Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

Leu, Ming‐Taun; Lin, C. L.; DeMore, W. B.

doi:10.1021/j100518a002

Cited by 50 publications

(27 citation statements)

References 7 publications

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“…[7,10,11] 2.2.1.2. Temperature-Dependent Rate Constants are in reasonable agreement with experimental data [3][4][5][6][7][8] in the experimental temperature ranges. The predicted third-order rate constants (with hDE down i = 400 cm…”

Section: Pressure-dependent Rate Constantssupporting

confidence: 84%

“…[3][4][5][6][7][8][9][10][11][12][13][14][15][16] In the low-pressure range of 0.5-9 Torr, it has been studied by four groups [3][4][5][6] using discharge flow techniques with various detection methods. Birks et al [3] first measured in 1977 the rate of formation of chlorine nitrate over the temperature range of 250-356 K and the pressure range of 1-5 Torr.…”

Section: Introductionmentioning

confidence: 99%

“…Later, Leu et al [4] measured the rate constants in different buffer gases in the temperature range of 248-417 K and pressure range of 1-9 Torr. Zahniser et al [5] reported the rates in N 2 and He at 297 K and 251-365 K, respectively.…”

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confidence: 99%

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Ab initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO₂ for the Forward and Reverse Processes

Zhu

Lin

2005

ChemPhysChem

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The potential-energy surface for the reaction of ClO with NO2 has been constructed at the CCSD(T)/6-311+G(3df)//B3LYP/6-311+G(3df) level of theory. Six ClNO3 isomers are located; these are ClONO2, pc-ClOONO, pt-ClOONO, OClNO2, pt-OClONO, pc-OClONO, with predicted energies relative to the reactants of -25.6, -0.5, 1.0, 1.9, 12.2 and 13.6 kcal mol-1, and heats of formation at 0 K of 7.8, 32.9, 34.4, 35.5, 45.6 and 47.0 kcal mol-1, respectively. Isomerizations among them are also discussed. The rate constants for the low-energy pathways have been computed by statistical theory calculations. For the association reaction producing exclusively ClONO2, the predicted low- and high-pressure-limit rate constants in N2 for the temperature range of 200-600 K can be represented by: (N2)=3.19 x 10-17 T-5.54 exp(-384 K/T) cm6 molecule-2 s-1 and =3.33 x 10-7 T-1.48 exp(-18 K/T) cm3 molecule-1 s-1. The predicted low- and high-pressure-limit rate constants for the decomposition of ClONO2 in N2 at 200-600 K can be expressed, respectively, by =6.08 x 1013 T-6.54 exp(-13813 K/T) cm3 molecule-1 s-1 and =4.59 x 1023 T-2.43 exp(-13437 K/T) s-1. The predicted values compare satisfactorily with available experimental data. The reverse Cl+NO3 reaction was found to be independent of the pressure, giving exclusively ClO+NO2; the predicted rate constant can be expressed as k(Cl+NO3)=1.19 x 10-9 T-0.60 exp(58 K/T) cm3 molecule-1 s-1..

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Section: Pressure-dependent Rate Constantssupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

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Ab initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO₂ for the Forward and Reverse Processes

Zhu

Lin

2005

ChemPhysChem

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“…The form of the Hz dependence is reasonably well described only at low (H2) with k l in the range 5.4-7.2 X cm"/molecule sec. At (H2) 2 8 X 1015 molecule/cm3 the low-frequency HOz concentration modulation is consistently overestimated, and (P(HZ02) is correspondingly higher than observed. An additional sink process is indicated here.…”

Section: Resultsmentioning

confidence: 78%

Kinetics of the reaction Cl + HO₂ = HCl + O₂, using molecular modulation spectrometry

Cox

1980

Int J of Chemical Kinetics

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The rate constant for the reaction (I), C1+ HOz -HCI + 0 2 , was measured using molecular modulation spectrometry to investigate HOz radical kinetics in the modulated photolysis of ClyH2-02 mixtures at 760 torr pressure. HOz was monitored directly in absorption at 220 nm, and k l was determined from computer simulations of the observed kinetic behavior of HOz, using a simple chemical model. The results gave kJk4 = 3.OtFh exp[+(2120 f 370)/T]where k s is the rate constant for the reaction of C1 with Hz. A consensus value of kq gave kl = 6.9 X lo-" cm3/molecule sec, independent of temperature in the range of 274338 K with an overall uncertainty of f50%. The relative importance of reaction (1) for the conversion of C1 to HC1 in the stratosphere is discussed briefly.

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“…Recently several more measurements on reaction (1) have been published with either a direct [ll-131 or an indirect [14-161 HOz detection method. The rate constant shows a negative temperature dependence [12,16], suggesting that k I might be pressure dependent.…”

Section: Introductionmentioning

confidence: 99%

Direct determination of the rate constant of the reaction NO + HO₂ → NO₂ + OH with the LMR

Hack¹,

Preuss²,

Temps³

et al. 1980

Int J of Chemical Kinetics

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The rate of the reaction (1)was determined in an isothermal discharge flow reactor with a combined ESR-LMR detection under pseudo-first-order conditions in HOz. The rate constant was identical in experiments with two different HOn sources: F + H202 and H + 0 2 + M. The absolute rate constant a t T = 293 K was measured as kl(293 K) = (4.6 f. 1)1012 cm3/mol sec In the range 2 5 p mbar 5 17 no pressure dependence for k l was found.

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Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

Cited by 50 publications

References 7 publications

Ab initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO₂ for the Forward and Reverse Processes

Ab initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO₂ for the Forward and Reverse Processes

Kinetics of the reaction Cl + HO₂ = HCl + O₂, using molecular modulation spectrometry

Direct determination of the rate constant of the reaction NO + HO₂ → NO₂ + OH with the LMR

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Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

Cited by 50 publications

References 7 publications

Ab initio Studies of ClOx Reactions: Prediction of the Rate Constants of ClO+NO2 for the Forward and Reverse Processes

Ab initio Studies of ClOx Reactions: Prediction of the Rate Constants of ClO+NO2 for the Forward and Reverse Processes

Kinetics of the reaction Cl + HO2 = HCl + O2, using molecular modulation spectrometry

Direct determination of the rate constant of the reaction NO + HO2 → NO2 + OH with the LMR

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Ab initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO₂ for the Forward and Reverse Processes

Ab initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO₂ for the Forward and Reverse Processes

Kinetics of the reaction Cl + HO₂ = HCl + O₂, using molecular modulation spectrometry

Direct determination of the rate constant of the reaction NO + HO₂ → NO₂ + OH with the LMR