Reactions of the hydrated electron with dilute electrolytes

1 REACTIONS OF THE HYDRATED ELECTRON WITH DILUTE ELECTROLYTES 

Hart and An bar [17] have tabulated many rate coefficients for reactions of the hydrated electron. While many reactions are not diffusion-limited at all, of those reactions with ions, some clearly seem to be diffusion-limited. Using the Debye—Smoluchowski rate coefficient [68], eqn. (51), Hart and Anbar [17] deduced the encounter radii of reaction. 

Even in aqueous media, such a deduction is difficult because the rate coefficient is only weakly dependent on R for unlike charges (rc negative, i.e. cations) and for like charges, the rate coefficient is very dependent upon R. A number of these radii are shown in Table 2 and are compared 

Encounter radii, R, for reaction between hydrated electrons and various ions [17], the corrected encounter radius, i H, incorporating the hydrodynamic effect, and the sum of the hydrated electron and ion crystallographic radii, Rc 

Nevertheless, as discussed in Chap. 9 Sect. 3.4, there are several reasons for considering that the Deutch and Felderhof [70] correction of the Debye—Smoluchowski theory [68] to incorporate hydrodynamic repulsive effects overestimates this correction [71]. Furthermore, for reactants 

Even in aqueous media, such a deduction is difficult because the rate coefficient is only weakly dependent on R for unlike charges (r negative, 

---