Abstract

Densities of aqueous solutions of sulfuric acid (H₂SO₄) have been measured by vibrating tube densimetry at molalities m varying from 0.02 to 3.0 mol·kg⁻¹, at temperatures over the range 323.15 ≤ T/K ≤ 523.15 at 10 MPa pressure. These results were used to calculate the corresponding apparent molar volumes V_ϕ(H₂SO₄,aq) and appear to be the first-ever systematic study of the volumetric properties of this important acid at elevated temperatures. At T ≤ 373.15 K, the present results aligned well with recent literature data and with values reported in the 1926 International Critical Tables. No reliable experimental data were found for comparison at higher temperatures. The present results confirm that at lower concentrations and temperatures, sulfuric acid solutions exist as a variable mixture of H⁺(aq) + HSO₄⁻(aq) + SO₄²⁻(aq). However, at higher temperatures, the degree of association increases markedly such that at T ≥ 448.15 K, sulfuric acid solutions behave like a simple 1:1 electrolyte [H⁺(aq) + HSO₄⁻(aq)] even at low concentrations. The variation of V_ϕ(H₂SO₄,aq) over the entire experimental region was well modelled using a simple Pitzer equation that specifically included (where appropriate) the effects of chemical speciation. Combination of this model with relevant literature data enabled estimation of the standard ionic volume V°(HSO₄⁻,aq) and the standard volume change Δ_rV° for the reaction H+(aq) + SO₄²⁻(aq) → HSO₄⁻(aq) at temperatures up to 523 K.