On transport phenomena and equilibration time scales in thermodenuders

Abstract. This paper presents a theoretical and experimental investigation of thermodenuders that addresses two controversial issues: (1) equilibration time scales and (2) the need for an activated carbon (AC) denuder in the cooling section. We describe a plug flow model for transport phenomena in a TD, which can be used to simulate the rate of vapor build-up in the gas phase and the corresponding change in particle size distribution. Model simulations were found to have excellent agreement with experiments performed with pure and mixed dicarboxylic acid aerosols. Both simulations and experiments showed that the aerosols approached equilibrium within reasonable residence times (15 s–30 s) for aerosol concentrations and size distributions typical for laboratory measurements, and that volatility studies at sufficiently high aerosol loadings, therefore, need not resort to kinetic models for inference of thermodynamic properties. However, for size distributions relevant for ambient aerosols, equilibration time scales were much larger than residence times available with current TD designs. We have also performed dimensional analysis on the problem of equilibration in TDs, and derived a dimensionless equilibration parameter which can be used to determine the residence time needed for an aerosol of given size distribution and kinetic properties to approach equilibrium. It is also shown theoretically and empirically that aerosol volatility has no effect on the equilibration time scales. Model simulations and experiments showed that with aerosol size distributions relevant to both ambient and laboratory measurements re-condensation in the cooling section, with and without an AC denuder, was negligible. Thus, there is no significant benefit in using an AC denuder in the cooling section. Due to the risk of stripping volatile material from the aerosol, the use of AC denuders in the cooling section should be avoided. Finally, we present a rationale for why ΔC is the proper measure of volatility, while using mass fraction remaining (MFR) can be misleading.