Abstract
This paper is an attempt to find out thorium oxide dissolution mechanism in HNO3-HF mixture. In a previous paper, several parameters effects on thorium oxide dissolution have been described, with specific focus on hydrofluoric acid effect, which can lead to an increase of the dissolution rate if present in small amount, but precipitates as ThF4 at higher content. Based on this previous study, experimental data were fitted using several dissolution models in order to find out the best one. Finally, a revisited model based on literature and considering the ThF4 formation was proposed. It describes the main steps of dissolution and is able to fit the experimental data for a wide range of solution compositions. This point is crucial since it allows considering an extrapolation of the established model to not-yet-studied conditions.
Acknowledgements
The authors would like to thank ORANO and CNRS for financial support.
References
1. Gresky, A.: Solvent extraction separation of U233 and Thorium from fission products by mean of TBP. Proceedings of the International Conference on the Peaceful Uses of Atomic Energy 9, 505 (1955).Search in Google Scholar
2. Shying, M. E., Florence, T. M., Carswell, D. J.: Oxide dissolution mechanisms I. J. Inorg. Chem. 32, 3493 (1970).10.1016/0022-1902(70)80158-0Search in Google Scholar
3. Takeuchi, T., Hanson, K. C., Wadsworth, M. E.: Kinetics and mechanism of the dissolution of thorium oxide in hydrofluoric acid and nitric acid mixtures. J. Inorg. Nucl. Chem. 33, 1089 (1971).10.1016/0022-1902(71)80178-1Search in Google Scholar
4. Barney, G. S.: The kinetics of plutonium oxide dissolution in nitric/hydrofluoric acid mixtures. J. Inorg. Nucl. Chem. 39(9), 1665 (1977).10.1016/0022-1902(77)80123-1Search in Google Scholar
5. Simonnet, M., Barré, N., Drot, R., Le Naour, C., Sladkov, V., Delpech, S.: Multiparametric study of thorium oxide dissolution in aqueous solution. Radiochim. Acta 104, 691 (2016).10.1515/ract-2016-2607Search in Google Scholar
6. Hingant, N., Clavier, N., Dacheux, N., Barre, N., Hubert, S., Obbade, S., Taborda, F., Abraham, F.: Preparation, sintering and leaching of optimized uranium thorium dioxides, J. Nucl. Mater. 385(2), 400 (2009).10.1016/j.jnucmat.2008.12.011Search in Google Scholar
7. Claparede, L., Tocino, F., Szenknect, S., Mesbah, A., Clavier, N., Moisy, P., Dacheux, N.: Dissolution of Th1−xUxO2: effects of chemical composition and microstructure. J. Nucl. Mater. 457, 304 (2015).10.1016/j.jnucmat.2014.11.094Search in Google Scholar
8. Crundwell, F. K.: The mechanism of dissolution of minerals in acidic and alkaline solutions: part I – a new theory of non-oxidation dissolution. Hydrometallurgy 149, 252 (2014).10.1016/j.hydromet.2014.06.009Search in Google Scholar
9. Lasaga, A. C.: Fundamental approaches in describing mineral dissolution and precipitation rates. Mineralogy and Geochemistry 31, 23 (1995)10.1515/9781501509650-004Search in Google Scholar
10. Davis, W., De Bruin, H. J.: New activity coefficients of 0–100 per cent aqueous nitric acid. J. Inorg. Chem. 26, 1069 (1964).10.1016/0022-1902(64)80268-2Search in Google Scholar
11. Hlushak, S., Simonin, J. P., De Sio, S., Bernard, O., Ruas, A., Pochon, P., Jan, S., Moisy, P.: Speciation in aqueous solutions of nitric acid. Dalton Trans. 42, 2853 (2013).10.1039/C2DT32256KSearch in Google Scholar PubMed
12. Ruas, A., Pochon, P., Simonin, J. P., Moisy, P.: Nitric acid: modeling osmotic coefficients and acid base dissociation using the BIMSA theory. Dalton Trans. 39, 10148 (2010).10.1039/c0dt00343cSearch in Google Scholar PubMed
13. Chemical Thermodynamics of Thorium, OECD publications, 2008. Available at: http://www.oecd.org/publications/chemical-thermodynamics-of-thorium-9789264056688-en.htm.Search in Google Scholar
14. Neck, V., Altmaier, M., Fanghänel, T.: on interaction (SIT) coefficients for the Th4+ ion and trace activity coefficients in NaClO4, NaNO3 and NaCl solution determined by solvent extraction with TBP. Radiochim. Acta 94, 501 (2006).10.1524/ract.2006.94.9-11.501Search in Google Scholar
15. Ordoñez-Regil, E., Drot, R., Simoni, E.: Surface Complexation Modeling of uranium(VI) sorbed onto lanthanum monophosphate. J. Colloid Interface Sci. 263, 391 (2003).10.1016/S0021-9797(03)00399-0Search in Google Scholar PubMed
16. Hayes, K. F., Redden, G., Ela, W., Leckie, J. O.: Surface complexation models: an evaluation of model parameter estimation using FITEQL and oxide mineral titration data. J. Colloid Interface Sci. 142(2), 448 (1991).10.1016/0021-9797(91)90075-JSearch in Google Scholar
17. Stumm, W.: Chemistry of the Solid–water Interface: Processes at the Mineral–water and Particle–water Interface in Natural Systems. Wiley, New York (1992).Search in Google Scholar
18. Almazan-Torres, M. G., Drot, R., Mercier-Bion, F., Catalette, H., Den Auwer, C., Simoni, E.: Surface complexation modelling of uranium (VI) sorbed onto zirconium oxophosphate versus temperature: thermodynamic and structural approaches. J. Colloid Interface Sci. 323, 42 (2008).10.1016/j.jcis.2008.03.041Search in Google Scholar PubMed
©2019 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- Cross-section measurements and production of 72Se with medium to high energy protons using arsenic containing targets
- Thorium oxide dissolution in HNO3-HF mixture: kinetics and mechanism
- Highly efficient carbonaceous nanofiber/layered double hydroxide nanocomposites for removal of U(VI) from aqueous solutions
- Effect of solution acidity on the structure of amino acid-bearing uranyl compounds
- A novel method for the determination of uranium and free acidity in nuclear fuel process samples by extraction spectrophotometry
- Experimental investigation of photon attenuation parameters for different binary alloys
- Radiation protective characteristics of some selected tungstates
- New high temperature resistant heavy concretes for fast neutron and gamma radiation shielding
Articles in the same Issue
- Frontmatter
- Cross-section measurements and production of 72Se with medium to high energy protons using arsenic containing targets
- Thorium oxide dissolution in HNO3-HF mixture: kinetics and mechanism
- Highly efficient carbonaceous nanofiber/layered double hydroxide nanocomposites for removal of U(VI) from aqueous solutions
- Effect of solution acidity on the structure of amino acid-bearing uranyl compounds
- A novel method for the determination of uranium and free acidity in nuclear fuel process samples by extraction spectrophotometry
- Experimental investigation of photon attenuation parameters for different binary alloys
- Radiation protective characteristics of some selected tungstates
- New high temperature resistant heavy concretes for fast neutron and gamma radiation shielding