Hafnium fluoride

Hafnium fluoride Hf + 4F —> HfF, also known as hafnium tetrafluoride. 

It was originally separated from zirconium by repeated recrystallization of the double ammonium or potassium fluorides by von Hevesey and Jantzen. Metallic hafnium was first prepared by van Arkel and deBoer by passing the vapor of the tetraiodide over a heated tungsten filament. Almost all hafnium metal now produced is made by reducing the tetrachloride with magnesium or with sodium (Kroll Process). 

Hafnium is readily soluble in hydrofluoric acid and is slowly attacked by concentrated sulfuric acid. Hafnium is unaffected by nitric acid in all concentrations. It is resistant to dilute solutions of hydrochloric acid and sulfuric acid. Hafnium is attacked by all mineral acids if traces of fluorides are present. Hafnium is very resistant to attack by alkaUes. 

Electrolysis. Electro winning of hafnium, zirconium, and titanium has been proposed as an alternative to the KroU process. Electrolysis of an all chloride hafnium salt system is inefficient because of the stabiHty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the StabiHty of in solution and results in much better current efficiencies. Hafnium is produced by this procedure in Erance (17). 

Oxygen and nitrogen also are deterrnined by conductivity or chromatographic techniques following a hot vacuum extraction or inert-gas fusion of hafnium with a noble metal (25,26). Nitrogen also may be deterrnined by the Kjeldahl technique (19). Phosphoms is determined by phosphine evolution and flame-emission detection. Chloride is determined indirecdy by atomic absorption or x-ray spectroscopy, or at higher levels by a selective-ion electrode. Fluoride can be determined similarly (27,28). Uranium and U-235 have been determined by inductively coupled plasma mass spectroscopy (29). 

Hafnium tetrafluoride [13709-52-9] is one component in the cladding layer of a proposed zirconium fluoride glass optical waveguide fiber composition which is expected to have a lower intrinsic light absorption than fused quart2 optical fiber (see Glass Fiber optics Fluorine compounds, inorganic-zirconium). 

Fluorosilicate Fusion. The fusion reaction of milled zircon with potassium hydrogen fluoride was used to prepare potassium hexafluorozirconate [16923-95-8] for studies leading to the first separation of hafnium and zirconium (30). Similar reactions using potassium hexafluorosihcate have been used (31,32) commercially in the United States and the former USSR ... 

Assay of beryUium metal and beryUium compounds is usuaUy accompHshed by titration. The sample is dissolved in sulfuric acid. Solution pH is adjusted to 8.5 using sodium hydroxide. The beryUium hydroxide precipitate is redissolved by addition of excess sodium fluoride. Liberated hydroxide is titrated with sulfuric acid. The beryUium content of the sample is calculated from the titration volume. Standards containing known beryUium concentrations must be analyzed along with the samples, as complexation of beryUium by fluoride is not quantitative. Titration rate and hold times ate critical therefore use of an automatic titrator is recommended. Other fluotide-complexing elements such as aluminum, sUicon, zirconium, hafnium, uranium, thorium, and rate earth elements must be absent, or must be corrected for if present in smaU amounts. Copper-beryUium and nickel—beryUium aUoys can be analyzed by titration if the beryUium is first separated from copper, nickel, and cobalt by ammonium hydroxide precipitation (15,16). 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

T.F. Levchishina, R.L. Davidovich, Complex fluorides of zirconium, hafnium, niobium and tantalum with cations of alkali earth metals, Dep. VINITI, No 3595-75 Dep 1975. 

Hafnium-centered Lewis acid usage is limited in organic chemistry, because of its lower availability and its similarity to zirconium. There are some reactions, however, for which HfIV compounds are used as effective activators. Glycosylation of glycosyl fluorides using a combination... 

In the fluorides, chlorides and oxides of the Group-A main-group metals and the transition metals zirconium and hafnium, aliovalent cation substitutions are generally charge-compensated by the introduction of native defects (e.g. an oxygen vacancy in Zr, ,Ca 02 x) because the intrinsic is large however, in some oxides neutral oxygen or water may... 

Halogen Compounds.—A text describing the chemistry of fluoride compounds of zirconium and hafnium has been published. ... 

Hafnium tetrafluoride may be prepared by passing anhydrous hydrogen fluoride over hafnium tetrachloride at 300°C ... 

A variety of peroxo and hydroperoxo complexes of zirconium(IV) and hafnium(IV) have been isolated from aqueous or aqueous methanolic hydrogen peroxide solutions that contain additional ligands such as sulfate, oxalate or fluoride. Examples of recently reported complexes are listed in Table 8 along with characteristic vibrational frequencies and the pH employed in the aqueous preparations. Earlier work on peroxo compounds has been reviewed by Connor and Ebsworth180 and by Larsen.5... 

Hafnium metal dissolves in HCI twarm) and slowly in H SOj, more rapidly if fluoride iun F is present, funning compounds of llfO . or fluttro complexes in the latter case. The metal resists the attack of weak acids and tbeir salts. 

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