ripening. The results of this study indicated that replacing 66% NaCl with KCl influenced the texture profile and sensorial characteristics of Telemea cheese.

  18. Equilibrium electrode U(4)-U and redox U(4)-U(3) potentials in molten alkali metal chlorides medium

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, M V; Kudyakov, V Ya; Komarov, V E; Salyulev, A B [AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii

    1979-02-01

    Conditional standard electrode potentials of uranium are determined for diluted solutions of its tetrachloride in alkali metal chloride melts (LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl) when using U(4) ion activity coefficient values experimentally found by the tensimetric method. These potentials shift to the electronegative side at the temperature decrease and alkali cation radius increase rsub(Msup(+)) according to the empiric ratio E*U(4)-U= -3.06+6.87x10/sup -4/ T-(1.67-10/sup -4/T-0.44) 1/rsub(Msup(+)) +-0.01. The temperature dependences of formal conditional redox potentials of the U(4)-U(3) system for above melted chlorides are estimated. The E*U(4)-U(3) value also becomes more electronegative in the series LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl. This alternation is satisfactorily described by the empiric expression E*U(4)-U(3)= -1.74+1.74x10/sup -4/T-(0.71x10/sup -4/T-0.20) 1rsub(Msup(+)) +-0.05. The calculated values Eu*(4)-U(3) are compared with those directly measured for the NaCl-KCl equimolar mixture and 3LiCl-2KCl eutectic mixture. A satisfactory confirmity has been observed.

  19. Equilibrium electrode U(4)-U and redox U(4)-U(3) potentials in molten alkali metal chlorides medium

    International Nuclear Information System (INIS)

    Smirnov, M.V.; Kudyakov, V.Ya.; Komarov, V.E.; Salyulev, A.B.

    1979-01-01

    Conditional standard electrode potentials of uranium are determined for diluted solutions of its tetrachloride in alkali metal chloride melts (LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl) when using U(4) ion activity coefficient values experimentally found by the tensimetric method. These potentials shift to the electronegative side at the temperature decrease and alkali cation radius increase rsub(Msup(+)) according to the empiric ratio E*U(4)-U= -3.06+6.87x10 -4 T-(1.67-10 -4 T-0.44) 1/rsub(Msup(+)) +-0.01. The temperature dependences of formal conditional redox potentials of the U(4)-U(3) system for above melted chlorides are estimated. The E*U(4)-U(3) value also becomes more electronegative in the series LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl. This alternation is satisfactorily described by the empiric expression E*U(4)-U(3)= -1.74+1.74x10 -4 T-(0.71x10 -4 T-0.20) 1rsub(Msup(+)) +-0.05. The calculated values Eu*(4)-U(3) are compared with those directly measured for the NaCl-KCl equimolar mixture and 3LiCl-2KCl eutectic mixture. A satisfactory confirmity has been observed

  20. Production and characterization of pellets using Avicel CL611 as spheronization aid.

    Science.gov (United States)

    Puah, Sin Yee; Yap, Hsiu Ni; Chaw, Cheng Shu

    2014-03-01

    The study looked into the feasibility of producing pellet using Avicel CL611 as spheronization aid by the extrusion/spheronization technique. Pellets were formulated to contain either 20% or 40% Avicel CL611 and lactose monohydrate as the other sole ingredient. Water is used as liquid binder. Quality of pellets and extrudates were analyzed for size distribution, shape, surface tensile strength and disintegration profile. More water was needed when higher Avicel CL611 fraction was used during the production of pellets. The pellets of larger size were obtained by increasing the water content. Pellets with aspect ratios of ∼1.1 were produced with high spheronization speed at short residence time. Higher tensile strength was achieved when increasing the water content and the fraction of Avicel CL611 during pellet production. These pellets also took longer time to disintegrate, nonetheless all the pellets disintegrated within 15 min. A positive linear relationship was obtained between the tensile strength and time for pellets to disintegrate. Strong but round pellets that disintegrate rapidly could be produced with Avicel CL611 as spheronization aid using moderately soluble compounds such as lactose.

  1. Reactive quenching of two-photon excited xenon atoms by Cl2

    International Nuclear Information System (INIS)

    Bruce, M.R.; Layne, W.B.; Meyer, E.; Keto, J.W.

    1987-01-01

    Total binary and tertiary quench rates have been measured for the reaction Xe (5p 5 6p) + Cl 2 at thermal temperatures. Xenon atoms are excited by state-selective, two-photon absorption with a uv laser. The time dependent fluorescence from the excited atom in the IR and from XeCl* (B) product near 308 nm have been measured with subnanosecond time resolution. The decay rates are measured as a function of Cl 2 pressure to 20 Torr and Xe pressure to 400 Torr. The measured reaction rates (k 2 ∼ 10 -9 cm 3 sec -1 ) are consistent with a harpoon model described in a separate paper. We also measure large termolecular reaction rates for collisions with xenon atoms (k 3 ∼ 10 -28 cm 6 sec -1 ). Total product fluorescence has been examined using a gated optical multichannel analyzer. We measure unit branching fractions for high vibrational levels of XeCl* (B) with very little C state fluorescence observed. The measured termolecular rates suggest similar processes will dominate at the high buffer-gas pressures used in XeCl lasers. The effect of these large reactive cross sections for neutral xenon atoms on models of the XeCl laser will be discussed

  2. Electrospun nanofibrous SF/P(LLA-CL) membrane: a potential substratum for endothelial keratoplasty.

    Science.gov (United States)

    Chen, Junzhao; Yan, Chenxi; Zhu, Mengyu; Yao, Qinke; Shao, Chunyi; Lu, Wenjuan; Wang, Jing; Mo, Xiumei; Gu, Ping; Fu, Yao; Fan, Xianqun

    2015-01-01

    Cornea transplant technology has progressed markedly in recent decades, allowing surgeons to replace diseased corneal endothelium by a thin lamellar structure. A thin, transparent, biocompatible, tissue-engineered substrat