Electrolytic nature of aqueous sulfuric acid. 1. Activity

According to the literature, when H(2)SO(4) dissolves in water, (1) it retains its molecular formula and tetrahedral structure of two O atoms and two OH groups bonded to a central S atom, and (2) it ionizes partially, as a 1-1 electrolyte, to H(+) (H(3)O(+)) and HSO(4)(-); the latter ion further dissociates at low concentrations (<0.1 M) to H(+) and SO(4)(2-). Using the Debye-Hückel (DH) limiting law at very low concentration, and the smaller-ion shell (SiS) model of strong electrolyte solutions-an extension of the DH model for ion size dissimilarity-up to moderate concentration, I examine the theory-experiment fit of the mean ionic activity coefficient (γ(±)) of the acid as a function of concentration (at 0 to ∼6 m) and of temperature (at 0-60 °C). The fit is impossible if H(2)SO(4) in water is assumed to be a 1-1 or 1-2 electrolyte, but is excellent when the acid is treated instead as a strong 1-3 electrolyte; that is, aqueous sulfuric acid behaves as a fully dissociated H(3)A acid. At 25 °C, the SiS best fit is achieved with the H(+) diameter being 1.16 Å (as obtained for strong mineral 1-1 protonic acids) and with the A(3-) ionic diameter being 5.77 Å. On the basis of the present study, H(2)SO(4) in water may be H(4)SO(5) (dubbed "sulfoxuric", or parasulfuric acid) completely ionized to 3H(+) and the ("bisulfoxate", or parabisulfate) anion HSO(5)(3-). The calculated standard potential of a newly proposed half-cell reaction, H(2) + HSO(5)(3-) ↔ H(+) + SO(4)(2-) + H(2)O + 2e(-), at 25 °C, is -1.0933 V.