Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents

Abstract

The absolute potential of the standard hydrogen electrode, SHE, was calculated on the basis of a thermodynamic cycle involving H(2(g)) atomization, ionization of H((g))* to H((g))(+), and hydration of H(+). The most up-to-date literature values on the free energies of these reactions have been selected and, when necessary, adjusted to the electron convention Fermi-Dirac statistics since both e(-) and H(+) are fermions. As a reference state for the electron, we have chosen the electron at 0 K, which is the one used in computational chemistry. Unlike almost all previous estimations of SHE, DeltaG(aq)(theta)(H(+)) was used instead of the real potential, alpha(aq)(H(+)). This choice was made to obtain a SHE value based on the chemical potential, which is the appropriate reference to be used in theoretical computations of standard reduction potentials. The result of this new estimation is a value of 4.281 V for the absolute potential of SHE. The problem of conversion of standard reduction potentials (SRPs) measured or estimated in water to the corresponding values in nonaqueous solvents has also been addressed. In fact, thermochemical cycles are often used to calculate SRPs in water versus SHE, and it is extremely important to have conversion factors enabling estimation of SRPs in nonaqueous solvents. A general equation relating E(theta) of a generic redox couple in water versus the SHE to the value of E(theta) in an organic solvent versus the aqueous saturated calomel electrode is reported.