WorldWideScience

Sample records for fluoroborates

  1. Electrochemical studies in molten sodium fluoroborate

    International Nuclear Information System (INIS)

    Brigaudeau, M.; Wagner, J.F.

    1979-01-01

    Physical properties of sodium fluoroborate are recalled and first results obtained during experimental study of molten NaBF 4 are exposed. The system Cu/CuF is used as an indicator of fluoride ion activity and dissociation constant of the solvent is determined by adding NaF to NaBF 4 saturated with BF 3 at a pressure of 1 atm and found equal to 2.7x10 -3 [fr

  2. Electrochemical study in molten sodium fluoroborate at 4200C

    International Nuclear Information System (INIS)

    Wagner, J.F.

    1983-06-01

    By analysing the behavior of the electrochemical system Cu (I)/Cu it was possible to study the acid-base properties of molten sodium fluoroborate. The anion of the solvent BF 4 - is shown to undergo a strong dissociation according to the equilibrium BF 4 - BF 3 (g) + F - , the Ki constant at 420 0 C being evaluated at 1.58 x 10 -2 mol kg -1 atm. The acidity variations of sodium fluoroborate at this temperature are limited to about two pF units (pKi=1.8). A potentiometric study of the copper, silver and nickel systems showed that the corresponding metallic cations are little complexed by fluoride ions in spite of the strong dissociation of the solvent [fr

  3. The emission of fluorine gas during incineration of fluoroborate residue

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Yuheng, E-mail: fengyh@tongji.edu.cn [Thermal & Environmental Engineering Institute, Tongji University, Shanghai 200092 (China); Jiang, Xuguang [State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027 (China); Chen, Dezhen [Thermal & Environmental Engineering Institute, Tongji University, Shanghai 200092 (China)

    2016-05-05

    Highlights: • Gaseous fluorine products were identified when combusting fluoroborate residue. • BF{sub 3} and SiF{sub 4} tend to be hydrolyzed into HF with the increase of temperature. • The emission of BF{sub 3} and SiF{sub 4} from the chamber could be negligible at 1100 °C. - Abstract: The emission behaviors of wastes from fluorine chemical industry during incineration have raised concerns because multiple fluorine products might danger human health. In this study, fluorine emission from a two-stage incineration system during the combustion of fluoroborate residue was examined. In a TG-FTIR analysis BF{sub 3}, SiF{sub 4} and HF were identified as the initial fluorine forms to be released, while fluorine gases of greenhouse effect such as CF{sub 4} and SF{sub 6} were not found. Below 700 °C, NaBF{sub 4} in the sample decomposed to generate BF{sub 3}. Then part of BF{sub 3} reacted with SiO{sub 2} in the system to form SiF{sub 4} or hydrolyzed to HF. At higher temperatures, the NaF left in the sample was gradually hydrolyzed to form HF. A lab-scale two-stage tube furnace is established to simulate the typical two-stage combustion chamber in China. Experimental tests proved that HF was the only fluorine gas in the flue gas, and emissions of BF{sub 3} and SiF{sub 4} can be negligible. Thermodynamic equilibrium model predicted that all SiF{sub 4} would be hydrolyzed at 1100 °C in the secondary-chamber, which agreed well with the experimental results.

  4. Discovery of aryl-tri-fluoroborates as potent sodium/iodide sym-porter (NIS) inhibitors

    International Nuclear Information System (INIS)

    Lecat-Guillet, N.; Ambroise, Y.

    2008-01-01

    The structure-based design of sodium/iodide sym-porter (NIS) inhibitors identified new active compounds. The organo-tri-fluoroborate shown was found to inhibit iodide uptake with an IC50 value of 0.4 μM on rat-derived thyroid cells. The biological activity is rationalized by the presence of the BF3 - ion as a minimal binding motif for substrate recognition at the iodide binding site. (authors)

  5. Discovery of aryl-tri-fluoroborates as potent sodium/iodide sym-porter (NIS) inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Lecat-Guillet, N.; Ambroise, Y. [CEA, DSV, Dept Bioorgan Chem and Isotop Labelling, Inst Biol and Technol, iBiTecS, F-91191 Gif Sur Yvette (France)

    2008-07-01

    The structure-based design of sodium/iodide sym-porter (NIS) inhibitors identified new active compounds. The organo-tri-fluoroborate shown was found to inhibit iodide uptake with an IC50 value of 0.4 {mu}M on rat-derived thyroid cells. The biological activity is rationalized by the presence of the BF3{sup -} ion as a minimal binding motif for substrate recognition at the iodide binding site. (authors)

  6. Optical properties of Nd3+ doped barium lithium fluoroborate glasses for near-infrared (NIR) emission

    Science.gov (United States)

    Mariselvam, K.; Arun Kumar, R.; Suresh, K.

    2018-04-01

    The neodymium doped barium lithium fluoroborate (Nd3+: BLFB) glasses with the chemical composition (70-x) H3BO3 - 10 Li2CO3 - 10 BaCO3- 5 CaF2-5 ZnO - x Nd2O3 (where x = 0.05, 0.1, 0.25, 0.5, 1, 2 in wt %) have been prepared by the conventional melt quenching technique and characterised through optical absorption, near infrared emission and decay-time measurements. The x-ray diffraction studies confirm the amorphous nature of the prepared glasses. The optical absorption spectra and emission spectra were recorded in the wavelength ranges of 190-1100 nm. The optical band gap (Eg) and Urbach energy (ΔE) values were calculated from the absorption spectra. The Judd-Ofelt intensity parameters were determined from the systematic analysis of the absorption spectrum of neodymium ions in the prepared glasses. The emission spectra exhibited three prominent peaks at 874, 1057, 1331 nm corresponding to the 4F3/2 → 4I9/2, 11/2, 13/2 transitions levels respectively in the near infrared region. The emission intensity of the 4F3/2 → 4I11/2 transition increases with the increase in neodymium concentration up to 0.5 wt% and the concentration quenching mechanism was observed for 1 wt% and 2 wt% concentrations. The lifetime of the 4F3/2 level was found to decrease with increasing Nd3+ ion concentration. The nature of energy transfer process was a single exponential curve which was studied for all the glasses and analysed.

