Chromium, valency states

Minoia C, Cavalleri A. 1988. Chromium in urine, serum and red blood cells in the biological monitoring of workers exposed to different chromium valency states. Sci Total Environ 71 323-327. 

Physical Properties. Molybdenum has many unique properties, leading to its importance as a refractory metal (see Refractories). Molybdenum, atomic no. 42, is in Group 6 (VIB) of the Periodic Table between chromium and tungsten vertically and niobium and technetium horizontally. It has a silvery gray appearance. The most stable valence states are +6, +4, and 0 lower, less stable valence states are +5, +3, and +2. 

Chemical Properties. The valence states of chromium are +2, +3, and +6, the latter two being the most common. The +2 and +3 states are basic, whereas the +6 is acidic, forming ions of the type CrO (chromates) and (Cr203 [ (dichromates). The blue—white metal is refractory and very hard. 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

The most common toxic metals in industrial use are cadmium, chromium, lead, silver, and mercury less commonly used are arsenic, selenium (both metalloids), and barium. Cadmium, a metal commonly used in alloys and myriads of other industrial uses, is fairly mobile in the environment and is responsible for many maladies including renal failure and a degenerative bone disease called "ITA ITA" disease. Chromium, most often found in plating wastes, is also environmentally mobile and is most toxic in the Cr valence state. Lead has been historically used as a component of an antiknock compound in gasoline and, along with chromium (as lead chromate), in paint and pigments. 

The oxidation of tartaric and glycollic acid by chromic acid also induces the oxidation of manganous ions. In the presence of higher concentrations of manganese(II) the rate of oxidation of the acids is diminished to about one-third of that in the absence of manganous ions. The decrease of the rate has been attributed to manganese(II) catalysis of the disproportionation of the intermediate valence states of chromium probably chromium(IV). 

Biological activity can be used in two ways for the bioremediation of metal-contaminated soils to immobilize the contaminants in situ or to remove them permanently from the soil matrix, depending on the properties of the reduced elements. Chromium and uranium are typical candidates for in situ immobilization processes. The bioreduction of Cr(VI) and Ur(VI) transforms highly soluble ions such as CrO and UO + to insoluble solid compounds, such as Cr(OH)3 and U02. The selenate anions SeO are also reduced to insoluble elemental selenium Se°. Bioprecipitation of heavy metals, such as Pb, Cd, and Zn, in the form of sulfides, is another in situ immobilization option that exploits the metabolic activity of sulfate-reducing bacteria without altering the valence state of metals. The removal of contaminants from the soil matrix is the most appropriate remediation strategy when bioreduction results in species that are more soluble compared to the initial oxidized element. This is the case for As(V) and Pu(IV), which are transformed to the more soluble As(III) and Pu(III) forms. This treatment option presupposes an installation for the efficient recovery and treatment of the aqueous phase containing the solubilized contaminants. 

Chromium occurs in both the Cr(lll) and Cr(VI) valence states. The rock and soil Cr reported in this study is dominantly insoluble and non-toxic Cr(lll), whereas the aqueous Cr reported in ground water is soluble and potentially toxic Cr(VI). We have analyzed core material (up to 30 m depth) from an area of the valley that exhibits elevated Cr(VI) concentrations in... 

Selenium (masses 74, 76, 77, 78, 80, and 82 Table 1) and chromium (masses 50, 52, 53 54 Table 1) are treated together in this chapter because of their geochemical similarities and similar isotope systematics. Both of these elements are important contaminants in surface and ground water. They are redox-active and their mobility and environmental impact depend strongly on valence state and redox transformations. Isotope ratio shifts occur primarily during oxyanion reduction reactions, and the isotope ratios should serve as indicators of those reactions. In addition to environmental applications, we expect that there will be geological applications for Se and Cr isotope measurements. The redox properties of Se and Cr make them promising candidates as recorders of marine chemistry and paleoredox conditions. 

