Oxidation reactions manganese

The brown crystalline manganese(III) acetate dihydrate is of considerable commercial importance because it is often used as the source material for other trivalent manganese compounds. It can be made by oxidation of manganese(II) acetate using chlorine or potassium permanganate, or by reaction of manganese(II) nitrate and acetic anhydride. 

Metals. Transition-metal ions, such as iron, copper, manganese, and cobalt, when present even in small amounts, cataly2e mbber oxidative reactions by affecting the breakdown of peroxides in such a way as to accelerate further attack by oxygen (36). Natural mbber vulcani2ates are especially affected. Therefore, these metals and their salts, such as oleates and stearates, soluble in mbber should be avoided. 

The direct electrochemical oxidation of manganese alloys was developed and commercialized at the Rustavi Chemical Combine in the Georgian Repubhc (formerly the USSR). The electrode reactions are... 

On the other hand, the catalytic oxidation of a n-butane, using either cobalt or manganese acetate, produces acetic acid at 75-80% yield. Byproducts of commercial value are obtained in variable amounts. In the Celanese process, the oxidation reaction is performed at a temperature range of 150-225°C and a pressure of approximately 55 atmospheres. ... 

The reaction of MnC03 is of particular interest because of the possibility of the formation and interconversion of the various oxides of manganese [733,1276], Westerdahl and Leader [762] identify the initial process as... 

Case a, i is well illustrated by the arsenite-induced oxidation of manganese(II) by chromic acid, studied by Lang and Zwerina. The overall equation of this induced reaction is... 

Considering the limiting values of the induction factor it may be postulated that in the case of iodide and bromide the induced oxidation is caused by chromium(V), whereas for induced oxidation of manganese(II) chromium(lV) is the coupling intermediate. Therefore, one has to assume that in the course of reaction between arsenic(ril) and chromium(VI) both chromium(V) and chromium(IV) intermediates are involved. The mechanism below, proposed by Westheimer seems to be in agreement with experiment. 

In the presence of manganese(II) ions the rate of oxidation of H2R by chromic acid decreases . Under favourable experimental conditions (high concentration of alcohol and low concentration of chromate) the diminution of rate is about 50 % which is in accordance with results listed in Table 6, according to which ci = 0.5. The inhibiting effect of manganese(II) on the oxidation of H2R can be explained by reaction (23) followed by step (24). Therefore the induced oxidation of manganese(II) can be described by reactions (26), (23) and (24). 

To decide whether the reaction involves 1- or 2-electron transfers, i.e. chromium-(rv) or chromium(V) is formed first, the induced oxidation of manganese(II) was investigated. When sodium perchlorate was used to maintain a constant ionic strength, the rate of oxidation of benzaldehyde dropped to one-half of the original rate in the presence of manganese(II) ions. On the contrary, when magnesium perchlorate was used as the neutral salt, the rate was reduced to of its original value. This peculiar observation, however, has not been interpreted. 

Steel making, broadly speaking, is an oxidation process in which impurities such as carbon, silicon, manganese, phosphorus and sulfur present in the pig iron are removed to specified levels. It can be anticipated from the Ellingham diagram that at about 1600 °C, the elements C, Si, and Mn would oxidize preferentially before iron undergoes excessive oxidation. The oxidation reactions may be represented by... 

The alcohol 172 obtained by reaction of 86 with ethynyl magnesium bromide on oxidation with manganese dioxide gave the ketone 17361 Glaser coupling of the ketone 173 gave an equimolar mixture of the two acyclic diketones 170 and 174. 

The low yield in this reaction might be caused by a number of reasons. First, the overall reaction is only rapid for readily enolizable compounds. 1,3-Dicarbonyl compounds will therefore be a better choice as compared to acetic acid. Second, to prevent oxidation of radical 54, it is advantageous to work with excess diene and therefore speed up trapping of 54 through diene addition. Finally, lactone 55 can, as an enolizable compound itself, also be oxidized by manganese(III) acetate and form various oxidation products. Shorter reaction time and the use of understoichiometric amounts of oxidant might therefore benefit the overall result. All these factors have been taken into account in the synthesis of bicyclic /-lactone 56, which has been obtained from cyanoacetic acid and 1,3-cyclohexadiene in 78% yield within 15 min reaction time (equation 25)60,88. 

Reactions between Fe(ll) in contaminated groundwater (5.8 mg/L) and oxic sediment also affected As mobility. Ferrous iron was oxidized by manganese oxides to ferric iron which precipitated as hydrous ferric oxide, creating additional sorption sites. Evidence for this reaction included an increase in ferric oxide concentrations in reacted column sediments and manganese concentrations in leachate that were greater than in the initial eluent. 

The same chemical oxidation strategy can be applied to unsymmetrical por-phyrazines, but a stronger oxidant than manganese dioxide is required. Reaction of the porphyrazines (127 and 130) with potassium permanganate gives the expected seco-porphyrazines 164 and 160, respectively, in 93 and 96% yield (Scheme 31). 

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