Reaction, Chain Mechanisms termination

This reaction proceeds through a chain mechanism. Free-radical additions to 1-butene, as in the case of HBr, RSH, and H2S to other olefins (19—21), can be expected to yield terminally substituted derivatives. Some polymerization reactions are also free-radical reactions. 

Also, the rates of the propagation steps are equal to one another (see Problem 8-4). This observation is no surprise The rates of all the steps are the same in any ordinary reaction sequence to which the steady-state approximation applies, since each is governed by the same rate-controlling step. The form of the rate law for chain reactions is greatly influenced by the initiation and termination reactions. But the chemistry that converts reactant to product, and is presumably the matter of greatest importance, resides in the propagation reactions. Sensitivity to trace impurities, deliberate or adventitious, is one signal that a chain mechanism is operative. 

The inlet monomer concentration was varied sinusoidally to determine the effect of these changes on Dp, the time-averaged polydispersity, when compared with the steady-state case. For the unsteady state CSTR, the pseudo steady-state assumption for active centres was used to simplify computations. In both of the mechanisms considered, D increases with respect to the steady-state value (for constant conversion and number average chain length y ) as the frequency of the oscillation in the monomer feed concentration is decreased. The maximum deviation in D thus occurs as lo 0. However, it was predicted that the value of D could only be increased by 10-325S with respect to the steady state depending on reaction mechanism and the amplitude of the oscillating feed. Laurence and Vasudevan (12) considered a reaction with combination termination and no chain transfer. 

In contrast to chain transfer, termination reactions destroy free radicals. Two mechanisms are considered. Termination by combination produces a single molecule of dead polymer ... 

A major difference between both kind of syntheses lies in polymerisation kinetics in the former case there is a chain mechanism (initiation, propagation, termination), in the latter case there is no chain reaction and each step is equiprobable. Main comparison points are highlighted in Table 4 [9]. 

The traditional chain oxidation with chain propagation via the reaction RO/ + RH occurs at a sufficiently elevated temperature when chain propagation is more rapid than chain termination (see earlier discussion). The main molecular product of this reaction is hydroperoxide. When tertiary peroxyl radicals react more rapidly in the reaction R02 + R02 with formation of alkoxyl radicals than in the reaction R02 + RH, the mechanism of oxidation changes. Alkoxyl radicals are very reactive. They react with parent hydrocarbon and alcohols formed as primary products of hydrocarbon chain oxidation. As we see, alkoxyl radicals decompose with production of carbonyl compounds. The activation energy of their decomposition is higher than the reaction with hydrocarbons (see earlier discussion). As a result, heating of the system leads to conditions when the alkoxyl radical decomposition occurs more rapidly than the abstraction of the hydrogen atom from the hydrocarbon. The new chain mechanism of the hydrocarbon oxidation occurs under such conditions, with chain... 

In the oxidized hydrocarbon, hydroperoxides break down via three routes. First, they undergo homolytic reactions with the hydrocarbon and the products of its oxidation to form free radicals. When the oxidation of RH is chain-like, these reactions do not decrease [ROOH]. Second, the hydroperoxides interact with the radicals R , RO , and R02. In this case, ROOH is consumed by a chain mechanism. Third, hydroperoxides can heterolytically react with the products of hydrocarbon oxidation. Let us consider two of the most typical kinetic schemes of the hydroperoxide behavior in the oxidized hydrocarbon. The description of 17 different schemes of chain oxidation with different mechanisms of chain termination and intermediate product decomposition can be found in a monograph by Emanuel et al. [3]. 

The heterogeneous catalyst accelerates hydrocarbon oxidation. The rate of oxidation increases with increasing concentration of the catalyst. However, this increase in the oxidation rate with the catalyst concentration is not unlimited. The oxidation rate reaches a maximum value and does not increase thereafter. Moreover, the cessation of the reaction was observed and very often at a very small increase in the catalyst concentration. Such phenomenon was named critical phenomenon. The basis of critical phenomenon lies in the chain mechanism of oxidation and the dual ability of the catalyst surface to initiate and terminate chains. Numerous observations and studies of critical phenomenon in catalytic liquid-phase oxidations were performed [271 283]. Here are a few examples. 

