The search for more environmentally-friendly reaction media has prompted th
e development of a wide array of alternative systems that will sustain biph
asic separations with aqueous solutions without the use of volatile organic
compounds (VOCs). We have begun to employ Room Temperature Ionic Liquids (
RTIL), specifically 1-alkyl-3-methylimidazolium hexafluorophosphate ([C(n)m
im][PF6]), as VOC replacements in liquid/liquid separations of metal ions f
rom aqueous solutions. Here we show that the partitioning of metal ions in
these novel biphasic systems is consistent with traditional liquid/liquid s
eparations: the metal ion affinity for the hydrophobic phase necessitates t
he presence of an extractant. In this report we explore the application of
well-known organic (1-(pyridylazo)-2-napthol, PAN, and (1-thiazolylazo)-2-n
apthol, TAN) and inorganic (CN-, OCN-, SCN-, and halides) extractants for p
artitioning a variety of metal cations between [C(4)mim][PF6] or [C(6)mim][
PF6] and an aqueous phase. PAN and TAN show pH dependent extraction of Cd2, Co2+ Ni2+, and Fe3+ where their partitioning to the RTIL increases at lea
st 2 orders of magnitude from pH 1 to 13. The effect of the halides on the
partitioning of Hg2+ complexes increases F- < Cl- < Br- < I-. Pseudohalides
, especially SCN-, had the greatest effect on enhancing the partitioning of
Hg2+ to the RTIL, whereas CN- and OCN- provided little benefit for the ext
raction of any of the metal ions examined.