Generation of excited nitrogen monochloride by the reaction of hydrogen atoms with nitrogen trichloride

Exton, D. B.; Gilbert, Julanna V.; Coombe, R. D.

doi:10.1021/j100160a014

Cited by 35 publications

(34 citation statements)

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“…Because emission from excited Cl 2 ( 3 Π) states was not observed for either 193 or 249 nm photolysis, it would appear that dissociation of NCl 3 to triplet fragments (eq 3) is not open at these wavelengths. As noted above, emission from excited Cl 2 is readily observed when the NCl 3 auto-decomposition flame is ignited by throttling the pump.…”

Section: Discussionmentioning

confidence: 99%

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Photodissociation of Gaseous NCl₃ at 193 and 249 nm

et al. 2002

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The optical absorption spectrum of gaseous NCl 3 was measured from 170 to 350 nm, and experiments were performed in which this molecule was irradiated with a pulsed laser at 193 nm and 249 nm. Photodissociation channels accessible at these wavelengths can produce fragments in singlet, doublet, or triplet manifolds of states. Photodissociation at 249 nm produces prompt banded emission in the visible and near-IR spectral regions that is tentatively ascribed to transitions in NCl 2 , suggesting that the dissociation channel leading to doublet fragments (NCl 2 and Cl) is operative at this photolysis wavelength. The absence of emission from excited singlet states of NCl or excited triplet states of Cl 2 suggests that the singlet and triplet dissociation channels are not important at 249 nm. For photolysis at 193 nm, prompt emission is observed from both the a 1 ∆ and b 1 Σ + excited states of NCl. No emission is observed from either NCl 2 or excited triplet states of Cl 2 . A measure of the quantum yield for NCl(a 1 ∆) production by the 193 nm photodissociation of NCl 3 was determined by observing the transfer of energy from excited NCl to iodine atoms in the pulsed photolysis system. This method suggests that the yield has a value of 0.8 ( 0.2.

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Section: Discussionmentioning

confidence: 99%

“…3,6 The NCl 3 was collected in a trap at 193 K, and subsequently allowed to warm to room temperature to allow any Cl 2 in the trap to evaporate into a stream of Ar. At room temperature, the residual NCl 3 is a golden yellow liquid.…”

Section: Methodsmentioning

confidence: 99%

Photodissociation of Gaseous NCl₃ at 193 and 249 nm

et al. 2002

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“…Our approach is to look at the possibility of using NCI3 as a fuel replacing HN3 and perhaps eliminating the need for a chlorine atom source. At Denver University, we have shown that the combustion of NCI3 by hydrogen atoms produces NCI(a1A) in high yield [4]. We used a microwave discharge to produce hydrogen atoms in those studies.…”

Section: Introductionmentioning

confidence: 99%

NCI 3 as a source of NCI(a) for an NCI(a)-I laser

et al. 2005

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NCI3 is a more stable source of NCI(a) than HN3. The use of NCI3 as a source of NCI(a1A) for use in an iodine transfer laser has been modeled. The model suggests that gain can be obtained on the spin orbit transition of the iodine atom at I .31 5pm in a purely chemical system. New quenching rates of NCI(a) by H2 and HCI show these species are not a serious problem in scaling the NCI3 system to high energy densities. The measurements of NCI(a) in our flow tube system are obscured at early times by C12(B-X) radiation from the Cl atom induced decomposition of NCI3. We have measured the contribution of this emission and find that the profile more closely matches the profile predicted by the kinetics code. We have measured the yield of Cl atoms produced by a microwave discharge of 5% Cl2 in He and find a dissociation fraction of about 25% in agreement with previous studies by Manke and Setser. The yield was measured by titrating the Cl atoms with HI and observing the HCI(v1 ) radiation. In studies of the production of NCI3, we have found that the yield of NCI3 is independent of the gas side mass transfer conditions. Our current reactor produces an NCI3 yield of about 20% relative to Cl2. Since the production of higher flows of NCI3 is important for a laser experiment, we present some ideas for scaling NCI3 to higher flow rates.The use of NCI3 as a source of NCl(a1) for use in an iodine transfer laser has been modeled. The model suggests that gain can be obtained on the spin orbit transition of the iodine atom at I .31 5pm in a purely chemical system. The experimental data obtained to this point supports the model predictions.

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“…There are at least three ways to produce the energy carrier NCl(a): the thermal decomposition or photo-dissociation of ClN 3 [13][14][15][16][17][18][19], the reaction of HN 3 and Cl atoms [2][3][4][8][9][10][11][12] and the reaction of NCl 3 and H atoms [20][21][22][23][24]. The positive gain and demonstration of lasing at 1315nm have been obtained with the latter two methods to generate NCl(a).…”

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Experimental study on supersonic all gas-phase iodine laser driven by NF₃/D₂/DCl/CF₃I combustion

Tang

Duo

et al. 2013

XIX International Symposium on High-Power Laser Systems and Applications 2012

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A supersonic all gas-phase iodine laser driven by NF 3 /D 2 /DCl/CF 3 I combustion has been experimentally studied. the gain signals of I( 2 P 3/2 ,F=4)← I( 2 P 1/2 ,F=3) at 1315.246nm and I( 2 P 3/2 ,F=3)← I( 2 P 1/2 ,F=3) at 1315.222nm were observed with an intensity of 3x10 -5 cm -1 and 1x10 -5 cm -1 respectively. The small signal gain of I( 2 P 3/2 ,F=4)← I( 2 P 1/2 ,F=3) at different location relative to HN 3 injector along the flow direction also was obtained. The experimental results indicate that the AGIL driven by NF 3 /D 2 /DCl/CF 3 I combustion is feasible.

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Generation of excited nitrogen monochloride by the reaction of hydrogen atoms with nitrogen trichloride

Cited by 35 publications

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Photodissociation of Gaseous NCl₃ at 193 and 249 nm

Photodissociation of Gaseous NCl₃ at 193 and 249 nm

NCI 3 as a source of NCI(a) for an NCI(a)-I laser

Experimental study on supersonic all gas-phase iodine laser driven by NF₃/D₂/DCl/CF₃I combustion

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Generation of excited nitrogen monochloride by the reaction of hydrogen atoms with nitrogen trichloride

Cited by 35 publications

References 0 publications

Photodissociation of Gaseous NCl3 at 193 and 249 nm

Photodissociation of Gaseous NCl3 at 193 and 249 nm

NCI 3 as a source of NCI(a) for an NCI(a)-I laser

Experimental study on supersonic all gas-phase iodine laser driven by NF3/D2/DCl/CF3I combustion

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Photodissociation of Gaseous NCl₃ at 193 and 249 nm

Photodissociation of Gaseous NCl₃ at 193 and 249 nm

Experimental study on supersonic all gas-phase iodine laser driven by NF₃/D₂/DCl/CF₃I combustion