UV spectroscopic determination of the chlorine monoxide (ClO) ∕ chlorine peroxide (ClOOCl) thermal equilibrium constant
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Published:2019-05-10
Issue:9
Volume:19
Page:6205-6215
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ISSN:1680-7324
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Container-title:Atmospheric Chemistry and Physics
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language:en
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Short-container-title:Atmos. Chem. Phys.
Author:
Klobas J. EricORCID, Wilmouth David M.ORCID
Abstract
Abstract. The thermal equilibrium constant between the chlorine monoxide radical (ClO)
and its dimer, chlorine peroxide (ClOOCl), was determined as a function of
temperature between 228 and 301 K in a discharge flow apparatus using broadband
UV absorption spectroscopy. A third-law fit of the equilibrium values
determined from the experimental data provides the expression
Keq=2.16×10-27e8527±35K/T cm3 molecule−1 (1σ uncertainty). A second-law
analysis of the data is in good agreement. From the slope of the van't Hoff
plot in the third-law analysis, the enthalpy of formation for ClOOCl is
calculated, ΔHf∘(298K)=130.0±0.6 kJ mol−1. The equilibrium constant results from this study
suggest that the uncertainties in Keq recommended in the most
recent (year 2015) NASA JPL Data Evaluation can be significantly reduced.
Funder
National Aeronautics and Space Administration
Publisher
Copernicus GmbH
Subject
Atmospheric Science
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