RUZHONG CHEN, YURIS AVOTINSH, and GORDON R. FREEMAN. Can. J. Chem. 72, 1083 (1994.The effective reaction radii a,, where R, is the reactive encounter radius and K is the probability of reaction per encounter, for e; with H: , NH,',,, Ag:, Cu?, and NOT, are all 0.7 f 0.1 nm in isobutanol containing 1G20 mol% water. The value remains at 0.7 f 0.1 nm for H: , Ag:, and Cu? in pure isobutanol, and for the two transition metal ions in pure water solvent.The value for NO;, reduces to 0.35 nm in pure isobutanol and pure water solvents, whereas for H: and NH;, in pure water solvent it is only 0.14 nm and 2.6 x nm, respectively. The low reactivity of NH,',, with e; in water is attributed to the symmetry of the hydrogen-bonded solvation structure of NH; in water, and the higher reactivity of H: (OH;,,) is attributed to the lower symmetry of its hydrogen-bonded solvation structure. The NH,' and OH; ions have no low-lying orbital for an electron to occupy, so either reaction occurs by proton transfer to the electron site or the neutral species must decompose. We suggest that the proton transfer or the decomposition of the neutral species is facilitated by an unsymmetrical solvation structure.Reaction of e; in A1(C104)3 solutions in water is due mainly to H: from hydrolysis of Alp, and partly to partially hydroxylated aluminum(II1) species. Reaction of e; with A12 itself appears to be negligible in water. The reactivity of the solutions of Al(C104)3 in isobutanol-rich solvents is 3-5 times greater than that in water.In pure CI to C4 1-alcanol solvents the value of k2(e; +NO,,) increases linearly with the dielectric relaxation time z, of the solvent. In these solvents the probability of permanent capture per encounter increases approximately as the square of the encounter duration. On attribue la faible rCactivitC du NH,',, avec les e; dans l'eau i la symCtrie de la structure de solvatation comportant des liaisons hydrogknes du NH,',, dans l'eau et on attribue la rCactivitC plus ClevCe des H: (OH;,) B la symCtrie plus faible de sa structure de solvatation comportant une liaison hydrogkne. Les ions NH; et OH; n'ont aucune orbitale de bas niveau pour accommoder un Clectron; la rkaction se produit donc par un transfert de proton vers un site dlClectron ou les espkces neutres doivent se dicomposer. On suggkre que le transfert de proton ou la dCcomposition d'espkces neutres est rendu plus facile par une structure de solvatation qui n'est pas symttrique.La rCaction des e; dans des solutions de A1(C104)3 dans l'eau est principalement due aux H: provenant de l'hydrolyse

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