The Isomerization of Dinitrogen Tetroxide: O2N-NO2 ONO-NO2
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- 作者：André ; S. Pimentel ; Francisco C. A. Lima ; Albé ; rico B. F. da Silva
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：April 19, 2007
- 年：2007
- 卷：111
- 期：15
- 页码：2913 - 2920
- 全文大小：92K
- 年卷期：v.111,no.15(April 19, 2007)
- ISSN：1520-5215
文摘
The NB>2O4 isomerization in gas phase has an energy barrier of 31 kcal mol-1 at 298 K. This energy barriermay be reduced due to the interaction of the N2O4 isomers with water or nitric acid clusters adsorbed onsurfaces. The Gibbs free energy barrier for this reaction in water medium is estimated to be reduced to 21.1kcal mol-1 by using the ab initio calculations and the polarizable continuum model (PCM). By using thetransition state theory (TST), this model estimates that the N2O4 isomerization may be as fast as 2.0 × 10-3s-1 in aqueous phase at room temperature, which confirms the Finlayson-Pitts model for the heterogeneoushydrolysis of NO2 on surfaces. The activation energy of the N2O4 isomerization is about 21 kcal mol-1. Therate coefficient for this reaction is considerably fast, 1.2 × 10-2 s-1, in aqueous phase at T = 373 K.