Temperature dependence of the Cl+HN3 reaction from 300 to 480 K

Manke, Gerald C.; Henshaw, Thomas L.; Madden, Timothy J.; Hager, Gordon D.

doi:10.1016/s0009-2614(99)00726-5

Cited by 13 publications

(12 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The value of k14 ) (4.9 ( 0.8) × 10 -13 cm 3 molecule -1 s -1 seems to be well established (42,43). Combining these reference rate coefficient data with our measured ratios yields values for There are a number of determinations of k10 in the literature (5)(6)(7)(8), including one temperature-dependent study (8), all obtained using flow tube methodologies. While there is very reasonable agreement between the various room-temperature measurements, which range from (9-13) × 10 -13 cm 3 molecule -1 s -1 , these measurements were of an indirect nature, involved substantial occurrence of, or correction for, secondary reactions, and/or required modeling of fairly complex reaction systems, and thus uncertainties on the order of (25% typically apply.…”

Section: Resultssupporting

confidence: 55%

Atmospheric Chemistry of Hydrazoic Acid (HN₃): UV Absorption Spectrum, HO^• Reaction Rate, and Reactions of the ^•N₃ Radical

Tyndall¹,

Betterton

Lowry³

et al. 2005

Environ. Sci. Technol.

View full text Add to dashboard Cite

Processes related to the tropospheric lifetime and fate of hydrazoic acid, HN3, have been studied. The ultraviolet absorption spectrum of HN3 is shown to possess a maximum near 262 nm with a tail extending to at least 360 nm. The photolysis quantum yield for HN3 is shown to be approximately 1 at 351 nm. Using the measured spectrum and assuming unity quantum yield throughout the actinic region, a diurnally averaged photolysis lifetime near the earth's surface of 2-3 days is estimated. Using a relative rate method, the rate coefficient for reaction of HO with HN3 was found to be (3.9 +/-0.8) x 10(-12) cm3 molecule(-1) s(-1), substantially larger than the only previous measurement. The atmospheric HN3 lifetime with respect to HO oxidation is thus about 2-3 days, assuming a diurnally averaged [HO] of 10(6) molecule cm(-3). Reactions of N3, the product of the reaction of HO with HN3, were studied in an environmental chamber using an FTIR spectrometer for end-product analysis. The N3 radical reacts efficiently with NO, producing N2O with 100% yield. Reaction of N3 with NO2 appears to generate both NO and N2O, although the rate coefficient for this reaction is slower than that for reaction with NO. No evidence for reaction of N3 with CO was observed, in contrast to previous literature data. Reaction of N3 with O2 was found to be extremely slow, k < 6 x 10(-20) cm3 molecule(-1) s(-1), although this upper limit does not necessarily rule out its occurrence in the atmosphere. Finally, the rate coefficient for reaction of Cl with HN3 was measured using a relative rate method, k = (1.0+/-0.2) x 10(-12) cm3 molecule(-1) s(-1).

show abstract

Section: Resultssupporting

confidence: 55%

Atmospheric Chemistry of Hydrazoic Acid (HN₃): UV Absorption Spectrum, HO^• Reaction Rate, and Reactions of the ^•N₃ Radical

Tyndall¹,

Betterton

Lowry³

et al. 2005

Environ. Sci. Technol.

View full text Add to dashboard Cite

show abstract

“…15 As many of the reactions occurring in this device have yet to be characterized, the laser demonstration has stimulated new efforts to understand the kinetics of NCl(a) generation and destruction. [16][17][18] In previous kinetic studies two different experimental techniques were used to determine NCl(a) quenching rate constants, and the results appeared to be strongly dependent on the technique used. Hewett et al 10 performed measurements in a discharge flow system.…”

Section: Introductionmentioning

confidence: 99%

Rate Constants for Quenching and Self-Annihilation of NCl(aΔ)

2002

View full text Add to dashboard Cite

Quenching and self-annihilation rate constants for NCl(a) have been determined using pulsed 248 nm photolysis of ClN 3 to generate the metastable. Previous quenching measurements that employed different sources for NCl(a) yielded dramatically different rate constants. The present study provided quenching rate constants for Cl 2 , HCl, and H 2 that are in good agreement with the discharge flow measurements of Hewett et al. (J. Phys. Chem. A 2000, 104, 539). Determination of the self-annihilation rate constant required knowledge of the branching fraction for NCl(a) formation for 248 nm photolysis of ClN 3 . This information was obtained from time-resolved measurements of NCl(X) formation and decay. A lower bound for the branching fraction of 0.7 was determined. Self-annihilation of NCl(a) was studied by using intense photolysis pulses to generate high concentrations of NCl(a). Analysis of the second-order decay component yielded a rate constant of (7.0 ( 1.5) × 10 -13 cm 3 s -1 . This value is an order of magnitude smaller than the previous estimate (Henshaw et al.

show abstract

“…The chemical generation of J*(2p112) and subsequent lasing is based on a sequential process in which Cl and I atoms are produced, F + DC1 -+ DF + Cl, k 1 X 1O cm3/s (7) (1) Cl + Hi -+ HC1 + I (2P312), oo K 1 .0 X 1 O' cm3ls, (8) (2) followed by NC1 (a1A) production, Cl + }jJ3 -_ HC1(v)+ N3, 300 K 1 x 1012 cm3/s (9) (3) Cl + N3 -NC1(a'A, b1, X3) + N2(X'), k300K 2 x 10h1 (10,11) …”

Section: Resultsmentioning

confidence: 99%

New chemically pumped I(²P 1/2 →²P 3/2 ) laser at 1.315 μm

et al. 2001

View full text Add to dashboard Cite

show abstract

Temperature dependence of the Cl+HN3 reaction from 300 to 480 K

Cited by 13 publications

References 29 publications

Atmospheric Chemistry of Hydrazoic Acid (HN₃): UV Absorption Spectrum, HO^• Reaction Rate, and Reactions of the ^•N₃ Radical

Atmospheric Chemistry of Hydrazoic Acid (HN₃): UV Absorption Spectrum, HO^• Reaction Rate, and Reactions of the ^•N₃ Radical

Rate Constants for Quenching and Self-Annihilation of NCl(aΔ)

New chemically pumped I(²P 1/2 →²P 3/2 ) laser at 1.315 μm

Contact Info

Product

Resources

About

Temperature dependence of the Cl+HN3 reaction from 300 to 480 K

Cited by 13 publications

References 29 publications

Atmospheric Chemistry of Hydrazoic Acid (HN3): UV Absorption Spectrum, HO• Reaction Rate, and Reactions of the •N3 Radical

Atmospheric Chemistry of Hydrazoic Acid (HN3): UV Absorption Spectrum, HO• Reaction Rate, and Reactions of the •N3 Radical

Rate Constants for Quenching and Self-Annihilation of NCl(aΔ)

New chemically pumped I(2P 1/2 →2P 3/2 ) laser at 1.315 μm

Contact Info

Product

Resources

About

Atmospheric Chemistry of Hydrazoic Acid (HN₃): UV Absorption Spectrum, HO^• Reaction Rate, and Reactions of the ^•N₃ Radical

Atmospheric Chemistry of Hydrazoic Acid (HN₃): UV Absorption Spectrum, HO^• Reaction Rate, and Reactions of the ^•N₃ Radical

New chemically pumped I(²P 1/2 →²P 3/2 ) laser at 1.315 μm