One would expect the presence of trapped electrons in the oxidized samples to give rise to n-type conductivity, conduction possibly taking place by jump migration of the odd electron in the lattice of Cr + ions in a somewhat similar manner to the mechanism discussed by Heikes 174) for the migration of Ni + holes in lithia-doped NiO. The observed p-type conductivity of chromia in an oxygen atmosphere is presumably due to electron holes in a solid which is predominantly CraOs for the low concentrations of chromia-on-alumina where the 7-phase resonance intensity is maximum, the chromium is predominantly in the d-6 valence state 167). 

The 5-phase resonance is not affected appreciably by oxidation at 500 and appears to be relatively stable as Cr +. Matsunaga 167) on the basis of susceptibility data at concentrations only as low as 1 wt. % Cr, concluded that at infinite dilution, all chromium in the -1-3 valence state would be converted to the d-6 state upon oxidation. EPR data indicate that this is not true the 5-phase predominates at low concentration and is stable towards oxidation. On the other hand, the /3-phase at high concentration is apparently rather stable towards complete oxidation at 500°C this indicates that the chromia is most susceptible to oxidation when in rather small clusters. 

Spectra of a variety of chromium compoimds in the +3 valence state are included in Fig. 16. The principal peak is centered at about 22-25 ev. in all cases. The CrjOa spectrum is almost identical to that of Mn02 of Fig. 5. Spectra of the oxalato complex and the ammonia complex are almost identical to spectra of the corresponding cobalt compounds of Figs. 13 and 11. 

The Phillips catalyst contains hexavalent chromium after calcining, but the early discoverers quickly realized that reduction takes place in the reactor on contact with ethylene, leaving chromium in a lower oxidation state as the active species. A worldwide debate has continued to this day about the valence of this reduced species. Chromium in every valence state from Cr(II) to Cr(VI) has been proposed as the active site, either alone or in combination with another valence. The question has received far more attention than it probably deserves, undoubtedly at the expense of more fundamental issues, like the polymerization mechanism. 

It is incorrect to regard only one particular valence state of chromium as the only one capable of catalyzing ethylene polymerization. Active catalysts have been made from organochromium compounds with every valence from Cr(I) to Cr(IV). On the commercial Cr(VI)/silica catalyst the predominant active valence after reduction by ethylene is probably Cr(II), but other states, particularly Cr(III), may also polymerize ethylene under certain conditions. 

Arsenic, chromium, mercury, selenium, and tin have been the object of numerous investigations. Because some of them are classified as probable human carcinogens23-25 (strictly speaking, some of their species), the accurate assessment of concentration and speciation in environmental matrices is enormously important. Unfortunately, such factors as chemical reactions between species, low concentration, microbial activity, redox conditions, as well as the presence of other dissolved metal ions, may cause the amounts and distributions of chemical species in a sample to vary. In response to these problems, analytical research efforts have focused on developing techniques enabling the original valence state of the metals to be preserved. Table 2.3 lists some of these stabilization methods. 

Chromium is a naturally occurring element found in animals, plants, rocks, and soil and in volcanic dust and gases. Chromium has oxidation states (or "valence states") ranging from chromium(-II) to chromium(VI). Elemental chromium (chromium(O)) does not occur naturally. Chromium compounds are stable in the trivalent state and occur in nature in this state in ores, such as ferrochromite. The hexavalent (VI) form is the second-most stable state. However, chromium(VI) rarely occurs naturally, but is usually produced from anthropogenic sources (EPA 1984a). 

Risk assessment. The model accounts for most of the major features of chromium(VI) and chromium(III) absorption and kinetics in the rat, and reduction from the chromium(VI) to the chromium(III) valence state, but the bioavailability/absorbability of chromium from environmental sources is mostly unknown, except for bioavailability/absorbability of a few chemically defined salts. Furthermore, the mechanisms by which chromium reserves from bone tissue are released into plasma as well as age, physiological conditions and species variations are important considerations in the refinement of any PBPK model for risk assessment purposes. 

FukaiR. 1967. Valency state of chromium in seawater. Nature 213 901. 

Mutti A, Pedroni C, Arfini G. et al. 1985b. Biological monitoring of occupational exposure to different chromium compounds at various valency states. In Merian E, Frei RW, Hardi W, et al., eds. 

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