title: Stability constants determination of successive metal complexes by hyphenated CE-ICPMS.
abstract: The study of radionuclides speciation requires accurate evaluation of stability constants, which can be achieved by CE-ICPMS. We have previously described a method for 1:1 metal complexes stability constants determination. In this paper, we present its extension to the case of successive complexations and its application to uranyl-oxalate and lanthanum-oxalate systems. Several significant steps are discussed: analytical conditions choice, mathematical treatment by non-linear regression, ligand concentration and ionic strength corrections. The following values were obtained: at infinite dilution, log(beta(1) degrees (UO(2)Oxa))=6.93+/-0.05, log(beta(2) degrees (UO(2)(Oxa)(2) (2-)))=11.92+/-0.43 and log(beta(3) degrees (UO(2)(Oxa)(3) (4-)))=15.11+/-0.12; log(beta(1) degrees (LaOxa(+)))=5.90+/-0.07, log(beta(2) degrees (La(Oxa)(2) (-)))=9.18+/-0.19 and log(beta(3) degrees (La(Oxa)(3) (3-)))=9.81+/-0.33. These values are in good agreement with the literature data, even though we suggest the existence of a new lanthanum-oxalate complex: La(Oxa)(3) (3-). This study confirms the suitability of CE-ICPMS for complexation studies.
authors.affiliation: CEA/DEN/DPC/SECR/LANIE, Bâtiment, Gif-sur-Yvette, France. jeremy.petit@centraliens.net
authors.forename: Jeremy
authors.initials: J
authors.lastname: Petit
authors.forename: Jean
authors.initials: J
authors.lastname: Aupiais
authors.forename: Sylvain
authors.initials: S
authors.lastname: Topin
authors.forename: Valérie
authors.initials: V
authors.lastname: Geertsen
authors.forename: Catherine
authors.initials: C
authors.lastname: Beaucaire
authors.forename: Moncef
authors.initials: M
authors.lastname: Stambouli
mesh_terms: D000465:Algorithms; D019075:Electrophoresis, Capillary / Q000379:methods*; D007811:Lanthanum / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D008956:Models, Chemical; D017711:Nonlinear Dynamics; D009994:Osmolar Concentration; D010070:Oxalates / Q000737:chemistry*; D012044:Regression Analysis; D013816:Thermodynamics; D014501:Uranium / Q000737:chemistry*
chemical_list: D010070:Oxalates; D014501:Uranium; D007811:Lanthanum