Experimental determination of the rate constants of the reactions of HO2 + DO2 and DO2 + DO2
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F20%3A00518926" target="_blank" >RIV/61388955:_____/20:00518926 - isvavai.cz</a>
Result on the web
<a href="http://hdl.handle.net/11104/0303930" target="_blank" >http://hdl.handle.net/11104/0303930</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/kin.21342" target="_blank" >10.1002/kin.21342</a>
Alternative languages
Result language
angličtina
Original language name
Experimental determination of the rate constants of the reactions of HO2 + DO2 and DO2 + DO2
Original language description
The rate constants of the reactions of DO2 + HO2 (R1) and DO2 + DO2 (R2) havenbeen determined by the simultaneous, selective, and quantitative measurement ofHO2nand DO2 by continuous wave cavity ring-down spectroscopy (cw-CRDS) in the nearninfrared, coupled to a radical generation by laser photolysis. HO2 was generated bynphotolyzing Cl2 in the presence of CH3OH and O2. Low concentrations of DO2 werengenerated simultaneously by adding low concentrations of D2O to the reaction mixture,nleading through isotopic exchange on tubing and reactor walls to formation ofnlow concentrations of CH3OD and thus formation of DO2. Excess DO2 was generatednby photolyzing Cl2 in the presence of CD3OD and O2, small concentrations ofnHO2 were always generated simultaneously by isotopic exchange between CD3ODnand residual H2O. The rate constant k1 at 295 K was found to be pressure independentnin the range 25–200 Torr helium, but increased with increasing D2O concentrationnk1 = (1.67 ± 0.03) × 10−12 × (1 + (8.2 ± 1.6) × 10−18 cm3 × [D2O]ncm−3) cm3 s−1. The rate constant for the DO2 self-reaction k2 has been measurednunder excess DO2 concentration, and the DO2 concentration has been determinednby fitting the HO2 decays, now governed by their reaction with DO2, tonthe rate constant k1. A rate constant with insignificant pressure dependence wasnfound: k2 = (4.1 ± 0.6) × 10−13 (1 + (2 ± 2) × 10−20 cm3 × [He] cm−3) cm3ns−1 as well as an increase of k2 with increasing D2O concentration was observed:nk2 = (4.14 ± 0.02) × 10−13 × (1 + (6.5 ± 1.3) × 10−18 cm3 × [D2O] cm−3) cm3 s−1.nThe result for k2 is in excellent agreement with literature values, whereas this is thenfirst determination of k1.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
International Journal of Chemical Kinetics
ISSN
0538-8066
e-ISSN
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Volume of the periodical
52
Issue of the periodical within the volume
3
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
197-206
UT code for WoS article
000504911000001
EID of the result in the Scopus database
2-s2.0-85077844502