Kinetic and Thermochemical Studies of the Recombination Reaction Na + O₂ + N₂ from 590 to 1515 K by a Modified High-Temperature Photochemistry Technique

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Article on kinetic and thermochemical studies of the recombination reaction sodium + oxygen + nitrogen from 590 to 1515 K by a modified high-temperature photochemistry technique.

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7 p.

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Marshall, Paul & Narayan, A. S. April 1, 1990.

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Article on kinetic and thermochemical studies of the recombination reaction sodium + oxygen + nitrogen from 590 to 1515 K by a modified high-temperature photochemistry technique.

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7 p.

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Abstract: An adaptation of the HTP (high-temperature photochemistry) technique to make it suitable for the study of metal atoms is described. In this, the first such HTP work, sodium salts are evaporated and ground-state atomic Na is generated by pulsed excimer or flash lamp photolysis. The decay of [Na] under pseudo-first-order conditions in the presence of O₂ is monitored by time-resolved resonance absorption at 589 nm and total N₂ pressures from 40 to 320 mbar. For the reaction Na + O₂ + N₂ → NaO₂ + N₂ (1), we thus determine log k(590-1515 K) = -44.29 + 11.70 log T - 2.347(log T)² (cm⁶ molecule⁻² s⁻¹) with a 2σ confidence interval of 21-26%, depending on temperature, which figures include a liberal allowance for potential systematic errors. Agreement with other studies of reaction 1 in isolation, over more limited temperature ranges, is good in regions of overlapping temperatures, but simple empirical extrapolations of the various data sets deviate. Results of calculations based on the Troe formalism for energy transfer well describe the present and most of these previous k(T) determinations. No evidence of equilibration of reaction 1 is observed, from which we conclude that the bond energy D₀(Na-O₂) ≥ 230 ± 5 kJ mol⁻¹, in accord with a recent flame modeling study but not with the ab initio calculations presented.

Reprinted with permission from the Journal of Physical Chemistry. Copyright 1990 American Chemical Society.

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  • Journal of Physical Chemistry, 1990, Washington D.C.: American Chemical Society, pp. 2998-3004

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  • Publication Title: Journal of Physical Chemistry
  • Volume: 94
  • Issue: 7
  • Page Start: 2998
  • Page End: 3004
  • Pages: 7
  • Peer Reviewed: Yes

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  • September 1, 1989

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  • November 9, 1989

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  • April 1, 1990

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  • April 25, 2015, 8:59 p.m.

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Marshall, Paul & Narayan, A. S. Kinetic and Thermochemical Studies of the Recombination Reaction Na + O₂ + N₂ from 590 to 1515 K by a Modified High-Temperature Photochemistry Technique, article, April 1, 1990; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc503270/: accessed November 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.