Radical reaction, relative rate

These results lead to a general mechanism for the reaction nitrenium ions with aromatic compounds (Fig. 13.71). Initial encounter leads to a 7i-complex (141). The latter is converted into isomeric a complexes (142-144) which, in turn, either tau-tomerize to give stable adducts (145-147) or else dissociate to give radicals. The relative rates of these processes depend on the reactivities of the nitrenium ion and the arene. With less reactive nitrenium ions the 7i-complex is relatively long lived. With more reactive nitrenium ions the n complex forms in a low steady-state... 

Thus Szwarc and co-workers (see ref. 396) have carried out extensive studies of H abstraction and addition to unsaturates of methyl radicals in iso-octane solution. Most of the work involved acetyl peroxide as the methyl radical source and subsequent experiments with azomethane confirmed the original findings. The systems yielded rate coefficients at 338°K for attack of the methyl radicals on the substrate relative to attack on iso-octane. If the rate coefficient for attack of methyl radicals on iso-octane in the gas phase was known it would be possible to make direct comparisons of gas and liquid phase reactions of methyl radicals with some substrate molecules. Unfortunately, the only available rate coefficient for methyl attack on iso-octane was measured at 773°K and it is of doubtful validity [3]. Nevertheless, the liquid phase studies of methyl radicals yield relative rate coefficients for attack on primary, secondary and tertiary C—H bonds which are fully compatible with the gas phase values. 

The rate-determining step of the radical substitution reaction is hydrogen atom abstraction to form a radical. The relative rates of radical formation are benzylic allyl > 3° > 2° > 1° > vinyl methyl. To determine the relative amounts of products obtained from the radical halo-genation of an alkane, both probability and the relative rate at which a particular hydrogen is abstracted must be taken into account. The reactivity-selectivity principle states that the more reactive a species is, the less selective it will be. A... 

Under these conditions, a component with a low rate constant for propagation for peroxy radicals may be cooxidized at a higher relative rate because a larger fraction of the propagation steps is carried out by the more reactive (less selective) alkoxy and hydroxy radicals produced in reaction 4. 

Catalysts and Promoters. The function of catalysts in LPO is not weU understood. Perhaps they are not really catalysts in the classical sense because they do not necessarily speed up the reaction (25). They do seem to be able to alter relative rates and thereby affect product distributions, and they can shorten induction periods. The basic function in shortening induction periods appears to be the decomposition of peroxides to generate radicals (eq. 33). 

Structure-reactivity relationships can be probed by measurements of rates and equiUbria, as was diseussed in Chapter 4. Direct comparison of reaction rates is used relatively less often in the study of radical reactions than for heterolytic reactions. Instead, competition methods have frequently been used. The basis of competition methods lies in the rate expression for a reaction, and the results can be just as valid a comparison of relative reactivity as directly measured rates, provided the two competing processes are of the same kinetic order. Suppose that it is desired to compare the reactivity of two related compounds, B—X and B—Y, in a hypothetical sequence ... 

These singlet and triplet state species exhibit the important differences in chemical behavior to be expected. The former species, with their analogy to carbonium ions, are powerful electrophiles and the relative rates of their reaction with a series of substrates increases with the availability of electrons at the reaction center their addition reactions with olefins are stereospecific. Triplet state species are expected to show the characteristics of radicals i.e., the relative rates of additions to olefins do not follow the same pattern as those of electrophilic species and the additions are not stereospecific. 

The competitive method employed for determining relative rates of substitution in homolytic phenylation cannot be applied for methylation because of the high reactivity of the primary reaction products toward free methyl radicals. Szwarc and his co-workers, however, developed a technique for measuring the relative rates of addition of methyl radicals to aromatic and heteroaromatic systems. - In the decomposition of acetyl peroxide in isooctane the most important reaction is the formation of methane by the abstraction of hydrogen atoms from the solvent by methyl radicals. When an aromatic compound is added to this system it competes with the solvent for methyl radicals, Eqs, (28) and (29). Reaction (28) results in a decrease in the amount... 

Tabic 1.3 Relative Rate Constants for Reactions of Radicals with Alkyl-Substituted Acrylate Esters CHR CFEcOaCHs"... 

There is an excellent, if non critical, compilation of absolute and relative rate data for reactions of oxygen-centered radicals covering the literature through 1982389 and for 1982-1992.39 1 Selected data from these and other sources are summarized in Table 3.7 and Table 3.8. The reactions of oxygen-centered radicals and their use in organic synthesis has been recently reviewed by Hartung el uIS )]... 

