A spectroscopic study of Cm(III) complexation with propionate in saline solutions at variable temperatures

作者：Froehlich Daniel R; Skerencak Frech Andrej; Morkos Marie Louise K; Panak Petra J

来源：New Journal of Chemistry, 2013, 37(5): 1520-1528.

DOI：10.1039/c3nj00109a

The complexation of Cm(III) with propionate is studied by time resolved laser fluorescence spectroscopy (TRLFS) in saline solutions (NaCl and CaCl2) as a function of ionic strength, ligand concentration, and temperature. The molar fractions of the different Cm(III) species are determined by peak deconvolution of the measured fluorescence spectra. By using the specific ion interaction theory (SIT), the stability constants at zero ionic strength (log K-n(0)) of the first and second complexation steps are determined. The stability constants of the mono- and dipropionate complexes increase continuously with increasing temperature between 20-90 degrees C in both background electrolytes. The log K-n(0) values are linearly correlated to the reciprocal temperature, indicating Delta H-r(m)0 = const. and Delta C-r(p,m)0 = 0. Therefore, the thermodynamic constants (Delta H-r(m)0, Delta S-r(m)0, Delta(r)G(m)(0)) for the formation of the [Cm(Prop)](2+) and [Cm(Prop)(2)](+) complexes are derived from the integrated van%26apos;t Hoff equation. The results show that both reactions are entropy driven. Furthermore, neither the formation of ternary species including Ca2+ nor a complexing effect of Cl- at elevated temperatures is observed under the chosen experimental conditions. Lastly, the ion-ion interaction coefficients of both complexed species with Cl- are derived for the first time.

• 出版日期2013