  7. Interactions of p-Nitrobenzene Diazonium Fluoroborate and Analogs with the Active Sites of Acetylcholine-Receptor and -Esterase*

    Science.gov (United States)

    Mautner, Henry G.; Bartels, Eva

    1970-01-01

    p-Nitrobenzene diazonium fluoroborate (NDF) is a potent inhibitor of the carbamylcholine-induced depolarization of the electroplax and of acetylcholinesterase. It probably forms covalent bonds with the acetylcholine-receptor and -esterase at the active site of the proteins. Its inhibitory strength is at least the same as that of trimethylammonium diazonium fluoroborate (TDF). The p-acetoxy analog, with its weaker electron-withdrawing group, is about ten times weaker as an inhibitor than the trimethylammonium or p-nitro analogs, both of which have strong electron-withdrawing groups. After treatment of the electroplax preparation with dithiothreitol, NDF remains an irreversible receptor-inhibitor, while TDF becomes a potent reversible receptor-activator. TDF is self-inhibitory: applied before reduction, it no longer depolarizes. Although the first observations on TDF suggested that the compound labels both proteins by virtue of the steric complementary of its trimethylammonium group to a negative subsite in the proteins, the present study indicates that it is the positively charged diazonium group that reacts with the active sites of the proteins to form a covalent bond with an appropriate amino-acid residue. PMID:5272331

  8. Spectroscopic and visible luminescence properties of rare earth ions in lead fluoroborate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Anjaiah, G. [Department of Physics, Osmania University, Hyderabad 500007 (India); Nayab Rasool, SK. [Department of Physics, Sri Venkateswara University, Tirupati 517502 (India); Kistaiah, P., E-mail: pkistaiah@yahoo.com [Department of Physics, Osmania University, Hyderabad 500007 (India)

    2015-03-15

    The lanthanide doped lead lithium calcium zinc fluoroborate glasses (LLCZFB:Ln) of composition 20PbF{sub 2}+10Li{sub 2}O+5Cao+5ZnO+59B{sub 2}O{sub 3}+1Ln{sub 2}O{sub 3} (where Ln=Sm, Eu and Dy in mol%) were prepared by conventional melt quench technique. The amorphous nature of these glasses was confirmed by X-ray diffraction studies. The glass transition temperatures (T{sub g}) were studied by DSC analysis. The glass structure and spectroscopic properties were investigated using optical absorption, vibrational and fluorescence spectra. The FT-IR spectra and Raman spectra reveal the presence of BO{sub 3}, BO{sub 4} and non-bridging oxygen's. The Judd–Ofelt intensity parameters Ω{sub λ} (λ=2, 4, 6) were determined from the spectral intensities of absorption bands. These parameters were used to calculate the radiative parameters such as radiative transition probability (A{sub R}), radiative life time (τ{sub R}) and branching ratio (β{sub r}) for various excited luminescent states of rare earth ions. The visible emission spectra for different rare earth ions were recorded by exciting the samples at different wavelengths and the decay rates for the different rare earth ions were measured. Using the emission spectra, full width half maxima (FWFM), stimulated emission cross section (σ{sup E}{sub p}) were evaluated. The nature of decay profiles of {sup 4}F{sub 9/2}, {sup 4}G{sub 5/2} and {sup 5}D{sub 0} states of Dy, Sm and Eu ions respectively are analyzed. Comparison of luminescence features of these glasses and also with those reported for different glass hosts indicates that the LLCZFB:Dy glass has strong luminescence in the visible region. - Highlights: • LLCZFB:Ln glasses are prepared with Ln: Sm, Eu and Dy. • Glasses are characterized by XRD, FTIR, Raman, absorption and emission spectra. • J–O theory is used to calculate different radiative properties. • Green, yellow and red emissions are observed. • Glasses are useful for the development

  9. Influence of CuO content on the structure of lithium fluoroborate glasses: Spectral and gamma irradiation studies.

    Science.gov (United States)

    Abdelghany, A M; ElBatal, H A; EzzElDin, F M

    2015-10-05

    Glasses of lithium fluoroborate of the composition LiF 15%-B2O3 85% with increasing CuO as added dopant were prepared and characterized by combined optical and FTIR spectroscopy before and after gamma irradiation. The optical spectrum of the undoped glass reveals strong UV absorption with two distinct peaks at about 235 and 310 nm and with no visible bands. This strong UV absorption is related to the presence of unavoidable trace iron impurity (Fe(3+)) within the materials used for the preparation of this glass. After irradiation, the spectrum of the undoped glass shows a decrease of the intensity of the UV bands together with the resolution of an induced visible broad band centered at about 520 nm. The CuO doped glasses reveal the same UV absorption beside a very broad visible band centered at 780 nm and this band shows extension and splitting to several component peaks with higher CuO contents. Upon gamma irradiation, the spectra of all CuO-doped glasses reveal pronounced decrease of their intensities. The response of irradiation on the studied glasses is correlated with suggested photochemical reactions together with some shielding effect of the copper ions. The observed visible band is related to the presence of copper as distorted octahedral Cu(2+) ions. Infrared absorption spectra of the prepared glasses show repetitive characteristic triangular and tetrahedral borate units similar to that published from alkali or alkaline earth oxides B2O3 glasses. A suggested formation of (BO3/2F) tetrahedral units is advanced through action of LiF on B2O3 and these suggested units showing the same position and number as BO4 tetrahedra. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Green fluorescence of terbium ions in lithium fluoroborate glasses ...

    Indian Academy of Sciences (India)

    tion and solid-state lasers attracted remarkable attention in the last few decades. .... Figure 1. Vis absorption spectrum of 1.0 mol% Tb3+-doped. LBZLFB glass. Figure 2. .... both ions quickly decay non-radiatively to the ground level. The energy ...

  11. Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

    Directory of Open Access Journals (Sweden)

    Silva Maurício A.P.

    2002-01-01

    Full Text Available The vitreous domain was established in the PbF2-CdF2-B2O 3 system from melting and quenching experiments. Er3+ containing glasses were prepared and glass ceramics were obtained by selected heat-treatments. Lead fluoride was identified (beta-PbF2 as the crystalline phase. Structural studies were performed in some glassy and partially crystallized samples by means of X-ray Diffraction (XRD and Extended X-ray Absorption Fine Structure (EXAFS measurements. The role of Cd2+ and Pb2+ atoms on the glass network formation and also on the crystallization behavior was put forward by these techniques. After crystallization Er3+ atoms segregated in the crystal phase.

  12. Quantifying the Performances of DFT for Predicting Vibrationally Resolved Optical Spectra: Asymmetric Fluoroborate Dyes as Working Examples.

