Ferrate,

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 ... 

Ferrate(VI) has powerful oxidising properties, for example ammonia is oxidised to nitrogen. Potassium ferratefVI) is isomorphous with potassium chromatefVI), and both anions are tetrahedral. 

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. 

It shows some amphoteric behaviour, since it dissolves in alkali (concentrated aqueous or fused) to give a ferrate(lll) the equation may be written as... 

The existence of anode and cathode areas can be seen by the following experiment. A few drops of phenolphthalein are added to a solution of potassium hexacyanoferrate(III) and hydrochloric acid added, drop by drop, until the solution is colourless. (The phenolphthalein turns pink due to hydrolysis of the potassium hexacyano-ferrate(III).) Drops of this solution, about 1 cm in diameter, are now placed on a sheet of freshly abraded steel when pink cathode areas and blue anode areas appear. 

Potassium hexacyano-ferrate(II). K,Fe(CN)(, Potassium hexacyano-ferrateilll), K3Fe CN)6 Potassium thiocyanate. K.CNS... 

IRON COMPOUNDS] (Vol 14) N,Ny-l,2-Ethanediylbis[N-(caiboxymethyl)-glycinato]ferrate(2-)... 

PHOSPHORIC ACID AND PHOSPHATES] (Vol 18) Triammomum tris(oxalato)ferrate trihydrate [14221-47-7]... 

Simple ABO compounds in addition to BaTiO are cadmium titanate [12014-14-17, CdTiO lead titanate [12060-00-3] PbTiO potassium niobate [12030-85-2] KNbO sodium niobate [12034-09-2], NaNbO silver niobate [12309-96-5], AgNbO potassium iodate [7758-05-6], KIO bismuth ferrate [12010-42-3], BiFeO sodium tantalate, NaTaO and lead zirconate [12060-01 -4], PbZrO. The perovskite stmcture is also tolerant of a very wide range of multiple cation substitution on both A and B sites. Thus many more complex compounds have been found (16,17), eg, (K 2 i/2) 3 ... 

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... 

Iron(II) ediylenediaminetetraacetic acid [15651 -72-6] Fe(EDTA) or A/,Ar-l,2-ethaiiediylbis[A[-(carboxymethyl)glyciQato]ferrate(2—), is a colorless, air-sensitive anion. It is a good reducing agent, having E° = —0.1171, and has been used as a probe of outer sphere electron-transfer mechanisms. It can be prepared by addition of an equivalent amount of the disodium salt, Na2H2EDTA, to a solution of iron(II) in hydrochloric acid. Diammonium [56174-59-5] and disodium [14729-89-6] salts of Fe(EDTA) 2— are known. 

Tris(ethanedioato)ferrate(3—) [15321 -61 -6] [Pe(C20 2] "> prepared by addition of an excess of oxalate to a solution of almost any soluble... 

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). 

Barium is reported in the kiln spill in three different forms water-soluble, eg, BaS, BaO acid-soluble, eg, BaCO, aluminate, siUcate, ferrate and insoluble, eg, unreduced barite. 

Syntheses in Solvent Systems. Very few examples of syntheses of metal carbonyls in aqueous solution are reported. An exception is the preparation of Co2(CO)g from CoSO (66% yield) or C0CI2 (56% yield) and CO at 9.6—11 MPa (95—110 atm) in aqueous ammonia at 120°C for 16—18 h (101). Triiron dodecacarbonyl is prepared almost exclusively in aqueous solution. Quantitative yields of Fe2(CO)22 have been obtained by oxidising alkaline solutions of carbonyl ferrates with manganese dioxide (102—104). 

Eor the many details of constmcting or interpreting stmctures and systematic names, the Hterature on nomenclature and indexing (6) can be consulted. Systematic nomenclature is illustrated by the Chemicaly hstracts name of the sodium iron(III) EHPG chelate sodium [[N,N -l,2-ethanediylbis[2-(2-hydroxyphenyl)glyciQatol]](4-)-N,N, 0,0, 0, 0 ]ferrate(l-) [16455-61-1], The ferrate anion (12) [20250-28-6] and the potassium salt [22569-56-8] are also Hsted ia Chemical Abstracts (7). 

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. 

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