Detection of NH (X p3Σ−) by resonance fluorescence in the pulsed vacuum uv photolysis of NH3 and its application to reactions of NH radicals

Hansen, I.; Höinghaus, K.; Zetzsch, Cornelius; Stuhl, F.

doi:10.1016/0009-2614(76)80387-9

Cited by 52 publications

(9 citation statements)

References 7 publications

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“…Although there is good agreement among the low temperature studies of Gordon et al [2], Hansen et al [3], Cox et al [4], and Harrison et al [5], the high temperature studies of Nip [6], Roose et al [7], Peterson [8], and Morley [9], disagree considerably with each other. These investigations are discussed later in more detail.…”

Section: Introductionmentioning

confidence: 81%

“…However, ours is the only direct high temperature measurement of k3, while all of the previous high temperature studies [6-91 involved an indirect determination of the reaction rate. Also shown are the extrapolations of the low temperature results of Gordon et al [2], Hansen et al [3], Cox et al [4], and Harrison et al [5], used by Miller and Bowman [l] and Miller et al [32] in their modeling of nitrogen chemistry. These extrapolations, which employ a negative temperature dependence, agree approximately with the magnitude of our results.…”

Section: Oh Measurementsmentioning

confidence: 98%

“…Following the onset of formation of NH by reaction (la), NH is removed by reaction (3): (3) NH + NO -+ products…”

Section: Experimental Approachmentioning

confidence: 99%

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A shock tube study of the reactions of NH with NO, O₂, and O

Mertens

Chang

Hanson

et al. 1991

Int J of Chemical Kinetics

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The reactions of NH(X3Z-) with NO, 02, and 0 have been studied in reflected and incident shock wave experiments. The source of NH in all the experiments was the thermal dissociation of isocyanic acid, HNCO. Time-histories of the NH(X3Z) and OH(X211) radicals were measured behind the shock waves using cw, narrow-linewidth laser absorption at 336 nm and 307 nm, respectively. The second-order rate coefficients of the reactions:NH + NO --+ products NH + O2 --+ products NH + 0 -products

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Section: Introductionmentioning

confidence: 81%

Section: Oh Measurementsmentioning

confidence: 98%

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A shock tube study of the reactions of NH with NO, O₂, and O

Mertens

Chang

Hanson

et al. 1991

Int J of Chemical Kinetics

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“…There have been several measurements of the overall rate constants for NHϩNO, including room temperature studies, [1][2][3][4][5][6][9][10][11][12] shock tube, 7,8 and flame measurements. [13][14][15] The rate constant is found to have values in the range 3.8 -5.8ϫ10 Ϫ11 cm 3 /s at 300 K, increasing slowly with temperature.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study of the NH+NO reaction

Bradley¹,

McCabe²,

Schatz³

et al. 1995

The Journal of Chemical Physics

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A threedimensional quantum mechanical study of the NH+NO reactionsWe present a quasiclassical trajectory study of the NHϩNO reaction using a global potential energy surface that is capable of describing branching to the HϩN 2 O and OHϩN 2 products after initial formation of a HNNO intermediate complex. The surface is based on a many-body expansion wherein fragment potentials for the species N 2 H, HNO, and N 2 O are incorporated, using either previously developed potentials, or in the case of N 2 O, a newly developed potential. The three-body parts of these fragment potentials are damped in the four-body region to provide a zeroth order four-body surface, and then additional four-body terms and mapping transformations are applied to make the final four-body potential match the results of ab initio calculations for eight important HNNO stationary points ͑minima and saddle points͒ and for several reaction paths. In addition to this ''best fit'' surface ͑surface I͒, a second surface ͑surface II͒ is developed in which the ordering of the saddle points leading to formation of HϩN 2 O and OHϩN 2 is reversed, and the energy release during 1,3 hydrogen migration is modified so that the N-N stretch experiences smaller distortions from N 2 equilibrium during the reaction leading to OHϩN 2 . Quasiclassical trajectory results on surface I show generally good correspondence with experiment, with a branching fraction of 13Ϯ3% for the formation of OHϩN 2 at 300 K, and relatively low OH and N 2 vibration/rotation excitation. The results on surface II are similar with respect to both branching and energy partitioning, indicating relatively weak sensitivity of the results of key features of the surface.

