Secondary decomposition and

Depending on the initiator and monomer system secondary decomposition (equation 2), induced decomposition (equations 3,9), primary radical termination (equation 11) or transfer reactions may or may not be important and will have to be considered accordingly in the balance equations. From the above reaction scheme the following equations have been derived under the SSH, the LCA, negligible secondary decomposition and negligible primary radical termination (9,19,20) ... 

Secondary Decomposition and Polymerization. Reactions which usually occur in the later stages of autoxidation at room temperature may assume increased significance, and their consequences may be encountered much more rapidly, at elevated temperatures. For example, the series of short chain esters, oxo-esters, and dicarboxylic acids - usually formed in only trace amounts in room-temperature oxidation of oleate, linoleate and linolenate - can be found in significant amounts after heating for 1 hr at 180°C. Possible reactions leading to the formation of such compounds are given below. 

The dehydrogenation of ethanol over copper catalysts is not complete at 300° C. when moderate times of contact are used but if the temperature is raised to 350° C. or higher, secondary reactions become more and more evident. At temperatures above 350° C., copper catalysts begin to activate the decomposition of acetaldehyde to methane and carbon monoxide, to induce polymerization of the aldehyde, to cause dehydration processes to set in, to cause hydrogenation of the ethylene, and, in general, to promote secondary decompositions and condensations which complicate the product and destroy the activity of the catalyst. Hence, for the production of aldehydes and ketones it is desirable to use moderate temperatures of about 300° C. and to obtain maximum yields from the decomposition rather than maximum decomposition of alcohol per pass over the catalyst. 

Figure 9b illustrates the temporal variation of the monomeric products within the tar fraction. Guaiacols and catechols achieved maximum yields of 0.018 and 0.024, respectively at 60 min. Yields to both decreased through secondary decomposition, and phenols became the most abundant single-ring products after about 65 min. The phenols yield reached 0.045 by 120 min, where simulated yields of anisoles and hydrocarbon products reached 0.007 and 0.002 respectively. 

Two secondary propagating reactions often accompany the initial peroxide decomposition radical-induced decompositions and -scission reactions. Both reactions affect the reactivity and efficiency of the initiation process. Peroxydicarbonates and hydroperoxides are particularly susceptible to radical-induced decompositions. In radical-induced decomposition, a radical in the system reacts with undecomposed peroxide, eg ... 

Metal Catalysis. Aqueous solutions of amine oxides are unstable in the presence of mild steel and thermal decomposition to secondary amines and aldehydes under acidic conditions occurs (24,25). The reaction proceeds by a free-radical mechanism (26). The decomposition is also cataly2ed by V(III) and Cu(I). 

The reaction of radicals with nitroxides is reversible. 09 This means that the highest temperature that the technique can reasonably be employed at is ca 80 °C for tertiary propagating species and ca 120 °C for secondary propagating species.22 These maximum temperatures are only guidelines. The stability of alkoxyamines is also dependent on solvent (polar solvents favor decomposition) and the structure of the trapped species. This chemistry has led to certain alkoxyamines being useful as initiators of living polymerization (Section 9.3.6). At elevated temperatures nitroxides are observed to add to monomer albeit slowly. 3IS 5" 523... 

It should be noted that the absence of a proton in the a position in the case of N-Br-aminoisobutyric acid makes unoperative its decomposition to form an a-ketoacid, and the slight increase in the observed reaction rate constant upon increasing the NaOH concentration can be attributed to a secondary decomposition process, probably leading to the formation of an hydrazine (refs. 22 - 24). 

Fig. 5.4-66 outlines the probability and consequences of a thermal runaway in case of a plant incident. For the solvent process, failure results in a temperature rise from 27 °C to 119 °C. This is far from the onset temperature of secondary processes, which only start at 150 °C or higher. Consequently, the solvent process can be considered safe. A failure of the water process can cause a temperature rise from 50 to 95 C, i.e. higher than the onset temperature (90 °C) of the secondary decomposition of the di-nitro compound. The decomposition would start before the reaction mixture started boiling. Hence, the water process cannot be considered inherently safe. 

