Thermal decomposition effect

These reactions are relatively selective in character, so that high yields of high octane fuels can be realized. Furthermore, these reactions can be made to proceed to different extents, so that fuels of variable aromaticity and volatility can be produced. A basic reason for this is the relatively low temperature of operation employed in Platforming, permitting the elimination of undesirable thermal decomposition effects. 

The controlled thermal decomposition of dry aromatic diazonium fluoborates to yield an aromatic fluoride, boron trifluoride and nitrogen is known as the Schiemann reaction. Most diazonium fluoborates have definite decomposition temperatures and the rates of decomposition, with few exceptions, are easily controlled. Another procedure for preparing the diazonium fluoborate is to diazotise in the presence of the fluoborate ion. Fluoboric acid may be the only acid present, thus acting as acid and source of fluoborate ion. The insoluble fluoborate separates as it is formed side reactions, such as phenol formation and coupling, are held at a minimum temperature control is not usually critical and the temperature may rise to about 20° without ill effect efficient stirring is, however, necessary since a continuously thickening precipitate is formed as the reaction proceeds. The modified procedure is illustrated by the preparation of -fluoroanisole ... 

Ruthenium is a hard, white metal and has four crystal modifications. It does not tarnish at room temperatures, but oxidizes explosively. It is attacked by halogens, hydroxides, etc. Ruthenium can be plated by electrodeposition or by thermal decomposition methods. The metal is one of the most effective hardeners for platinum and palladium, and is alloyed with these metals to make electrical contacts for severe wear resistance. A ruthenium-molybdenum alloy is said to be... 

Prolonged exposure to thermal decomposition products causes so-called polymer fume fever, a temporary influenza-like condition. It may be contracted by smoking tobacco that has been contaminated with the polymer. It occurs several hours after exposure and passes within 36—48 hours the temporary effects are not cumulative. 

Kerogen Decomposition. The thermal decomposition of oil shale, ie, pyrolysis or retorting, yields Hquid, gaseous, and soHd products. The amounts of oil, gas, and coke which ultimately are formed depend on the heating rate of the oil shale and the temperature—time history of the Hberated oil. There is Htde effect of shale richness on these relative product yields under fixed pyrolysis conditions, as is shown in Table 5 (10). 

The ultimate fate of the oxygen-centered radicals generated from alkyl hydroperoxides depends on the decomposition environment. In vinyl monomers, hydroperoxides can be used as efficient sources of free radicals because vinyl monomers generally are efficient radical scavengers which effectively suppress induced decomposition. When induced decomposition occurs, the hydroperoxide is decomposed with no net increase of radicals in the system (see eqs. 8, 9, and 10). Hydroperoxides usually are not effective free-radical initiators since radical-induced decompositions significantly decrease the efficiency of radical generation. Thermal decomposition-rate studies in dilute solutions show that alkyl hydroperoxides have 10-h HLTs of 133—172°C. 

In the pyrolysis of pure amine oxides, temperature has a significant effect on the ratio of products obtained (22). The principal reaction during thermal decomposition of /V,/V-dimetby11 amyl amine oxide [1643-20-5] at 80—100°C is deoxygenation to /V,/V-dimetby11 amyl amine [112-18-5] (lauryl = dodecyl). 

Succinic anhydride is stabilized against the deteriorative effects of heat by the addition of small amounts (0.5 wt %) of boric acid (27), the presence of which also decreases the formation of the dilactone of gamma ketopimelic acid (28). Compared with argon, CO2 has an inhibiting effect on the thermal decomposition of succinic acid, whereas air has an accelerating effect (29,30). 

Solutions of these fire retardant formulations are impregnated into wood under fliU cell pressure treatment to obtain dry chemical retentions of 65 to 95 kg/m this type of treatment greatly reduces flame-spread and afterglow. These effects are the result of changed thermal decomposition reactions that favor production of carbon dioxide and water (vapor) as opposed to more flammable components (55). Char oxidation (glowing or smoldering) is also inhibited. 

The temperature at which decarboxylation occurs is of particular interest in manufacturing processes based on polymerisation in the molten state where reaction temperatures may be near the point at which decomposition of the diacid occurs. Decarboxylation temperatures are tabulated in Table 2 along with molar heats of combustion. The diacids become more heat stable at carbon number four with even-numbered acids always more stable. Thermal decomposition is strongly influenced by trace constituents, surface effects, and other environmental factors actual stabiUties in reaction systems may therefore be lower. 

The atmospheric reduced crude is the feedstock for the vacuum distillation unit. To prevent thermal decomposition (cracking) of the higher boiling point hydrocarbons in the crude oil, the pressure in the vacuum distillation fractionation column is reduced to about one-twentieth of an atmosphere absolute (one atmosphere pressure is 14.7 psia or 760 mm Fig). This effectively reduces the boiling points of the hydrocarbons several hundred degrees Fahrenheit. The components boiling below about 1050°F (565°C) are vaporized and removed as vacuum gas... 

