Thermal secondary reaction

Changes of the overall quantum yield with postirradiation time indicate that some thermal secondary reaction occurs. In this case, the type of extrapolation performed on the experimental quantum yield (see Section III.B.l) qualifies its mechanistic interpretation. For example, according to the mechanism of Figure 3, the quantum yield for F formation obtained through the double extrapolation to zero time of irradiation accounts for the amount of F formed by process 03-34, while that obtained through the extrapolation to infinite postirradiation time accounts for the amount of F formed by both process 03-34 and the secondary reaction a. 

THERMAL SECONDARY REACTION a chemical transformation of an equilibrated ground-state species which is formed in a photochemical step and which is unstable in the system. 

By changing from the simplest to larger aliphatic and cyclic ketones, structural factors may be introduced which favor alternative unimolecular primary photoprocesses or provide pathways to products not available to the simple model compound. In addition, both the increase in molecular size and irradiation in solution facilitate rapid vibrational relaxation of the electronically excited reactant as well as the primary products to thermally equilibrated species. In this way the course of primary and secondary reactions will also become increasingly structure-selective. In a,a -unsym-metrically substituted ketones, the more substituted bond undergoes a-cleavage preferentially. 

Cyclic hydroxamic acids and V-hydroxyimides are sufficiently acidic to be (9-methylated with diazomethane, although caution is necessary because complex secondary reactions may occur. N-Hydroxyisatin (105) reacted with diazomethane in acetone to give the products of ring expansion and further methylation (131, R = H or CH3). The benzalphthalimidine system (132) could not be methylated satisfactorily with diazomethane, but the V-methoxy compound was readil3 obtained by alkylation with methyl iodide and potassium carbonate in acetone. In the pyridine series, 1-benzyl-oxy and l-allyloxy-2-pyridones were formed by thermal isomeriza-tion of the corresponding 2-alkyloxypyridine V-oxides at 100°. 

The high yields—about 50%—which were observed in all cases, indicate the strong involvement of secondary fission products (i.e., those produced by /S-decay of precursors). A consideration of mechanisms of formation of the organometallic products led to the conclusion (13) that the j8-decay itself must be the cause of the molecule formation. Neither purely mechanical collisional substitution, nor thermal chemical reactions, nor radical reactions, nor radiation-induced reactions seemed to be responsible for the synthesis reactions. 

In order to develop the safest process the worst runaway scenario must be worked out. This scenario is a sequence of events that can cause the temperature runaway with the worst possible consequences. Typically, the runaway starts with failure that results in an adiabatic course of exothermic reaction, inducing secondary reactions that proceed with a high thermal effect. Such a. sequence of typical events is shown in Fig. 5.4-55 (after Gygax, 1988-1990 Stoessel, 1993). It starts with, for instance, a cooling failure at time tx when the temperature is at the set level, Tv ,- Then the temperature rises up to the Maximum Temperature for Synthetic Reaction (MTSR) within the time Atn. Assuming adiabatic conditions MTSR = + ATad,R... 

Bulk temperature Liquid vapor pressure Thermal activation Bubble content, intensity of collapse Enhanced secondary reaction rates... 

The development of composite micro/mesoporous materials opens new perspectives for the improvement of zeolytic catalysts. These materials combine the advantages of both zeolites and mesoporous molecular sieves, in particular, strong acidity, high thermal and hydrothermal stability and improved diffusivity of bulky molecules due to reduction of the intracrystalline diffusion path length, resulting from creation of secondary mesoporous structure. It can be expected that the creation of secondary mesoporous structure in zeolitic crystals, on the one hand, will result in the improvement of the effectiveness factor in hydroisomerization process and, on the other hand, will lead to the decrease of the residence time of products and minimization of secondary reactions, such as cracking. This will result in an increase of both the conversion and the selectivity to isomerization products. 

The mechanism of thermal decomposition (pyrolysis) of methane has been extensively studied [90,91]. Because C-H bonds in the methane molecule are significantly stronger than C-H and C-C bonds of the products, the secondary and tertiary reactions contribute at the very early stages of the reaction, which obscure the initial processes. According to Holmen et al. [92], the overall methane thermal decomposition reaction at high temperatures can be described as a stepwise dehydrogenation as follows ... 

