Hafnium compounds properties

Most hafnium compounds have been of slight commercial interest aside from intermediates in the production of hafnium metal. However, hafnium oxide, hafnium carbide, and hafnium nitride are quite refractory and have received considerable study as the most refractory compounds of the Group 4 (IVB) elements. Physical properties of some of the hafnium compounds are shown in Table 4. 

Table 4. Physical Properties of Some Hafnium Compounds...

K. L. Komarek, ed.. Hafnium Physico-Chemical Properties of Its Compounds andEUhys, International Atomic Energy Agency, Vieima, 1981, pp. 11,13,14, 16. Covers tbermocbemical properties, phase diagrams, crystal stmcture, and density data on hafnium, hafnium compounds, and alloys. 

Zirconium and hafnium have very similar chemical properties, exhibit the same valences, and have similar ionic radii, ie, 0.074 mm for, 0.075 mm for (see Hafniumand hafnium compounds). Because of these similarities, their separation was difficult (37—40). Today, the separation of zirconium and hafnium by multistage counter-current Hquid—Hquid extraction is routine (41) (see Extraction, liquid—liquid). 

Haber process, 22 792 Hackling, 77 292 Hackmanite, color, 7 338 Haemanthamine, 2 87 Hafnium (Hf), 73 78-97 26 637. See also Hafnium compounds analytical methods for, 73 87-88 chemical properties of, 73 80 economic aspects of, 73 86-87 health and safety factors related to, 73 88... 

As exemplified by the reactions of Schemes 1 and 4, fluorotitanium compounds could open new possibilities for metal-catalyzed processes. Their fascinating structural diversity [7] as well as further catalytic possibilities in the field of olefin polymerizations [7i, 16] have been put forward by the pioneering work of Roesky, Noltemeyer and co-workers. Similar properties were also exhibited by the analogous zirconium and hafnium compounds [7b,i]. A Zr binaphtholate has already been successfully applied for the enantioselective allylstannylation of aldehydes [2f], Buch-wald and co-workers successfully used a chiral titanocene difluoride as precursor for the corresponding Ti(lII) hydride, a very efficient catalyst for the enantioselective hydrosilylation of imines [17]. 

Element 104, the first transactinide element, is expected to have chemical properties similar to those of hafnium. It would, for example, form a relatively volatile compound with chlorine (a tetrachloride). 

The chemistry of hafnium has not received the same attention as that of titanium or zirconium, but it is clear that its behaviour follows that of zirconium very closely indeed with only minor differences in such properties as solubility and volatility being apparent in most of their compounds. The most important oxidation state in the chemistry of these elements is the group oxidation state of +4. This is too high to be ionic, but zirconium and hafnium, being larger, have oxides which are more basic than that of titanium and give rise to a more extensive and less-hydrolysed aqueous chemistry. In this oxidation state, particularly in the case of the dioxide and tetrachloride, titanium shows many similarities with tin which is of much the same size. A large... 

Hafnium carbide (HfC) is an interstitial carbide which, with tantalum carbide, is the most refractory compound known. Its characteristics and properties are summarized in Table 9.4. 

Zirconium can be a shiny grayish crystal-Uke hard metal that is strong, ductile, and malleable, or it can be produced as an undifferentiated powder. It is reactive in its pure form. Therefore, it is only found in compounds combined with other elements—mosdy oxygen. Zirconium-40 has many of the same properties and characteristics as does hafhium-72, which is located just below zirconium in group 4 of the periodic table. In fact, they are more similar than any other pairs of elements in that their ions have the same charge (+4) and are of the same general size. Because zirconium is more abundant and its chemistry is better known than hafnium s, scientists extrapolate zirconium s properties for information about hafnium. This also means that one twin contaminates the other, and this makes them difficult to separate. 

H+, NOjl/HNOj redox couple, 33 103 Hafnium, see also specific compounds alkoxides, 26 295 bimetallics, 26 327-328 alkoxides of preparation and properties, 15 272-290... 

Due to its 5t/-6.v- electron configuration, hafnium forms tctravalent compounds readily, although the Ilf1 ion docs not exist as such In aqueous solution except at very low pH values, Ihe common cation being HfO lor Hf OH)i ) and many of the tctravalent compounds are partly covalent. There are also less stable Hf(lll) compounds, There is close similarity in chemical properties to those of zirconium due to the similar outer electron configuration (4identical ionic radii (ZrJ is 0.80 A) the relatively low value for Hf being due lo the Lanthanide contraction. 

The similarity in size causes a very close similarity in chemical properties hafnium and zirconium compounds occur together in nature and are very difficult to distinguish from each other, and other pairs of elements following zirconium and hafnium resemble each other more closely than is usual for two successive members of a family. 

There has been no recent comprehensive review of this area, although a book on the organometallic chemistry of titanium, zirconium, and hafnium deals, in part, with some of the hydride derivatives (1). In the present review, the first part of the discussion reflects the fact that much of the early work on organotitanium hydrides was, often unknowingly at the time, interwoven with attempts to prepare titanocene, Cp2Ti (Cp = tj3-C5H5). Subsequent sections deal with similar compounds containing an additional metal (e.g., aluminum), miscellaneous titanium hydride compounds, and a summary of the main properties of the above species. 

Zirconium and hafnium trifluoracetylacetonates were prepared by Larsen, Terry, and Leddy, who measured some of their properties. They prepared these compounds by the dropwise addition of the ligand to an aqueous solution of the metal oxide chloride, using intermittent addition of sodium carbonate to maintain the proper pH. 

Element 104. (eka-hafnium) is predicted to resemble its homolc hafnium (element 72) in its chemical properties. It is expected to be predominantly tetra-positive, both in aqueous solution and in its solid compounds, although it should exhibit sohd halides and perhaps aqueous ions of the +2 and +3 oxidation state as well. 

One probably can predict some of the crystallographic properties, of the tetrapositive element 104 by extrapolation from those of its homologs zirconium and hafnium. The ionic radii of tetrapositive zirconium (0.74 A) and hafnium (0.75 A) suggest an ionic radius of about 0.78 A for tetrapositive element 104, allowing for the smaller actinide rather than lanthanide contraction. Further one would expect the hydrolytic properties of element 104 and the solubilities of its compounds (such as the fluoride) to be similar to those of hafnium. The sum of... 

Hafnium is also used to make binary compounds with interesting properties. A binary compound consists of two elements. These compounds are among the best refractory materials known. A refractory material is one that can withstand very high temperatures. It reflects heat away from itself Refractory materials are used to line the inside... 

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