Oxidation tetravalent

Masking by oxidation or reduction of a metal ion to a state which does not react with EDTA is occasionally of value. For example, Fe(III) (log K- y 24.23) in acidic media may be reduced to Fe(II) (log K-yyy = 14.33) by ascorbic acid in this state iron does not interfere in the titration of some trivalent and tetravalent ions in strong acidic medium (pH 0 to 2). Similarly, Hg(II) can be reduced to the metal. In favorable conditions, Cr(III) may be oxidized by alkaline peroxide to chromate which does not complex with EDTA. 

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabili2ation of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

Tetravalent lead is obtained when the metal is subjected to strong oxidizing action, such as in the electrolytic oxidation of lead anodes to lead dioxide, Pb02 when bivalent lead compounds are subjected to powerful oxidizing conditions, as in the calcination of lead monoxide to lead tetroxide, Pb O or by wet oxidation of bivalent lead ions to lead dioxide by chlorine water. The inorganic compounds of tetravalent lead are relatively unstable eg, in the presence of water they hydrolyze to give lead dioxide. 

Oxidation of manganese dioxide to higher valence states takes place in the fusion process of Mn02 and KOH. A tetravalent manganese salt identified as K MnO [12142-27-7] (63) which disproportionates spontaneously is formed. 

Representative compounds for the +4 oxidation state are shown in Figure 4. The violet tetravalent molybdenum dioxide [18868-43 ] M0O2, is formed by the reduction of M0O3 with H2 at temperatures below which Mo metal is formed or M0O3 is volatile (ca 450°C). MoCl [13320-71 -3] is formed upon treatment of M0O2 at 250°C with CCl (see Fig. 1). 

Geochemical Nature and Types of Deposits. The cmst of the earth contains approximately 2—3 ppm uranium. AlkaHc igneous rock tends to be more uraniferous than basic and ferromagnesian igneous rocks (10). Elemental uranium oxidizes readily. The solubiHty and distribution of uranium in rocks and ore deposits depend primarily on valence state. The hexavalent uranium ion is highly soluble, the tetravalent ion relatively insoluble. Uraninite, the most common mineral in uranium deposits, contains the tetravalent ion (II). 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Sulfation Roasting. Acid roasting technology (Fig. 2) rehes on differences in the volatiUty of the tetravalent oxides of selenium and tellurium at roasting temperatures of 500—600°C to selectively volatilise selenium from slimes. Acid roasting uses sulfuric acid as the oxidant for the conversion of selenium/selenides and tellurium/teUurides to their respective tetravalent oxides. Typical oxidation reactions are as foUow ... 

Thorium has a wide distribution in nature and is present as a tetravalent oxide in a large number of minerals in minor or trace amounts. Thorium is significantly more common in nature than uranium, having an average content in the earth s cmst of approximately 10 ppm. By comparison, Pb is approximately 16 ppm. Thorium has a seawater concentration of <0.5 x 10 . Thorium refined from ores free of uranium would be almost... 

Coordination Complexes. The coordination and organometaHic chemistry of thorium is dominated by the extremely stable tetravalent ion. Except in a few cases where large and stericaHy demanding ligands are used, lower thorium oxidation states are generally unstable. An example is the isolation of a molecular Th(III) complex [107040-62-0] Th[Tj-C H2(Si(CH2)3)2]3 (25). Reports (26) on the synthesis of soluble Th(II) complexes, such as... 

Salts containing tetravalent tungsten have been prepared by various methods. The most important are the octacyanides, M(I)4(W(CN)g), which form yellow crystals and are very stable. They are isolated as salts or free acids and can be oxidized by KMnO in H2SO4 to compounds containing pentavalent tungsten, M(I)2(W(CN)g) (yellow). 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

The fluorite stmcture, which has a large crystal lattice energy, is adopted by Ce02 preferentially stahi1i2ing this oxide of the tetravalent cation rather than Ce202. Compounds of cerium(IV) other than the oxide, ceric fluoride [10060-10-3] CeF, and related materials, although less stable can be prepared. For example ceric sulfate [13590-82-4] Ce(S0 2> certain double salts are known. 

Cerium Oxide. The most stable oxide of cerium is cerium dioxide [1306-38-3] Ce02, also called ceria or ceric oxide. When cerium salts are calcined in air or if oxygen is present, this tetravalent Ce(IV) oxide is formed, cerium sesquioxide [1345-13-7] can be prepared in strongly reducing... 

Sohd solutions of ceria with trivalent ions, eg, Y and La, can readily be formed. The ions substitute for the tetravalent Ce and introduce one oxygen vacancy for every two ions. The dopant ions and the oxygen vacancies form charge associates. The resulting defect-fluorites have good oxide... 

Hydroxide. Freshly precipitated cerous hydroxide [15785-09-8] Ce(OH)2, is readily oxidized by air or oxygenated water, through poorly defined violet-tinged mixed valence intermediates, to the tetravalent buff colored ceric hydroxide [12014-56-17, Ce(OH)4. The precipitate, which can prove difficult to filter, is amorphous and on drying converts to hydrated ceric oxide, Ce02 2H20. This commercial material, cerium hydrate [23322-64-7] behaves essentially as a reactive cerium oxide. 

In oxygenated seawater, uranium is thermodynamically predicted to be present in a hexavalent (-b 6) oxidation state, but it can also exist as the tetravalent U(IV) if conditions are sufficiently reducing. Reduced uranium in the +A oxidation state is highly insoluble or particle reactive. In contrast, U(VI) is readily soluble due to the rapid formation of stable inorganic carbonate complexes. According... 

Pentafluorophenylditelluridc yields 79-80% pentafluorophenyltellunum tri fluoride on treatment with fluorine or xenon difluoride [105] The fluonnated tetravalent tellurium can be further oxidized to hexavalent tellurium with either xenon difluoride [/22] or fluorine [123]... 

The boronic acid 2 is first converted to an activated species 8 containing a tetravalent boron center by reaction with a base. Halides or triflates (OTf = trilluoromethanesulfonate) are used as coupling partners R-X for the boronic acids. In many cases the rate-limiting step is the oxidative addition. With respect to the leaving group X, the rate decreases in the order ... 

The only prominent antitumor tetravalent platinum complex so far is iproplatin (102). In vitro it has been shown to cause interstrand DNA-breaking and cross linking. Free radical scavengers inhibit these effects. The complex is less neurotoxic and less nephrotoxic than cisplatin. Its synthesis begins with hydrogen peroxide oxidation of cis-dichlorobis(isopropvlamine) platinum (100) to the dimethylacetamide complex 101. The latter is heated in vacuum to liberate iproplatin [25]. 

The introduction of divalent calcium and barium oxides into frits in preference to monovalent sodium and potassium generally increases water resistance. Furthermore, oxides of tetravalent and pentavalent metals have a favourable effect on the resistance of glasses and enamels to water. The influence of B2O3 and fluorine in the frit upon chemical resistance is variable and is dependent upon the content of them and the balance of the frit constituents, but they usually cause a diminution in resistance. In general, mill-added clay, silica and opaciher increase water resistance provided the firing or fusing of the enamel is at the optimum. 

As it was shown in73, 74), methods that can be used to synthesize these copolymers of PAN are those of radical AN block copolymerization in the presence of an oxidation-reduction system in which the hydroxyl end groups of polyethylene oxide) (PEO)73) and polypropylene oxide) (PPO)74- oligomers serve as the reducing agents and tetravalent cerium salts as the oxidizing agents. 

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. 

---