Termination reaction recombination

Termination reaction with vinyl acetate is nearly exclusively by disproportionation (216), although there are reports that recombination increases in... 

When the initiation and termination reactions are the reverse of one another, the kinetic form is usually simpler than when the two are independent. Also, the transition-state composition follows directly from the rate law, which is why the term well-behaved is applied. Imagine, for example, that the termination step in the system most recently presented was the recombination of two sulfate radical ions rather than Eq. (8-38) ... 

Bhawe (14) has simulated the periodic operation of a photo-chemically induced free-radical polymerization which has both monomer and solvent transfer steps and a recombination termination reaction. An increase of 50% in the value of Dp was observed over and above the expected value of 2.0. An interesting feature of this work is that when very short period oscillations were employed, virtually time-invariant products were predicted. 

Equations 4.2.31 and 4.2.32 represent radical recombination reactions that might be considered as alternative termination reactions. Since these reactions and reaction 4.2.26 are radical recombination reactions, they will all have very low activation energies. The relative rates of these processes will then be governed by the collision frequencies and thus the concentrations of the reacting species. The relative concentrations of hydrogen and bromine atoms can be determined from the steady-state form of equation 4.2.17. 

Kinetic vs. material chain. Kinetically, a chain reaction exists throughout the "life" of the radical, that is, from the initiation of a radical up to its termination by recombination or by disproportionation. The lifetime of a radical determines the so-called kinetic chain length Lp defined as the number of monomers consumed per initiating radical. Lp, by definition, can be calculated from the ratio between the propagation rate Rp to the initiation rate R, or, using steady-state hypothesis (Equation (1)), from the ratio between propagation rate to the termination rate Rt (Equation (3)). 

As mentioned earlier, when NO concentration exceeds that of superoxide, nitric oxide mostly exhibits an inhibitory effect on lipid peroxidation, reacting with lipid peroxyl radicals. These reactions are now well studied [42-44]. The simplest suggestion could be the participation of NO in termination reaction with peroxyl radicals. However, it was found that NO reacts with at least two radicals during inhibition of lipid peroxidation [50]. On these grounds it was proposed that LOONO, a product of the NO recombination with peroxyl radical LOO is rapidly decomposed to LO and N02 and the second NO reacts with LO to form nitroso ester of fatty acid (Reaction (7), Figure 25.1). Alkoxyl radical LO may be transformed into a nitro epoxy compound after rearrangement (Reaction (8)). In addition, LOONO may be hydrolyzed to form fatty acid hydroperoxide (Reaction (6)). Various nitrated lipids can also be formed in the reactions of peroxynitrite and other NO metabolites. 

When the polymerization of St was carried out with 51 under conditions identical to those in Fig. 3, i.e., [7]/4=[8]/2=51=2X 10-3 mol/1, the formation of benzene-insoluble polymers was observed from the initial stage of the polymerization. Although 7 and 8 induced living radical mono and diradical polymerization similar to that previously mentioned, benzene-insoluble polymers were formed in the polymerization with 51, and the molecular weight of the soluble polymers separated decreased with the reaction time. This suggests that a part of the propagating polymer radicals underwent ordinary bimolecular termination by recombination, leading to the formation of the cross-linked polymer, which was prevented by the addition of 13. 

Termination of active radicals can occur via three mechanisms carbon-carbon termination, cross termination and recombination of DTC radicals. These reactions appear as ... 

In addition to the stabilization by suitable substituents and the absence of other termination reactions than recombination, it is the strength of the bond formed in the dimerization which is a necessary cofactor for the observation of free radicals by esr spectroscopy. The stability of nitroxides [4] or hydrazyls [5] (Forrester et al., 1968) derives not only from their merostabilized or captodative character but also from a weak N-N bond in the dimer. The same should be the case for captodative-substituted aminyls... 

Two possible termination steps are shown, one of which produces the same product as the chain reaction. Recombination of two chlorine radicals is feasible, but less likely. Either of the termination products could be suggested as an alternative product but, in practice, what we are going to get is derivatives with more than one chlorine substituent. It is difficult to control a radical process once the chain reaction is under way, so we usually get a mixture of products. Note particularly that further substitution is on the original or alternative... 

Then, they depend also on the viscosity of the system. Specific diffusion control is characteristic of fast reactions like fluorescence quenching. In polymer formation, specific diffusion control is responsible for the acceleration of chain polymerization due to the retardation of the termination by recombination of two macroradicals (Trommsdorff effect). Step reactions are usually too slow to exhibit a dependence on translational diffusion also, the temperature dependence of their rate constants is of the Arrhenius type. 

