Secondary heterogeneity

Fujiki, T., Concept of Secondary Heterogeneous Structure of Long-Chain Branched Poiyethyiene, /. Appl. Polym. Set, 15, 47 (1971)... 

Table 3.5.2 summarises the energetics of alternative primaiy processes at shorter wavelengths). In many of the earlier studies a variable deficiency of O2 was observed in the dissociation products compared with the expected stoichiometric ratio 02 C0 = 0,5 but more recent work has established that the discrepancy is apparent rather than real, and is caused by secondary heterogeneous reactions on the vessel wall The primary quantum yield of CO (detected via resonance fluorescence excitation) in the spin-forbidden channel has been measured as (CO) = 1.0 0.25 over the range X (174—210) nm ... 

Chromium compounds decompose primary and secondary hydroperoxides to the corresponding carbonyl compounds, both homogeneously and heterogeneously (187—191). The mechanism of chromium catalyst interaction with hydroperoxides may involve generation of hexavalent chromium in the form of an alkyl chromate, which decomposes heterolyticaHy to give ketone (192). The oxidation of alcohol intermediates may also proceed through chromate ester intermediates (193). Therefore, chromium catalysis tends to increase the ketone alcohol ratio in the product (194,195). 

That this is not always the case should be expected. In fact, if it was not for heterogeneous localization of some flow phenomena, it would be very diflicult to initiate secondary explosives, or to effect shock-induced chemical reactions in solids. Heterogeneous shear deformation in metals has also been invoked as an explanation for a reduction in shear strength in shock compression as compared to quasi-isentropic loading. We present here a brief discussion of some aspects of heterogeneous deformation in shock-loaded solids. 

Finally, atmospheric chemical transformations are classified in terms of whether they occur as a gas (homogeneous), on a surface, or in a liquid droplet (heterogeneous). An example of the last is the oxidation of dissolved sulfur dioxide in a liquid droplet. Thus, chemical transformations can occur in the gas phase, forming secondary products such as NO2 and O3 in the liquid phase, such as SO2 oxidation in liquid droplets or water films and as gas-to-particle conversion, in which the oxidized product condenses to form an aerosol. 

The secondary x-rays emitted by certain substances are remarkably homogeneous in character, though the primary radiation producing them is very heterogeneous. 34... 

We have investigated the arylation of different primary or secondary amines with different aryl chlorides or bromides in heterogeneous or homogeneous catalysis conditions using palladium(O) or palladium(II) derivatives (Fig. 5). 

When an aldehyde or a ketone is treated with ammonia or a primary or secondary amine in the presence of hydrogen and a hydrogenation catalyst (heterogeneous or... 

The beneficial effects are demonstrated of heterogeneous secondary pyrolysis reactions on the liquid products of PU pyrolysis. Pyrolysis volatiles are passed through a packed bed of carbonaceous solids that promote the secondary reactions. Activated carbon and reaction injection moulded PU (RIM) char were found to be suitable bed materials. The long-term object was to develop marketable solid products by pyrolysis of wastes, so obtaining high char yields. In addition to affecting the liquid products, RIM char also increased the total char... 

Processes associated with two opposing electrode processes of a different nature, where the anodic process is the oxidation of a metal, are termed electrochemical corrosion processes. In the two above-mentioned cases, the surface of the metal phase is formed of a single metal, i.e. corrosion occurs on a chemically homogeneous surface. The fact that, for example, the surface of zinc is physically heterogeneous and that dissolution occurs according to the mechanism described in Section 5.8.3 is of secondary importance. 

One of the exciting results to come out of heterogeneous catalysis research since the early 1980s is the discovery and development of catalysts that employ hydrogen peroxide to selectively oxidize organic compounds at low temperatures in the liquid phase. These catalysts are based on titanium, and the important discovery was a way to isolate titanium in framework locations of the inner cavities of zeolites (molecular sieves). Thus, mild oxidations may be run in water or water-soluble solvents. Practicing organic chemists now have a way to catalytically oxidize benzene to phenols alkanes to alcohols and ketones primary alcohols to aldehydes, acids, esters, and acetals secondary alcohols to ketones primary amines to oximes secondary amines to hydroxyl-amines and tertiary amines to amine oxides. 

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