PEO−[M(CN)5NO]x- (M = Fe, Mn, or Cr) Interaction as a Driving Force in the Partitioning of the Pentacyanonitrosylmetallate Anion in ATPS: Strong Effect of the Central Atom

Abstract

The partitioning behavior of pentacyanonitrosilmetallate complexes[Fe(CN) 5 NO] (2-), [Mn(CN) 5 NO] 3(-), and [Cr(CN) 5 NO] 3(-)has been studied in aqueous two-phase systems (ATPS) formed by adding poly(ethylene oxide) (PEO; 4000 g mol (-1)) to an aqueous salt solution (Li2 SO4, Na2 SO4, CuSO4, or ZnSO4). The complexes partition coefficients ( K complex) in each of these ATPS have been determined as a function of increasing tie-line length (TLL) and temperature. Unlike the partition behavior of most ions, [Fe(CN) 5 NO] 2(-) and [Mn(CN) 5 NO] 3(-) anions are concentrated in the polymer-rich phase with K values depending on the nature of the central atom as follows: K [Fe(C N) 5 NO] 2 - >> K [ Mn (CN 5 NO] 3 - > K [C r (C N) 5 NO ]3 - . The effect of ATPS salts in the complex partitioning behavior has also been verified following the order Li2 SO 4 > Na2 SO 4 > ZnSO4. Thermodynamic analysis revealed that the presence of anions in the polymer-rich phase is caused by an EO-[M(CN) 5 NO] ( x- ) (M = Fe, Mn, or Cr) enthalpic interaction. However, when this enthalpic interaction is weak, as in the case of the [Cr(CN) 5 NO]3(-) anion ( K [Cr(CN 5 NO] 3 - < 1), entropic driving forces dominate the transfer process, then causing the anions to concentrate in the salt-rich phase.