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Adsorption of organics on surfaces is important in both outdoor and indoor environments. Surfaces can serve as sinks for gas-phase species, act as reservoirs by emitting previously partitioned organics back into the gas phase, and can facilitate heterogeneous chemistry. We report here studies of the uptake and desorption energetics of gas-phase limonene, a volatile and widely-distributed monoterpene, on solid silica nanoparticles using a unique apparatus that allows for temperature programmed desorption (TPD) measurements of surface binding energies as well as Knudsen cell gas uptake measurements. A multiphase kinetic model was applied to these data to provide additional molecular-level understanding of the processes involved. TPD experiments yielded an average desorption energy of 47.5 ± 8.2 kJ mol-1 (±1s, sample standard deviation), the first direct experimental measurement of this parameter over a broad temperature range (150–320 K). Initial net uptake coefficients (0,net) range from (1.7 ± 0.3) ×10-3 (±1s) at 210 K to (2.3 ± 0.4) ×10-4 (±1s) at 250 K, reflecting increased rates of desorption with an increase in temperature combined with increased rates of diffusion and re-adsorption within the pores between adjacent silica nanoparticles. Effective Langmuir constants, which also reflect the effects of pore diffusion and re-adsorption, were determined from the uptake data and vary from (1.8–0.3)×10-13 cm3 molecule-1 over the same temperature range. These results are in excellent agreement with previous studies around room temperature and with theoretical calculations of the energetics of the limonene-silica interaction. The strong attraction between limonene and the polar silica surface shows the importance of including such interactions in models of the atmospheric fates of terpenes both indoors and outdoors. 

Description: Mechanistic analysis of ion desorption from glutaric acid particles used in the development of surface-sensitive mass spectroscopy ionization methods. Abstract: Ionization via desorption of charged analytes from the surface of solid amorphous glutaric acid particles, without the assistance of an external energy source, has been shown to be a promising method that can be coupled to mass spectrometry. We conduct mechanistic studies of the later stages of this ionization process using atomistic molecular dynamics. Our analysis focuses on the hydrogen bonding, diffusion, and ion desorption from nano-aggregates of glutaric acid. These nano-aggregates exhibit an extended H-bonded network, often comprising H-bonded chains, linear dimeric assemblies, and occasionally cyclic trimeric assemblies. These local structures serve as centers for proton transfer reactions. The intermediate hydrocarbon chain between the proton-carrying oxygen sites prevents proton diffusion over a long distance unless there is significant translational or rotational movement of the proton-carrying diacid molecule. Our calculations show that diffusion on the surface is an order of magnitude faster than in the core of the nano-aggregate, which aids effective proton transfer on the particle's exterior. We find that ionic species desorb from the aggregate's surface through independent evaporation events of small clusters, where the ion is coordinated by only a few glutaric acid molecules. Near the nano-aggregate's Rayleigh limit, jets capable of releasing multiple ions were not observed. These observations suggest a more general ion-evaporation mechanism that applies to low-dielectric particles of various sizes, complementing the original ion-evaporation mechanism proposed for aqueous droplets with an approximate radius of 10–15 nm. The combined evidence from molecular modeling presented here and the thermodynamic properties of solid and supercooled liquid glutaric acid indicates that the stronger signals of glutaric acid observed in the mass spectra, relative to other experimentally tested diacids, can be attributed to its significantly lower melting point and the reduced enthalpy of vaporization of its amorphous state compared to other tested diacids.