Banded iron types

By far the most important ores of iron come from Precambrian banded iron formations (BIF), which are essentially chemical sediments of alternating siliceous and iron-rich bands. The most notable occurrences are those at Hamersley in Australia, Lake Superior in USA and Canada, Transvaal in South Africa, and Bihar and Karnataka in India. The important manganese deposits of the world are associated with sedimentary deposits the manganese nodules on the ocean floor are also chemically precipitated from solutions. Phosphorites, the main source of phosphates, are special types of sedimentary deposits formed under marine conditions. Bedded iron sulfide deposits are formed by sulfate reducing bacteria in sedimentary environments. Similarly uranium-vanadium in sandstone-type uranium deposits and stratiform lead and zinc concentrations associated with carbonate rocks owe their origin to syngenetic chemical precipitation. 

At the suggestion of Elsevier Scientific Publishing Company , the term ferruginous quartzite used earlier has been replaced by the broader term banded iron-formation (BIF). The status of these rocks has been successfully shown by Beukes (1973) in a diagram which it is advisable to give here (Fig. 10). For the iron-rich shales (schists) often associated with BIF proper, especially of Superior or Krivoy Rog type, it is advisable to use the terms iron-rich shales or ferruginous shales (or schists). 

Oxygenic photosynthesis has been dated to before 2.0 billion years ago by some distinctive geological records. The extensive banded iron formation (BIEs) dated 2.0-2.5 billion years ago, can serve as an evidence of the development of this type of photosynthesis. The iron occurs in the form of almost pure ferric oxide and silica, and the formation of BIFs can be explained by the oxidation of ferrous iron in solution with oxygen, produced in large quantities in photosynthesis. The only pre-Cambrian photosynthetic organisms that could carry this out were cyanobacteria. There are extensive fossil records of similar organisms in geological formations of that age. 

Iron Porphyrins. Porphyrias (15—17) are aromatic cycHc compouads that coasist of four pyrrole units linked at the a-positions by methine carbons. The extended TT-systems of these compounds give rise to intense absorption bands in the uv/vis region of the spectmm. The most intense absorption, which is called the Soret band, falls neat 400 nm and has 10. The TT-system is also responsible for the notable ring current effect observed in H-nmr spectra, the preference for planar conformations, the prevalence of electrophilic substitution reactions, and the redox chemistry of these compounds. Porphyrins obtained from natural sources have a variety of peripheral substituents and substitution patterns. Two important types of synthetic porphyrins are the meso-tetraaryl porphyrins, such as 5,10,15,20-tetraphenylporphine [917-23-7] (H2(TPP)) (7) and P-octaalkylporphyrins, such as 2,3,7,8,12,13,17,18-octaethylporphine [2683-82-1] (H2(OEP)) (8). Both types can be prepared by condensation of pyrroles and aldehydes (qv). 

Along a different line of research on shock compression of solids, namely, recovery experiments, great progress was also being made. Shock-induced recovery-type chemical reactions in encapsulated samples were first reported by Riabinin in 1956. Shock-induced metallographic transformation and the observation of twin bands in iron were first reported by Smith in 1958. Another major breakthrough was the shock-induced synthesis of diamond in 1961 by DeCarli and Jamieson. 

Parrott Gun. A type of muzzle-loading cast-iron rifled gun with a wrought-iron band shrunk... 

Let us now return to MMCT effects in semiconductors. In this class of compounds MMCT may be followed by charge separation, i.e. the excited MMCT state may be stabilized. This is the case if the M species involved act as traps. A beautiful example is the color change of SrTiOj Fe,Mo upon irradiation [111]. In the dark, iron and molybdenum are present as Fe(III) and Mo(VI). The material is eolorless. After irradiation with 400 nm radiation Fe(IV) and Mo(V) are created. These ions have optical absorption in the visible. The Mo(VI) species plays the role of a deep electron trap. The thermal decay time of the color at room temperature is several minutes. Note that the MMCT transition Fe(III) + Mo(VI) -> Fe(IV) -I- Mo(V) belongs to the type which was treated above. In the semiconductor the iron and molybdenum species are far apart and the conduction band takes the role of electron transporter. A similar phenomenon has been reported for ZnS Eu, Cr [112]. There is a photoinduced charge separation Eu(II) -I- Cr(II) -> Eu(III) - - Cr(I) via the conduction band (see Fig. 18). 

The frequency of the light absorbed to effect the photo-excitation is in the red and near-infrared parts of the visible region, so the complementary colour seen is blue. This explains why sapphire is blue. It is again a charge-transfer excitation, but not of the mixed-valence type. The optical band formed is intense, so a strong colour is seen even though the concentrations of iron and titanium are minuscule. 

Porphyrins 21 are the backbone of major players in life cycles—cytochromes (Scheme 8). There are three types of cytochromes, classified by their color, or more precisely by their long-wavelength absorption band, as a (600 mn), b (563 nm), and c (550 nm). They are protein conjugates of a porphyrin complex with iron(II), which is a coenzyme called heme (22). In plants, porphyrins form a complex with magnesium-(II) chlorophylls a and b (23), vital in photosynthesis. Porphyrin derivatives are used in photodynamic therapy for dermatological diseases such as psoriasis, and for skin or subcutaneous cancer.5c-e... 

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