Solid vapor pressure for five heavy PAHs via the Knudsen effusion method

Highlights: → We report on vapor pressures and enthalpies of fusion and sublimation of five heavy PAHs. → Solid vapor pressures were measured using Knudsen effusion method. → Solid vapor pressures for benzo[b]fluoranthene, and indeno[1,2,3-cd]pyrene have not been published in the open literature. → Reported subcooled liquid state vapor pressures may or may not lend themselves to correction to sublimation vapor pressure. → Subcooled liquid state vapor pressures might sometimes actually be closer to actual solid state sublimation vapor pressures. - Abstract: Polycyclic aromatic hydrocarbons (PAHs) are compounds resulting from incomplete combustion and many fuel processing operations, and they are commonly found as subsurface environmental contaminants at sites of former manufactured gas plants. Knowledge of their vapor pressures is the key to predict their fate and transport in the environment. The present study involves five heavy PAHs, i.e. benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and dibenz[a,h]anthracene, which are all as priority pollutants classified by the US EPA. The vapor pressures of these heavy PAHs were measured by using Knudsen effusion method over the temperature range of (364 to 454) K. The corresponding values of the enthalpy of sublimation were calculated from the Clausius-Clapeyron equation. The enthalpy of fusion for the five PAHs was also measured by using differential scanning calorimetry and used to convert earlier published sub-cooled liquid vapor pressure data to solid vapor pressure in order to compare with the present results. These adjusted values do not agree with the present measured actual solid vapor pressure values for these PAHs, but there is good agreement between present results and other earlier published sublimation data.