    Science.gov (United States)

    Bednarska, Joanna; Zaleśny, Robert; Bartkowiak, Wojciech; Ośmiałowski, Borys; Medved', Miroslav; Jacquemin, Denis

    2017-09-12

    This article aims at a quantitative assessment of the performances of a panel of exchange-correlation functionals, including semilocal (BLYP and PBE), global hybrids (B3LYP, PBE0, M06, BHandHLYP, M06-2X, and M06-HF), and range-separated hybrids (CAM-B3LYP, LC-ωPBE, LC-BLYP, ωB97X, and ωB97X-D), in predicting the vibrationally resolved absorption spectra of BF 2 -carrying compounds. To this end, for 19 difluoroborates as examples, we use, as a metric, the vibrational reorganization energy (λ vib ) that can be determined based on the computationally efficient linear coupling model (a.k.a. vertical gradient method). The reference values of λ vib were determined by employing the CC2 method combined with the cc-pVTZ basis set for a representative subset of molecules. To validate the performances of CC2, comparisons with experimental data have been carried out as well. This study shows that the vibrational reorganization energy, involving Huang-Rhys factors and normal-mode frequencies, can indeed be used to quantify the reliability of functionals in the calculations of the vibrational fine structure of absorption bands, i.e., an accurate prediction of the vibrational reorganization energy leads to absorption band shapes better fitting the selected reference. The CAM-B3LYP, M06-2X, ωB97X-D, ωB97X, and BHandHLYP functionals all deliver vibrational reorganization energies with absolute relative errors smaller than 20% compared to CC2, whereas 10% accuracy can be achieved with the first three functionals. Indeed, the set of examined exchange-correlation functionals can be divided into three groups: (i) BLYP, B3LYP, PBE, PBE0, and M06 yield inaccurate band shapes (λ vib,TDDFT poor band topologies (λ vib,TDDFT > λ vib,CC2 ). This study also demonstrates that λ vib can be reliably estimated using the CC2 model and the relatively small cc-pVDZ basis set. Therefore, the linear coupling model combined with the CC2/cc-pVDZ level of theory can be used as a very efficient approach to determine λ vib values that can be used to select the most adequate functional for more accurate vibronic calculations, e.g., including more refined models and environmental effects.

  13. Alternative Synthesis of 1,8-Difluoroanthracene via the Balz-Schiemann Reaction

    Directory of Open Access Journals (Sweden)

    Rabih O. Al-Kaysi

    2016-01-01

    Full Text Available An alternative and improved method for the synthesis of 1,8-difluoroanthracene 5 is described. The precursor 1,8-difluoro-9,10-anthraquinone 4 was synthesized by precipitating the water-soluble 1,8-diazonium-9,10-anthraquinone fluoroborate 3 using isopropanol, before thermally decomposing it via the Balz-Schiemann reaction to yield 4 in the form of pure sublimed crystals. Compound 5 was later synthesized with 84% yield by reducing 4 in a Zn/NH4OH mixture. Using isopropanol to quantitatively precipitate water-soluble diazonium fluoroborate salts was also used to synthesize other fluoroanthraquinone derivatives with improved yields.

  14. Alternative route to metal halide free ionic liquids

    International Nuclear Information System (INIS)

    Takao, Koichiro; Ikeda, Yasuhisa

    2008-01-01

    An alternative synthetic route to metal halide free ionic liquids using trialkyloxonium salt is proposed. Utility of this synthetic route has been demonstrated by preparing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid through the reaction between 1-methylimidazole and triethyloxonium tetra-fluoroborate in anhydrous ether. (author)

  15. Alkylation of enolate anions formation of enol ethers

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The alkylation of ambident enolate anions-obtained from aliphatic ketones (and one particular type of aldehyde)-was studied using various solvents, bases, alkylating agents and substrates. Alkylation with a reactive alkylating agent (dialkyl sulfates, triethyloxonium fluoroborate) in an aprotic

  16. New Nitration Concepts

    Science.gov (United States)

    1987-09-01

    exclusive fluoride ion carbanion (Schemes I and 11, respectively). The driving force for either mechanism is the formation of the strong (1) Petrov, A. A...CIECLASSiPCAflON DOWNGRAAING SCHEDULE d is trib ut ion unlimited N/A _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4 PERFORM!NG ORGANIZATION REPORT NUMBER(S) s. moio OGNZTON...substitute nitroso for silicon by reaction of the silylated compound with nitrosonium fluoroborate but time and funding did not permit completion of

  17. Distribution and behavior of tritium in the Coolant-Salt Technology Facility

    International Nuclear Information System (INIS)

    Mays, G.T.; Smith, A.N.; Engel, J.R.

    1977-04-01

    A 1000-MW(e) Molten-Salt Breeder Reactor (MSBR) is expected to produce 2420 Ci/day of tritium. As much as 60 percent of the tritium produced may be transported to the reactor steam system (assuming no retention by the secondary coolant salt), where it would be released to the environment. Such a release rate would be unacceptable. Experiments were conducted in an engineering-scale facility--the Coolant-Salt Technology Facility (CSTF)--to examine the potential of sodium fluoroborate, the proposed coolant salt for an MSBR, for sequestering tritium. The salt was believed to contain chemical species capable of trapping tritium. A series of 5 experiments--3 transient and 2 steady-state experiments--was conducted from July of 1975 through June of 1976 where tritium was added to the CSTF. The CSTF circulated sodium fluoroborate at temperatures and pressures typical of MSBR operating conditions. Results from the experiments indicated that over 90 percent of tritium added at steady-state conditions was trapped by sodium fluoroborate and appeared in the off-gas system in a chemically combined (water-soluble) form and that a total of approximately 98 percent of the tritium added at steady-state conditions was removed through the off-gas system overall

  18. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    Research and development activities dealing with the chemical problems related to design and ultimate operation of molten-salt reactor systems are described. An experimental test stand was constructed to expose metallurgical test specimens to Te 2 vapor at defined temperatures and deposition rates. To better define the chemistry of fluoroborate coolant, several aspects are being investigated. The behavior of hydroxy and oxy compounds in molten NaBF 4 is being investigated to define reactions and compounds that may be involved in corrosion and/or could be involved in methods for trapping tritium. Two corrosion products of Hastelloy N, Na 3 CrF 6 and Na 5 Cr 3 F 14 , were identified from fluoroborate systems. The evaluation of fluoroborate and alternate coolants continued. Research on the behavior of hydrogen and its isotopes is summarized. The solubilities of hydrogen, deuterium, and helium in Li 2 BeF 4 are very low. The sorption of tritium on graphite was found to be significant (a few milligrams of tritium per kilogram of graphite), possibly providing a means of sequestering a portion of the tritium produced. Development of analytical methods continued with emphasis on voltammetric and spectrophotometric techniques for the in-line analysis of corrosion products such as Fe 2+ and Cr 3+ and the determination of the U 3+ /U 4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF 4 --NaF coolant salt. Information developed during the previous operation of the CSTF has been assessed and used to formulate plans for evaluation of in-line analytical methods in future CSTF operations. Electroanalytical and spectrophotometric research suggests that an electroactive protonic species is present in molten NaBF 4 --NaF, and that this species rapidly equilibrates with a volatile proton-containing species. Data obtained from the CSTF indicated that tritium was concentrated in the volatile species. (JGB)

  19. Intermediate heat exchanger and steam generator designs for the HYLIFE-II fusion power plant using molten salts

    International Nuclear Information System (INIS)

    Lee, Y.T.; Hoffman, M.A.

