Zirconium, elemental oxidation states

Zirconium (Zr, CAS 7440-67-7, atomic number 40, atomic mass 91.22) has a melting point of 1852 °C and a boiling point of 4377 °C. It is a hard, lustrous, silvery metal, in contrast to fine zirconium powder, which is black. Zirconium belongs to Subgroup IV of the Periodic Table of the elements, between the elements titanium and hafnium - two metals with which it is often found in nature. Zirconium has oxidation states ranging from II to IV, of which the tetravalent is relatively stable and abundant (Venugopal and Luckey 1979). Zirconium is very corrosion-resistant and is unaffected by alkalis or acids (except for HF). 

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... 

Unsubstituted bisphthalocyanines 2 are formed in the presence of several elements which exist in a stable oxidation state of + III or +IV such as titanium, zirconium, hafnium, indium and most of the lanthanide and actinide elements. 

The only crystalline phase which has been isolated has the formula Pu2(OH)2(SO )3(HaO). The appearance of this phase is quite remarkable because under similar conditions the other actinides which have been examined form phases of different composition (M(OH)2SOit, M=Th,U,Np). Thus, plutonium apparently lies at that point in the actinide series where the actinide contraction influences the chemistry such that elements in identical oxidation states will behave differently. The chemistry of plutonium in this system resembles that of zirconium and hafnium more than that of the lighter tetravalent actinides. Structural studies do reveal a common feature among the various hydroxysulfate compounds, however, i.e., the existence of double hydroxide bridges between metal atoms. This structural feature persists from zirconium through plutonium for compounds of stoichiometry M(OH)2SOit to M2 (OH) 2 (S0O 3 (H20) i,. Spectroscopic studies show similarities between Pu2 (OH) 2 (SOO 3 (H20) i, and the Pu(IV) polymer and suggest that common structural features may be present. 

Indicate the position of titanium, zirconium, and hafnium in Mendeleev s periodic table of the elements, the electron configurations and size of their atoms, and their oxidation states. 

Titanium is the first member of the 3d transition series and has four valence electrons, 3d24s2. The most stable and most common oxidation state, +4, involves the loss of all these electrons. However, the element may also exist in a range of lower oxidation states, most importantly as Ti(III), (II), (0) and —(I), Zirconium shows a similar range of oxidation states, but the tervalent state is much less stable relative to the quadrivalent state than is the case with titanium. The chemistry of hafnium closely resembles that of zirconium in fact, the two elements are amongst the most difficult to separate in the periodic table. 

In the lower oxidation states the chemistry of titanium has little or no counterpart in the chemistries of the group IVB elements. The only lower oxidation state of these elements is two, for which the stability order is Ge < Sn < Pb. However,, both zirconium(III) and hafnium(III) are similar to if less stable (towards oxidation) than titanium(III) and have comparable although less extensively investigated chemistries. 

The oxidation states and stereochemistries of zirconium and hafnium are summarized in Table 18-A-l. These elements, because of the larger atoms and ions, differ from Ti in having more basic oxides, having somewhat more extensive aqueous chemistry, and more commonly attaining higher coordination numbers, 7 and 8. They have a more limited chemistry of the III oxidation state. 

These two elements have very similar chemistries, though not so nearly identical as in the case of zirconium and hafnium. They have very little cationic behavior, but they form many complexes in oxidation states II, III, IV, and V. In oxidation states II and III M—M bonds are fairly common and in addition there are numerous compounds in lower oxidation states where metal atom clusters exist. An overview of oxidation states and stereochemistry (excluding the cluster compounds) is presented in Table 18-B-l. In discussing these elements it will be convenient to discuss some aspects (e.g., oxygen compounds, halides, and clusters) as classes without regard to oxidation state, while the complexes are more conveniently treated according to oxidation state. 

Titanium has a more extensive redox chemistry than either zirconium or hafnium. In addition to the +4 oxidation state, the most stable for all three elements of this group, titanium(lll) and titanium(II) compounds are known. Titanium(III) is a good reducing agent and exists in aqueous solution as under acidic conditions, Ti-... 

The coordination chemistry of this oxidation state is virtually confined to that of titanium. Reduction of zirconium and hafnium from the quadrivalent to the tervalent state is not easy and cannot be attempted in water which is itself reduced by Zr and A few adducts of the trihalides of these two elements with N- or P- donor ligands have been prepared. ZrBrj treated with liquid ammonia yields a hexaammine stable to room temperature... 

The lanthanide contraction, however, has also effects for the rest of the transition metals in the lower part of the periodic system. The lanthanide contraction is of sufficient magnitude to cause the elements which follow in the third transition series to have sizes very similar to those of the second row of transition elements. Due to this, for instance hafnium (Hf ) has a 4" -ionic radius similar to that of zirconium, leading to similar behavior of these elements. Likewise, the elements Nb and Ta and the elements Mo and W have nearly identical sizes. Ruthenium, rhodium and palladium have similar sizes to osmium iridium and platinum. They also have similar chemical properties and they are difficult to separate. The effect of the lanthanide contraction is noticeable up to platinum (Z = 78), after which it no longer noticeable due to the so-called Inert Pair Effect (Encyclopedia Britannica 2015). The inert pair effect describes the preference of post-transition metals to form ions whose oxidation state is 2 less than the group valence. 

The chemical properties span a range similar to the representative elements in the first few rows of the periodic table. Francium and radium are certainly characteristic of alkah and alkaline earth elements. Both Fr and Ra have only one oxidation state in chemical comhina-tions and have little tendency to form complexes. Thallium in the 1+ oxidation state has alkah-like properties, but it does form complexes and has extensive chemistry in its 3+ state. Similarly, lead can have alkaline earth characteristics, hut differs from Ra in forming complexes and having a second, 4+, oxidation state. Bismuth and actinium form 3+ ions in solution and are similar to the lanthanides and heavy (Z > 94) actinides. Thorium also has a relatively simple chemistry, with similarities to zirconium and hafiuum. Protactinium is famous for difficult solution chemistry it tends to hydrolyze and deposit on surfaces unless stabilized (e.g., by > 6 M sulfuric acid). The chemistry of uranium as the uranyl ion is fairly simple, hut... 

Some general considerations when sample digestion is applied involve the possibility of loss of some analytes due to their volatilization. Halogen compounds of certain elements, such as antimony, arsenic, boron, chromium, germanium, silicon, lead, mercury, tin, zirconium, zinc, and titanium, can be partially lost as volatiles if formed during the sample preparation. Oxides of some late transition metals in their highest oxidation state, such as ruthenium(VIII), osmium(VIII), and rhenium(VII), are also known to be volatile. Closed-vessel digestion technique can in some cases provide solution to these potential issues. 

To obtain and stabilize the actinides under study in the elemental/metallic state, the reduction of actinide oxides with lanthanum metal and the desorption of actinide atoms from metals like tantalum, titanium, and zirconium have been applied successfully. 

Oxidation number (IV), as in Z1O2 or Hf02. The oxidation states for Rf calculated relativistically to occur in water (III) and (IV), especially (IV), and possibly (II). Zirconium and Hf are so similar, with the lanthanoid contraction and relativistic effects canceling the otherwise expected larger size of the latter in its ions, that we treat them together. The same goes for many subsequent elements. In what follows here, the rarer Hf can often be substituted for Zr, except in comparisons or separations. 

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