Polonium oxide

At ordinary temperatures polonium oxidizes slowly in air forming the basic oxide, P0O2 ... 

M3C6H2)2 PoCl2 has been obtained by treating 13 with CI2, in benzene. Dimesithyl-polonium oxide has been obtained by air oxidation. 

Metals typically form basic oxides and nonmetals typically form acidic oxides, but what about the elements that lie on the diagonal frontier between the metals and nonmetals Along this frontier from beryllium to polonium, metallic character blends into nonmetallic character, and the oxides of these elements have both acidic and basic character (Fig. 10.7). Substances that react with both acids and bases are classified as amphoteric, from the Greek word for both. For example, aluminum oxide, A1203, is amphoteric. It reacts with acids ... 

Metals form basic oxides, nonmetals form acidic oxides the elements on a diagonal line from beryllium to polonium and several d-block metals form amphoteric oxides. 

In 1896, the French scientist Fienri Becquerel happened to store a sample of uranium oxide in a drawer that contained some photographic plates (Fig. 17.2). He was astonished to find that the uranium compound darkened the plates even though they were covered with an opaque material. Becquerel realized that the uranium compound must give off some kind of radiation. Marie Sklodowska Curie (Fig. 17.3), a young Polish doctoral student, showed that the radiation, which she called radioactivity, was emitted by uranium regardless of the compound in which it was found. She concluded that the source must be the uranium atoms themselves. Together with her husband, Pierre, she went on to show that thorium, radium, and polonium are also radioactive. 

Within the sulfur sub-group, there are two main types of oxides, the dioxides X 02 (X = S, Se, Te, Po) and the trioxides X Os (X = S, Se, Te). In addition, sulfur also forms disulfur monoxide, S2O. Transient XO species are known in the gaseous phase for S, Se, and Te. Polonium forms a black monoxide PoO. 

When the flow through the CNC was exhausted outside of the laboratory, we observed particle formation at higher SOp concentrations as expected (Table II). To prove that the radical scavenger effect is reproducible, another radical scavenger (92 ppb nitric oxide) was used in the presence of 110 ppb SOp concentration and 2% humidity, and the supression in particle formation was observed. Another possible mechanism that supressed the particle formation is that more neutralization of polonium ions occurred at the higher humidities and thus ion-induced nucleation would be suppressed. 

All five elements in the oxygen group have six electrons in their outer orbits. They are all oxidizers (they accept electrons), but they are not all alike. They range from a nonmetal gas (oxygen) to a nonmetal solid (sulfur) to a nonmetallic semiconductor (selenium) to a semimetal (tellurium) and finally to a radioactive metal (polonium). 

Following are two examples of polonium s +2 and +4 oxidation states, in which the element mostly forms compounds with nonmetals. 

Another method to separate polonium from bismuth involves heating at 650°C to convert the metals into their oxides. This is followed by further heating to about 800° C at reduced pressure in which polonium metal is removed by volatilization. 

Because of its radioactivity and alpha emission, polonium forms many types of radiolytic oxidation-reduction products. 

Solvent extraction by tributyl phosphate (TBP) (13, 96), dithizone (20, 71, 72), cupferron (89), thenoyl trifluoroacetone (TTA) (55), diiso-propyl ketone (26), mesityl oxide (92), tri-n-benzylamine and methyl di-n-octylamine (99), diisopropyl and diisobutyl carbinol (100) have all found some application on the trace scale. Acetylaeetone and methyl isobutyl ketone extract milligram amounts of polonium almost quantitatively from hydrochloric acid, but the stable polonium-organic compounds which are formed make it difficult to recover the polonium in a useful form from solutions in these ketones (7). Ion exchange (22, 115, 119) and paper chromatography (44, 87) have also been used for trace scale separations of polonium, but the effects of the intense alpha-radiation on organic com-... 

The radiation decomposition in 10-3 M polonium solution ( 1 curic/ml) causes a visible evolution of gas (5, 34). The radiolysis products are strongly oxidizing, which adds difficulty to the study of the element in its lower, bipositive, state. Peroxide formation appears to be the factor which prevents a study of solutions of the element in the sexapositive state (13), at any rate on the milligram scale. 

The treatment of polonium(lV) with nitric acid/potassium permanganate under reflux yields a sludge of manganese dioxide which contains all the polonium originally present the valency state is uncertain. Polonium (IV) in weighable amounts is not oxidized by persulfate, ceric salts or chlorine in alkaline solution (12), although trace scale work indicates that both ceric salts and dichromate do oxidize polonium to polonium(VI) (94). 

The black monoxide appears to be formed by the spontaneous decomposition of polonium sulfotrioxide and selenotrioxide (10). The corresponding hydroxide (or hydrated oxide) is obtained as a dark brown precipitate when alkali is added to a freshly prepared solution of bipositive polonium (6). Both are rapidly oxidized to polonium(IV) in air or in contact with water. 

A white solid, possibly polonium tetrafluoride, is obtained by treating polonium hydroxide or tetrachloride with dilute aqueous hydrofluoric acid treatment of this solid, in suspension in dilute hydrofluoric acid, with sulfur dioxide yields a bluish grey product (possibly PoF2) which rapidly reverts to the original white solid on standing, presumably owing to radio-lytic oxidation 12). The solubility of polonium(IV) in aqueous hydrofluoric acid increases rapidly with acid concentration, indicating complex ion formation (/ft), p. 48). 

Bipositive polonium in hydrochloric acid solution (pink) is oxidized to polonium(lV) by hydrogen peroxide, by hypochlorous acid or by the radiolysis products of the alpha bombardment of the solvent. Solutions of polonium(II) in acid are obtained by the reduction of polonium(lV) with sulfur dioxide or hydrazine in the cold, or with arsenious oxide on warming. Polonium (IV) is not reduced in hydrochloric acid by either hydroxylamine or oxalic acid, even on boiling 6). 

The solubility of "oxidized polonium—probably the dioxide—in aqueous sodium carbonate is about 0.3 mg (of Po210)/liter and does not change appreciably with the carbonate concentration. However, the solubility in aqueous ammonium carbonate increases from 0.089 mg (of Po210)/ liter in 0.25 M solution to 5.2 mg/liter in 0.75 M solution (104, P- 53). 

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