Interaction between niobium oxide and fluorides, chlorides or carbonates of alkali metals in an ammonium hydrofluoride melt, yielded monooxyfluoroniobates with different compositions, MxNbOF3+x, where they were subsequently investigated [123-127]. According to DTA patterns of the Nb205 - 6NFL HF2 - 2MF system, (Fig. 18) a rich variety of endothermic effects result from the formation of ammonium monooxyfluoroniobate, its thermal decomposition and its interaction with alkali metal fluorides. The number of effects decreases and separation of ammonium ceases at lower temperatures and when going from lithium to cesium in the sequence of alkali metal fluorides. 

The thermal decomposition of ethyl diazoacetate in 9//-indcno[2,l -6]pyridine (3) effects expansion of the pyridine ring to give ethyl indeno[l,2-Z>]azepine-3-carboxylate (4), the first example of the indeno[l,2-Z>]azepine system.56... 

The effective rate of initiation (7 s) in the case of thermal decomposition of an initiator (T) decomposing by Scheme 3.11 is given by eq. 2... 

Effect of Heat, (see Thermal Decomposition) Electrostatic Sensitivity. An electrostatic discharge of over 5 joules is required to initiate AP (NG 3 joules) (Ref 24, p 46). ... 

The conductometric results of Meerwein et al. (1957 b) mentioned above demonstrate that, in contrast to other products of the coupling of nucleophiles to arenediazonium ions, the diazosulfones are characterized by a relatively weak and polarized covalent bond between the p-nitrogen and the nucleophilic atom of the nucleophile. This also becomes evident in the ambidentate solvent effects found in the thermal decomposition of methyl benzenediazosulfone by Kice and Gabrielson (1970). In apolar solvents such as benzene or diphenylmethane, they were able to isolate decomposition products arising via a mechanism involving homolytic dissociation of the N — S bond. In a polar, aprotic solvent (acetonitrile), however, the primary product was acetanilide. The latter is thought to arise via an initial hetero-lytic dissociation and reaction of the diazonium ion with the solvent (Scheme 6-11). 

The thermal decomposition reactions of KN3, T1N3, and AgN3 have been studied in the corresponding halide matrices [301]. The formation of NCCT from trapped C02 was described and labelling with ISN established that only a single end-N atom of the azide ion was involved in NCO formation. The photodecomposition of PbN6 and the effects of dopants have been followed [302] by the changes produced in the near and the far infrared. 

Kabanov [351] has provided an excellent review of the application of measurements of electrophysical effects in studies of the thermal decomposition of solids, including surveys of electrical conductivity, photoconductivity, dielectric measurements and interface (contact), Hall and thermal (Seebeck) potentials. Care must be exercised in applying the results obtained in such studies to the interpretation of data for thermal decomposition in the absence of an applied electric field since many examples have been given [352] in which such a field markedly influences the course of decomposition. 

Kabanov and Zingel [352] have recently published a comprehensive review of studies of the effect of application of continuous or periodic electric fields on the reactant during thermal decomposition of a solid. They comment on the superficiality of most of the work discussed. The application of an electric field is contrasted with the effect of selected additives as a means of obtaining information on the mechanism of a decomposition reaction. Both may alter the concentration of free electrons in the solid, but the effect of the field is more apparent in the vicinity of the surface. An example of an investigation of the effect of an electric field on a reaction is to be found in the work of the Panafieu et al. [373] on KN3. 

The energy available in various forms of irradiation (ultraviolet, X-rays, 7-rays) may be sufficient to produce in the reactant effects comparable with those which result from mechanical treatment. A continuous exposure of the crystal to radiation of appropriate intensity will result in radiolysis [394] (or photolysis [29]). Shorter exposures can influence the kinetics of subsequent thermal decomposition since the products of the initial reaction can act as nuclei in the pyrolysis process. Irradiation during heating (co-irradiation [395,396]) may exert an appreciable effect on rate behaviour. The consequences of pre-irradiation can often be reduced or eliminated by annealing [397], If it is demonstrated that irradiation can produce or can destroy a particular defect structure (from EPR measurements [398], for example), and if decomposition of pre-irradiated material differs from the behaviour of untreated solid, then it is a reasonable supposition that the defect concerned participates in the normal decomposition mechanism. 

Two alternative methods have been used in kinetic investigations of thermal decomposition and, indeed, other reactions of solids in one, yield—time measurements are made while the reactant is maintained at a constant (known) temperature [28] while, in the second, the sample is subjected to a controlled rising temperature [76]. Measurements using both techniques have been widely and variously exploited in the determination of kinetic characteristics and parameters. In the more traditional approach, isothermal studies, the maintenance of a precisely constant temperature throughout the reaction period represents an ideal which cannot be achieved in practice, since a finite time is required to heat the material to reaction temperature. Consequently, the initial segment of the a (fractional decomposition)—time plot cannot refer to isothermal conditions, though the effect of such deviation can be minimized by careful design of equipment. 

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