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Electrode Kinetics of Solvated Electrons in Liquid Ammonia
Author(s) -
Harima Y.,
Aoyagui S.
Publication year - 1979
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.197900009
Subject(s) - chemistry , chronoamperometry , alkali metal , iodide , solvated electron , electron transfer , inorganic chemistry , electrode , electrolyte , diffusion , analytical chemistry (journal) , electron , metal , ion , supporting electrolyte , electrochemistry , cyclic voltammetry , aqueous solution , thermodynamics , radiolysis , physics , organic chemistry , quantum mechanics , chromatography
Electrode reaction of ammoniated electrons was investigated with voltammetry, potentiometry and chronoamperometry. Experiments were conducted on Pt, Au and W electrodes in 0.5 M LiI, NaI, KI, CsI and KBr solutions of liq. NH 3 . The results in dilute solutions (< 10< −4 M) do not reflect the differences in alkali metal, electrode metal and supporting electrolyte and are explained by a simple one‐electron transfer process whose transferring species is a free solvated electron and its ion‐pair with a metal cation in a rapid equilibrium. The formal standard potential is −2.155 ± 0.005 V vs. Pb/Pb(NO 3 ) 2 (0.05 M) at −40°C in liq. NH 3 involving 0.5 M alkali metal iodide. The lower limit of the averaged diffusion coefficient is 0.7 × 10 −4 cm 2 s −1 . At higher metal concentrations (> 10 −2 M), a two‐electron transfer process tends to prevail, which is explained by considering the dimer of ion‐pairs as the diffusing species.