Distinct Temperature Trends in the Uptake of Gaseous n-Butylamine on Two Solid Diacids

Abstract

Uptake coefficients of n-butylamine (BA) on solid succinic (SA) and glutaric acids (GA) from 298 to 177 K were measured using a newly combined Knudsen cell temperature-programmed desorption apparatus. The uptake coefficients on SA increase monotonically from (1.9 ± 0.5) × 10 −4 at 298 K to 0.14 ± 0.05 at 177 K (errors represent 2σ statistical errors, overall errors are estimated to be ±60%). This is consistent with a surface reaction mechanism to form solid aminium carboxylate. In contrast, the uptake coefficients on GA increase from 0.11 ± 0.04 at 298 K to 0.25 ± 0.04 at 248 K but then decrease to 0.030 ± 0.010 at 177 K. This unusual trend in temperature dependence of the uptake coefficient is due to formation of an ionic liquid (IL) layer upon the surface reaction of BA with GA, leading to a competition between the rate of desorption of BA and the rates of diffusion and reaction within the IL. Overall, the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) satisfactorily reproduces these unique trends. This work provides mechanistic insight and predictive capability for the temperature-dependence of reactive uptake processes involving multiple phase changes upon surface reaction.