    1992-01-01

    The HYLIFE-II fusion power plant employs the molten salt, Flibe, for the liquid jets which form the self-healing 'first wall' of the reactor. The molten salt, sodium fluoroborate then transports the heat from the IHX's to the steam generators. The design and optimization of the IHX's and the steam generators for use with molten salts has been done as part of the HYLIFE-II conceptual design study. The results of this study are described, and reference designs of these large heat exchangers are selected to minimize the cost of electricity while satisfying other important constraints

  20. Improvement of organic compounds labelling method with the use of thermally activated tritium gas

    International Nuclear Information System (INIS)

    Nejman, L.A.; Smolyakov, V.S.; Antropova, L.P.

    1982-01-01

    Use of a support (various types of papers) is recommended for organic compounds labelling by tritium gas activated at a hot tungsten filament. This improvement increases chemical and radiochemical yields and makes the experiment simpler and faster. Generally labelled triethyloxonium tetra-fluoroborate, ethyl-p-aminobenzoate, p-aminobenzoic acid (Na-salt), A-factor (a natural regulator of streptomycin biosynthesis), decapeptide angiotensin I, phospholipid 1, 2 - dimyristoyl-sn-glycero-3--phosphocholine and E. coli tRNAs have been prepared by this method. Molar radioactivity of the labelled compounds is in the range of 1-200 GBg/mmole [ru

  1. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1976-01-01

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF 4 --H equilibria, porous electrode studies of molten salts, fuel salt-coolant salt reactions, thermodynamic properties of transition-metal fluorides, and properties of sodium fluoroborate. Developmental work on analytical methods is summarized including in-line analysis of molten MSBR fuel, analysis of coolant-salts for tritium, analysis of molten LiF--BeF 2 --ThF 4 for Fe and analysis of LiF--BeF--ThF 4 for Te

  2. Synthesis and kinetics of [18F]4'-fluoroantipyrine in normal mice

    International Nuclear Information System (INIS)

    Robbins, P.J.; Fortman, D.L.; Scholz, K.L.; Fusaro, G.A.; Sodd, V.J.

    1978-01-01

    Antipyrine labeled with radioiodine has proven useful for studying the symmetry of human brain perfusion by gamma-camera techniques. The feasibility of preparing F-18-labeled antipyrine for eventual use with a positron camera was investigated. The preparation of [ 18 F] 4'-fluoroantipyrine and its distribution in normal mice were used to evaluate this potential. 4'-Fluoroantipyrine was prepared in 7 to 20% chemical yield by the pyrolysis of the 4'-diazonium fluoroborate salt of antipyrine. This Schiemann salt was prepared by a five-step synthesis from 1-(4'-nitrophenyl)-3-methyl-5-chloro-pyrazole. Fluorine-18 labeling of the diazonium fluoroborate salt by exchange with aqueous F-18 and pyrolysis of the dried labeled salt produced [ 18 F] 4'-fluoroantipyrine with specific activities of 0.83 to 2.7 μCi/mg. The incorporated F-18 activity ranged from 0.53 to 1.9%. The labeling procedure took about 3 hr. The labeled antipyrine was administered by tail vein to fasting female Swiss-Cox mice. Distribution of F-18 at 12, 30, 60, and 120 sec, and 10 min, after injection showed that radioactivity persisted in the brain up to 120 sec at a level greater than that of the skin and the bone. (Skin and bone samples were chosen as representative of activities in the scalp and skull surrounding the brain.) Thus, perfusion imaging of the CNS should be possible when greater quantities of high-specific-activity F-18-labeled antipyrine becomes available

  3. Testing and evaluation of eight decontamination chemicals

    International Nuclear Information System (INIS)

    Demmer, R.

    1994-09-01

    This report covers experimental work comparing eight different decontamination chemicals. Seven of these chemicals have some novelty, or are not currently in use at the ICPP. The eighth is a common ICPP decontamination reagent used as a baseline for effective comparison. Decontamination factors, waste generation values, and corrosion rates are tabulated for these chemicals. Recommendations are given for effective methods of non-sodium or low-sodium decontamination chemicals. The two most effective chemical for decontamination found in these test were a dilute hydrofluoric and nitric acid (HF/HNO 3 ) mixture and a fluoroboric acid solution. The fluoroboric acid solution (1 molar) was by far the most effective decontamination reagent, but suffered the problem of generating significant final calcine volume. The HF/HNO 3 solution performed a very good decontamination of the SIMCON coupons while generating only small amounts of calcine volume. Concentration variables were also tested, and optimized for these two solutions. Several oxidation/reduction decon chemical systems were also tested. These systems were similar to the TURCO 4502 and TURCO 4521 solutions used for general decontamination at the ICPP. A low sodium alternative, nitric acid/potassium permanganate, to the ''high sodium'' TURCO 4502 was tested extensively, optimized and recommended for general ICPP use. A reductive chemical solution, oxalic acid/nitric acid was also shown to have significant advantages

  4. Evaluation of alternate secondary (and tertiary) coolants for the molten-salt breeder reactor

    International Nuclear Information System (INIS)

    Kelmers, A.D.; Baes, C.F.; Bettis, E.S.; Brynestad, J.; Cantor, S.; Engel, J.R.; Grimes, W.R.; McCoy, H.E.; Meyer, A.S.

    1976-04-01

    The three most promising coolant selections for an MSBR have been identified and evaluated in detail from the many coolants considered for application either as a secondary coolant in 1000-MW(e) MSBR configurations using only one coolant, or as secondary and tertiary coolants in an MSBR dual coolant configuration employing two different coolants. These are, as single secondary coolants: (1) a ternary sodium--lithium--beryllium fluoride melt; (2) the sodium fluoroborate--sodium fluoride eutectic melt, the present reference design secondary coolant. In the case of the dual coolant configuration, the preferred system is molten lithium--beryllium fluoride (Li 2 BeF 4 ) as the secondary coolant and helium gas as the tertiary coolant

  5. Evaluation of six decontamination processes on actinide and fission product contamination

    International Nuclear Information System (INIS)

    Conner, C.; Chamberlain, D.B.; Chen, L.

    1995-01-01

    In-situ decontamination technologies were evaluated for their ability to: (1) reduce equipment contamination levels to allow either free release of the equipment or land disposal, (2) minimize residues generated by decontamination, and (3) generate residues that are compatible with existing disposal technologies. Six decontamination processes were selected. tested and compared to 4M nitric acid, a traditional decontamination agent: fluoroboric acid (HBF 4 ), nitric plus hydrofluoric acid, alkaline persulfate followed by citric acid plus oxalic acid, silver(II) plus sodium persulfate plus nitric acid, oxalic acid plus hydrogen peroxide plus hydrofluoric acid, and electropolishing using nitric acid electrolyte. The effectiveness of these solutions was tested using prepared 304 stainless steel couponds contaminated with uranium, plutonium, americium, or fission products. The decontamination factor for each of the solutions and tests conditions were determined; the results of these experiments are presented

