Rate Constants at Low Concentrations. I. Rate of Reaction of Ozone with Nitrogen Dioxide

Ford, H. W.; Doyle, George J.; Endow, N.

doi:10.1063/1.1743518

Cited by 24 publications

(9 citation statements)

References 2 publications

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“…The activation energy measured experimentally for reaction (1) lies within the range 4.8–5.0 kcal mol −1 12–21. The IUPAC22‐recommended activation energy is 4.87 kcal mol −1 .…”

Section: Resultsmentioning

confidence: 74%

“…Because of its important implications for atmospheric chemistry, considerable research effort has been devoted to measure the rate of reaction (1). A number of studies12–21 have determined the rate coefficient to be within the range 3.2 × 10 −17 –3.8 × 10 −17 cm 3 molecule −1 s −1 . On the basis of the temperature dependence of reaction (1), activation energies within the range 4.8–5.0 kcal mol −1 are obtained.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the mechanism of the atmospheric reaction: NO₂ + O₃ → NO₃ + O₂

Peiró-Garcı́a

Nebot–Gil

2003

J Comput Chem

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The atmospheric reaction NO2 + O3 --> NO3 + O2 (1) has been investigated theoretically by using the MP2, G2, G2Q, QCISD, QCISD(T), CCSD(T), CASSCF, and CASPT2 methods with various basis sets. The results show that the reaction pathway can be divided in two different parts at the MP2 level of theory. At this level, the mechanism proceeds along two transition states (TS1 and TS2) separated by an intermediate, designated as A. However, when the single-reference higher correlated QCISD methodology has been employed, the minimum A and the transition state TS2 are not found on the hypersurface of potential energy, which confirms a direct reaction mechanism. Single-reference high correlated and multiconfigurational methods consistently predict the barrier height of reaction (1) to be within the range 2.5-6.1 kcal mol(-1), in reasonable agreement with experimental data. The calculated reaction enthalpy is -24.6 kcal mol(-1) and the reaction rate calculated at the highest CASPT2 level, of k = 6.9 x 10(-18) cm(3) molecule(-1) s(-1). Both results can be regarded also as accurate predictions of the methodology employed in this article.

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“…The activation energy measured experimentally for reaction (1) lies within the range 4.8–5.0 kcal mol −1 12–21. The IUPAC22‐recommended activation energy is 4.87 kcal mol −1 .…”

Section: Resultsmentioning

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Ab initio study of the mechanism of the atmospheric reaction: NO₂ + O₃ → NO₃ + O₂

Peiró-Garcı́a

Nebot–Gil

2003

J Comput Chem

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“…Further confirmation is the work of Dunham (1960), which indicates that few, if any, condensation nuclei H2SO4 are formed from the S 0 2 -0 3 reaction. The rate constants for the reaction of O3 with N O and NO,, k41 = 2.8 X lo7 liter mol-' sec-l (Ford et al, 1957) and k,, = 4.3 X lo4 liter mol-' sec-l (Johnston and Yost, 1949), signify the importance of the 0,-NO reaction in the SOr-NO, photochemical system. Wilson et al (1970) have observed that SO, is removed by a product of the reaction of NO, and 03.…”

Section: Environmental Science and Technologymentioning

confidence: 99%

Oxidation sulfur dioxide in polluted atmospheres. Review

Bufalini¹

1971

Environ. Sci. Technol.

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“…(Measurement of the NO yield at very short delays would, of course, have been preferable, but was unfortunately not possible with the equipment at our disposal.) The lifetimes of NO and NO, with respect to destruction in [5] and [6] at 1 Torr O,, the pressure used throughout this study, were estimated from available rate constants (19,20) to belo-, and -1 s, respectively, so that extrapolation to zero time of our measurements for [NO,] in the time interval 0.2-5 s was expected to give a reliable value for the initial yield of NO. (An electronic disturbance prevented the direct measurement of [NO,] at times less than 0.2 s and necessitated the extrapolation procedure.)…”

Section: Ozone Photolysismentioning

confidence: 99%

The Reaction of the Electronically Excited Oxygen Atom O(¹D₂) with Nitrous Oxide

Scott¹,

Preston²,

Andersen³

et al. 1971

Can. J. Chem.

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An investigation has been made of the relative importance of the possible pathways [2a]–[2d][Formula: see text]for the reaction in the gas phase at room temperature between the excited oxygen atom O(1D2) and N2O, using the photolysis of NO2, O3, and N2O as sources of the excited atom. Measurement of the yields of N2 and NO from the photolysis at 2288 Å of mixtures of NO2 and N2O has led to a value of 1.01 ± 0.06 for k2a/k2b, the ratio of the rate constants for [2a] and [2b], in excellent agreement with the value of 0.99 ± 0.06 obtained from determination of the yields of N2 and NO2 arising from the flash photolysis of O3–N2O mixtures. The isotopic composition of the N2 produced in the photolysis of 15NO2–N2O mixtures indicated that k2c/k2a < 5 × 10 – 3. Furthermore, the value of k2a/(k2b + k2d) = 1.08 ± 0.19, obtained from a study of the effect of CO2 and Xe additions on the yield of N2 from the photolysis of N2O at 2288 Å, suggests that deactivation [2d] does not make an important contribution to the total rate constant for destruction of O(1D2).

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Rate Constants at Low Concentrations. I. Rate of Reaction of Ozone with Nitrogen Dioxide

Cited by 24 publications

References 2 publications

Ab initio study of the mechanism of the atmospheric reaction: NO₂ + O₃ → NO₃ + O₂

Ab initio study of the mechanism of the atmospheric reaction: NO₂ + O₃ → NO₃ + O₂

Oxidation sulfur dioxide in polluted atmospheres. Review

The Reaction of the Electronically Excited Oxygen Atom O(¹D₂) with Nitrous Oxide

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Rate Constants at Low Concentrations. I. Rate of Reaction of Ozone with Nitrogen Dioxide

Cited by 24 publications

References 2 publications

Ab initio study of the mechanism of the atmospheric reaction: NO2 + O3 → NO3 + O2

Ab initio study of the mechanism of the atmospheric reaction: NO2 + O3 → NO3 + O2

Oxidation sulfur dioxide in polluted atmospheres. Review

The Reaction of the Electronically Excited Oxygen Atom O(1D2) with Nitrous Oxide

Contact Info

Product

Resources

About

Ab initio study of the mechanism of the atmospheric reaction: NO₂ + O₃ → NO₃ + O₂

Ab initio study of the mechanism of the atmospheric reaction: NO₂ + O₃ → NO₃ + O₂

The Reaction of the Electronically Excited Oxygen Atom O(¹D₂) with Nitrous Oxide