Ab initio chemical kinetics for the NH2 + HNOx reactions, part III: Kinetics and mechanism for NH2 + HONO2
Abstract
The kinetics and mechanism for the reaction of NH2 with HONO2 have been investigated by ab initio calculations with rate constant prediction. The potential energy surface of this reaction has been computed by single‐point calculations at the CCSD(T)/6‐311+G(3df, 2p) level based on geometries optimized at the B3LYP/6‐311+G(3df, 2p) level. The reaction producing the primary products, NH3 + NO3, takes place via a precursor complex, H2N…HONO2 with an 8.4‐kcal/mol binding energy. The rate constants for major product channels in the temperature range 200–3000 K are predicted by variational transition state or variational Rice–Ramsperger–Kassel–Marcus theory. The results show that the reaction has a noticeable pressure dependence at T ktotal = 1.71 × 10−3 × T−3.85 exp(−96/T) cm3 molecule−1 s−1 at T = 200–550 K, 5.11 × 10−23 × T+3.22 exp(70/T) cm3 molecule−1 s−1 at T = 550–3000 K. The branching ratios of primary channels at 760 Torr Ar‐pressure are predicted: k1 producing NH3 + NO3 accounts for 1.00–0.99 in the temperature range of 200–3000 K and k2 + k3 producing H2NO + HONO accounts for less than 0.01 when temperature is more than 2600 K. The reverse reaction, NH3 + NO3 → NH2 + HONO2 shows relatively weak pressure dependence at P 3…O3N with a lower binding energy of 1.8 kcal/mol. The predicted rate constants can be represented by k−1 = 6.70 × 10−24 × T+3.58 exp(−850/T) cm3 molecule−1 s−1 at T = 200–3000 K and 760 Torr N2 pressure, where the predicted rate at T = 298 K, 2.8 × 10−16 cm3 molecule−1 s−1 is in good agreement with the experimental data. The NH3 + NO3 formation rate constant was found to be a factor of 4 smaller than that of the reaction OH + HONO2 producing the H2O + NO3 because of the lower barrier for the transition state for the OH + HONO2. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 69–78, 2010
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Dec 10, 2009
- Source ID
- 10.1002/kin.20463
Entities
People
- Ming‐Fong Lin
- Shucheng Xu
Organizations
- Office of Naval Research