  6. Polyfluorinated boron cluster based salts: A new electrolyte for application in nonaqueous asymmetric AC/Li{sub 4}Ti{sub 5}O{sub 12} supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Ionica-Bousquet, C.M.; Munoz-Rojas, D.; Palacin, M.R. [Institut de Ciencia de Materials de Barcelona, CSIC, Campus UAB, E-08193 Bellaterra (Spain); Casteel, W.J. Jr.; Pearlstein, R.M.; Kumar, G. Girish; Pez, G.P. [Air Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, PA 18195 (United States)

    2011-02-01

    Solutions of novel fluorinated lithium dodecaborate (Li{sub 2}B{sub 12}F{sub x}H{sub 12-x}) salts have been evaluated as electrolytes in nonaqueous asymmetric supercapacitors with Li{sub 4}Ti{sub 5}O{sub 12} as negative electrode, and activated carbon (AC) as positive electrode. The results obtained with these new electrolytes were compared with those obtained with cells built using standard 1 M LiPF{sub 6} dissolved in ethylene carbonate and dimethyl carbonate (EC:DMC; 1:1, v/v) as electrolyte. The specific energy, rate capability, and cycling performances of nonaqueous asymmetric cells based on these new electrolyte salts were studied. Cells assembled using the new fluoroborate salts show excellent reversibility, coulombic efficiency, rate capability and improved cyclability when compared with the standard electrolyte. These features confirm the suitability of lithium-fluoro-borate based salts to be used in nonaqueous asymmetric supercapacitors. (author)

  7. Method to precipitate metals on zirconium articles without using current

    International Nuclear Information System (INIS)

    Donaghy, R.E.

    1978-01-01

    Tubes or other bodies made of zirconium or Zr alloys used for taking up nuclear fuels are coated without current with a metal film to improve the mechanical and corrosion properties. The article is activated in a solution of ammonium bifluoride and sulphuric acid where an electrical conducting fixed and loose layer are fermed. This loose film is removed chemically by reacting with fluoroboric acid or hydrofluorosilica acid by ultrasonic treatment or by stripping from organic material (cotton, polyester, nylon). The current-free plating with Cu and Ni is described. The article is washed with deionized water between the process steps and finally degassed at a temperature of 150-200 0 C. (IHOE) [de

  8. Solvation behaviour of L-leucine in aqueous ionic liquid at different temperatures: Volumetric approach

    Science.gov (United States)

    Sharma, Samriti; Sandarve, Sharma, Amit K.; Sharma, Meena

    2018-05-01

    For the investigation of interactions of L-leucine in aqueous solutions of an ionic liquid (1-butyl-3-methylimidazolium tetra fluoroborate [Bmim][BF4]) at atmospheric pressure over a temperature range of (293.15K to 313.16K), we use the volumetric approach. By using the density data we have calculated the apparent molar volume, VΦ, limiting apparent molar volume, V0Φ, the slope, Sv, partial molar volume of transfer, V0Φ,tr. The values of these acoustical parameters have been used for the interpretation of different interactions like hydrophilic-hydrophilic, hydrophilic-hydrophobic, ion hydrophilic, solute-solvent and solute-solute interactions in the amino acid and ionic liquid solutions.

  9. Highly efficient red-emitting BaMgBO3F:Eu3+,R+ (R: Li, Na, K, Rb) phosphor for near-UV excitation synthesized via glass precursor solid-state reaction

    Science.gov (United States)

    Shinozaki, Kenji; Akai, Tomoko

    2017-09-01

    Eu3+-doped fluoroborate crystals of BaMgBO3F were synthesized by a solid-state reaction using a glassy precursor material, and their photoluminescence (PL) was investigated. To compensate for the incorporation of Eu3+ into Ba2+ sites, samples codoped with alkali ions (Li+, Na+, K+, Rb+) were also prepared. The Eu3+-doped sample showed red PL with a quantum yield (QY) of 65% caused by near-UV excitation (λ = 393 nm), and PL intensity and QY increased with the codoping of Eu3+ and alkali ions. It was found that the Eu3+,Li+-codoped sample showed the highest PL intensity and a QY of 83%.

  10. Fluoride ion recognition by chelating and cationic boranes.

    Science.gov (United States)

    Hudnall, Todd W; Chiu, Ching-Wen; Gabbaï, François P

    2009-02-17

    Because of the ubiquity of fluoride ions and their potential toxicity at high doses, researchers would like to design receptors that selectively detect this anion. Fluoride is found in drinking water, toothpaste, and osteoporosis drugs. In addition, fluoride ions also can be detected as an indicator of uranium enrichment (via hydrolysis of UF(6)) or of the chemical warfare agent sarin, which releases the ion upon hydrolysis. However, because of its high hydration enthalpy, the fluoride anion is one of the most challenging targets for anion recognition. Among the various recognition strategies that are available, researchers have focused a great deal of attention on Lewis acidic boron compounds. These molecules typically interact with fluoride anions to form the corresponding fluoroborate species. In the case of simple triarylboranes, the fluoroborates are formed in organic solvents but not in water. To overcome this limitation, this Account examines various methods we have pursued to increase the fluoride-binding properties of boron-based receptors. We first considered the use of bifunctional boranes, which chelate the fluoride anion, such as 1,8-diborylnaphthalenes or heteronuclear 1-boryl-8-mercurio-naphthalenes. In these molecules, the neighboring Lewis acidic atoms can cooperatively interact with the anionic guest. Although the fluoride binding constants of the bifunctional compounds exceed those of neutral monofunctional boranes by several orders of magnitude, the incompatibility of these systems with aqueous media limits their utility. More recently, we have examined simple triarylboranes whose ligands are decorated by cationic ammonium or phosphonium groups. These cationic groups increase the electrophilic character of these boranes, and unlike their neutral analogs, they are able to complex fluoride in aqueous media. We have also considered cationic boranes, which form chelate complexes with fluoride anions. Our work demonstrates that Coulombic and chelate

  11. Tuning the Composition of Electrodeposited Bimetallic Tin-Lead Catalysts for Enhanced Activity and Durability in Carbon Dioxide Electroreduction to Formate.

    Science.gov (United States)

    Moore, Colin E; Gyenge, Előd L

    2017-09-11

    Bimetallic Sn-Pb catalysts with five different Sn/Pb atomic ratios were electrodeposited on Teflonated carbon paper and non-Teflonated carbon cloth using both fluoroborate- and oxide-containing deposition media to produce catalysts for the electrochemical reduction of CO 2 (ERC) to formate (HCOO - ). The interaction between catalyst composition, morphology, substrate, and deposition media was investigated by using cyclic voltammetry and constant potential electrolysis at -2.0 V versus Ag/AgCl for 2 h in 0.5 m KHCO 3 . The catalysts were analyzed before and after electrolysis by using SEM and XRD to determine the mechanisms of Faradaic efficiency loss and degradation. Catalysts that are mainly Sn with 15-35 at % Pb generated Faradaic efficiencies up to 95 % with a stable performance. However, pure Sn catalysts showed high initial stage formate production rates but experienced an extensive (up to 30 %) decrease of the Faradaic efficiency. The XRD results demonstrated the presence of polycrystalline SnO 2 after electrolysis using Sn-Pb catalysts with 35 at % Pb and its absence in the case of pure Sn. It is proposed that the presence of Pb (15-35 at %) in mainly Sn catalysts stabilized SnO 2 , which is responsible for the enhanced Faradaic efficiency and catalytic durability in the ERC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Investigations in the field of diazo compounds

    International Nuclear Information System (INIS)

    Kozlov, V.V.; Smirnova, V.G.; Sagalovich, V.P.

