Formates, metal, decompositions

Drier Mechanism. Oxidative cross-linking may also be described as an autoxidation proceeding through four basic steps induction, peroxide formation, peroxide decomposition, and polymerization (5). The metals used as driers are categorized as active or auxiUary. However, these categories are arbitrary and a considerable amount of overlap exists between them. Drier systems generally contain two or three metals but can contain as many as five or more metals to obtain the desired drying performance. 

So far ignored, but perhaps the most important factor in catalysis by metals able to form hydrides, are the dynamical conditions of formation and decomposition of hydride phases. 

From the above discussion it follows that the probability of carbonium ion formation during decomposition of RTIX2 compounds by a Type 5 process is low when X is carboxylate, but significantly higher when X is nitrate, sulfate, perchlorate, or fluoroborate. The important role played by the anion of the metal salt in oxymetallation has in fact been recognized only very recently for both oxymercuration 11, 12) and oxythallation (92). The... 

According to R. Brdicka and K. Vesely the carbonyl form of formaldehyde is reduced and the limiting kinetic current is given by the rate of the chemical volume reaction of dehydration. An analogous situation occurs for the equilibria among complexes, metal ions and complexing agents if the rates of complex formation and decomposition are insufficient to preserve the equilibrium. A simple example is the deposition of cadmium at a mercury electrode from its complex with nitrilotriacetic COO"... 

Dining interaction at ambient temperature in a bomb to produce poly (carbon monofluoride), admission of fluorine beyond a pressure of 13.6 bar must be extremely slow and carefully controlled to avoid a violently exothermic explosion [1], Previously it had been shown that explosive interaction of carbon and fluorine was due to the formation and decomposition of the graphite intercalation compound, poly (carbon monofluoride) [2], Presence of mercury compounds prevents explosion during interaction of charcoal and fluorine [3], Reaction of surplus fluorine with graphite or carbon pellets was formerly used as a disposal method, but is no longer recommended. Violent reactions observed when an exhausted trap was opened usually involved external impact on the metal trap, prodding the trap contents to empty the trap, or possibly ingress of moist air... 

We tentatively prefer the latter, since compounds of this type have been isolated and, in one case, characterized crystallographic ally (12). The analog of this intermediate has not yet been observed with other metal carbonyls, but since the relative rates of its formation and decomposition may well differ from one... 

In reviews on formic acid decomposition, Mars and coworkers194,198 wrote that the formation and decomposition of formate anions were monitored by infrared spectroscopy. These studies were carried out by Fahrenfort, Sachtler, and coworkers188,193 for the case of formates on metals produced by formic acid adsorption—Cu, Ni, Pd, Rh, Pt, and Zn and in the case of metal oxides, Hirota et al. investigated ZnO,187,189,190,197 while Scholten et al. studied MgO.199,200 The infrared... 

Methyl, ethyl and propyl perchlorates, readily formed from the alcohol and anhydrous perchloric acid, are highly explosive oils, sensitive to shock, heat and friction [1], Many of the explosions which have occurred on contact of hydrox-ylic compounds with cone, perchloric acid or anhydrous metal perchlorates are attributable to the formation and decomposition of perchlorate esters [2,3,4], Safe procedures for preparation of solutions of 14 sec-alkyl perchlorates are described. Heated evaporation of solvent caused explosions in all cases [5], l-Chloro-2-propyl, iram-2-chlorocyclohexyl, l-chloro-2-propyl, 1,6-hexanediyl, hexyl, and 2-propyl perchlorates, prepared by a new method, are all explosive oils [6],... 

B. Vigeholm, J. Kj0Uer, B. Larsen, A.S. Pedersen, Formation and decomposition of magnesium hydride, J. Less-Comm. Metals 89 (1983) 135-144. 

