New infrared spectra of pure bulk molecular sulfuric acid and its mono- and
tetrahydrates under equilibrium water partial pressure conditions have bee
n obtained using an internal reflection geometry. For each of the species p
resent (H2SO4, HSO4- and SO42-), a well-defined set of core SO4 vibrations
has been identified and assigned to individual vibrational modes. Using the
se data, earlier literature data has been reexamined. Existing methods for
the quantification of composition and ion speciation in H2SO4/H2O mixtures
are examined and the need for a more sophisticated method for the determina
tion of sulfate aerosol composition is proposed.