Ions can be transferred between immiscible liquid phases across
a common interface, with the help of a three-electrode potentiostat,
when one phase is an organic droplet attached to a solid
electrode and containing a redox probe. This novel approach has
been used in studies to determine the Gibbs energy of anion and
cation transfer, ranging from simple inorganic and organic ions
to the ionic forms of drugs and small peptides. This method of
studying ion transfer has the following advantages: 1) no base
electrolytes are necessary in the organic phase; 2) the aqueous
phase contains only the salt to be studied; 3) a three-electrode
potentiostat is used; 4) organic solvents such as n-octanol and
chiral liquids such as d- and l-2-octanol can be used; 5) the
range of accessible Gibbs energies of transfer is wider than in the
classic 4-electrode experiments; 6) the volume of the organic
phase can be very small, for example, 1 mL or less; 7) the experiments
can be performed routinely and fast. Herein, the basic
principle is outlined, as well as a summary of the results obtained
to date, and a discussion on the theoretical treatments concerning
the kinetic regime of the three-phase electrodes with immobilized
droplets
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