Powder Formation. Metallic powders can be formed by any number of techniques, including the reduction of corresponding oxides and salts, the thermal dissociation of metal compounds, electrolysis, atomization, gas-phase synthesis or decomposition, or mechanical attrition. The atomization method is the one most commonly used, because it can produce powders from alloys as well as from pure metals. In the atomization process, a molten metal is forced through an orifice and the stream is broken up with a jet of water or gas. The molten metal forms droplets to minimize the surface area, which solidify very rapidly. Currently, iron-nickel-molybdenum alloys, stainless steels, tool steels, nickel alloys, titanium alloys, and aluminum alloys, as well as many pure metals, are manufactured by atomization processes. 

The different types of coordination modes of carbonate in metal carbonato complexes offer challenges to investigate intimate mechanisms of their formation. The study of the kinetics and mechanisms of the formation and decomposition of such complexes, therefore, continue to be an interesting area of activity as it has a direct bearing on... 

A detailed study of the CO insertion, or methyl migration, observing formation and decomposition of the transients, was performed so far only for one Cu(I) model system (93). It was reported that methyl radicals form transient complexes containing metal carbon -bonds with carbonmonoxide (n = 1, 3, 4) complexes of Cu(I). These complexes decompose yielding Cu(II) and acetaldehyde as final products via an copper acetyl intermediate formed by insertion of /migration of CH3 as described in Scheme 4. 

The proposed mechanism will give the experimental kinetic equation (25) by assuming that the rate-determining step is the formation or decomposition of the complex and that the metal (III)-metal (II) ratio is approximately constant during reaction. 

When we deal with the kinetics of hydride reactions we have to be aware that hydride thermodynamics cannot be properly formulated without taking into account the (relative) immobility of the metal component. This immobility can sometimes render the interpretation of the experimental reaction kinetics ambiguous. With this difficulty in mind, let us outline concepts which describe the kinetics of hydride formation and decomposition. An extensive account, including a first order phenomenological treatment, has been given by [P.S. Rudman (1983)]. The conceptual framework for a more rigorous discussion is found in, for example, [G. B. Stephenson (1988)]. 

Many compounds, especially various metallic oxides, also induce very rapid decomposition of hydrogen peroxide without themselves being permanently changed.4 In addition to the solutions of the alkali hydroxides already,mentioned, manganese dioxide, cobalt oxide, and lead oxide (massicot) are remarkably active, and as might be expected a colloidal solution of manganese dioxide 5 is also able to exert powerful catalytic influence.6 The effect in such cases may be partly a surface effect, but is also probably due in part to the intermediate formation and decomposition of unstable highly oxidised derivatives. 

Type of carbene X Method of formation metal (rhodium or copperj-catalysed decomposition of diazocarbonyl compound... 

Pulse radiolysis has been used to study the transient formation and decomposition of cobalt-alkyl bonds in aqueous solution in the same manner as it has been used for chromium alkyls. And as for chromium alkyls, bond homolysis is a major decomposition pathway (28). For bond formation reactions, pulse radiolysis shows that they are assisted by increases in pressure. This feature results from the homolysis having a larger activation volume than the bond formation reaction, resulting in a significantly negative overall reaction volume for the process (29). In general for all of these metal-alkyl bond homolysis reactions of the aquo complexes, steric hindrance facilitates the reaction. Ligand effects also play a role, but the factors involved are more subtle. 

The sulphide ore is oxidised in the presence of silica which enables the iron to be removed as a silicate slag. The nickel oxide left is reduced at 350° by water gas to an impure metal leaving the iron as ferric oxide. Purification is based on the formation and decomposition of gaseous Ni(CO)4. Carbon monoxide is passed over the impure metal at 60° and the gas containing a few per cent of the tetracarbonyl is brought into contact with agitated nickel pellets at 200°. The pellets grow as nickel is deposited on them the CO is recirculated (Fig. 258). 

Calculations shoved that the amounts adsorbed or desorbed were much larger than would he anticipated on the basis of adsorption, and these results were explained in terms of the formation and decomposition of metal sulphates,... 

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