Tungsten fluorides: syntheses and electrochemical characterization in the FLINAK molten salt eutectic.

The following tungsten fluorides have been synthesized by simple addition reactions or by reduction with tungsten metal at elevated temperature: KWF7, K2WF8, MWF6 (M = K, Na, Rb, Cs), K2WF7, M3WF8 (M = K, Na, Rb), and K3WF6. The compounds were characterized by their Raman spectra and by cyclic voltammetry in the molten FLINAK eutectic melt (46.5, 11.5, and 42.0 mol % of LiF, NaF, and KF, respectively) at 475-800 degrees C. X-ray crystal structures are reported for two new compounds K2WF7 and K3WF6. The crystals of K2WF7 were orthorhombic, space group Pnma (No. 62) with a = 9.800(2) A, b = 5.7360(11) A, c = 11.723(2) A, and Z = 4. Crystals of K3WF6 were cubic, space group Fm3 (No. 225) with a = b = c = 8.9160(10) A, Z = 4. Electrodeposition of tungsten metal on Pt from FLINAK, prepared by the addition of WF6 gas and metallic tungsten to the melt, is suggested to result from reduction of an equilibrium mixture of WF8(3-) and WF6(3-).

Determination of oxide in fluoride salts using an yttria-stabilized-zirconia oxygen pump.

An improved method over a previous technique has been developed to determine the ppm oxide concentration of fluoride salts. The oxide is released as oxygen gas by the reaction of the test salt with potassium bromotetrafluoride at 450 °C. The molecular oxygen released is then passed through a zirconia oxygen pump which selectively removes the oxygen. The current response is recorded as a chronoamperogram, from which the ppm oxide content of the salt can be obtained. Oxygen recovery from an yttrium oxide standard was better than 99%. The precision of analysis of FLINAK was better than 13% for samples containing 110-170 ppm oxide. The LOD was 12 µg of oxygen, and the analytical range was 120 ppm to >20% for a 0.1-g sample.

Supercritical fluid extraction of vapor-deposited pyrene from carbonaceous coal stack ash.

The efficiencies of extraction of vapor-deposited pyrene from a high-carbon coal stack ash by Soxhlet extraction with methanol, ultrasonic extraction with toluene, acid pretreatment and subsequent ultrasonic extraction with toluene, batch extraction with toluene, and supercritical fluid extraction (SFE) are compared. SFE using CO(2) or isobutane yielded extraction recoveries virtually identical with those obtained using ultrasonic or Soxhlet extraction processes. Collection of the SFE extract was performed by expansion into a solvent or onto the head of a gas chromatography (GC) column. No loss of extracted pyrene was observed upon collection of methanol-modified CO(2) SFE by expansion into methanol. Also, no loss of pure CO(2) SFE extract was observed upon collection on the head of a GC column. However, use of a methanol or toluene modifier for CO(2) SFE directly coupled to GC effected complete loss of extracted pyrene.

Oxidative transformations of polycyclic aromatic hydrocarbons adsorbed on coal fly ash.

Polycyclic aromatic hydrocarbons adsorbed onto coal fly ash were found to be stabilized against photochemical decomposition. However, a number of adsorbed polycyclic aromatic hydrocarbons will spontaneously oxidize in the absence of light, with those compounds containing a benzylic carbon being particularly susceptible. The decomposition rate appears to be fly ash-dependent.