Chromium valency

Peterson, M.L. Brown Jr., G.E. Parks, G.A. (1997) Quantitative determination of chromium valence in environmental samples using XAFS spectroscopy. In Voigt, J.A. Bunker, B.C. Casey,W.H. Wood,T.E. Crossey, L.J. (eds.) Aqueous chemistry and geochemistry of oxides, oxyhydroxides, and related materials. Materials Research Society, Pittsburgh... 

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. 

A number of organochromium compounds form highly active polymerization catalysts when deposited onto an already calcined oxide carrier. Usually the carrier plays an essential role, because without it such compounds rarely exhibit any activity. In many respects, the organochromium catalysts are quite different from their chromium oxide counterparts. Examples of organochromium compounds which form active catalysts include those with chromium in any of the formal chromium valences from Cr(0) to Cr(IV). 

FIGURE 246 Chromium valence cycle during commercial catalyst life. 

In EC decay, the chemical effects of the X-ray intensity ratio KJK was first observed by Tamaki et al. for various chromium compounds labeled with Cr. A Si(Li) detector was used to measure the X-rays emitted from the nuclide. When the measured data of K, /K, are plotted against the formal oxidation number of diromium, it is seen that the ratio generally increases with the chromium valence number. This is shown in Fig. 2. A notable exception is, however, metallic chromium, where the formal oxidation number does not reflect the electronic state surroimding the chromium atom at all. 

Fregert S (1981) Chromium valencies and cement dermatitis. Br J Dermatol i05[suppl 2i] 7-9... 

Not all ligands use just two electrons to bond to transition metals Chromium has the electron configuration [Ar]4s 3rf (6 valence electrons) and needs 12 more to satisfy the 18 electron rule In the compound (benzene)tricarbonylchromium 6 of these 12 are the tt elec Irons of the benzene ring the remammg 6 are from the three carbonyl ligands... 

Ground-state electronic configuration is ls 2s 2p 3s 3p 3i 4s. Manganese compounds are known to exist in oxidation states ranging from —3 to +7 (Table 2). Both the lower and higher oxidation states are stabilized by complex formation. In its lower valence, manganese resembles its first row neighbors chromium and especially iron ia the Periodic Table. Commercially the most important valances are Mn, Mn ", or Mn ". ... 

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. 

Chromium Exposure Levels and U.S. Government Regulations. The level of exposure to chromium compounds for employees in industry and for the general population via waste disposal and industrial emissions is the subject of much regulation, research, and controversy. Some U.S. Government regulations, such as the Comprehensive Environmental Response, Compensation, and LiabiUty Act (CERCLA), also known as the Superfund Act, make no distinction as to the oxidation state of chromium (144). However, there is valence distinction in other regulations. 

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. 

L3M45M4 5 would often appear as L3M2,3V and L3W, respectively, and similarly 1 2,3 4,5 4,51 as M2,3W. In Fig. 2.22 the increase in the intensity of the L3W peak relative to the other two, upon going from chromium to iron, is because of the progressive increase in the electron density in the valence band. The characteristic doublet seen in the MNN series arises from the M4 5N4,sN4,5 transitions, in which the doublet separation is that of the core levels M4 and M5. 

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. 

Consider the dichromate ion. It has no metal-metal nor oxygen-oxygen bonds. Write a Lewis structure for die dichromate ion. Consider chromium to have six valence electrons. 

Hexafluorometalates of ammonia are formed in the presence of trivalent metals [51, 52]. It was shown, for instance, that fluorination of chromium oxides using ammonium hydrofluoride yields (NFLi)3CrF6. It was also found that the oxidation degree of chromium does not depend on the initial valency of the original oxide used as a precursor [110]. 

Manganese crystallizes in three known modifications, no one of which, however, contains only atoms with the normal expected valence 5.78. For this valence we predict the value 1.168 A. for 22(1), by interpolation between chromium and iron. 

In a similar vein, we observe nickel(O), possessing ten electrons in its valence shell, to require four carbonyl ligands to satisfy the eighteen electron rule and form [Ni(CO)4l, whilst chromium(O), with six electrons in its valence shell forms [Cr(CO)6]. These latter compounds are tetrahedral and octahedral respectively. 

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