Product identification and kinetics of reactions of HCl with HNO3/H2SO4/H2O solutions

Title:
Product identification and kinetics of reactions of HCl with HNO3/H2SO4/H2O solutions
Authors:
Cappa, Christopher D.; Kuipers, Sarah E.; Roberts, Jeanine M.; Gilbert, Abigail S.; Elrod, Matthew J.
Abstract:
The gas-phase products of the reaction between HNO3/H2SO4/H2O acid solutions and HCl were identified using IR and UV−Vis spectroscopy and chemical ionization mass spectrometry. The major products of the reaction were Cl2 and ClNO, with quantifiable amounts of ClNO2 sometimes present. On the basis of quantitative product yield determinations, the overall proposed reaction is 3HCl + HNO3 → Cl2 + ClNO + 2H2O. Kinetic studies were also performed and the reaction was found to follow a second-order rate law:  Rate = k[HCl][HNO3]. On the basis of the products and intermediates observed and the rate law, a mechanism is proposed which involves the NO2+ ion as the key reactive species. The rate of the reaction is shown to depend strongly on the total acid concentration of the solution and temperature-dependent studies were also performed. The potential significance of this reaction in connection to stratospheric ozone depletion is evaluated by using the composition and temperature dependence of the rate to estimate the chlorine activation rate at polar stratospheric conditions.
Citation:
Cappa, C.D., S.E. Kuipers, J.M. Roberts, A.S. Gilbert, and M.J. Elrod. 2000. "Product Identification and Kinetics of Reactions of HCl with HNO3/H2SO4/H2O Solutions." Journal of Physical Chemistry A 104(19): 4449-4457.
Publisher:
American Chemical Society
DATE ISSUED:
2000-05-18
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/jp992666p
PERMANENT LINK:
http://hdl.handle.net/11282/309794

Full metadata record

DC FieldValue Language
dc.contributor.authorCappa, Christopher D.en_US
dc.contributor.authorKuipers, Sarah E.en_US
dc.contributor.authorRoberts, Jeanine M.en_US
dc.contributor.authorGilbert, Abigail S.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.date.accessioned2013-12-23T16:18:00Zen
dc.date.available2013-12-23T16:18:00Zen
dc.date.issued2000-05-18en
dc.identifier.citationCappa, C.D., S.E. Kuipers, J.M. Roberts, A.S. Gilbert, and M.J. Elrod. 2000. "Product Identification and Kinetics of Reactions of HCl with HNO3/H2SO4/H2O Solutions." Journal of Physical Chemistry A 104(19): 4449-4457.en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/11282/309794en
dc.description.abstractThe gas-phase products of the reaction between HNO3/H2SO4/H2O acid solutions and HCl were identified using IR and UV−Vis spectroscopy and chemical ionization mass spectrometry. The major products of the reaction were Cl2 and ClNO, with quantifiable amounts of ClNO2 sometimes present. On the basis of quantitative product yield determinations, the overall proposed reaction is 3HCl + HNO3 → Cl2 + ClNO + 2H2O. Kinetic studies were also performed and the reaction was found to follow a second-order rate law:  Rate = k[HCl][HNO3]. On the basis of the products and intermediates observed and the rate law, a mechanism is proposed which involves the NO2+ ion as the key reactive species. The rate of the reaction is shown to depend strongly on the total acid concentration of the solution and temperature-dependent studies were also performed. The potential significance of this reaction in connection to stratospheric ozone depletion is evaluated by using the composition and temperature dependence of the rate to estimate the chlorine activation rate at polar stratospheric conditions.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/jp992666pen
dc.subject.departmentChemistryen_US
dc.titleProduct identification and kinetics of reactions of HCl with HNO3/H2SO4/H2O solutionsen_US
dc.typearticleen_US
dc.identifier.journalJournal of Physical Chemistry Aen_US
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