Mercury oxidation state

Fig. 15.8 Frost diagrams of copper and mercury (oxidation states 0, +1, +11)...

Exists as the (Hg —Hg) ion. Other polymercury cations, e.g. Hgj (Hg plus AsFj), Hg4 etc., are also known. All positive oxidation state compounds of Hg are readily reduced to the metal, mercury chlorides... 

The more noble metals (for example copper, mercury and silver) can form oxides, and exhibit variable oxidation state in such compounds (for example CU2O, CuO), but it is not easy to prepare such oxides by direct action of oxygen on the metal, and elevated temperatures are necessary. Moreover, in the case of silver and mercury, loss of oxygen from the oxide by heating is easy. The oxidesare, however, basic (for example Ag20 - Ag, CuO - Cu in acids). 

Halogens can act as ligands and are commonly found in complex ions the ability of fluorine to form stable complex ions with elements in high oxidation states has already been discussed (p. 316). However, the chlorides of silver, lead(Il) and mercury(l) are worthy of note. These chlorides are insoluble in water and used as a test for the metal, but all dissolve in concentrated hydrochloric acid when the complex chlorides are produced, i.e. [AgCl2] , [PbC ] and [Hg Clj]", in the latter case the mercury(I) chloride having also disproportionated. 

These elements formed Group IIB of Mendeleef s original periodic table. As we have seen in Chapter 13, zinc does not show very marked transition-metaf characteristics. The other two elements in this group, cadmium and mercury, lie at the ends of the second and third transition series (Y-Cd, La-Hg) and, although they resemble zinc in some respects in showing a predominantly - - 2 oxidation state, they also show rather more transition-metal characteristics. Additionally, mercury has characteristics, some of which relate it quite closely to its immediate predecessors in the third transition series, platinum and gold, and some of which are decidedly peculiar to mercury. 

Mercury salts exist ia two oxidation states mercurous, Hg", and mercuric, The former exist as double salts for example, mercurous... 

Many mercury compounds are labile and easily decomposed by light, heat, and reducing agents. In the presence of organic compounds of weak reducing activity, such as amines (qv), aldehydes (qv), and ketones (qv), compounds of lower oxidation state and mercury metal are often formed. Only a few mercury compounds, eg, mercuric bromide/77< 5 7-/7, mercurous chloride, mercuric s A ide[1344-48-5] and mercurous iodide [15385-57-6] are volatile and capable of purification by sublimation. This innate lack of stabiUty in mercury compounds makes the recovery of mercury from various wastes that accumulate with the production of compounds of economic and commercial importance relatively easy (see Recycling). 

Some metals used as metallic coatings are considered nontoxic, such as aluminum, magnesium, iron, tin, indium, molybdenum, tungsten, titanium, tantalum, niobium, bismuth, and the precious metals such as gold, platinum, rhodium, and palladium. However, some of the most important poUutants are metallic contaminants of these metals. Metals that can be bioconcentrated to harmful levels, especially in predators at the top of the food chain, such as mercury, cadmium, and lead are especially problematic. Other metals such as silver, copper, nickel, zinc, and chromium in the hexavalent oxidation state are highly toxic to aquatic Hfe (37,57—60). 

Some metal thiosulfates are inherently unstable because of the reducing properties of the thiosulfate ion. Ions such as Fe " and Cu " tend to be reduced to lower oxidation states, whereas mercury or silver, which form sulfides of low solubiUty, tend to decompose to the sulfides. The stabiUty of other metal thiosulfates improves in the presence of excess thiosulfate by virtue of complex thiosulfate formation. 

Except for mercury, the elements at the ends of each row of the d block occur in only one oxidation state other than 0. All the other elements of each row have at least two oxidation states and manganese, at the center of its row, has seven oxidation states. 

Notice that ruthenium and osmium have all possible oxidation states and that even gold and mercury, which lie near the end of the block, can be found in three oxidation states. 

It may be mentioned that the possibility of bivalence of tin in grey tin and the mercury alloy, suggested by the bipositive oxidation state of the element in many of its compounds, is ruled out because it leads to too small a value of R 1)—smaller than that for quadrivalent tin, whereas a larger value would be expected as the result of the appropriation of much of the s orbital by the unshared pair. 

