Room-temperature ionic liquids (ILs)
are a class of nonaqueous
solvents that have expanded the realm of modern chemistry, drawing
increasing interest over the last few decades, not only in terms of
their own unique physical chemistry but also in many applications
including organic synthesis, electrochemistry, and biological systems,
wherein charged solutes (i.e., electrolytes) often play vital roles.
However, our fundamental understanding of the dissolution of an electrolyte
in an IL is still rather limited. For example, the activity of a charged
species has frequently been assumed to be unity without a clear experimental
basis. In this study, we have discussed a standard component-based
scheme for the dissolution of an electrolyte in an IL, supported by
our observation of ideal Nernstian responses for the reduction of
silver and ferrocenium salts in a representative IL, 1-ethyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide ([emim
+
][NTf
2
–
] or [emim
+
][TFSI
–
]). Using this scheme, which was also supported by temperature-dependent
measurements with ILs having longer alkyl chains in the imidazolium
ring, and the solubility of the IL in water, we established the concept
of Gibbs transfer energies of “pseudo-single ions” from
the IL to conventional neutral molecular solvents (water, acetonitrile,
and methanol). This concept, which bridges component- and constituent-based
energetics, utilizes an extrathermodynamic assumption, which itself
was justified by experimental observations. These energies enable
us to eliminate inner potential differences between the IL and molecular
solvents (solvent–solvent interactions), that is, on a practical
level, conditional liquid junction potential differences, so that
we can discuss ion–solvent interactions independently. Specifically,
we have examined the standard electrode potential of the ferrocenium/ferrocene
redox couple, Fc
+
/Fc, and the absolute intrinsic standard
chemical potential of a proton in [emim
+
][NTf
2
–
], finding that the proton is more acidic in the
IL than in water by 6.5 ± 0.6 units on the unified pH scale.
These results strengthen the progress on the physical chemistry of
ions in IL solvent systems on the basis of their activities, providing
a rigorous thermodynamic framework.