Co-extraction of Iron and Sulfate by Bis(2,4,4-trimethylpentyl)phosphinic Acid, CYANEX®272

The mode of action of iron(III) uptake from sulfate solutions by the commercial extractant CYANEX®272, bis(2,4,4-trimethylpentyl)phosphinic acid, has been studied using conventional solvent extraction methods, together with 31P{1 H} NMR spectroscopy, electrospray ionisation mass spectrometry, and DFT calculations that have not previously been used to analyse the content of the ISOPAR M water-immiscible phase. The maximum Fe-loading recorded was 177% of the theoretical maximum, based on the formation of an Fe(III) complex [Fe(L)3] with a 1:3 molar ratio of Fe to phosphinate (L). Inductively coupled plasma optical emission spectroscopy (ICP-OES) indicates that sulfate or hydrogen sulfate ions are co-extracted in a 1:2 molar ratio with iron across the whole of the Fe-loading range, which helps to account for the loadings being greater than 100% of the theoretical value. 31P{1 H} NMR spectroscopy indicates that the limiting factor in Fe-loading is the availability of uncomplexed CYANEX®272 (sulfate is present in large excess). In contrast to the behaviour of Co(II) and Zn(II) extraction by CYANEX®272, there is no evidence for the formation of polymeric Fe(III) complexes and highly viscous solutions at high metal loadings. The identity of the extracted species is likely to be a polynuclear Fe(III) sulfate complex.