Insoluble oxidants

Antioxidant additives can not totally prevent the oxidation phenomenon, especially with the modern trend in oil-change intervals at the end of the interval, oil contains a significant quantity of insoluble oxidized material. 

The examples in the preceding section, of the flotation of lead and copper ores by xanthates, was one in which chemical forces predominated in the adsorption of the collector. Flotation processes have been applied to a number of other minerals that are either ionic in type, such as potassium chloride, or are insoluble oxides such as quartz and iron oxide, or ink pigments [needed to be removed in waste paper processing [92]]. In the case of quartz, surfactants such as alkyl amines are used, and the situation is complicated by micelle formation (see next section), which can also occur in the adsorbed layer [93, 94]. 

K2S2O7 300 Ft or porcelain Acid flux for insoluble oxides and oxide-containing samples... 

Oxides and hydroxides react with HCl to form a salt and water as in a simple acid—base reaction. However, reactions with low solubiHty or insoluble oxides and hydroxides is complex and the rate is dependent on many factors similar to those for reactions with metals. Oxidizing agents such as H2O2, H2SeO, and V2O3 react with aqueous hydrochloric acid, forming water and chlorine. 

Beryllium Oxide. Beryllium oxide [1304-56-9], BeO, is the most important high purity commercial beryllium chemical. In the primary industrial process, beryllium hydroxide extracted from ore is dissolved in sulfuric acid. The solution is filtered to remove insoluble oxide and sulfate impurities. The resulting clear filtrate is concentrated by evaporation and upon cooling high purity beryllium sulfate, BeSO 4H20, crystallizes. This salt is... 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

Reactions analogous to the precipitation of AgOH and of insoluble oxides from aqueous solution are ... 

Other corrosion inhibitors also enhance passivity without electrochemical reduction, by depositing insoluble oxidation products into the passivating film. For example benzoate ions cause deposition of ferric benzoate into the oxide, but do not provide any cathodic reaction. 

Generally, the most common cations in the soil solution are potassium, sodium, magnesium and calcium. Alkali soils are high in sodium and potassium, while calcareous soils contain predominantly magnesium and calcium. Salts of all four of these elements tend to accelerate metallic corrosion by the mechanisms mentioned. The alkaline earth elements, calcium and magnesium, however, tend to form insoluble oxides and carbonates in nonacid conditions. These insoluble precipitates may result in a protective layer on the metal surface and reduced corrosive activity. 

The formation of deposits on platinised anodes can cause anode degradationThus dissolved impurities present in water which are liable to oxidation to insoluble oxides, namely Mn, Fe, Pb and Sn, can have a detrimental effect on anode life. In the case of MnOj films it has been stated that MnOj may alter the relative proportions of Cl, and O, produced and thus increase the Pt dissolution rate Fe salts may be incorporated into the TiO, oxide film and decrease the breakdown potential or form thick sludgy deposits. The latter may limit electrolyte access and iead to the development of localised acidity, at concentrations sufficient to attack the underlying substrate . 

As a result of this reaction, Mn3+ cations are never found in water solution. Manganese(m) occurs only in insoluble oxides and hydroxides such as Mn203 and MnO(OH). 

In addition to effects on the concentration of anions, the redox potential can affect the oxidation state and solubility of the metal ion directly. The most important examples of this are the dissolution of iron and manganese under reducing conditions. The oxidized forms of these elements (Fe(III) and Mn(IV)) form very insoluble oxides and hydroxides, while the reduced forms (Fe(II) and Mn(II)) are orders of magnitude more soluble (in the absence of S( — II)). The oxidation or reduction of the metals, which can occur fairly rapidly at oxic-anoxic interfaces, has an important "domino" effect on the distribution of many other metals in the system due to the importance of iron and manganese oxides in adsorption reactions. In an interesting example of this, it has been suggested that arsenate accumulates in the upper, oxidized layers of some sediments by diffusion of As(III), Fe(II), and Mn(II) from the deeper, reduced zones. In the aerobic zone, the cations are oxidized by oxygen, and precipitate. The solids can then oxidize, as As(III) to As(V), which is subsequently immobilized by sorption onto other Fe or Mn oxyhydroxide particles (Takamatsu et al, 1985). 

Transport in solution or aqueous suspension is the major mechanism for metal movement from the land to the oceans and ultimately to burial in ocean sediments. In solution, the hydrated metal ion and inorganic and organic complexes can all account for major portions of the total metal load. Relatively pure metal ores exist in many places, and metals from these ores may enter an aquatic system as a result of weathering. For most metals a more common sequence is for a small amount of the ore to dissolve, for the metal ions to adsorb onto other particulate matter suspended in flowing water, and for the metal to be carried as part of the particulate load of a stream in this fashion. The very insoluble oxides of Fe, Si, and A1 (including clays), and particulate organic matter, are the most important solid adsorbents on which metals are "carried."... 

Both Fe and Al form insoluble oxides that precipitate from solution. Overall, then, O2 oxidizes each... 

The Arrhenius definition is not suitable for AB cements for several reasons. It cannot be applied to zinc oxide eugenol cements, for these are non-aqueous, nor to the metal oxychloride and oxysulphate cements, where the acid component is not a protonic acid. Indeed, the theory is, strictly speaking, not applicable at all to AB cements where the base is not a water-soluble hydroxide but either an insoluble oxide or a silicate. 