    1977-01-01

    Water suspension of hardly soluble isopolytungstates and -molybdates of diazonium have been decomposed. It has been established that the corresponding phenols are the main reaction products with the yield of 69.6-84.5%. Kinetics of thermal decomposition of phenyldiazonium fluoroborate (1) has been studied at 40+-0.1 deg C in 0.01 and 0.1 N H 2 O 4 in the presence of para(hepta)molybdate of ammonium (2). Decomposition of (1) in 0.1 N H 2 O 4 in the presence of (2) obeys the equation of the first order reaction up to the concentration of (2), equal to 0.250. Kinetic experiments have shown that a maximum decrease of the rate constant of decomposition of (1) in an acid aqueous solution in the presence of meta(octa) molybdate of sodium does not exceed 18%. Interaction of phenyldiazonium chloride with para(hepta) molybdate of ammonium gives meta(octa) molybdate of phenyldiazonium. Kinetic experiments do not confirm a considerable stabilizing effect of isopolymolybdates on diazosolutions

  13. Electrochemically modified sulfisoxazole nanofilm on glassy carbon for determination of cadmium(II) in water samples

    International Nuclear Information System (INIS)

    Gupta, Vinod Kumar; Yola, Mehmet Lütfi; Atar, Necip; Solak, Ali Osman; Uzun, Lokman; Üstündağ, Zafer

    2013-01-01

    Highlights: • Sulfisoxazole was grafted onto glassy carbon electrode. • The electrode was characterized by spectroscopic and electrochemical methods. • It has been used for the determination of Cd(II) ions in real samples in very low concentrations. -- Abstract: Sulfisoxazole (SO) was grafted to glassy carbon electrode (GCE) via the electrochemical oxidation of SO in acetonitrile solution containing 0.1 M tetrabutylammoniumtetra-fluoroborate (TBATFB). The prepared electrode was characterized by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), reflection–absorption infrared spectroscopy (RAIRS) and X-ray photoelectron spectroscopy (XPS). The ellipsometric thickness of SO nanofilm at the glassy carbon surface was obtained as 14.48 ± 0.11 nm. The stability of the SO modified GCE was studied. The SO modified GCE was also utilized for the determination of Cd(II) ions in water samples in the presence of Pb(II) and Fe(II) by adsorptive stripping voltammetry. The linearity range and the detection limit of Cd(II) ions were 1.0 × 10 −10 to 5.0 × 10 −8 M and 3.3 × 10 −11 M (S/N = 3), respectively

  14. Leaching Studies for Copper and Solder Alloy Recovery from Shredded Particles of Waste Printed Circuit Boards

    Science.gov (United States)

    Kavousi, Maryam; Sattari, Anahita; Alamdari, Eskandar Keshavarz; Fatmehsari, Davoud Haghshenas

    2018-06-01

    Printed circuit boards (PCBs) comprise various metals such as Cu, Sn, and Pb, as well as platinum group metals. The recovery of metals from PCBs is important not only due to the waste treatment but also for recycling of valuable metals. In the present work, the leaching process of Cu, Sn, and Pb from PCBs was studied using fluoroboric acid and hydrogen peroxide as the leaching agent and oxidant, respectively. Pertinent factors including concentration of acid, temperature, liquid-solid ratio, and concentration of oxidizing agent were evaluated. The results showed 99 pct of copper and 90 pct solder alloy were dissolved at a temperature of 298 K (25 °C) for 180 minutes using 0.6 M HBF4 for the particle size range of 0.15 to 0.4 mm. Moreover, solid/liquid ratio had insignificant effect on the recovery of metals. Kinetics analysis revealed that the chemical control regime governs the process with activation energy 41.25 and 38.9 kJ/mol for copper and lead leaching reactions, respectively.

  15. Tunable lasers in isotope separation: a colorful view of a dye chemist

    International Nuclear Information System (INIS)

    Hammond, P.R.

    1977-01-01

    Some of the problems to be encountered in the possible large scale use of dye lasers in an isotope separation plant are discussed.The effect of laser dye deterioration on performance is examined algebraically in terms of disappearance of dye molecules and the appearance of a new, single chemical product having absorption in the fluorescence band for a single pass through a transversely pumped amplifier. Loss of output, defined as ''quantum yield of laser deterioration'', Q/sub L/, is related to the true quantum yield of molecular destruction of the dye Q/sub M/, and other known parameters. 6-Diethylamino 3-keto fluoran, an example of an oxygen tricyclic merocyanine, is described. It was first reported in the pre-1900 German literature under the name of Chromogen Red B and it is an ineffective lasing dye on account of low fluorescence quantum yield. The techniques for measurement and the excited state absorption cross-sections are reported for the dyes rhodamine 6G fluoroborate in alcohol, rhodamine B basic solution in trifluoroethanol and kiton red S in trifluoroethanol

  16. Leaching Studies for Copper and Solder Alloy Recovery from Shredded Particles of Waste Printed Circuit Boards

    Science.gov (United States)

    Kavousi, Maryam; Sattari, Anahita; Alamdari, Eskandar Keshavarz; Fatmehsari, Davoud Haghshenas

    2018-03-01

    Printed circuit boards (PCBs) comprise various metals such as Cu, Sn, and Pb, as well as platinum group metals. The recovery of metals from PCBs is important not only due to the waste treatment but also for recycling of valuable metals. In the present work, the leaching process of Cu, Sn, and Pb from PCBs was studied using fluoroboric acid and hydrogen peroxide as the leaching agent and oxidant, respectively. Pertinent factors including concentration of acid, temperature, liquid-solid ratio, and concentration of oxidizing agent were evaluated. The results showed 99 pct of copper and 90 pct solder alloy were dissolved at a temperature of 298 K (25 °C) for 180 minutes using 0.6 M HBF4 for the particle size range of 0.15 to 0.4 mm. Moreover, solid/liquid ratio had insignificant effect on the recovery of metals. Kinetics analysis revealed that the chemical control regime governs the process with activation energy 41.25 and 38.9 kJ/mol for copper and lead leaching reactions, respectively.

