Spectroscopic studies on the thermodynamics of the complexation of trivalent curium with propionate in the temperature range from 20 to 90 °C
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...
Gespeichert in:
| Hauptverfasser: | , , , , |
|---|---|
| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
2013
|
| In: |
Journal of solution chemistry
Year: 2013, Jahrgang: 42, Pages: 1-17 |
| ISSN: | 1572-8927 |
| DOI: | 10.1007/s10953-012-9945-x |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1007/s10953-012-9945-x Verlag, lizenzpflichtig, Volltext: https://link.springer.com/article/10.1007%2Fs10953-012-9945-x 
|
| Verfasserangaben: | Andrej Skerencak, Stefanie Höhne, Sascha Hofmann, Christian M. Marquardt, Petra J. Panak |
| Zusammenfassung: | 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. |
|---|---|
| Beschreibung: | Published: 12 January 2013 Gesehen am 03.02.2022 |
| Beschreibung: | Online Resource |
| ISSN: | 1572-8927 |
| DOI: | 10.1007/s10953-012-9945-x |