Chemical speciation effects on the volumetric properties of aqueous sulfuric acid solutions

[Display omitted] •Behaviour of molar volume of H2SO4(aq) at low concentrations consistent with change in speciation.•Standard molar volume of HSO4−(aq) and volume change for protonation of SO42−(aq) at 293 ≤ T/K ≤ 343.•Volumetric database for H2SO4(aq) expanded considerably in the dilute range at 293 ≤ T/K ≤ 343. Densities of fifteen aqueous solutions of sulfuric acid (H2SO4) have been measured by vibrating-tube densimetry at solute molalities (m) from (0.01 to 3.0) mol·kg−1 over the temperature range 293.15 ≤ T/K ≤ 343.15. These data have been used to calculate the corresponding apparent molar volumes Vϕ(H2SO4,aq), which represent a significant expansion of the volumetric database for this industrially-important acid. At 298.15 K the present results agree well with literature data, notably with the century-old values given in the 1926 International Critical Tables. At other temperatures, where comparisons are possible agreement with the present Vϕ values is also very satisfactory. Consistent with earlier studies, Vϕ(H2SO4,aq) was found to exhibit an abnormally-large decrease at low concentrations (m ≤ 0.1 mol·kg−1). This effect is consistent with a change in the chemical speciation of H2SO4(aq), from an essentially 1:1 electrolyte (H+(aq) + HSO4− (aq)) at higher concentrations to a predominantly 1:2 electrolyte (2H+(aq) + SO42− (aq)) in dilute solutions. The Vϕ values were modelled using variants of Young’s rule and the Pitzer formalism. Combination of these results with literature values for the standard volume V°(SO42−,aq) enabled estimation of V°(HSO4−,aq) and the standard volume change, ΔrV°, for the first protonation of the sulfate ion (H+(aq) + SO42−(aq) → HSO4−(aq)) as functions of temperature. It is shown that V°(HSO4−,aq) is sensitive to the value of the first protonation constant and probably cannot be determined to better than ± 0.3 cm3·mol−1 at present.