Sr(ii) extraction by crown ether in HFC: entropy driven mechanism through H2PFTOUD

Abstract

The solvent extraction of Sr(II) was carried out using dicyclohexano-18-crown-6 (DCH18C6) and two HFC mixed solvents MS1 and MS2, where MS1 was composed of 30/60 (w/w)% trans-1,2-dichloroethylene/HFC-43 (HFC-43: 1,1,1,2,2,3,4,5,5,5-decafluoropentane) and MS2 was 5/95 (w/w)% heptane/HFC-43. Nitric acid and perfuruoro-3-6-9-trioxaundecane-1,11-dioic acid (H₂PFTOUD) were used to study the effect of acid on the extraction. The maximum distribution ratio of Sr(II) (D_Sr) observed for H₂PFTOUD conditions was ∼180, and >10 times larger than aqueous nitric acid conditions. The D_Sr value was influenced by concentrations of the DCH18C6, Sr(II), and acid, and by temperature. The composition of extracted complexes was estimated using slope analysis as an Sr(II)–anion–DCH18C6 ratio of ∼1 : 2 : 1. From the extended X-ray absorption fine structure (EXAFS) measurements of Sr(II) in the aqueous and organic phases, it is inferred that regardless of the acid used, DCH18C6 coordinates to the first coordination sphere of the Sr(II) extracted complexes and Sr(II) is hydrated (complexation with H₂PFTOUD cannot be distinguished) in the aqueous phase. Thermodynamic data were significantly changed by choice of acid, i.e., both enthalpy and entropy values were negative for nitric acid conditions, on the other hand, entropy values were large and positive for H₂PFTOUD conditions. These results have demonstrated that the combination of HFC solvent and crown ether is applicable for metal extraction.