Activation energy and nonequilibrium effects in thermal reactions

✍ Scribed by Alvin P. Penner; Rakhal C. Bhattacharjee; Wendell Forst

• Publisher: John Wiley and Sons
• Year: 1977
• Tongue: English
• Weight: 414 KB
• Volume: 9
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550090306

✦ Synopsis

Abstract

Calculations of the nonequilibrium rate constant for the model system H~2~O~2~ + M → 2 OH + M over the temperature range of 300–1900°K, assuming that only vibrational, or that both vibrational and rotational, energy is transferred in a collision, show that (1) inefficient energy transfer leads to a distinctly non‐Arrhenius temperature dependence, the nonlinearity being in principle different for different M, and (2) despite different activation energies for different M, the order of M efficiencies is preserved throughout the temperature range. A reversal of M efficiencies can occur only if there is a change of mechanism of the reaction over the temperature range investigated.