Density functional calculations have been performed on several protonation states of the oxyacids of Si, P, V, As, Cr, and S. Structures and vibrational frequencies are in good agreement with experimental values where these are available. A reasonably well-defined correlation between the calculated gas-phase acidities and the measured pK(a) in aqueous solution has been found. The pK(a)/gas-phase acidity slopes are consistent with those derived from previous molecular mechanics calculations on ferric hydrolysis and the first two acidity constants for orthosilicic acid. The successive deprotonation of other HnTO4 species, for a given tetrahedral anion T are roughly consistent with this slope, but not to the extent that there is a universal correlation among all species.