Thermodynamics And Kinetics Of The Hydrolysis Of Atmospherically Relevant Organonitrates And Organosulfates

Title:
Thermodynamics And Kinetics Of The Hydrolysis Of Atmospherically Relevant Organonitrates And Organosulfates
Authors:
Hu, K. S.; Darer, Adam I.; Elrod, Matthew J.
Abstract:
The presence of alcohol, organonitrate, and organosulfate species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA) has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has suggested that certain isoprene-derived organonitrates are able to efficiently convert to organosulfates and alcohols on ambient SOA. In order to better understand the structure activity relationships previously observed for the isoprene-derived organonitrates and organosulfates, the hydrolysis reactions of a number of monofunctional and difunctional organonitrates and organosulfates with varying carbon substitution properties were investigated. Nuclear magnetic resonance techniques were used to study the bulk phase aqueous reactions of these organonitrates and organosulfates in order to determine hydrolysis reaction rate and, in some cases, thermodynamics information. Electronic structure calculations were also carried out to determine the enthalpy of hydrolysis for these species, and for the previously studied isoprene-derived species. The results suggest that while organonitrates and organosulfates are thermodynamically unstable with respect to the corresponding alcohols at standard state, only the tertiary organonitrates (and perhaps some tertiary organosulfates) are able to efficiently hydrolyze on SOA timescales and acidities.
Citation:
Hu, K. S., A. I. Darer, and M. J. Elrod. 2011. "Thermodynamics And Kinetics Of The Hydrolysis Of Atmospherically Relevant Organonitrates And Organosulfates." Atmospheric Chemistry And Physics 11(16): 8307-8320.
Publisher:
Copernicus Publications
DATE ISSUED:
2011
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.5194/acp-11-8307-2011
PERMANENT LINK:
http://hdl.handle.net/11282/310105

Full metadata record

DC FieldValue Language
dc.contributor.authorHu, K. S.en_US
dc.contributor.authorDarer, Adam I.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.date.accessioned2013-12-23T16:25:26Zen
dc.date.available2013-12-23T16:25:26Zen
dc.date.issued2011en
dc.identifier.citationHu, K. S., A. I. Darer, and M. J. Elrod. 2011. "Thermodynamics And Kinetics Of The Hydrolysis Of Atmospherically Relevant Organonitrates And Organosulfates." Atmospheric Chemistry And Physics 11(16): 8307-8320.en_US
dc.identifier.issn1680-7316en_US
dc.identifier.urihttp://hdl.handle.net/11282/310105en
dc.description.abstractThe presence of alcohol, organonitrate, and organosulfate species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA) has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has suggested that certain isoprene-derived organonitrates are able to efficiently convert to organosulfates and alcohols on ambient SOA. In order to better understand the structure activity relationships previously observed for the isoprene-derived organonitrates and organosulfates, the hydrolysis reactions of a number of monofunctional and difunctional organonitrates and organosulfates with varying carbon substitution properties were investigated. Nuclear magnetic resonance techniques were used to study the bulk phase aqueous reactions of these organonitrates and organosulfates in order to determine hydrolysis reaction rate and, in some cases, thermodynamics information. Electronic structure calculations were also carried out to determine the enthalpy of hydrolysis for these species, and for the previously studied isoprene-derived species. The results suggest that while organonitrates and organosulfates are thermodynamically unstable with respect to the corresponding alcohols at standard state, only the tertiary organonitrates (and perhaps some tertiary organosulfates) are able to efficiently hydrolyze on SOA timescales and acidities.en_US
dc.publisherCopernicus Publicationsen_US
dc.identifier.doi10.5194/acp-11-8307-2011en
dc.subject.departmentChemistryen_US
dc.titleThermodynamics And Kinetics Of The Hydrolysis Of Atmospherically Relevant Organonitrates And Organosulfatesen_US
dc.typearticleen_US
dc.identifier.journalAtmospheric Chemistry And Physicsen_US
dc.subject.keywordSecondary organic aerosolen_US
dc.subject.keywordSubstituted ethylene oxidesen_US
dc.subject.keywordParticle acidityen_US
dc.subject.keywordAmbient aerosolen_US
dc.subject.keywordPhotooxidationen_US
dc.subject.keywordOrganosulfatesen_US
dc.subject.keywordOzonolysisen_US
dc.subject.keywordOxidationen_US
dc.identifier.volume11en_US
dc.identifier.issue16en_US
dc.identifier.startpage8307en_US
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