Fragmentation rate constants

Table 3.3. Fragmentation Rate Constants and Standard Potentials for Aryl Chlorides Anion Radicals in DMF...

FIGURE 3.19. Correlation between the fragmentation rate constant (in s-1) and the standard potential and the fragmentation standard free energy (in V vs. SCE) (top) and activationdriving force relationship (free enthalpies in eV) (bottom) for aryl chloride anion radicals. Data from Table 33. Adapted from Figure 3 of reference 30, with permission from the American Chemical Society. 

With systems such as those represented in Figure 3.22a, one therefore expects that the log of the fragmentation rate constant varies with the driving force with a slope of 1/0.059 eV, at 25°C, within a large portion of the accessible domain of driving forces. 

The distinctive structure of CP (III), coupled with an absence of any published oxidation rate constants for it, requires that kox be estimated from additivity of fragment rate constants for the major structural units 3,5,6-trichloropyridinyl (TCP), diethoxyphospho-rothioate (DEP), and the phosphorothioate =P=S bond. 

Zhao and Rice have calculated the fragmentation rate constant k by fitting the numerical simulation data from the time at which dissociation first starts to the time when... 

This method of calculating the fragmentation rate constant gives good agreement with the rate constants determined by trajectory calculations. 

The key variable in both explanations is the fragmentation rate constant. There is a difference of six orders of magnitude between the fragmentation rate constants obtained via explanations (i) and (ii). The question of which explanation is correct has been hotly debated for over three years, but is still unresolved. 

Reversible chain transfer [4]. As a broadly used assumption lately, we shall take that intermediates fragmentation rate constant doesn t depend on leaving radical s length [7],... 

Hence, reactions of intermediates fragmentation rate constant will be as such ... 

The reactions of intermediates fragmentation rate constant were built into the model in the form of dependence (the Eq. (17)) considering Eqs. (15) and (16). 

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