Temperature dependence of the laser-enhanced reaction NO+O3 (001). II. Contributions from reactive and nonreactive channels

Ezra Bar-Ziv; Jerry Moy; Robert J. Gordon

doi:10.1063/1.435792

Temperature dependence of the laser-enhanced reaction NO+O₃ (001). II. Contributions from reactive and nonreactive channels

Ezra Bar-Ziv, Jerry Moy, Robert J. Gordon

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Abstract

The reaction NO+O₃(001) was studied over the temperature range 158-437 K. A CO₂ TEA laser was used to excite ozone in a rapidly flowing mixture of O₃, Ar, and NO. The total decay rate of the laser-induced chemiluminescent signal showed a strong non-Arrhenius temperature dependence. This decay rate is the sum of contributions from three processes: the laser-enhanced luminescent reaction, the laser-enhanced nonluminescent reaction, and vibrational relaxation of O₃(001) by NO. A kinetic model is proposed to determined each of the rate coefficients from the size and shape of the laser-induced signal. Our analysis shows that the rate coefficient of the laser-enhanced nonluminescent reaction has an Arrhenius form, with an activation energy that is lowered by approximately 1.6±0.4 kcal/mol. The rate coefficient for relaxation of ozone has a minimum at 225 K, suggesting that attractive forces are important in the nonreactive channel.

Original language	English
Pages (from-to)	1013-1021
Number of pages	9
Journal	Journal of Chemical Physics
Volume	68
Issue number	3
DOIs	https://doi.org/10.1063/1.435792
State	Published - 1 Jan 1978
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Temperature dependence of the laser-enhanced reaction NO+O3 (001). II. Contributions from reactive and nonreactive channels",

abstract = "The reaction NO+O3(001) was studied over the temperature range 158-437 K. A CO2 TEA laser was used to excite ozone in a rapidly flowing mixture of O3, Ar, and NO. The total decay rate of the laser-induced chemiluminescent signal showed a strong non-Arrhenius temperature dependence. This decay rate is the sum of contributions from three processes: the laser-enhanced luminescent reaction, the laser-enhanced nonluminescent reaction, and vibrational relaxation of O3(001) by NO. A kinetic model is proposed to determined each of the rate coefficients from the size and shape of the laser-induced signal. Our analysis shows that the rate coefficient of the laser-enhanced nonluminescent reaction has an Arrhenius form, with an activation energy that is lowered by approximately 1.6±0.4 kcal/mol. The rate coefficient for relaxation of ozone has a minimum at 225 K, suggesting that attractive forces are important in the nonreactive channel.",

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AU - Bar-Ziv, Ezra

AU - Moy, Jerry

AU - Gordon, Robert J.

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N2 - The reaction NO+O3(001) was studied over the temperature range 158-437 K. A CO2 TEA laser was used to excite ozone in a rapidly flowing mixture of O3, Ar, and NO. The total decay rate of the laser-induced chemiluminescent signal showed a strong non-Arrhenius temperature dependence. This decay rate is the sum of contributions from three processes: the laser-enhanced luminescent reaction, the laser-enhanced nonluminescent reaction, and vibrational relaxation of O3(001) by NO. A kinetic model is proposed to determined each of the rate coefficients from the size and shape of the laser-induced signal. Our analysis shows that the rate coefficient of the laser-enhanced nonluminescent reaction has an Arrhenius form, with an activation energy that is lowered by approximately 1.6±0.4 kcal/mol. The rate coefficient for relaxation of ozone has a minimum at 225 K, suggesting that attractive forces are important in the nonreactive channel.

AB - The reaction NO+O3(001) was studied over the temperature range 158-437 K. A CO2 TEA laser was used to excite ozone in a rapidly flowing mixture of O3, Ar, and NO. The total decay rate of the laser-induced chemiluminescent signal showed a strong non-Arrhenius temperature dependence. This decay rate is the sum of contributions from three processes: the laser-enhanced luminescent reaction, the laser-enhanced nonluminescent reaction, and vibrational relaxation of O3(001) by NO. A kinetic model is proposed to determined each of the rate coefficients from the size and shape of the laser-induced signal. Our analysis shows that the rate coefficient of the laser-enhanced nonluminescent reaction has an Arrhenius form, with an activation energy that is lowered by approximately 1.6±0.4 kcal/mol. The rate coefficient for relaxation of ozone has a minimum at 225 K, suggesting that attractive forces are important in the nonreactive channel.

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Temperature dependence of the laser-enhanced reaction NO+O₃ (001). II. Contributions from reactive and nonreactive channels

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