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Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals.

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Title: Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals.
Author: Bertram, Allan K.; Gross, Simone
Issue Date: 2009-01
Publicly Available in cIRcle 2011-04-15
Publisher American Geophysical Union
Citation: Gross, Simone, Bertram, Allan K. 2009. Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals. Journal of Geophysical Research Atmospheres 114(D2) D02307/1-D02307/14 dx.doi.org/10.1029/2008JD010987.
Abstract: The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO3 radicals (in the presence of NO2 and O2) were studied. For the alkane monolayer, IR spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO2). The observation of organonitrates is in contrast to the recent XPS data, which showed very little nitrogen-contg. surface species. The identification of organonitrates may help explain why significant volatilization of the org. chain was not obsd. in recent studies of alkane monolayer oxidn. by NO3 radicals. The reactive uptake coeff. (gamma ) of NO3 on alkene monolayers detd. in our study is higher than the values obtained in a recent study using liq. and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the gamma value detd. in our studies, we show that under conditions where NO3 is high the lifetime of an alkene monolayer in the atm. may be short (approx. 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidn. of the alkene monolayers by NO3. The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen contg. species. An edited version of this paper was published by AGU. Copyright 2009 American Geophysical Union.
Affiliation: Chemistry, Dept of
URI: http://hdl.handle.net/2429/33685
Peer Review Status: Reviewed
Scholarly Level: Faculty

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