The metal and ammonium salts of dithiophosphinic acids tend to exhibit far greater stability with respect to this thermal decomposition reaction, and consequently these acids are often prepared directly in their salt form for convenience and ease of handling. Alkali-metal dithiophosphinates are accessible from the reaction of diphosphine disulfides with alkali-metal sulfides (Equation 22) or from the reaction of alkali-metal diorganophosphides with two equivalents of elemental sulfur (Equation 23). Alternatively, they can be prepared directly from the parent dithiophosphinic acid on treatment with an alkali-metal hydroxide or alkali-metal organo reagent. Reaction of secondary phosphines with elemental sulfur in dilute ammonia solution gives the dithiophosphinic acid ammonium salts (Equation 24). 

The chemically amplified resists reported here for deep-UV applications require a post-exposure thermal treatment process step to effect the deprotection reaction. This step has proven to be critical, and in order to understand the processing considerations it is instructive to discuss, qualitatively, the various primary and secondary reactions that occur with these systems during both exposure and PEB, ie ... 

Table 8 gives expressions for the rate coefficients of secondary reactions in the thermal decompositions of N20, where these have been measured. To our knowledge no determination has been made of ks. 

A kinetic study of the photolysis at low conversions by Berces and Forgeteg305 leads to the conclusion that OH is the sole reactive species formed in the primary process. At 2650 A and 2537 A, respectively, the quantum yields are 0.1 and 0.3. Secondary reactions are expected to be similar to those involved in the thermal decomposition of HN03, as discussed in the preceding section. 

That the also produced eight-membered ring hydrocarbon 316 is a (thermal) secondary product was shown by repetition of the reaction at room temperature, where the relative amount of 316 had increased significantly at the expense of the ds-isomer 313. 

The obtained A 7 a() value and the energy equivalent of the calorimeter, e, are then used to calculate the energy change associated with the isothermal bomb process, AE/mp. Conversion of AE/ibp to the standard state, and subtraction from A f/jgp of the thermal corrections due to secondary reactions, finally yield Ac f/°(298.15 K). The energy equivalent of the calorimeter, e, is obtained by electrical calibration or, most commonly, by combustion of benzoic acid in oxygen [110,111,113]. The reduction of fluorine bomb calorimetric data to the standard state was discussed by Hubbard and co-workers [110,111]. 

The flash vacuum pyrolysis of alkynes, arynes, and aryl radicals has been reviewed. A discussion of secondary reactions and rearrangements is included. The pyrolysis of cyclopentadienes has also been examined. The rates for the initial C—H bond fission and the decomposition of C-C5H5 have been calculated. A single-pulse shock study on the thermal decomposition of 1-pentyl radicals found alkene products that are formed by radical isomerization through 1,4- and 1,3-hydrogen migration to form 2- and 3-pentyl radicals. The pyrrolysis of f-butylbenzene in supercritical water was the subject of a report. ... 

Figure 16. Metastable ion cyclotron resonance (MICR) spectra for the unimolecular dissociation of the chemically activated adduct ion derived from association of the methoxymethyl cation with pivaldehyde during a 2-s reaction delay at a pressure of pivaldehyde of 1.0 x 10 torr. The three spectra correspond to values of rf amplitude appropriate to eject transient intermediates with lifetimes longer than (a) 60 ps, (b) 80 ps, and (c) 1 70 ps. A partial pressure of CH4 of 1.0 x 10 torr was also present to thermalize ions. The peak at m/z 125 is a secondary reaction product of m/z 85.

The primary process following a photoexcitation of nltrosamldes XIV Is the dissociation of the N-N bond to form a radical pair XV and the ensuing chemical events are the reactions of amldyl and nitric oxide radicals In the paired state or Individually In the bulk of solutions. Naturally, secondary reactions, thermal or photolytic, have to be taken Into consideration under Irradiation conditions (21). First of all, the relatively straightforward chemistry of selective excitation In the n-ir transition band (>400 nm) will be discussed, followed by the chemistry of Irradiation with a Pyrex filter (>280 nm). As nitric oxide Is known to be rather unreactlve (23), primary chemical processes In the Irradiation with >400 nm light under... 

A first point to consider is that thermal or photochemical decomposition of a precursor often does not lead to a single product, due to parallel or consecutive secondary reactions. Since absorption spectroscopy invariably probes all components of a mixture, the problem of how to distinguish between these components may arise in the context of studies on reactive intermediates. This problem can be... 

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