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“…Studies of NH reactions with a variety of partners have been conducted from room temperature up to temperatures relevant to combustion processes. In particular, studies of NH with NO have been investigated at high temperatures in shock heated gases, , in flames, , and at room temperature and above in order to gain experimental information on the mechanism and branching ratio of a relatively simple reactive system. − In addition, high-temperature studies of NH with hydrocarbons have been conducted to investigate the role of abstraction and addition pathways. − The self-reaction and those of NH + OH and NH + O 2 , ,− have also been reported, and to the best of our knowledge, no studies below 250 K with any partner have been conducted.…”

Section: Introductionmentioning

confidence: 99%

Low Temperature NH(X ³Σ^-) Radical Reactions with NO, Saturated, and Unsaturated Hydrocarbons Studied in a Pulsed Supersonic Laval Nozzle Flow Reactor between 53 and 188 K

Mullen

Smith

2005

J. Phys. Chem. A

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The reactions of ground-state imidogen radicals (NH(X 3sigma-)) with NO and select saturated and unsaturated hydrocarbons have been measured in a pulsed supersonic expansion Laval nozzle flow reactor in the temperature range 53-188 K. The rate coefficients for the NH + NO system display negative temperature dependence in the temperature regime currently investigated and a global temperature-dependent fit is best represented in a modified power law functional form, with k1(NH + NO) = (4.11 +/- 0.31) x 10(-11) x (T/300)(-0.30+/-0.17) x exp(77+/-21/T) cm3/s. The reactions of NH with ethylene, acetylene, propene, and diacetylene were measured over the temperature range 53-135 K. In addition, the reactions of NH with methane and ethane were also measured at 53 K, for reasons discussed later. The temperature dependence of the reactions of NH with the unsaturated hydrocarbons are fit using power law expressions, k(T) = A(T/300)(-n), and are as follows: k4 = (2.3 +/- 1.2) x 10(-12) x (T/300)(-1.09+/-0.33) cm3/s, k5 = (4.5 +/- 0.3) x 10(-12) x (T/300)(-1.07+/-0.04) cm3/s, k6 = (5.6 +/- 1.9) x 10(-12) x (T/300)(-1.23+/-0.21) cm3/s, and k7 = (7.4 +/- 1.8) x 10(-12) x (T/300)(-1.23+/-0.15) cm3/s for ethylene, acetylene, propene, and diacetylene, respectively. The rate for NH + ethane at 53 K is measured to be k3 = (6.8 +/- 1.7) x 10(-12) cm3/s, while that for methane at the same temperature represents an upper bound of k2 < or = (1.1 +/- 4.3) x 10(-12) cm3/s, as this is at the limits of measurement with our current technique. The behavior of these systems throughout the temperature range explored indicates that these reactions occur over a potential energy surface without an appreciable barrier through a complex formation mechanism. Implications for chemistry in low temperature environments where these species are found are briefly discussed.

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Detection of NH (X p3Σ−) by resonance fluorescence in the pulsed vacuum uv photolysis of NH3 and its application to reactions of NH radicals

Cited by 52 publications

References 7 publications

A shock tube study of the reactions of NH with NO, O₂, and O

A shock tube study of the reactions of NH with NO, O₂, and O

A theoretical study of the NH+NO reaction

Low Temperature NH(X ³Σ^-) Radical Reactions with NO, Saturated, and Unsaturated Hydrocarbons Studied in a Pulsed Supersonic Laval Nozzle Flow Reactor between 53 and 188 K

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Detection of NH (X p3Σ−) by resonance fluorescence in the pulsed vacuum uv photolysis of NH3 and its application to reactions of NH radicals

Cited by 52 publications

References 7 publications

A shock tube study of the reactions of NH with NO, O2, and O

A shock tube study of the reactions of NH with NO, O2, and O

A theoretical study of the NH+NO reaction

Low Temperature NH(X 3Σ-) Radical Reactions with NO, Saturated, and Unsaturated Hydrocarbons Studied in a Pulsed Supersonic Laval Nozzle Flow Reactor between 53 and 188 K

Contact Info

Product

Resources

About

A shock tube study of the reactions of NH with NO, O₂, and O

A shock tube study of the reactions of NH with NO, O₂, and O

Low Temperature NH(X ³Σ^-) Radical Reactions with NO, Saturated, and Unsaturated Hydrocarbons Studied in a Pulsed Supersonic Laval Nozzle Flow Reactor between 53 and 188 K