Aqueous chemistry of Ce(IV): estimations ...
Document type :
Article dans une revue scientifique: Article original
DOI :
PMID :
Title :
Aqueous chemistry of Ce(IV): estimations using actinide analogues
Author(s) :
Marsac, Rémi [Auteur correspondant]
Géosciences Rennes [GR]
Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Lal Banik, Nidhul [Auteur]
Pédrot, Mathieu [Auteur]
Géosciences Rennes [GR]
Pourret, Olivier [Auteur]
Agro-écologie, Hydrogéochimie, Milieux et Ressources [AGHYLE]
UniLaSalle
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Géosciences Rennes [GR]
Réal, Florent [Auteur]

Physico-Chimie Moléculaire Théorique [PCMT]
Lal Banik, Nidhul [Auteur]
Pédrot, Mathieu [Auteur]
Géosciences Rennes [GR]
Pourret, Olivier [Auteur]
Agro-écologie, Hydrogéochimie, Milieux et Ressources [AGHYLE]
UniLaSalle
Vallet, Valérie [Auteur]

Physico-Chimie Moléculaire Théorique [PCMT]
Journal title :
Dalton Transactions
Pages :
13553-13561
Publisher :
Royal Society of Chemistry
Publication date :
2017-09-13
ISSN :
1477-9226
HAL domain(s) :
Planète et Univers [physics]/Sciences de la Terre/Géochimie
Chimie/Chimie théorique et/ou physique
Chimie/Chimie inorganique
Chimie/Chimie théorique et/ou physique
Chimie/Chimie inorganique
English abstract : [en]
The prediction of cerium (Ce) aqueous speciation is relevant in many research fields. Indeed, Ce compounds are used for many industrial applications, which may require the control of Ce aqueous chemistry for their synthesis. ...
Show more >The prediction of cerium (Ce) aqueous speciation is relevant in many research fields. Indeed, Ce compounds are used for many industrial applications, which may require the control of Ce aqueous chemistry for their synthesis. The aquatic geochemistry of Ce is also of interest. Due to its growing industrial use and its release into the environment, Ce is now considered as an emerging contaminant. Cerium is also used as a proxy of (paleo)redox conditions due to the Ce(iv)/Ce(iii) redox transition. Finally, Ce(iv) is often presented as a relevant analogue of tetravalent actinides (An(iv)). In the present study, quantum chemical calculations were conducted to highlight the similarities between the structures of Ce(iv) and tetravalent actinide (An(iv); An = Th, Pa, U, Np, Pu) aqua-ions, especially Pu(iv). The current knowledge of An(iv) hydrolysis, solubility and colloid formation in water was briefly reviewed but important discrepancies were observed in the available data for Ce(iv). Therefore, new estimations of the hydrolysis constants of Ce(iv) and the solubility of Ce(iv)-(hydr)oxides are proposed, by analogy with Pu(iv). By plotting pH-Eh (Pourbaix) diagrams, we showed that the pH values corresponding to the onset of Ce(iv) species formation (i.e. Ce(iv)-(hydr)oxide or dissolved Ce(iv)) agreed with various experimental results. Although further experimental studies are required to obtain a more accurate thermodynamic database, the present work might yet help to predict more accurately the Ce chemical behavior in aqueous solution.Show less >
Show more >The prediction of cerium (Ce) aqueous speciation is relevant in many research fields. Indeed, Ce compounds are used for many industrial applications, which may require the control of Ce aqueous chemistry for their synthesis. The aquatic geochemistry of Ce is also of interest. Due to its growing industrial use and its release into the environment, Ce is now considered as an emerging contaminant. Cerium is also used as a proxy of (paleo)redox conditions due to the Ce(iv)/Ce(iii) redox transition. Finally, Ce(iv) is often presented as a relevant analogue of tetravalent actinides (An(iv)). In the present study, quantum chemical calculations were conducted to highlight the similarities between the structures of Ce(iv) and tetravalent actinide (An(iv); An = Th, Pa, U, Np, Pu) aqua-ions, especially Pu(iv). The current knowledge of An(iv) hydrolysis, solubility and colloid formation in water was briefly reviewed but important discrepancies were observed in the available data for Ce(iv). Therefore, new estimations of the hydrolysis constants of Ce(iv) and the solubility of Ce(iv)-(hydr)oxides are proposed, by analogy with Pu(iv). By plotting pH-Eh (Pourbaix) diagrams, we showed that the pH values corresponding to the onset of Ce(iv) species formation (i.e. Ce(iv)-(hydr)oxide or dissolved Ce(iv)) agreed with various experimental results. Although further experimental studies are required to obtain a more accurate thermodynamic database, the present work might yet help to predict more accurately the Ce chemical behavior in aqueous solution.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
ANR Project :
Source :
Files
- https://hal-insu.archives-ouvertes.fr/insu-01588240/document
- Open access
- Access the document
- https://hal-insu.archives-ouvertes.fr/insu-01588240/file/support-info-marsac-2017.pdf
- Open access
- Access the document
- https://hal-insu.archives-ouvertes.fr/insu-01588240/document
- Open access
- Access the document
- https://hal-insu.archives-ouvertes.fr/insu-01588240/document
- Open access
- Access the document
- document
- Open access
- Access the document
- marsac-2017.pdf
- Open access
- Access the document
- support-info-marsac-2017.pdf
- Open access
- Access the document
- document
- Open access
- Access the document
- marsac-2017.pdf
- Open access
- Access the document
- support-info-marsac-2017.pdf
- Open access
- Access the document
- document
- Open access
- Access the document
- marsac-2017.pdf
- Open access
- Access the document
- support-info-marsac-2017.pdf
- Open access
- Access the document