Decomposition kinetics for HONO and HNO2

被引：59

作者：

Chen, Xi ^{[1
]}

Fuller, Mark E. ^{[2
]}

Goldsmith, C. Franklin ^{[2
]}

机构：

[1] Brown Univ, Dept Chem, Providence, RI 02912 USA

[2] