Experimental and theoretical studies of the rate coefficients of the reaction O(3P) + HCl at high temperatures

Chih Chang Hsiao, Yuan Pern Lee, Niann S. Wang, J. H. Wang, M. C. Lin

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Abstract

Rate coefficients of the reaction O(3P) + HCl in the temperature range 1093-3197 K were determined using a diaphragmless shock tube. O atoms in the ground electronic 3P states were generated either by photolysis of SO2 with a KrF excimer laser at 248 nm or by pyrolysis of N2O with the shock wave. Their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O2 and He. Rate coefficients determined in this work show non-Arrhenius behavior, with values consistent with previously reported measurements for T < 1486 K; they fit well with the equation k1(T) = (9.27 ± 0.03) × 10-24 T3.67±0.18 exp[-(1030 ± 160)/T] cm3 molecule-1 s-1; listed errors represent one standard deviation in fitting. Theoretical calculations at the CCSD(T)/6-311+G(d, p) level locate a bent 3A″ (TS1) and a linear 3A′ (TS3) transition state characterized previously. On the basis of the results computed by CCSD(T)/ 6-311+G(3df,2p)//CCSD(T)/6-311+G(d,p), the rate coefficients predicted with conventional transition-state theory, including Eckart-tunneling corrections and with variational transition-state theory including zero- and small-curvature tunneling corrections, all agree satisfactorily with experimental observations.

Original languageEnglish
Pages (from-to)10231-10237
Number of pages7
JournalJournal of Physical Chemistry A
Volume106
Issue number43
DOIs
Publication statusPublished - 2002 Oct 31

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Excimer Lasers
Shock tubes
Photolysis
Electronic states
Excimer lasers
Microwaves
Shock waves
Shock
Pyrolysis
Theoretical Models
Atoms
Molecules
Temperature
coefficients
shock tubes
excimer lasers
pyrolysis
photolysis
shock waves
standard deviation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Experimental and theoretical studies of the rate coefficients of the reaction O(3P) + HCl at high temperatures. / Hsiao, Chih Chang; Lee, Yuan Pern; Wang, Niann S.; Wang, J. H.; Lin, M. C.

In: Journal of Physical Chemistry A, Vol. 106, No. 43, 31.10.2002, p. 10231-10237.

Research output: Contribution to journalArticle

Hsiao, Chih Chang ; Lee, Yuan Pern ; Wang, Niann S. ; Wang, J. H. ; Lin, M. C. / Experimental and theoretical studies of the rate coefficients of the reaction O(3P) + HCl at high temperatures. In: Journal of Physical Chemistry A. 2002 ; Vol. 106, No. 43. pp. 10231-10237.
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