  17. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF 3 and dissolved UF 4 , and, in some cases, between the dissolved uranium fluorides and graphite, and the UC 2 . Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF 4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U 4+ /U 3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  18. FTIR Spectroscopic and DC Ionic conductivity Studies of PVDF-HFP: LiBF4: EC Plasticized Polymer Electrolyte Membrane

    Science.gov (United States)

    Sangeetha, M.; Mallikarjun, A.; Jaipal Reddy, M.; Siva Kumar, J.

    2017-08-01

    In the present paper; the FTIR and Temperature dependent DC Ionic conductivity studies of polymer (80 Wt% PVDF-HFP) with inorganic lithium tetra fluoroborate salt (20 Wt% LiBF4) as ionic charge carrier and plasticized with various weight ratios of Ethylene carbonate plasticizer (10 Wt% to 70 Wt% EC) as gel polymer electrolytes. Solution casting method is used for the preparation of plasticized polymer-salt electrolyte films. FTIR analysis shows the good complexation between PVDF-HFP: LiBF4 and the presence of functional groups in the plasticized polymer-salt electrolyte membrane. Also the analysis and results show that the highest DC ionic conductivity of 1.66 × 10-3 SCm -1 was found at 373 K for a particular concentration of 80 Wt% PVDF-HFP: 20 Wt% LiBF4: 40 Wt% EC porous gel type polymer-salt plasticized porous membrane. Increase of temperature results expansion and segmental motion of polymer chain that generates free volume in turn promotes hopping of the lithium ions satisfying Vogel-Tammann-Fulcher equation.

  19. Electrochemical stability of organic electrolytes in supercapacitors: Spectroscopy and gas analysis of decomposition products

    Energy Technology Data Exchange (ETDEWEB)

    Kurzweil, P.; Chwistek, M. [University of Applied Sciences, Kaiser-Wilhelm-Ring 23, D-92224 Amberg (Germany)

    2008-02-01

    The fundamental aging mechanisms in double-layer capacitors based on alkylammonium electrolytes in acetonitrile were clarified for the first time. After abusive testing at cell voltages above 4 V, ultracapacitors cast out a crystalline mass of residual electrolyte, organic acids, acetamide, aromatics, and polymer compounds. The mixture could be reproduced by electrolysis. The decomposition products of active carbon electrodes and electrolyte solution after a heat treatment at 70 C were identified by infrared and ultraviolet spectroscopy, liquid and headspace GC-MS, thermogravimetric analysis, and X-ray diffraction. The alkylammonium cation is destroyed by the elimination of ethene. The fluoroborate anion works as source of fluoride and hydrogenfluoride, and boric acid derivates. Acetonitrile forms acetamide, acetic and fluoroacetic acid, and derivates thereof. Due to the catalytic activity of the electrode, heterocyclic compounds are generated in the liquid phase. The etched aluminium support under the active carbon layer is locally destroyed by fluorination. Exploring novel electrolytes, ionic liquids were characterized by impedance spectroscopy. (author)

  20. The Program Planned for the Molten Salt Reactor Experiment

    International Nuclear Information System (INIS)

    Haubenreich, Paul N.

    1967-01-01

    This document outlines the program planned for the MSRE in fiscal years 1968 and 1969. It includes a bar diagram of the program, a critical-path type diagram of the operations, and a brief description of each task. In addition to the work at the reactor site, the outline also covers activities elsewhere at ORNL and by the AEC that directly affect the reactor schedule. The amount of detail and the accuracy with which we can estimate times varies considerably among the different items on the schedule. Some items, such as annual checkouts and core sample replacement, have been done before and our time estimates do not include any contingency, In the case of such tasks as planning, reviewing, and preparing for experiments or operations, we have set target dates that appear reasonable and we fully expect to meet these. Processing the salt is a different matter. If there are no unforeseen difficulties we should finish easily in the time shown, but the operation is in part a shakedown, so delays would not be too surprising, The time for modifying the system and adding fluoroborate is, of course, uncertain because the requirements are not yet known. As the requirements develop in more detail the estimate will be updated, but we do not foresee any major dislocation in the schedule, The scheduled time for preparation of enriching salt is becoming tight because of delays in facility construction. Should there be further delays in this key item, the entire schedule would have to be reconsidered.

  1. Acute redistribution of thyroxine after the administration of univalent anions, salicylate, theophylline and barbiturates in rats

    Energy Technology Data Exchange (ETDEWEB)

    Langer, P; Kokesova, H; Gschwendtova, K [Slovenska Akademia Vied, Bratislava (Czechoslovakia). Ustav Experimentalni Endocrinologie

    1976-01-01

    Rats were injected with (/sup 125/I)L-thyroxine (T/sub 4/) ip 16 h before the experiment and samples of blood were frequently taken from polyethylene tubing inserted into the femoral artery in anaesthetized and heparin-injected animals. In each sample of plasma T/sub 4/ counts per ml were estimated with the acid of paper chromatography. Rapid decrease of circulating T/sub 4/ level was found at 20 min after iv injection of thiocyanate, iodide, fluoroborate, theophylline and salicylate and a dose-response relationship was established between such a decrease and the administered dose of salicylate (5-160 mg/400 g b.w.). A similar decrease was observed at 60 min after ip injection of some general anaesthetics or tranquilizers. An increase of T/sub 4/ fractional disposal rate was found between 120 and 480 min after the administration of some of the anaesthetics and this effect was abolished by the administration of thiocyanate. It was concluded that there are two different effects of drugs on the circulating T/sub 4/ level: 1. the immediate effect resulting apparently from a decreased plasma protein binding. 2. the prolonged effect which presumably results from the increased turnover of T/sub 4/ by peripheral tissues, the metabolic basis of which remains unexplained.

  2. Separation of Binary Mixtures of Propylene and Propane by Facilitated Transport through Silver Incorporated Poly(Ether-Block-Amide Membranes

    Directory of Open Access Journals (Sweden)

    Surya Murali R.

    2015-02-01

    Full Text Available The separation of propylene and propane is a challenging task in petroleum refineries due to the similar molecular sizes and physical properties of two gases. Composite Poly(ether-block-amide (Pebax-1657 membranes incorporated with silver tetra fluoroborate (AgBF4 in concentrations of 0-50% of the polymer weight were prepared by solution casting and solvent evaporation technique. The membranes were characterized by Scanning Electron Microscopy (SEM, Fourier Transform InfraRed (FTIR and wide-angle X-ray Diffraction (XRD to study surface and cross-sectional morphologies, effect of incorporation on intermolecular interactions and degree of crystallinity, respectively. Experimental data was measured with an indigenously built high-pressure gas separation manifold having an effective membrane area of 42 cm2. Permeability and selectivity of membranes were determined for three different binary mixtures of propylene-propane at pressures varying in the range 2-6 bar. Selectivity of C3H6/C3H8 enhanced from 2.92 to 17.22 and 2.11 to 20.38 for 50/50 and 66/34 C3H6+C3H8 feed mixtures, respectively, with increasing loading of AgBF4. Pebax membranes incorporated with AgBF4 exhibit strong potential for the separation of C3H6/C3H8 mixtures in petroleum refineries.

