Reactions of the solvated electron in concentrated ionic solutions

2 REACTIONS OF THE SOLVATED ELECTRON IN CONCENTRATED IONIC SOLUTIONS 

Coyle et al. [94] and Dainton and Logan [113] have studied the reactions of hydrated electrons in aqueous solution of two electron scavengers, one of which was usually N20. Since the rate coefficient for the reaction 

A detailed study of the rates of reaction of hydrated electrons formed 

Buxton et al. [18] have studied the reaction of hydrated electrons in low-temperature aqueous solutions of 9.5moldm 3 LiCl and lOmol dm 3 

For reaction of e q with IrCl , almost identical behaviour to that with nitrobenzene was observed [120]. At lower concentrations of LiCl or CsCl ( 1 mol dm-3), the rate coefficient for this reaction decreases to the dilute electrolyte value of 1.2 x 1010 dm3 mol-1 s-1 from the viscosity-corrected high concentration value of 2.7 x 1010 dm3 moT1 s 1 in lithium 

5 X 10 m s ) of 2.4 x 10 ° dm mol s and in substantial agreement with a similar determination by Aldrich et al. [117]. Both groups found that the rate coefficient was independent of acetone concentration. It is substantially activation-limited. With nitromethane, the operational rate coefficient increased with concentration from 2.9 x 10 in dilute solutions to 4.3 X 10 dm mol s at O.Smoldm nitromethane. Such an increase would be expected for reactions occurring before the steady-state is established. Wolff et al. [118] found that the rate coefficients for hydrated electrons reacting with NOJ, H, acetone and NO2 was independent of concentration of scavenger above 0.1 mol dm , though only nitrate reacts at the diffusion-limited rate, even if hydro-dynamic corrections are applied (Chap. 9, Sect. 4). 

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