However, the idea, that 96 may rearrange to the ortho isomer 93 via substituent migration or valence bond tautomerization, which would enable the CH3 loss to proceed as described in (20), could not be substantiated by experimental facts. For example, the secondary decompositions of the [M—CH3]+ ions formed from 93 and 96 are different with regard to the reaction channels and both the kinetic energy release and peak shapes associated with the reactions of interest. Moreover, the CA spectra of the [M—CH3]+ ions exhibit distinct differences. Thus, the [M—CH3]+ ions posses different ion structures and, consequently, a common intermediate and/or reaction mechanism for the process of methyl elimination from ionized 93 and 96 are very unlikely (22). 

Conventionally, central and special metabolic pathways are distinguished. Central pathways are common to the decomposition and synthesis of major macromolecules. Actually, they are much alike in all representatives of the living world. Special cycles are characteristic of the synthesis and decomposition of individual monomers, macromolecules, cofactors, etc. Special cycles are extremely diversified, especially in the plant kingdom. For this reason, the plant metabolism is conventionally classified into primary and secondary metabolisms. The primary metabolism includes the classical processes of synthesis and deeradation of major macromolecules (proteins, carbohydrates, lipids, nucleic acids, etc.), while the secondary metabolism ensuing from the primary one includes the conversions of special biomolecules (for example, alkaloids, terpenes, etc.) that perform regulatory or other functions, or simply are metabolic end byproducts. 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

A very serious problem was to clear up the formation of hydroperoxides as the primary product of the oxidation of a linear aliphatic hydrocarbon. Paraffins can be oxidized by dioxygen at an elevated temperature (more than 400 K). In addition, the formed secondary hydroperoxides are easily decomposed. As a result, the products of hydroperoxide decomposition are formed at low conversion of hydrocarbon. The question of the role of hydroperoxide among the products of hydrocarbon oxidation has been specially studied on the basis of decane oxidation [82]. The kinetics of the formation of hydroperoxide and other products of oxidation in oxidized decane at 413 K was studied. In addition, the kinetics of hydroperoxide decomposition in the oxidized decane was also studied. The comparison of the rates of hydroperoxide decomposition and formation other products (alcohol, ketones, and acids) proved that practically all these products were formed due to hydroperoxide decomposition. Small amounts of alcohols and ketones were found to be formed in parallel with ROOH. Their formation was explained on the basis of the disproportionation of peroxide radicals in parallel with the reaction R02 + RH. 

Regarding ozonization, it is only applied in a limited number of WWTPs after secondary treatment [61]. Several investigations have proven that it is a very effective technique to eliminate pharmaceutical [25, 62, 63]. Oxidation reactions take place due to direct reaction with ozone (03), which are very selective or with free OH radicals, which are generated by ozone decomposition and are very powerful and not selective oxidants. In advanced oxidation processes, 03 is completely transformed onto OH radicals and they are recommended when compounds are ozone resistant. 

If a container with styrene monomer is subjected to a large heat flux, for example, fire or steam, the polymerization of the monomer causes the temperature to rise. At a certain elevated temperature, spontaneous decomposition of the styrene monomer and/or its polymer starts. This secondary decomposition process generates twice as much energy as the polymerization process itself. 

These are the most common diazeniumdiolates, formed by the reaction of secondary amines and polyamines with nitric oxide in basic media [214, 215]. They are stable solids, capable of regenerating two equivalents of nitric oxide along with the starting amine in neutral or acidic buffers. The half-life of NO generation varies from a few seconds to many hours, depending on the amine. The decomposition to NO is a spontaneous, first-order reaction at constant pH. 

The concept of intact emission of adsorbed molecular species for identifying reaction intermediates is also well illustrated in several recent studies. Benninghoven and coworkers (2-4,12) used SIMS to study the reactions of H2 with O2, C2H4 an< 2H2 on P°ly polycrystalline Ni. For the C2H /Ni interaction, for example, direct relationships could be established between characteristic secondary ions and the presence of specific surface complexes (12). In another study, Drechsler et al. (13) used SIMS to identify NH(ads) as the active intermediate during temperature-programmed decomposition of NH3 on Fe(110). 

