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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19 Citations (Scopus)

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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