Acid-Catalyzed Oligomerization at the Air–Water Interface Modified by Competitive Adsorption of Surfactants

Abstract

Amphiphilic organic compounds that accumulate naturally on the outermost layers of aqueous aerosols totally change the mechanisms involved in the uptake and reactions of volatile organic compounds adsorbed on the surfaces. By means of mass spectrometry of aqueous microjets, we examined how quaternary alkylammonium cations Me(CH2)n−1N+Me3 (n = 1, 4, 8, 10, 12, and 14) and nonionic octan-1-ol influence acid-catalyzed oligomerization of gaseous isoprene (ISO) at the air–water interface. The oligomerization is initiated by proton-transfer (PT) reaction from an interfacial hydronium ion to isoprene to form a (ISO)H+ and is subsequently followed by chain-propagation (CP) reaction to form (ISO)m≥2H+. We found that although the total mass spectral signals of (ISO)mH+ products were suppressed by the presence of either the alkylammonium cations or octan-1-ol, the suppression by the former surfactants was much larger than that of the latter. The suppression was observed even at aqueous microjets of 5 μM equimolar solution of the alkylammonium cations at which the air–water interface is only sparsely occupied by the alkylammonium cations. We propose that electrostatic repulsions between the alkylammonium cation and the interfacial H3O+ cause the hindrance of the PT reaction. In contrast, the subsequent CP reactions were not suppressed by the presence of either the alkylammonium cations or octan-1-ol. We suggest that the presence of long-chain organic surfactants hinders the initial PT reaction but hardly suppresses the subsequent CP reaction. Our study has revealed hitherto unrecognized interface-specific roles of surfactants that affect multiphase chemistry in the atmosphere.