High-Temperature Photochemistry Kinetics Studies of the Reactions of H(1²S) and D(1²S) with N₂O

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Article on high-temperature photochemistry kinetics studies of the reactions of hydrogen atom(1²S) and deuterium atom (1²S) with nitrous oxide.

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6 p.

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Marshall, Paul; Ko, Taecho & Fontijn, A. (Arthur) March 1, 1989.

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Article on high-temperature photochemistry kinetics studies of the reactions of hydrogen atom(1²S) and deuterium atom (1²S) with nitrous oxide.

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6 p.

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Abstract: The H + N₂O (1) and D + N₂O (2) reactions have been investigated by using the high-temperature photochemistry (HTP) technique. Empirical fits to the pressure-independent rate coefficients yield k₁(T) = 4.2 x 10⁻¹⁴ exp(-2290 K/T) + 3.7 x 10⁻¹⁶ exp(-8430 K/T) and k₂(T) = 3.5 x 10⁻¹³ exp(-3600 K/T) + 5.3 x 10⁻¹⁰ exp(-9170 K/T) cm³ molecule⁻¹ s⁻¹ over the ranges 410-1230 K, respectively. The 2σ precision of these results is better than 11% and the 95% accuracy limits are assessed at about ± 25%. The kinetic isotope effect x(T) = k₁(T)/k₂(T) decreases from 2.2 at 450 K to 1.3 at 1200 K, behavior contrary to classical transition-state theory which predicts x(T) increasing with temperature. The data are qualitatively consistent with a rate-controlling step that is dominated by tunneling at the lower end of the temperature range.

Reprinted with permission from the Journal of Physical Chemistry. Copyright 1989 American Chemical Society.

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  • Journal of Physical Chemistry, 1989, Washington D.C.: American Chemical Society, pp. 1922-1927

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  • Publication Title: Journal of Physical Chemistry
  • Volume: 93
  • Issue: 5
  • Page Start: 1922
  • Page End: 1927
  • Pages: 6
  • Peer Reviewed: Yes

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  • June 16, 1988

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  • March 1, 1989

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  • April 25, 2015, 8:59 p.m.

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Marshall, Paul; Ko, Taecho & Fontijn, A. (Arthur). High-Temperature Photochemistry Kinetics Studies of the Reactions of H(1²S) and D(1²S) with N₂O, article, March 1, 1989; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc503257/: accessed August 23, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.