Local structural analyses on molten terbium fluoride in lithium fluoride and lithium-calcium fluoride mixtures

X-ray absorption fine structure (XAFS) measurements on terbium fluoride in molten lithium fluoride and in molten lithium-calcium fluoride mixtures, (e.g. 0.20TbF₃-0.80LiF, 0.20TbF₃-0.62LiF-0.18CaF₂, 0.20TbF₃-0.48LiF-0.32CaF₂, 0.50TbF₃-0.50LiF, and 0.50TbF₃-0.38LiF-0.12CaF₂), have been carried out. In the solid state, coordination number of terbium (N_i) and inter ionic distances between terbium and fluorine in the first neighbor (r_i) are nearly constant in all mixtures. In 0.20TbF₃-0.80LiF, 0.20TbF₃-0.62LiF-0.18CaF₂ and 0.50TbF₃-0.50LiF mixtures, N_i's decrease from ca. 8 to 6 and r_i's also decrease from ca. 2.29 to 2.26 Å on melting. On the other hands, in molten 0.20TbF₃-0.48LiF-0.32CaF₂ and 0.50TbF₃-0.38LiF-0.12CaF₂ mixtures, N_i's are slightly larger than 6 and r_i's do not change. These facts correspond to the amount of F⁻ supplied by solvent melts, i.e. the effect of CaF₂ becomes predominant at bCaF₂ > 0.32 in ternary 0.20TbF₃-aLiF-bCaF₂ mixtures and at bCaF₂ > 0.12 in ternary 0.50TbF₃-aLiF-bCaF₂ mixtures.     

Tetramethylphosphonium fluoride: "naked" fluoride and phosphorane

Me(4)PF was investigated in the solid state, in the gas phase, and in solutions. Vibrational spectra of the solid and a single-crystal structure show an ionic tetramethylphosphonium fluoride. The compound crystallizes in the space group Pbca with a = 1016.0(1), b = 1018.0(1), c = 1205.8(4) pm, and Z = 8. The fluoride ion is nearly trigonal planar surrounded by three Me(4)P+ cations forming six H...F contacts between 218 and 240 pm. The compound is stable below 120 degrees C and sublimes in a vacuum. It possesses a phosphorane structure in the gas phase that was studied by electron diffraction and vibrational spectra, and additionally by theoretical calculations. The Me(4)PF molecule has a trigonal bipyramidal structure with one methyl group and the fluorine atom in axial positions and bond lengths of d(PC(eq)) = 182.6(4) pm, d(PC(ax)) = 188.4(8) pm, and d(PF) = 175.3(6) pm. The compound is remarkably soluble in acetonitrile, water, and alcohols, and slightly soluble in benzene, dimethyl ether, and diethyl ether. The solutions were studied by (1)H, (13)C, (19)F, and (31)P NMR spectroscopy. The hygroscopic Me(4)PF forms a tetrahydrate which crystallizes in the space group I4(1)/a with a = 1106.1(1) pm, c = 816.3(1) pm, and Z = 4. The fluoride ion in Me(4)PF.4 H(2)O is surrounded by four water molecules. These units form a three-dimensional network in which the Me(4)P+ cations are embedded without any contacts.     

The potentiometric titration of fluoride without fluoride ion-selective electrodes

Graphite and platinum sensors were investigated as indicators in the potentiometric titration of fluoride vs lanthanum(III) and thorium(IV). In every case a partially nonaqueous medium yielded larger breaks than in aqueous solution, similar to the fluoride electrode. All the sensors yielded endpoint breaks which were smaller than those obtained with a fluoride ion-selective electrode. The largest breaks were obtained with the vitreous carbon, pyrolytic graphite, and platinum sensors. Conditioning in neutral permanganate solution significantly enhanced the breaks for all types of graphite, except vitreous carbon. The break obtained with the platinum electrode can be enhanced by application of a polarizing current of 2.0 μA in the reducing direction.     

Anhydrous tetrabutylammonium fluoride

Tetrabutylammonium fluoride (TBAF) is prepared at low temperature by nucleophilic aromatic substitution of hexafluorobenzene with tetrabutylammonium cyanide. Adventitious water is scavenged during this synthesis by the generated hexacyanobenzene, which readily adds water under basic conditions. Contrary to expectations, TBAF is stable to Hofmann elimination in polar aprotic solvents under anhydrous conditions. Added hydroxylic solvents are shown to catalyze the decomposition of TBAF and to catalyze proton exchange with DMSO. The synthetic utility of this salt is described briefly.     

The fluoride dilemma

The implications of environmental contamination by fluoride on human health call upon the need for the development of monitoring systems for the ‘in situ’ detection of fluoride in contaminated sources and new technologies approaches for their removal. This paper reports recent work on the design of calixpyrrole receptors selective for the fluoride anion. The various steps undertaken for the thermodynamic characterization of these receptors and their anionic complexes are discussed. Thus based on thermodynamic data, the medium and ligand effects on selectivity are quantitatively assessed using representative calixpyrrole derivatives.     