There are several environmentally significant mercury species. In the lithosphere, mercury is present primarily in the +II oxidation state as the very insoluble mineral cirmabar (HgS), as a minor constituent in other sulfide ores, bound to the surfaces of other minerals such as oxides, or bound to organic matter. In soil, biological reduction apparently is primarily responsible for the formation of mercury metal, which can then be volatilized. Metallic mercury is also thought to be the primary form emitted in high-temperature industrial processes. The insolubility of cinnabar probably limits the direct mobilization of mercury where this mineral occurs, but oxidation of the sulfide in oxygenated water can allow mercury to become available and participate in other reactions, including bacterial transformations. 

Along with Cu ", MnO and Ag" , the two oxidation states of mercury are reduced by molecular hydrogen -Halpern " considers that hydrogen is oxidised by two general mechanisms corresponding to rate equations of the type... 

The reaction between Hg(II) and olefins has been examined from several angles and work prior to 1950 has been summarised by Chatt . Several types of complex and product are formed, depending on the olefin, which involve no change in the oxidation state of the mercury atom. Propenyl ethers have long been known to produce the corresponding glycol plus metallic mercury but no kinetics are available . 

During oxidation of tin(II) ions by hydrogen peroxide, iodine, bromine, mercury(ir) and thallium(III) the induced reduction of cobalt(in) complexes cannot be observed. Therefore, it was concluded that these reactions proceed by 2-equivalent changes in the oxidation states of the reactants. 

Structural aspects of minerals and related synthetic materials with mercury in lower oxidation states and with oxocentered building blocks, OHg , have been reviewed.72,73... 

As mentioned at the end of Section 6.9.3, reviews of the crystal chemistry of mercury minerals with lower oxidation states and with oxo-centered building blocks have been published72,73 and the structural role of Hg22+ and Hg34+ groups discussed.407... 

Of the three group 12 metals, only mercury has a well-developed chemistry with the metal in the +1 oxidation state, while cadmium and zinc, respectively, exhibit this oxidation state either exceedingly seldom or not at all. This increase in the stability of the lower oxidation state as one descends the group is characteristic of main group metals, but not of transition metals. 

Cathodic stripping voltammetry has been used [807] to determine lead, cadmium, copper, zinc, uranium, vanadium, molybdenum, nickel, and cobalt in water, with great sensitivity and specificity, allowing study of metal specia-tion directly in the unaltered sample. The technique used preconcentration of the metal at a higher oxidation state by adsorption of certain surface-active complexes, after which its concentration was determined by reduction. The reaction mechanisms, effect of variation of the adsorption potential, maximal adsorption capacity of the hanging mercury drop electrode, and possible interferences are discussed. 

With respect to Cr a distinction should be made between Cr(III), which is the common oxidation state in the soils, being rather immobile and so toxic, and Cr(VI), which is very mobile and very toxic. With respect to Hg, the situation is even more complex, due to the occurrence of mercuric mercury (Hg2+), mercurous mercury (Hg2+), elemental mercury (Hg°) and organic mercury species, such as methyl mercury, (CH3)2Hg (see Section 18.5). Furthermore, volatilization of elemental mercury and organic mercury species is common. A description of these... 

Similar to terrestrial ecosystems, no distinction is made between various oxidation states of the metals. This assumption seriously limits the application of the model to calculate critical loads for mercury. 

To circumvent some of the above-mentioned drawbacks of sulfur-based mercury chemodosimeters, a system based on the alkyne oxymercuration of 58 has been developed (Fig. 22) [146]. 58 shows high selectivity, a limit of detection of ca. 8 ppm, resistance against strong oxidants, and a positive reaction even in the presence of cysteine, which is known to form stable mercury complexes and is used for the extraction of mercury from tissue samples. Another metal that is well-known for its catalytic ability is palladium, catalyzing different reactions depending on its oxidation state. Since this metal is toxic, assessment of the maximum allowable concentration of Pd in consumer products such as pharmaceuticals requires highly sensitive and selective detection schemes. For this purpose, indicator 60 was conceived to undergo allylic oxidative insertion to the fluorescein... 

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