Ferrates oxidation

Iron oxides react with other metal oxides to give ferrates. ... 

Alkali metal ferrates(VI), for example K2pe04, are obtained by oxidation of a suspension of hydrous iron(III) oxide (assumed to be Fe(OH)3 in the equation below) by chlorate(I) in concentrated alkali ... 

Decomposition of potassium ferratefVI) at 1000 K gives a ferrate V), K3Fe04, and several types of ferrate(IV), for example FeOj", Fe04 are known these ferrates(IV) have no solution chemistry and are probably best regarded as mixed oxides, since the FeOl" ion has no identifiable structure. 

The best known oxoanion of iron is the ferrate(VI) prepared by oxidizing a suspension of hydrous iron(III) oxide in concentrated alkah with potassium hypochlorite or by anodic oxidation of iron in concentrated alkah. Crystals of potassium ferrate [13718-66-6], K FeO, are deep purple, orthorhombic, and contain discrete tetrahedral [FeOJ anions. Barium ferrate [13773-23A] can be precipitated from solutions of soluble ferrate salts. 

Other ferrate salts include calcium ferrate [35764-67-1], and sodium ferrate [13773-03-0]. The magnetic moments of these materials are 2.63.0 X 10 J/T (2.8-3.2 ), which is consistent with the expectation of two unpaired electrons. The [FeOJ ion is an extremely strong oxidizing... 

Basic oxides of metals such as Co, Mn, Fe, and Cu catalyze the decomposition of chlorate by lowering the decomposition temperature. Consequendy, less fuel is needed and the reaction continues at a lower temperature. Cobalt metal, which forms the basic oxide in situ, lowers the decomposition of pure sodium chlorate from 478 to 280°C while serving as fuel (6,7). Composition of a cobalt-fueled system, compared with an iron-fueled system, is 90 wt % NaClO, 4 wt % Co, and 6 wt % glass fiber vs 86% NaClO, 4% Fe, 6% glass fiber, and 4% BaO. Initiation of the former is at 270°C, compared to 370°C for the iron-fueled candle. Cobalt hydroxide produces a more pronounced lowering of the decomposition temperature than the metal alone, although the water produced by decomposition of the hydroxide to form the oxide is thought to increase chlorine contaminate levels. Alkaline earths and transition-metal ferrates also have catalytic activity and improve chlorine retention (8). 

Metals and Metallic Ions. Under appropriate conditions, ozone oxidizes most metals with the exception of gold and the platinum group. When oxidized by ozone, heavy metal ions, such as Fe and Mn , result in the precipitation of insoluble hydroxides or oxides upon hydrolysis (48—50). Excess ozone oxidizes ferric hydroxide in alkaline media to ferrate, and Mn02 to MnO. ... 

Sodium nitrite has been synthesized by a number of chemical reactions involving the reduction of sodium nitrate [7631-99-4] NaNO. These include exposure to heat, light, and ionizing radiation (2), addition of lead metal to fused sodium nitrate at 400—450°C (2), reaction of the nitrate in the presence of sodium ferrate and nitric oxide at - 400° C (2), contacting molten sodium nitrate with hydrogen (7), and electrolytic reduction of sodium nitrate in a cell having a cation-exchange membrane, rhodium-plated titanium anode, and lead cathode (8). 

Other ions, eg, ferrate, chloride, and formate, are determined by first removing the cyanide ion at ca pH 3.5 (methyl orange end point). Iron is titrated, using thioglycolic acid, and the optical density of the resulting pink solution is measured at 538 nm. Formate is oxidized by titration with mercuric chloride. The mercurous chloride produced is determined gravimetricaHy. Chloride ion is determined by a titration with 0.1 Ai silver nitrate. The end point is determined electrometricaHy. 

Oxidants commonly used include ozone, permanganate, chlorine, chlorine dioxide, and ferrate, often in combination with catalysts. Standard-type mixed reactors are used with contact times of several minutes to an hour. Special reactors for use with ultraviolet light have been developed. 

Heating with the following solids, their fusions, or vapours (a) oxides, peroxides, hydroxides, nitrates, nitrites, sulphides, cyanides, hexacyano-ferrate(III), and hexacyanoferrate(II) of the alkali and alkaline-earth metals (except oxides and hydroxides of calcium and strontium) (b) molten lead, silver, copper, zinc, bismuth, tin, or gold, or mixtures which form these metals upon reduction (c) phosphorus, arsenic, antimony, or silicon, or mixtures which form these elements upon reduction, particularly phosphates, arsenates,... 

