The Kinetics of the NH Reaction with H2 and Reassessment of HNO Formation from NH + CO2, H2O

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Article on kinetics of the NH reaction with H2 and reassessment of HNO formation from NH + CO2, H2O.

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26 p.

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Fontijn, A. (Arthur); Shamsuddin, Sayed M.; Crammond, Duane; Marshall, Paul & Anderson, William R. May 1, 2006.

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Article on kinetics of the NH reaction with H2 and reassessment of HNO formation from NH + CO2, H2O.

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26 p.

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This is the accepted manuscript version of the article. Reprinted with permission from Elsevier Science Ltd., all rights reserved. The final definitive version is available here: http://www.sciencedirect.com/science/article/pii/S0010218006000113

Abstract: The reaction of ground-state NH with H2 has been studied in a high-temperature photochemistry (HTP) reactor. The NH(X3Σ)NH(X3Σ) radicals were generated by the 2-photon 193 nm photolysis of NH3, following the decay of the originally produced NH(A3Π)NH(A3Π) radicals. Laser-induced fluorescence on the View the MathML sourceNH(A3Π–X3Σ0,0) transition at 336 nm was used to monitor the progress of the reaction. We obtained View the MathML sourcek(833–1432 K)=3.5×10−11exp(−7758K/T)cm3molecule−1s−1, with ±2σ±2σ precision limits varying from 12 to 33% and corresponding accuracy levels from 23 to 39%. This result is in excellent agreement with that of Rohrig and Wagner [Proc. Combust. Inst. 25 (1994) 975] and the data sets can be combined to yield View the MathML sourcek(833–1685 K)=4.4×10−11exp(−8142K/T). Starting with this agreement, it is argued that their rate coefficients for NH + CO2 could not be significantly in error [Proc. Combust. Inst. 25 (1994) 975]. This, combined with models of several combustion systems, indicates that HNO + CO cannot be the products, contrary to their suggestion [Proc. Combust. Inst. 25 (1994) 975]. Ab initio calculations have been performed which confirm this conclusion by showing the barriers leading to these products to be too high compared to the measured activation energies. The calculations indicate the likelihood of formation of adducts, of low stability. These then may undergo further reactions. The NH + H2O reaction is briefly discussed and it is similarly argued that HNO + H2 cannot be the products, as had been previously suggested.

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  • Combustion and Flame, 2006, Amsterdam: Elsevier Science Ltd., pp. 543-551

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  • Publication Title: Combustion and Flame
  • Volume: 145
  • Issue: 3
  • Page Start: 543
  • Page End: 551
  • Peer Reviewed: Yes

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  • May 1, 2006

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  • Oct. 2, 2015, 9:40 a.m.

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Fontijn, A. (Arthur); Shamsuddin, Sayed M.; Crammond, Duane; Marshall, Paul & Anderson, William R. The Kinetics of the NH Reaction with H2 and Reassessment of HNO Formation from NH + CO2, H2O, article, May 1, 2006; [Amsterdam, Netherlands]. (digital.library.unt.edu/ark:/67531/metadc725851/: accessed October 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.