Temperature dependence of the absolute third-order rate constant for the reaction between K + O2 + N2 over the range 680-1010K studied by time-resolved atomic resonance absorption spectroscopy

D. Husain, Yook Heng Lee, P. Marshall

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22 Citations (Scopus)

Abstract

We present a direct kinetic study of the third-order recombination reaction K+O2+N2→KO2+N2 across the temperature range 680-1010K. K(42S 1 2) was generated by pulsed irradiation and monitored by time-resolved atomic resonance absorption spectroscopy in the "single shot mode" in the presence of O2 and N2 using the Rydberg transition at λ = 404 nm (K(52PJ) ← K(42S 1 2)). While the resulting data for k4 can be empirically expressed within this temperature range by the form k4(680-1010K) = (6.63 ± 0.66 × 10-23)( T K)-2.6±0.28 cm6 molecule-2 s-1, a full extrapolation based on the unimolecular rate theory of Tröe was carried out in order to extend the data to flame temperatures (2000K), given the importance of potassium additives in flame inhibition. The full extrapolation across the range 200-2000K can be expressed to within 10% by (k4/cm6 molecule-2S-1)=-0.2558 [ln( T K)]2+1.361 ln( T K)-66.14. These results are compared with data derived from measurements on a fast flow reactor which show a much smaller temperature dependence and indicate an extrapolated value for k4 at flame temperatures significantly higher than derived from the present investigations.

Original languageEnglish
Pages (from-to)143-154
Number of pages12
JournalCombustion and Flame
Volume68
Issue number2
DOIs
Publication statusPublished - 1987
Externally publishedYes

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flame temperature
Absorption spectroscopy
extrapolation
Rate constants
absorption spectroscopy
recombination reactions
temperature dependence
shot
molecules
flames
potassium
Extrapolation
reactors
Temperature
irradiation
temperature
kinetics
Molecules
Potassium
Irradiation

ASJC Scopus subject areas

  • Energy Engineering and Power Technology
  • Fuel Technology
  • Mechanical Engineering

Cite this

@article{be5fac23318b4c4aa80ddf7bca60f057,
title = "Temperature dependence of the absolute third-order rate constant for the reaction between K + O2 + N2 over the range 680-1010K studied by time-resolved atomic resonance absorption spectroscopy",
abstract = "We present a direct kinetic study of the third-order recombination reaction K+O2+N2→KO2+N2 across the temperature range 680-1010K. K(42S 1 2) was generated by pulsed irradiation and monitored by time-resolved atomic resonance absorption spectroscopy in the {"}single shot mode{"} in the presence of O2 and N2 using the Rydberg transition at λ = 404 nm (K(52PJ) ← K(42S 1 2)). While the resulting data for k4 can be empirically expressed within this temperature range by the form k4(680-1010K) = (6.63 ± 0.66 × 10-23)( T K)-2.6±0.28 cm6 molecule-2 s-1, a full extrapolation based on the unimolecular rate theory of Tr{\"o}e was carried out in order to extend the data to flame temperatures (2000K), given the importance of potassium additives in flame inhibition. The full extrapolation across the range 200-2000K can be expressed to within 10{\%} by (k4/cm6 molecule-2S-1)=-0.2558 [ln( T K)]2+1.361 ln( T K)-66.14. These results are compared with data derived from measurements on a fast flow reactor which show a much smaller temperature dependence and indicate an extrapolated value for k4 at flame temperatures significantly higher than derived from the present investigations.",
author = "D. Husain and Lee, {Yook Heng} and P. Marshall",
year = "1987",
doi = "10.1016/0010-2180(87)90053-8",
language = "English",
volume = "68",
pages = "143--154",
journal = "Combustion and Flame",
issn = "0010-2180",
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TY - JOUR

T1 - Temperature dependence of the absolute third-order rate constant for the reaction between K + O2 + N2 over the range 680-1010K studied by time-resolved atomic resonance absorption spectroscopy

AU - Husain, D.

AU - Lee, Yook Heng

AU - Marshall, P.

PY - 1987

Y1 - 1987

N2 - We present a direct kinetic study of the third-order recombination reaction K+O2+N2→KO2+N2 across the temperature range 680-1010K. K(42S 1 2) was generated by pulsed irradiation and monitored by time-resolved atomic resonance absorption spectroscopy in the "single shot mode" in the presence of O2 and N2 using the Rydberg transition at λ = 404 nm (K(52PJ) ← K(42S 1 2)). While the resulting data for k4 can be empirically expressed within this temperature range by the form k4(680-1010K) = (6.63 ± 0.66 × 10-23)( T K)-2.6±0.28 cm6 molecule-2 s-1, a full extrapolation based on the unimolecular rate theory of Tröe was carried out in order to extend the data to flame temperatures (2000K), given the importance of potassium additives in flame inhibition. The full extrapolation across the range 200-2000K can be expressed to within 10% by (k4/cm6 molecule-2S-1)=-0.2558 [ln( T K)]2+1.361 ln( T K)-66.14. These results are compared with data derived from measurements on a fast flow reactor which show a much smaller temperature dependence and indicate an extrapolated value for k4 at flame temperatures significantly higher than derived from the present investigations.

AB - We present a direct kinetic study of the third-order recombination reaction K+O2+N2→KO2+N2 across the temperature range 680-1010K. K(42S 1 2) was generated by pulsed irradiation and monitored by time-resolved atomic resonance absorption spectroscopy in the "single shot mode" in the presence of O2 and N2 using the Rydberg transition at λ = 404 nm (K(52PJ) ← K(42S 1 2)). While the resulting data for k4 can be empirically expressed within this temperature range by the form k4(680-1010K) = (6.63 ± 0.66 × 10-23)( T K)-2.6±0.28 cm6 molecule-2 s-1, a full extrapolation based on the unimolecular rate theory of Tröe was carried out in order to extend the data to flame temperatures (2000K), given the importance of potassium additives in flame inhibition. The full extrapolation across the range 200-2000K can be expressed to within 10% by (k4/cm6 molecule-2S-1)=-0.2558 [ln( T K)]2+1.361 ln( T K)-66.14. These results are compared with data derived from measurements on a fast flow reactor which show a much smaller temperature dependence and indicate an extrapolated value for k4 at flame temperatures significantly higher than derived from the present investigations.

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