Relative stabilities of Ce(IV) and Ce(III) limiting carbonate complexes at 5 to 50°C in Na+ aqueous solutions, an electrochemical study

Autor: Ludovic Legrand, Nathalie Larabi-Gruet, Annie Chaussé, Pierre Vitorge
Přispěvatelé: Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Jazyk: angličtina
Rok vydání: 2006
Předmět:
Zdroj: ESEAC06
ESEAC06, Jun 2006, Bordeaux, France
Electrochimica Acta
Electrochimica Acta, 2007, 52 (7), pp.2401-2410. ⟨10.1016/j.electacta.2006.08.046⟩
Electrochimica Acta, Elsevier, 2007, 52 (7), pp.2401-2410
ISSN: 0013-4686
DOI: 10.1016/j.electacta.2006.08.046⟩
Popis: International audience; The normal potential of the Ce(IV)/Ce(III) redox couple was determined by square wave voltammetry (SWV) at different temperatures in solutions with a constant ratio [CO32-]/[HCO3-] approximate to 10 for high ionic strengths (3.29 mol dm(-3) at 4.39 mol dm(-3)): E-IV/III(0') varies from 259.5 to 198.0 mV/S.H.E. in the 15-50 degrees C range. Linear variations were found for E-IV/III(0') versus (RT/F)In(m(CO32-)), leading, to the stoichiometry, Ce(CO3)(6)(8-) for the Ce(IV) limiting complex. But the slopes of these linear variations were actually found in the range 1.8-1.9, not exactly 2. This was interpreted as dissociation of the Ce(IV) limiting complex following the reaction: Ce(CO3)(5)(6-) +CO32- - -> Ce(CO3)(6)(8-) and as dissociation of the Ce(III) limiting complex following the reaction: Ce(CO3)(3)(3-) + CO32- -> Ce(CO3)(4)(5-): for which maximum possible values of log(10) K-IV,K-6 and log(10)K(III.4) were estimated via fitting in the 15-50 degrees C temperature range (log(10) K-IV.6 = 0.42 (0.97) and log(10) K-III.4 = 0.88 (7.00) at 15 degrees C (50 degrees C). The normal potential was found to decrease linearly with T, these variations correspond to T-0 Delta S-r(T0) approximate to -46 kJ mol(-1), with T-0 = 298.15 K and Delta H-r(T0) approximate to 70 kJ mol(-1). The apparent diffusion coefficient of Ce(IV) was determined by direct current polarography (DCP), cyclic voltammetry (CV) and square wave voltammetry. It was found to depend on the ionic strength and to be proportional to T.
Databáze: OpenAIRE
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