Lewis et al.106 calculated four possible decomposition pathways of the ot-HMX polymorph N-N02 bond dissociation, HONO elimination, C-N bond scission, and concerted ring fission. Based on energetics, it was determined that N-N02 dissociation was the initial mechanism of decomposition in the gas phase, whereas they proposed HONO elimination and C-N bond scission to be favorable in the condensed phase. The more recent study of Chakraborty et al.42 using density functional theory (DFT), reported detailed decomposition pathways of p-HMX, which is the stable polymorph at room temperature. It was concluded that consecutive HONO elimination (4 HONO) and subsequent decomposition into HCN, OH, and NO are the most energetically favorable pathways in the gas phase. The results also showed that the formation of CH20 and N20 could occur preferably from secondary decomposition of methylenenitramine. 

If the adiabatic temperature increase of the reaction is less than 50 K during normal operation and the starting materials, reaction mixture or products have no thermal instabilities within a temperature range of (Tpr0cess + ATadiab) then the normal operation can be regarded as safe. The same applies when secondary decomposition reactions produce so little heat that the sum of this decomposition heat and the heat of reaction does not cause an adiabatic temperature increase of more than 50 K. 

V,/V-Disubstituted thioformamides, R1R2NCH=S, are obtained from primary or secondary amines and dimethylthioformamide at 110°C. Aromatic amines do not react for electronic reasons nor does A-methylcyclohexylamine because of steric hindrance323. Decomposition of carbon disulphide in a high-voltage discharge gives CS, which reacts... 

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. ... 

However, there are two articles which report evidence against these relationships between biosynthesis of this secondary metabolite and lignin decomposition (43,44). For example, a mutant of P. chrysosporium, which does not produce veratryl alcohol, has ligninolytic activity (43). Another mutant, which lacks glucose oxidase, is unable to decompose lignin to CO2 and therefore is ligninase Mess. It is, however, able to produce about 30% of the amount of veratryl alcohol normally found in the fungus (44). 

The aminolysis of dibenzo[l,2]oxathiin 6-oxide 10 with primary and secondary amines in water was quantitively followed by the absorption at 270 nm in UV spectroscopy, from which the reaction was found to obey pseudo-first-order kinetics < 1999TL8901 >. Because of the lack of a distinct difference in the magnitude of y obs between primary and secondary amines, and between acyclic and cyclic amines, the aminolysis reaction must proceed in two steps the first is a fast formation of intermediate 102 followed by a second slow decomposition step to the reaction product 103 (Scheme 24). 

The H atom detachment in Eq. (6) is followed by H atom abstraction from another cyclohexane molecule in Eq. (8) and the cyclohexyl radicals disappear in disproportionation and combination reactions giving in nearly equal amounts cyclohexene and dicyclohexyl end products. In the liquid phase, the secondary decomposition of the primarily formed energy-rich reaction products is of minor importance because of the effective collisional deactivation. This is in contrast to the gas phase reaction, where the primarily formed products readily undergo decomposition in the absence of deactivation (at low pressures), e.g. ... 

The DS is high for many insulating polymers and may be as high as 103 mV/ m. The upper limit of the DS of a material is dependent on the ionization energy present in the material. Electric or intrinsic decomposition (breakdown) occurs when electrons are removed from their associated nuclei this causes secondary ionization and accelerated breakdown. The DS is reduced by mechanical loading of the specimen and by increasing the temperature. 

N-oxidation. The oxidation of nitrogen in tertiary amines, amides, imines, hydrazines, and heterocyclic rings may be catalyzed by microsomal enzymes or by other enzymes (see below). Thus the oxidation of trimethylamine to anN-oxide (Fig. 4.19) is catalyzed by the microsomal FAD-containing mono oxygenase. The N-oxide so formed may undergo enzyme-catalyzed decomposition to a secondary amine and aldehyde. This N to C transoxygenation is mediated by cytochromes P-450. The N-oxidation of 3-methylpyridine, however, is catalyzed by cytochromes P-450. This reaction may be involved in the toxicity of the analogue,... 

On the basis of these and other observations, it was proposed that the diatomic species result from the secondary decomposition of vibrationally... 

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