Pulse radiolysis of ammonia gas. II. Rate of disappearance of the NH2(X2B1) radical

Gordon, S.; Mulac, William A.; Nangia, Prakash S.

doi:10.1021/j100683a004

Cited by 133 publications

(89 citation statements)

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“…Boyd et al [17] determined a value of 8 X 107M-1-s-1, which is obviously too small, but was derived from the analysis of a complex reaction mechanism concerning the radiolysis of N H~-C~H G mixtures. Gordon et al [3] determined k17 = 4.95 X 101oM-l.s-l using pulse radiolysis in experiments similar to those reported in the present work. This value is significantly higher than our own, probably because it was based on the high value of k18(C3H7 + C3H7) which was determined using the rotating sector method [15].…”

Section: Discussionsupporting

confidence: 87%

“…In the absence of alkenes or alkanes, reactions (6) provide the only pathway for the NH2 recombination, the reaction with H atoms being negligible [3]. However, a slight deviation from pure second-order kinetics is observed in the NH2 decay.…”

Section: Rate Constant For the Nh2 Mutual Interactionmentioning

confidence: 99%

“…undergo recombination reactions. Moreover, at the low total pressure employed (3 torr), the self-recombination of NH2 radicals is slow since the rate is pressure dependent up to 1000 torr [3,4]. Thus the principal reaction of NH2 is the interaction with alkyl radicals, which is a very suitable situation for measuring this reaction rate constant.…”

Section: Introductionmentioning

confidence: 99%

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Absolute rate constants for the reactions between amino and alkyl radicals at 298 K

Demissy

Lesclaux

1982

Int J of Chemical Kinetics

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The absolute rate constants for the reactions of NH2 radicals with ethyl, isopropyl, and t-butyl radicals have been measured at 298 K, using a flash photolysis-laser resonance absorption method. Radicals were generated by flashing ammonia in the presence of an olefin.A new measurement of the NH2 extinction coefficient and oscillator strength at 597.73 nm was performed. The decay curves were simulated by adjusting the rate constants of both the reaction of NH2 with the alkyl radical and the mutual interactions of alkyl radicals. The results are k(NH2 + alkyl) = 2.5 (f0.5), 2.0 (f0.41, and 2.5 (f0.5) X 1Olo A4-l.s-l for ethyl, isopropyl, and t-butyl radicals, respectively. The best simulations were obtained when taking k(alky1 + alkyl) = 1.2,0.6, and 0.65 X 10IOM-'-s-l for ethyl, isopropyl, and t -butyl radicals, respectively, in good agreement with literature values.

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Section: Discussionsupporting

confidence: 87%

Section: Rate Constant For the Nh2 Mutual Interactionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Absolute rate constants for the reactions between amino and alkyl radicals at 298 K

Demissy

Lesclaux

1982

Int J of Chemical Kinetics

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“…Furthermore if one assumes that the recombination rate is independent of temperature, then from the room temperature results [24] one obtains [6] at 1100OK a preexponential factor of sec-I as compared with 1016.25 sec-I. The overall agreement at 1100°K is therefore excellent and well within the uncertainties of 10*0.4 sec-I in the preexponential factor and 8 kJ in the activation energy.…”

Section: Rate Constants For Hydrazine Decomposition and Cross Combinamentioning

confidence: 69%

Thermal stability of primary amines

Tsang

1978

Int J of Chemical Kinetics

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Tertiary-amyl amine has been decomposed in single-pulse shock-tube experiments. Rate expressions for several of the important primary steps areThe present and earlier comparative rate single-pulse shock-tube data when combined with high-pressure hydrazine decomposition results (after correcting for fall off effects through RRKM calculations) gives [k?(tCSH1 1.,NHP.)/kr(tCSH1l-,tC5H11.) k,(NHz.,NH2-)]1/z -2 a t 1lOOOKwhere k,(--) is the recombination rate involving the appropriate radicals. This suggests that in this context amino radical behavior is analogous to that of alkyl radicals. If this agreement is exact, then km(N2H4 -2NHz-) = 1016-25 exp(-32,300/T) sec-'

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“…Units on the left axis are in cm 6 molecule −2 s −1 for k 0 and cm 3 molecule −1 s −1 for k r . Experimental data are taken from: H + NH 2 (Gordon et al 1971), H + CH 3 (Brouard et al 1989), CH 3 + O 2 (Fernandes et al 2006), CH 3 + NO (Kaiser 1993), CH 3 + NH 2 (Jodkowski et al 1995), CH 3 + CH 3 (Slagle et al 1988;Cody et al 2002). The solid and dashed lines correspond to the general expression we derived for the low-pressure limiting rate constants k 0 for H addition and CH 3 addition, respectively.…”

Section: A8 Photolysis Of C 3 Hmentioning

confidence: 99%

Photochemistry of C₃H_phydrocarbons in Titan’s stratosphere revisited

Hébrard¹,

Dobrijévic²,

Loison³

et al. 2013

A&A

124

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The description of C 3 hydrocarbon chemistry in current photochemical models of Titan's atmosphere is found to be far from complete. We have carefully investigated the photochemistry involving C 3 H p compounds in the atmosphere of Titan (considering both photolysis and neutral reactions), which considerably impacts the abundances of many other hydrocarbon species (including C 2 compounds). Model results indicate that three species (C 3 , c−C 3 H 2 and C 3 H 3 ) could be abundant enough to be present in the Cassini/INMS data. Because the error bars on predicted C 3 -hydrocarbon abundances are considerably larger than those of the observational data, new experimental and theoretical studies targeting the measurement of low-temperature reaction rate constants and product branching ratios are required to reduce current model uncertainties. In particular, we highlight 30 "key reactions", the uncertainty factors of which should be lowered to improve the quality of photochemical models involving C 3 H p molecules.

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Pulse radiolysis of ammonia gas. II. Rate of disappearance of the NH2(X2B1) radical

Cited by 133 publications

References 1 publication

Absolute rate constants for the reactions between amino and alkyl radicals at 298 K

Absolute rate constants for the reactions between amino and alkyl radicals at 298 K

Thermal stability of primary amines

Photochemistry of C₃H_phydrocarbons in Titan’s stratosphere revisited

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Pulse radiolysis of ammonia gas. II. Rate of disappearance of the NH2(X2B1) radical

Cited by 133 publications

References 1 publication

Absolute rate constants for the reactions between amino and alkyl radicals at 298 K

Absolute rate constants for the reactions between amino and alkyl radicals at 298 K

Thermal stability of primary amines

Photochemistry of C3Hphydrocarbons in Titan’s stratosphere revisited

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Product

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Photochemistry of C₃H_phydrocarbons in Titan’s stratosphere revisited