Bismuth-containing fluoride glasses

The example of bismuth-containing glasses based on InF₃ and ZrF₄ is used to consider the effect of bismuth on glass formation, properties, and structure and the appearance of broadband luminescence at low wavelengths in the IR spectra of fluorozirconate glasses.     

Bioavailability of fluoride administered as sodium fluoride or monofluorophosphate to humans

A double-bind cross-over study was conducted on four healthy subjects, aged 19-29 years, in order to determine the relative bioavailability and other pharmacokinetics features of fluoride (F) after single oral administration in fasting conditions of 2 mg F as sodium F (NaF) or sodium monofluorophosphate (MFP). The bioavailability was evaluated on the basis of the plasma levels and of the urinary excretion of F. Blood was sampled before and during the 8 h after the administration of the test solutions. For F excretion urine was sampled 12 h before the study and over the 8 h after the administration. Data were tested for statistically significant differences by ANOVA and Tukey's post hoc tests, and also by Student's t-test (p < 0.05). For the two formulations, the pharmacokinetics of F in plasma was characterized by a rapid absorption and by a peak (C_max = 0.1 μg/mL) which was reached 20 min after administration, followed by a biphasic elimination. In the 8 h following the administration the urinary excretion of F accounted for 35-41% of the administered dose, without significant differences between the two formulations. The AUCs (±S.D.) for NaF and MFP were 21.15 (±0.58) and 19.04 (±1.75) min μg mL⁻¹, respectively, and were not significantly different (p = 0.079). Based on the AUC and C_max of F in plasma and on the urinary excretion of F during the 8 h following administration, the relative bioavailabilities of the two F formulations were equivalent.     

Removal of fluoride from fluoride contaminated industrial waste water by electrolysis

Wastewater containing fluoride are generally treated with lime or calcium salt supplemented with aluminium salts. Wastewater generated from different industries does not always behave in the same way due to the presence of interfering contaminants. A number of techniques have been developed and studied for the removal of excessive fluoride. Most of these are based on use of aluminium salt. In alum coagulation the sorption properties of product of hydrolysis of aluminium salts and capacity of fluoride for complex formation plays a very important role. These hydrolysis products of aluminium can be produced by passing direct current through aluminium electrode. The text presented in the paper deals with the various aspect of removal of fluoride by electrolysis using aluminium electrode from fluoride chemical based industrial wastewater.     

Fluorodenitrations using tetrabutylammonium fluoride

Fluoroaromatics are prepared in good yield under mild conditions using the tetrabutylammonium fluoride promoted fluorodenitration of nitroaromatics.     

Thiophosphoryl fluoride and phosphoryl fluoride as initiators for the polymerisation of tetrahydrofuran

Thiophosphoryl fluoride and phosphoryl fluoride have been found to initiate the polymerisation of tetrahydrofuran. The living polymer formed has a high molecular weight of the order of a million and the density is found to be between 0.98 - 1.02 g/cc. A cationic mechanism for the polymerisation has been proposed.     

Photopolymerization of vinyl fluoride

The photopolymerization of vinyl fluoride, in the presence of peroxide, was studied in dimethyl sulfoxide (DMSO) solution and in bulk. It was found that high rates of reaction could be obtained in spite of the fact that the polymer precipitates at an early stage. By continuous supply of monomer the precipitated polymer was converted into a transparent bulk polymer.     

Enthalpimetric determination of fluoride

An injection calorimeter used for analytical and thermochemical purposes is described. Amounts of sodium fluoride between 6 and 8 mg are determined with an error of +/-0.04 mg. The calorimeter is also used in determining DeltaH for the precipitation of lead chloro-fluoride from water solutions with an ionic strength of 1M. DeltaH = 36.6 +/- 0.3 kJ mole . Quantitative analysis is made by flow microcalorimeter with amounts of sodium fluoride between 40 and 400mug and an error of +/-4 mug. An ion-exchange system for separation of fluoride from phosphate, sulphate, nitrate and chloride is also described.     

Copolymers of vinyl fluoride

Vinyl fluoride was polymerized by photochemical initiation in a continuous-flow cylindrical reactor at room temperature and at pressures of up to 30 atm. Copolymers with vinyl acetate were prepared in order to improve the solubility and processability of poly(vinyl fluoride) (PVF). The copolymers were hydrolyzed to the corresponding vinyl alcohol copolymers and yielded hydrophilic films that are strong and flexible only when swollen by water. It was found that on hydrolysis the T_g, T_m, and heat of fusion as well as degree of crystallinity increased. It was suggested that PVF and the copolymers with vinyl alcohol are isomorphous.