Spectroscopic studies on the thermodynamics of the complexation of trivalent curium with propionate in the temperature range from 20 to 90 °C

• Verfasst von: Skerencak-Frech, Andrej [VerfasserIn]
• Verfasst von: Höhne, Stefanie [VerfasserIn]
• Verfasst von: Hofmann, Sascha [VerfasserIn]
• Verfasst von: Marquardt, Christian M. [VerfasserIn]
• Verfasst von: Panak, Petra [VerfasserIn]
• Titel: Spectroscopic studies on the thermodynamics of the complexation of trivalent curium with propionate in the temperature range from 20 to 90 °C
• Verf.angabe: Andrej Skerencak, Stefanie Höhne, Sascha Hofmann, Christian M. Marquardt, Petra J. Panak
• Jahr: 2013
• Umfang: 17 S.
• Fussnoten: Published: 12 January 2013 ; Gesehen am 03.02.2022
• Titel Quelle: Enthalten in: Journal of solution chemistry
• Ort Quelle: New York, NY [u.a.] : Springer Science + Business Media B.V., 1972
• Jahr Quelle: 2013
• Band/Heft Quelle: 42(2013), Seite 1-17
• ISSN Quelle: 1572-8927
• DOI: doi:10.1007/s10953-012-9945-x
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1788468147

Abstract

The thermodynamics of the stepwise complexation reaction of Cm(III) with propionate was studied by time resolved laser fluorescence spectroscopy (TRLFS) and UV/Vis absorption spectroscopy as a function of the ligand concentration, the ionic strength and temperature (20-90 °C). The molar fractions of the 1:1 and 1:2 complexes were quantified by peak deconvolution of the emission spectra at each temperature, yielding the log10$$ K_{n}^{\prime } $$values. Using the specific ion interaction theory (SIT), the thermodynamic stability constants log10$$ K_{n}^{0} (T) $$were determined. The log10$$ K_{n}^{0} (T) $$values show a distinct increase by 0.15 (n = 1) and 1.0 (n = 2) orders of magnitude in the studied temperature range, respectively. The temperature dependency of the log10$$ K_{n}^{0} (T) $$values is well described by the integrated van’t Hoff equation, assuming a constant enthalpy of reaction and $$ \Updelta_{\text{r}} C^\circ_{{p,{\text{m}}}} = 0, $$yielding the thermodynamic standard state $$ \left( {\Updelta_{\text{r}} H^\circ_{\text{m}} ,\Updelta_{\text{r}} S^\circ_{\text{m}} ,\Updelta_{\text{r}} G^\circ_{\text{m}} } \right) $$values for the formation of the $$ {\text{Cm(Prop)}}_{n}^{3 - n} $$, n = (1, 2) species.