If the complex has an overall negative charge (an anionic complex), the suffix -ate is added to the stem of the metal s name. If the symbol of the metal originates from a Latin name (as listed in Appendix 2D), then the Latin stem is used. For example, the symbol for iron is Fe, from the Latin ferrum. Therefore, any anionic complex of iron ends with -ferrate followed by the oxidation number of the metal in Roman numerals ... 

Until now examples for catalytic reactions involving ferrates with iron in the oxidation state of -l-3 are very rare. One example is the hexacyanoferrate 8-catalyzed oxidation of trimethoxybenzenes 7 to dimethoxy-p-benzoquinones 9/10 by means of hydrogen peroxide which was published by Matsumoto and Kobayashi in 1985 [2]. Using hexacyanoferrate 8 product 9 was favored while other catalysts like Fe(acac)3 or Fe2(S04)3 favored product 10 (Scheme 2). The oxidation is supposed to proceed via the corresponding phenols which are formed by the attack of OH radicals generated in the Fe/H202 system. 

One of the most prominent characteristics of Fe(+2) is its ability to undergo oxidation leading to Fe(+3). This was used by Uchiyama et al. when they reported on Fe(+2)-ate complexes as potent electron transfer catalysts [7, 8]. These ferrates are accessible from FeCl2 and 3 equiv. of MeLi. The Fe(+2/+3) oxidation potential of [Me3Fe(+2)]Li 19 in THF is —2.50 V, thus being in between those of Sml2 (—2.33 V) and Mg (—3.05 V). With these alkyliron-ate complexes it was possible to realize a reductive desulfonylation of various A -sulfonylated amines 20 with different basicity. By using Mg metal to restore the active Fe(+2) species 19 a catalytic reductive desulfonylation process was achieved (Scheme 4). 

Another possible alternative oxidant that has recently been investigated is an Fe(VI) species, potassium ferrate, K2Fe04, supported on montmorillonite clay.14 This reagent gives clean, high-yielding oxidation of benzylic and allylic alcohols, but saturated alcohols are less reactive. 

Sharma VK, Smith JO, Millero FJ. 1997. Ferrate(VI) oxidation of hydrogen sulfide. Environmental Sciences and Technology 31 2486-2491. 

Most lanthanide compounds are sparingly soluble. Among those that are analytically important are the hydroxides, oxides, fluorides, oxalates, phosphates, complex cyanides, 8-hydroxyquinolates, and cup-ferrates. The solubility of the lanthanide hydroxides, their solubility products, and the pH at which they precipitate, are given in Table 2. As the atomic number increases (and ionic radius decreases), the lanthanide hydroxides become progressively less soluble and precipitate from more acidic solutions. The most common water-soluble salts are the lanthanide chlorides, nitrates, acetates, and sulfates. The solubilities of some of the chlorides and sulfates are also given in Table 2. 

Konox A process for removing hydrogen sulfide from industrial gases by absorption in aqueous sodium ferrate (Na2Fe04) solution. The ferrate is reduced to ferrite (NaFe02) and the sulfide is oxidized to elemental sulfur. The main reactions are ... 

Strontium compounds, 23 319-324 estimated distribution of, 23 3201 world production of, 23 319-320 Strontium cyanide, 8 197 Strontium ferrate (1 1), 5 598 Strontium fluoride, 23 323 Strontium fluoroborate tetrahydrate, 4 153 Strontium halides, 23 323 Strontium hexaferrite, 23 323 Strontium hydride, 13 613 Strontium hydroxide, 23 324 Strontium iodide, 23 323 Strontium-lead alloys, 14 779 Strontium minerals, 23 320 producers of, 23 319 Strontium nitrate, 23 319, 321, 323 Strontium oxide, 23 318, 324 Strontium peroxide, 18 396, 23 324 Strontium-silicon alloy, 22 520 Strontium sulfate, 23 322, 324 Strontium sulfide, 23 322 Strontium titanate... 

Ferrate salts have been used under phase-transfer catalytic conditions for the oxidation of alcohols. Selective oxidation of allylic and benzylic alcohols to the corresponding aldehydes occurs under mild conditions [4],... 

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