Quasi-Chemical Theory and the Standard Free Energy of H+(aq)

Quasi-chemical theory and electronic structure results on inner-sphere H(H 2 O) n + clusters are used to discuss the absolute hydration free energy of H + (aq). It is noted that this quantity is not thermodynamically measurable, and this leads to some relative misalignment of available tables of absolute hydration free energies of ions in water. The simplest quasi-chemical model produces a reasonable quantitative result in the range of −256 to −251 kcal/mol. The primitive concepts on which the model is based naturally identify the Zundel cation H 5 O 2 + as the principal chemical structure contributing to this hydration free energy. The specific participation of an Eigen cation H 9 O 4 + is not required in this model because the definition of that structure depends on outer-sphere arrangements, and a crude dielectric continuum model is here used for outer-sphere contributions.