The rate constant for p-scisskm is dependent on ring substituents. Rate constants for radicals X-Q.H. CCh are reported to increase in the series where X is / -Fi There is qualitative evidence that the relative rales for p-scission and addition are insensitive to solvent changes. For benzoyloxy radicals, similar relative reactivities are obtained from direct competition experiments10 as from studies on individual monomers when p-scission is used as a clock reaction.399,401... 

Kochi (1956a, 1956b) and Dickerman et al. (1958, 1959) studied the kinetics of the Meerwein reaction of arenediazonium salts with acrylonitrile, styrene, and other alkenes, based on initial studies on the Sandmeyer reaction. The reactions were found to be first-order in diazonium ion and in cuprous ion. The relative rates of the addition to four alkenes (acrylonitrile, styrene, methyl acrylate, and methyl methacrylate) vary by a factor of only 1.55 (Dickerman et al., 1959). This result indicates that the aryl radical has a low selectivity. The kinetic data are consistent with the mechanism of Schemes 10-52 to 10-56, 10-58 and 10-59. This mechanism was strongly corroborated by Galli s work on the Sandmeyer reaction more than twenty years later (1981-89). 

Waters61 have measured relative rates of p-toluenesulfonyl radical addition to substituted styrenes, deducing from the value of p + = — 0.50 in the Hammett plot that the sulfonyl radical has an electrophilic character (equation 21). Further indications that sulfonyl radicals are strongly electrophilic have been obtained by Takahara and coworkers62, who measured relative reactivities for the addition reactions of benzenesulfonyl radicals to various vinyl monomers and plotted rate constants versus Hammett s Alfrey-Price s e values these relative rates are spread over a wide range, for example, acrylonitrile (0.006), methyl methacrylate (0.08), styrene (1.00) and a-methylstyrene (3.21). The relative rates for the addition reaction of p-methylstyrene to styrene towards methane- and p-substituted benzenesulfonyl radicals are almost the same in accord with their type structure discussed earlier in this chapter. 

Relative Rates of Reactions Between Cation Radicals and Lutidines... 

Our treatment of chain reactions has been confined to relatively simple situations where the number of participating species and their possible reactions have been sharply bounded. Most free-radical reactions of industrial importance involve many more species. The set of possible reactions is unbounded in polymerizations, and it is perhaps bounded but very large in processes such as naptha cracking and combustion. Perhaps the elementary reactions can be postulated, but the rate constants are generally unknown. The quasi-steady hypothesis provides a functional form for the rate equations that can be used to fit experimental data. 

The relative rates of oxidation of phenylmethanes cover too small a range to be compatible with carbonium ion formation cf. the discussion on chromic acid oxidation of diphenylmethane, p. 295), and an initial reaction to give a radical plus Cr(V) followed by rapid transfer of a second electron to form Cr(IV) is more... 

If the chains are long, the composition of the copolymer and the arrangement oi units along the chain are determined almost entirely by the relative rates of the various chain propagation reactions. On the other hand, the rate of polymerization depends not only on the rates of these propagation steps but also on the rates of the termination reactions. Copolymer composition has received far more attention than has the rate of copolymerization. The present section will be confined to consideration of the composition of copolymers formed by a free radical mechanism. 

The kinetics of the various reactions have been explored in detail using large-volume chambers that can be used to simulate reactions in the troposphere. They have frequently used hydroxyl radicals formed by photolysis of methyl (or ethyl) nitrite, with the addition of NO to inhibit photolysis of NO2. This would result in the formation of 0( P) atoms, and subsequent reaction with Oj would produce ozone, and hence NO3 radicals from NOj. Nitrate radicals are produced by the thermal decomposition of NjOj, and in experiments with O3, a scavenger for hydroxyl radicals is added. Details of the different experimental procedures for the measurement of absolute and relative rates have been summarized, and attention drawn to the often considerable spread of values for experiments carried out at room temperature (-298 K) (Atkinson 1986). It should be emphasized that in the real troposphere, both the rates—and possibly the products—of transformation will be determined by seasonal differences both in temperature and the intensity of solar radiation. These are determined both by latitude and altitude. 

It is relevant to the low pressure studies, particularly those of Figure 5, that at 735°C, CH4 + O2 had a positive effect on the rate of Nj formation and on the rate of CHj- radical production, relative to the case when only CH4 + NO were the reagents. These results are consistent with the view that CHj- radicals are intermediates in the reaction of CH 4 with NO when O2 is present, but in the absence of Oj, the reduction of NO by CH4 over Sr/LajOs may occur via another pathway that does not involve CH,- radicals. 

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