If ki and k.i are much larger than kj, the reaction Is controlled by kj. If however, ki and k.i are larger than or comparable to kz, the reaction rate becomes controlled by the translational diffusion determining the probability of collisions which Is typical for specific diffusion control. The latter case Is operative for fast reactions like fluorescence quenching or free-radical chain reactions. The acceleration of free-radical polymerization due to the diffusion-controlled termination by recombination of macroradicals (Trommsdorff effect) can serve as an example. 

In radical template polymerization, when only weak interaction exists between monomer and template and pick-up mechanism is commonly accepted, the reaction partially proceeds outside the template. If macroradical terminates by recombination with another macroradical or primary radical, some macromolecules are produced without any contact with the template. In fact, such process can be treated as a secondary reaction. Another very common process - chain transfer - proceeds simultaneously with many template polymerizations. As a result of chain transfer to polymer (both daughter and template) branched polymers appear in the product. The existence of such secondary reactions is indicated by the difficulty in separating the daughter polymer from the template as described in many papers. For instance, template polymerization of N-4-vi-nyl pyridine is followed, according to Kabanov et aZ., by the reaction of poly(4-vinylpyridine) with proper ions. The reaction leads to the branched structure of the product ... 

In consideration of the kinetic law obtained, Rp i0 of magnitude range, one can conclude that the common polymerization mechanism, based on bimolecular termination reactions, is no longer valid for these multifunctional systems when irradiated in condensed phase. Indeed, for conventional radical-induced polymerizations, the termination step consists of the interaction of a growing polymer radical with another radical from the initiator (R), monomer (M) or polymer (P) through recombination or disproportionation reactions ... 

Termination rate constants for alkyl and benzyl radicals in solution range between 109 and 1010 M 1 sec-1.85 These rates correspond quite closely to that calculated for a diffusion-controlled reaction, about 8 x 109 M x sec-1 for the common solvents at room temperature.86 Gas-phase rotating sector results are similar a newer method, however, shows that in the gas phase the rotating sector technique overestimates termination rates. Recombination is fastest for methyl radicals (1010,5 M-1 sec-1) and slower for others (-CF3, 109-7 at 146°C ... 

C olvents have different effects on polymerization processes. In radical polymerizations, their viscosity influences the diffusion-controlled bimolecular reactions of two radicals, such as the recombination of the initiator radicals (efficiency) or the deactivation of the radical chain ends (termination reaction). These phenomena are treated in the first section. In anionic polymerization processes, the different polarities of the solvents cause a more or less strong solvation of the counter ion. Depending on this effect, the carbanion exists in three different forms with very different propagation constants. These effects are treated in the second section. The final section shows that the kinetics of the... 

Termination reactions. A very common termination reaction, known as the Russel mechanism from its discoverer, is the recombination of two peroxy radicals to form an unstable tetroxide that decomposes through a concerted mechanism to yield a hydroxy moiety and a carbonyl moiety (13) ... 

As noted in both radical and redox mechanisms of telomerisation of fluoro-alkenes, termination reactions always occur by recombination and not by disproportionation [29]. 

Reaction under these conditions is 3/2 order as is expected for a reaction where the dominant termination is recombination of like radicals produced in initiation. 

Fig. 5. Chemical evolution in a low temperature plasma. Illustrated are the types of charged particle reaction processes which may occur when ionization is created in a gas and which are terminated by recombination reactions, these returning the plasma to the neutral state... 

Experimental conditions are also a very important factor to consider reaction of a-methylthioacrylonitrile with AIBN was found to give either 69% of isolated low-molecular weight products [2] or 92% of polymer [67], depending on the conditions. The nature and concentration of the initiator also influence the polymerization. The rate of addition of the primary radical (initiator radical) to the captodative olefin is dependent on the nature of the initiator as observed by ESR [85]. Moreover termination by recombination of the persistent propagating radical with a primary radical becomes very important, as expected from the small molecule chemistry. Therefore the initiator influences both the initiation and termination. 

Starting in 1969, D.E. Rice used this method to prepare dicarboxylic oligomers which contained vinylidene fluoride and perfluoropropene. He used the way these fluorinated monomers fit the reaction of chain-termination by recombination but the basic difficulty lay in the preparation of the difunctional initiator [80-83] ... 

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