It was in 1924 when Christiansen [3] put forward the conception of the chain mechanism of oxidation and explained the action of antioxidants via chain termination by the antioxidant [3]. Three years later, Backstrom and coworkers [4—6] experimentally proved the chain mechanism of benzaldehyde oxidation (see Chapter 1) and the mechanism of antioxidant (hydroquinone) action via chain termination. The systematic study of the oxidation kinetics of esters of nonsaturated acids was performed by Bolland and ten Have [7,8], They observed in the kinetic experiments that substrates are oxidized by the chain mechanism with chain propagation via the cycle of reactions (see Chapter 2). 

This region is determined by proportions between the rates of elementary reactions. For instance, when RH oxidation is chain-like and chains are terminated by the reaction R02 of with InH (mechanism III), the following six inequalities must be satisfied. 

Phosphites can react not only with hydroperoxides but also with alkoxyl and peroxyl radicals [9,14,17,23,24], which explains their susceptibility to a chain-like autoxidation and, on the other hand, their ability to terminate chains. In neutral solvents, alkyl phosphites can be oxidized by dioxygen in the presence of an initiator (e.g., light) by the chain mechanism. Chains may reach 104 in length. The rate of oxygen consumption is proportional to v 1/2, thus indicating a bimolecular mechanism of chain termination. The scheme of the reaction... 

The situation is different for aryl phosphites, which give rise to shorter chains than alkyl phosphites do (about 100 elementary reactions). The rate of aryl phosphite oxidation, v v suggests that chains are terminated in a linear manner [4,14,27]. Linear chain termination was interpreted in terms of the following mechanism of chain oxidation of aryl phosphites ... 

The thermal decomposition of this alkyl was studied in a static system over the temperature range 162-192.4 °C121. The surface of the reaction vessel was unintentionally activated before each run by rinsing with distilled water before baking out. Under these conditions the decomposition occurs by a chain mechanism with initiation and termination at the walls. The overall rate coefficient for the decomposition is 1.58 x 108 exp(—29,000/RT) sec-1. 

The presence of O2 clues you in that this is a free-radical mechanism, specifically a free-radical substitution. Because it is an intermolecular substitution reaction, it probably proceeds by a chain mechanism. As such it has three parts initiation, propagation, and termination. (We do not draw termination parts in this book.) The initiation part turns one of the stoichiometric starting materials into an odd-electron radical. This can be done here by abstraction of H- from C by 02. 

The mechanistic issues to be discussed are the initiation modes of the reaction, the propagation mechanism, the perfect alternation of the polymerisation reaction, chain termination reactions, and the combined result of initiation and termination as a process of chain transfer. Where appropriate, the regio- and stereoselectivity should be discussed as well. A complete mechanistic picture cannot be given without a detailed study of the kinetics. The material published so far on the kinetics comprises only work carried out at temperatures of -82 to 25 °C, which is well below the temperature of the catalytic process. 

Another unique attribute of polymerizations of multifunctional monomers is the dominance of reaction diffusion as a termination mechanism [134,136, 143-146]. Reaction diffusion involves the mobility of radicals by propagation through unreacted functional groups. This termination mechanism is physically different from translation and segmental diffusion termination mechanisms which involve the diffusion of polymer macroradicals and chain segments to bring radicals within a reaction zone before terminating. Whereas normal termination mechanisms are related to the diffusion coefficient of the polymer, reaction diffusion must be considered differently. In essence, reaction diffusion is... 

Reactions (28-30) generate additional quantities of the RSSR(2"-1)-radicals, leading to the catalysed redox decomposition of the [Fe(CN)sN(0)SR](" + 2)- complex. Finally, the reaction between NP and RSSR(2n-1, terminates the chain mechanism, Eq. (31). 

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