Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity

Abstract

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H2O2 irradiations. The average gas to wall loss rate constant (kgw) of OVOCs in a 400 L reactor (S/V = 7.5 m−1) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m−1) under dry conditions. In contrast, the average desorption rate constant (kwg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on kgw is not prominent. The average kgw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average kwg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.