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Published December 20, 2007 | Supplemental Material
Journal Article Open

Electrospray Mass Spectrometric Detection of Products and Short-Lived Intermediates in Aqueous Aerosol Microdroplets Exposed to a Reactive Gas

Abstract

The intermediates ISO_3^- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (NaI/Na_2S2O_3) microdroplets traversing dilute O_3 gas plumes are detected via online electrospray mass spectrometry within ∼1 ms, and their stabilities gauged by collisionally induced dissociation. The simultaneous detection of anionic reactants and the S_2O_6^(2-), HSO_4^-, IO_3^-, and I_3^- products as a function of experimental conditions provides evidence of genuinely interfacial reaction kinetics. Although O_3(aq) reacts about 3 times faster with I- than with S_2O_3^(2-) in bulk solution, only S_2O_3^(2-) is significantly depleted in the interfacial layers of [I^-]/[S_2O_3^(2-)] = 10 microdroplets below [O_3(g)] ∼ 50 ppm.

Additional Information

© 2007 American Chemical Society. Received: July 13, 2007; In Final Form: September 26, 2007. This work was financially supported by the National Science Foundation grant ATM-0534990. We thank Nathan F. Dalleska for valuable advice on ESMS, and Mike Vondrus for assistance in setting up the ozone injector. S.E. is grateful to Prof. M. Kawasaki (Kyoto University), Prof. Y. Matsumi (Nagoya University), and the JSPS Research Fellowship for Young Scientists.

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