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MME BILLARD Isabelle

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My main topic is : "Solution chemistry in Ionic Liquids (ILs) in view of metal recycling by liquid/liquid extraction and/or electrochemistry".
I am mostly experienced and interested in the understanding and modeling of solution chemistry data:

1) Deriving equilibrium constants for successive complexations in aqueous solutions or in ILs.  Cl-, NO3-, ReO4-, ClO4- and others inorganic ligands are known to be weak ligands of metallic cations (U(VI), Co(II), Cu(II), Au(III) etc. ) in water. Therefore, deriving their successive equilibrium constants  is a rather difficult task because one needs very high ligand concentrations to reach the 1:2, 1:3 or 1:4 complexes, which may be impossible due to solubility limits. In addition to this practical problem, one should consider the ionic strength effects in such higly concentrated solutions, which is a very difficult theoretical problem. By contrast, in ILs based on the Tf2N- anion (CF3(SO2)2N-), all these "weak" ligands appear to be rather strong actually: ILs induce a levelling of complexing abilities to high values. Furthermore, in ILs, one may consider that the global ionic strength is constant. ILs may thus be considered as ideal solvents to study limiting metallic complexes that could never be observed in water.
Experimental studies currently under progress concern d-metals, PGM and a variety of "weak" ligands (as such in water).
 
2) Modelling of extraction of metallic ions from acidic aqueous solutions towards IL phases, either containing an organic ligand or not. The solvation properties of ILs are dramatically different from those encountered in molecular solvents. Thus extraction mechanism and rules for synergism (using two ligands in conjunction enhances extraction as compared to any of the two ligands individually) are very different in ILs. As for extraction, ion exchange is a rather common mechanism, while only neutral species are extracted towards molecular solvents. Synergism is known to be rather efficient using an acidic ligand together with a neutral one in molecular diluents, while this association is not very effective in ILs.
 
3) Electrochemistry for metal recovery. The aim is to take advantage of the accumulated knowledge on metallic ion solution chemistry in ILs to derive the best ILs and chemical conditions (ligands etc.) to get metallic deposits of various metals (d-metals, PGM, rare earths) that are of recycling interest. This should be easy in ILs, owing to their large electrochemical window (up to 6 V) but the high viscosity of ILs, and thus, low diffusion of ions, are drawbacks. Furthermore, on a practical point of view, stable and reliable reference électrodes are not easy to implement in such media. We are now able to cope with these problems and we have now started electrodeposition experiments with some success.  

Activités / CV

From 1990 until 2014, I was working in Strasbourg, being a radiochemist. I first worked in fundamental nuclear physics (positronium chemistry under a magnetic field, until 1993) then I  studied actinide laser-induced fluorescence in aqueous solutions at very high ionic strength (up to 12 M of acid) and finally  turned to actinide and lanthanide solution chemistry in Ionic Liquids (ILs, from 2001 onwards). I recently moved to Grenoble, and joined the LEPMI lab  in oct. 2014.
 I am now studying solution chemistry of (non radioactive) metallic ions (lanthanides and d-metals, mostly PGM) in Ionic Liquids in terms of solvation, complexation and liquid/liquid extraction, the final goal being the recycling of these metallic elements by use of ILs, either by liquid/liquid extraction and/or electrodeposition from IL phases.
Although studies on actinides are now over, my competences in Ln solution chemistry are still of interest to my new activities and I am still collaborating with radiochemical groups (Germany, India).  

keywords: Ionic liquids; solution chemistry, metallic ions; liquid/liquid extraction

Publications (peer review): 79; Book chapters: 5


Some recent papers: 

 Maguy Nahra, Eric Chainet, Lenka Svecova, Laure Cointeaux, Isabelle Billard

Reliability of Arrhenius and several VTF laws to describe the effect of TaF5 addition onto the transport properties of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, Fluid Phase Equilibria, 415(2016)101
 

Nicolas Papaiconomou, Lenka Svecova, Céline Bonnaud, Loïc Cathelin, Isabelle Billard, Eric Chainet,

Possibilities and limitations in separating Pt(IV) from Pd(II) combining imidazolium and phosphonium ionic liquids, Dalton Trans,44(2015)20131.

 

Maria Atanassova, Valérie Mazan, Isabelle Billard

Modulating ILs’ components solubilities in aqueous-ionic liquid biphasic systems: a Q-NMR investigation

Chem. Phys. Chem. 16(2015)1703 
 

S.A. Ansari, P. K. Mohapatra V. Mazan, I. Billard,

Extraction of actinides by tertiary amines in room temperature ionic liquids: evidence for anion exchange as a major process at high acidity and impact of acid nature

RSC Adv., 5(2015)35821-35829 
 

Clotilde Gaillard, Maria Boltoeva, Isabelle Billard, Sylvia Georg, Valerie Mazan, Ali Ouadi, Daria Ternova, Christoph Hennig,

New insights in the extraction mechanism of uranium(VI) by TBP from nitric acid solution into ionic liquid, ChemPhysChem, 16(2015)2653.  
 
 

Maria Atanassova, Vanya Kurteva, Lubomir Lubenov, Sabi Varbanov, Isabelle Billard

Are fancy acidic or neutral ligands really needed for synergism in ionic liquids ? A comparative study of lanthanoid extraction in CHCl3 and an ionic liquid.

New J. Chem. 39(2015)7932. 
 

Nicolas Papaiconomou, Lenka Svecova, Céline Bonnaud, Loïc Cathelin, Isabelle Billard, Eric Chainet,

Possibilities and limitations in separating Pt(IV) from Pd(II) combining imidazolium and phosphonium ionic liquids, Dalton Trans,44(2015)20131




 
 




 



 

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Rédigé par Isabelle Billard

mise à jour le 14 mars 2017

Communauté Université Grenoble Alpes
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