  3. Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

    Science.gov (United States)

    Hudnall, Todd W; Gabbaï, François P

    2007-10-03

    With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

  4. Development and electrochemistry of a novel Ag/AgCl reference electrode suitable for mixed chloride-fluoride melts

    International Nuclear Information System (INIS)

    Pal, Rahul; Ananthasivan, K.; Anthonysamy, S.; Ganesan, V.

    2011-01-01

    Research highlights: → An Ag/AgCl reference electrode for mixed chloride-fluoride melts was developed. → Non-polarizability, reversibility and stability of the electrode were tested. → Dependence of emf vs T for Fe/Fe 2+ and Ni/Ni 2+ couples in KCl-KF melt was reported. - Abstract: Accurate values of electrode potentials are useful in understanding the electrodeposition of boron from a melt containing fluoride, chloride and fluoroborate, as well as in the determination of the thermodynamic properties of this system. A suitable reference electrode for use with this molten mixture is essential for the determination of these potentials. An Ag/AgCl reference electrode was fabricated for this purpose and its stability, reversibility and polarizability in a melt containing chloride and fluoride were studied in the temperature range 1073-1123 K. Cyclic-voltammograms (CVs) of this melt on a platinum working electrode were recorded at regular intervals over a period of 12 h. These CVs did not show any appreciable variation with time, indicating the stability of this reference electrode. The reversibility of this reference electrode was established by carrying out a micropolarization test. Cathodic and anodic polarization tests were carried out by passing a current of 1 mA and 5 mA through the cell for a duration of 300 s. After these polarization tests, the electrode swung back to its equilibrium potential within about 250 s. Reduction potentials of Fe 2+ /Fe and Ni 2+ /Ni couples in the KF-KCl melt were measured for the first time.

  5. Linear optical properties of Ca4EuO(BO3)3 and Eu3+ : Ca4GdO(BO3)3 crystals

    International Nuclear Information System (INIS)

    Antic-Fidancev, E.; Lemaitre-Blaise, M.; Porcher, P.; Caramanian, A.; Aka, G.

    1998-01-01

    Full text: The title compounds are now intensively studied due to their quadratic nonlinear properties in view of applications, e.g. high power laser frequency conversion. Rare earth calcium oxoborates, Ca 4 REO(BO 3 ) 3 , constitute an isostructural family along the rare earth series with RE = La - Lu, Y included. These compounds crystallize in the monoclinic biaxial crystal system with Cm (N 8) space group. They are isostructural to the calcium fluoroborate Ca 5 (BO 3 ) 3 F which is related to the fluoroapatite structure Ca 5 (PO 4 ) 3 F. The rare earth ions are located in the distorted octahedron with C s point site symmetry in the mirror plane. Two types of distorted octahedral sites exist for calcium ions. The existence of some disorder between calcium and rare earth atoms is suspected from the structural analysis. Good optical quality crystals of europium (or gadolinium) oxoborate, EuCOB (GdCOB) have been grown from the stoichiometric melt by the Czochralski pulling method. From the luminescence of the Eu 3+ doped gadolinium or in the europium stoichiometric compound very complex emission spectra have been obtained. It principally depends on the preparation method of studied samples: i) for a monocrystalline sample, a single phase with a single site is observed; ii) for a polycrystalline sample complex feature occurs. It is probably due to an expanded disorder between calcium and rare earth atoms. Practically, there is one principal site corresponding to the low symmetry site of the rare earth as expected from the structural investigation. Other minor sites are attributed to the local distortion created around the active rare earth ion. The intensity of the emission lines of Eu 3+ used as a local structural probe related to these minor sites increases when the gadolinium in Ca 4 GdO(BO 0 ) 3 is substituted by lanthanum or yttrium ions. It seems therefore evident that the synthesis of these rare earth calcium oxoborates must be realised carefully. The crystal

  6. Applications of Fluorine-18 in Biological Studies with Special Reference to Bone and Thyroid Physiology; Emploi du Fluor-18 dans des Études Biologiques, Notamment sur la Physiologie des Os et de la Thyroïde; ИСПОЛЬЗОВАНИЕ ФТОРА-18 В БИОЛОГИЧЕСКИХ ИССЛЕДОВАНИЯХ С УДЕЛЕНИЕМ ОСОБОГО ВНИМАНИЯ ВОПРОСАМ ФИЗИОЛОГИИ КОСТЕЙ И ФИЗИОЛОГИИ ПИТОВИДНОЙ ЖЕЛЕЗЫ; Aplicaciones del Fluor-18 en Estudios Biologicos, con Especial Referencia a la Fisiologia del Esqueleto y de la Tiroides

    Energy Technology Data Exchange (ETDEWEB)

    Anbar, M. [Weizmann Institute of Science (Israel); IAEC Soreq Research Establishment, Rehovot (Israel)

    1963-03-15

    At the authors laboratories fluorine-18 was applied during the last three years to a great variety of problems in biology and medicine. Methods were developed to prepare fluorine by each of the O{sup 18}(p, n), O{sup 16}(H{sup 3}, n) and F{sup 18}(n, 2n) reactions. Radiofluorine-labelled compounds were prepared by isotopic exchange, by synthesis, by recoil labelling and by retention of fluorine in fluoro-organic compounds undergoing the (n, 2n) reaction. Special low- level counting techniques were developed to cope with the low activities of tracer amounts of organic fluoro-compounds. Fluoride-18 ions were applied to studies in bone physiology. It was found that F{sup -} follows calcium in many aspects of its physiological behaviour; the accumulation ol F in bone was found to increase under the influence of vitamin D and of testosterone, whereas cortizone and estrogens diminished the extent of fluoride accretion. The pattern of distribution of fluorine in the organism was modified when administered in the form of a cationic complex. Fluorine-18 labelled YF{sup ++} or ZF{sup +3} were found to follow the pattern of distribution of the parent cations. Fluoroborate ions were shown to accumulate in the thyroid gland to an extent comparable to that of iodide ions. Fluoroborate ions do not undergo any organic binding in the thyroid, and their uptake is a specific, indication of the function of the 'trapping stage' in the gland. Fluorine-18 labelled fluoroborate has been applied to a variety of problems in thyroid physiology. It has been shown that TSH diminishes the uptake of BF{sub 4}{sup -} in the first few hours after administration and enhances it after 24 h. The inhibitory action of iron, copper, zinc, cadmium, fluoride, thiocyanate and other ions on the iodine uptake was simulated by BF{sub 4}{sup -}; thus the trapping stage was shown to be involved. In an analogous series of experiments sulphydryl- containing compounds, as well as azide ions, were found to enhance

  7. New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

    Science.gov (United States)

    Bugga, Ratnakumar V.; West, William C.; Kindler, Andrew; Smart, Marshall C.

    2013-01-01

    reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.