Sintered Electrodes In these electrodes the active materials are present in pores of a sintered nickel support plate. This plate is manufactured by sintering of highly disperse nickel powder produced by thermal decomposition of nickel pentacarbonyl Ni(CO)5. The plates are filled by impregnating them in alternation with concentrated solutions of salts of the corresponding metals (Ni or Cd) and with an alkali solution serving to precipitate insoluble oxides or hydroxides. 

Most phytoactive compounds do not persist in soil in a free and active form for very long, yet they have been plausibly implicated, for example, in a mechanism of infection or nutrient acquisition therefore some suitable explanation must be found. The right set of circumstances was invoked by Uren and Reisenauer (17) to explain how labile reducing agents may be protected physically from Oi and be directed toward insoluble oxides of Mn. The right set of circumstances may have relevance in other situations, and some po.ssibilities are discussed later in this chapter. 

As an example, consider the use of PVPy as a solid poison in the study of poly(noibomene)-supported Pd-NHC complexes in Suzuki reactions of aryl chlorides and phenylboroiuc acid in DMF (23). This polymeric piecatalyst is soluble under some of the reaction conditions employed and thus it presents a different situation from the work using porous, insoluble oxide catalysts (12-13). Like past studies, addition of PVPy resulted in a reduction in reaction yield. However, the reaction solution was observed to become noticeably more viscous, and the cause of the reduced yield - catalyst poisoning vs. transport limitations on reaction kinetics - was not immediately obvious. The authors thus added a non-functionalized poly(styrene), which should only affect the reaction via non-specific physical means (e.g., increase in solution viscosity, etc.), and also observed a decrease in reaction yield. They thus demonstrated a drawback in the use of the potentially swellable PVPy with soluble (23) or swellable (20) catalysts in certain solvents. 

Minerals belonging to the category of insoluble oxide and silicate minerals are many in number. Insoluble oxide minerals include those superficially oxidized and those of oxide type. The former category comprises mainly superficially oxidized sulfide minerals, including metals such as aluminum, tin, manganese, and iron which are won from their oxidic sources. As far as silicate minerals are concerned, there can be a ready reference to several metals such as beryllium, lithium, titanium, zirconium, and niobium which are known for their occurrence as (or are associated with) complex silicates in relatively low-grade deposits. 

Metal insoluble- oxide These are similar to the previous electrodes. An example is the antimony, antimony trioxide electrode, Sb Sb2031 OH-. An antimony rod is covered with a thin layer of oxide and dips into a solution containing OH ions. The electrode reaction is Sb (s) + 3 OH- 0.5 Sb203 + 1.5 H20 (1) + 3 e-. 

At mercury electrodes the geometric and actual surface areas are identical. There is no site on the electrode that is energetically preferable to any other site (except for the deposition of heterogeneous patches). Except at rather positive potentials, the mercury electrode is usually not covered with a film of insoluble oxides or other compounds. 

Anodizing is an electrolytic oxidation process that converts the surface of the metal to an insoluble oxide. 

Manganese deficiency occurs principally in soils with a high pH or calcareous soils since Mn in these soils is mostly present in insoluble oxides. Manganese deficiency has been found for more than 20 crops including oats, rye, wheat, rice, maize, peas, soy beans, potatoes, cotton, tobacco, sugar beets, tea, sugar-cane, pineapples, pecans, peaches, spinach, citrus, and a number of forest trees (Table 7.8) (Sillanpaa, 1982). The critical DTPA-extractable Mn for Mn deficiency has been suggested to be 1.6-3.9 mg/kg, and soils with up to 5.2-6.5 mg/kg DTPA-extractable Mn has been considered to indicate susceptibility (Sillanpaa, 1982). 

Figure 12.5 IODO-GEN is a water-insoluble oxidizing agent that can react with 1251 - to form a highly reactive mixed halogen species, 125IC1. This intermediate can add radioactive iodine atoms to tyrosine or histidine side chain rings.

Surface hydroxyl groups are to be expected on all metal oxides. Only a few of the many insoluble oxides have been studied in this respect so far. With advances in the techniques of determination of traces of impurity elements or groups by physical methods or by micro-analytical methods in combination with skillful preparative techniques, further progress in our knowledge of the surface chemistry should be expected. Interesting technological applications may be foreseen. 

Trace metals are introduced to the ocean by atmospheric feUout, river runoff, and hydrothermal activity. The latter two are sources of soluble metals, which are primarily reduced species. Upon introduction into seawater, these metals react with O2 and are converted to insoluble oxides. Some of these precipitates settle to the seafloor to become part of the sediments others adsorb onto surfaces of sinking and sedimentary particles to form crusts, nodules, and thin coatings. Since reaction rates are slow, the metals can be transported considerable distances before becoming part of the sediments. In the case of the metals carried into the ocean by river runoff, a significant fraction is deposited on the outer continental shelf and slope. Hydrothermal emissions constitute most of the somce of the metals in the hydrogenous precipitates that form in the open ocean. 

The mechanism of developing corrosion protective properties in an inorganic coating principally consists of forming insoluble oxides on the netal surface. Additionally, oxides must have certain corrosion inhibition (redox) properties which can protect the nnetal substrate from corrosive species like Cl and 804 . In the case of chromate conversion coating, OCC, the oxides of aluminum and chromium have been responsible for their corrosion inhibitive properties which were derived from their soluble and insoluble portions of the... 

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