Vapor pressure of SeO2 (s) and optical density of SeO2 (g)

The optical density of the vapor generated by SeO₂ (s) between about 416 and 505 K has been measured between 400 and 200 nm for optical path lengths of 10.14 and 10.15 cm and temperatures of 533, 733, 1133, and 1420 K. A pressure of oxygen of about 0.7 to 0.9 atm was present in the cells and that of Se₂ was below the minimum detectable of about 0.001 atm. For one cell, complete vaporization occurred at 481.5 K and a vapor pressure of 5.02 × 10⁻³ atm was calculated from the weight of SeO₂ (s), the volume profile of the optical cell, and the temperature distribution along the cell. Assuming Beer’s law is obeyed for a number of vibronic peaks, the vapor pressure is obtained as log₁₀ P (atm)=−5705/T+9.5443 in close agreement with two studies with fused silica Bourdon gauges. Beer’s law constants relating the pressure to the optical density at various wavelengths are obtained for the optical path temperatures listed above. Thermodynamic data previously published for solid and liquid SeO₂ need be changed only slightly to be consistent with the present vapor pressure. We obtain a standard enthalpy of sublimation at 298 K of 112.70 kJ/mol and standard entropies at 298 K of 258.72 and 66.693 J · mol⁻¹ · K⁻¹ for, respectively, gaseous and solid SeO₂.