Structure and thermal expansion of sulfuric acid octahydrate

Synchrotron X‐ray powder diffraction has been used to structurally characterize crystallization products from 37.8 and 40.5 wt% aqueous sulfuric acid solutions. It is confirmed that, despite speculation in the literature, the structure that predominately crystallized from these solutions is sulfuric acid octahydrate (SAO). The existence of an uncharacterized phase is also noted. It was found that existing models proposed for the crystal structure of SAO did not satisfactorily fit to the data acquired here, and hence a new structure solution was sought. It is reported here that the structure of SAO is contained within a unit cell with I2 symmetry with a = 7.44247 (11), b = 7.4450 (1), c = 26.1168 (3) Å, β = 125.0428 (7)°, V = 1184.78 (3) Å3 at 80 K. Data were collected at temperatures between 80 and 198 K, which enabled determination of the thermal expansion of SAO.