Abstract / Description of output
Combining computational modelling with experimental measurements has revealed the self-assembly of nano-aggregate structures in the transfer of HCl and PtCl62- from an aqueous phase into toluene by the common industrial extractant tri-butyl phosphate (TBP). Molecular dynamics simulations have been coupled to analytical measurements to provide an atomistic interpretation of the mode of action of TBP under 6 M and 10 M HCl conditions. The structures conform to reverse micelles, where the Cl- or PtCl62- core is encapsulated by a hydration shell that acts as a mediating bridge to the electronegative oxygen atom in the TBP phosphate groups. For the 6 M HCl extraction model, the data support stable aggregates forming from 2-3 TBP molecules around one chloride anion if the number of water molecules encapsulating the chloride anion is no more than five; increasing the water content to ten molecules allows a fourth TBP molecule to coordinate. For the 10 M HCl extraction model, stable structures are obtained that conform to the empirical formula (TBP.HCl.H2O)3-5. At 6 M HCl, extraction of PtCl62- is achieved by encapsulation by four TBP molecules; the data for extraction at 10 M HCl indicate larger aggregates containing multiple PtCl62- anions are likely to be forming. In all cases, the hydrated core regions of the reverse micelles are considerably exposed. The diameters of the self-assembled structures around chloride ions agree well with available literature data from small angle neutron scattering experiments.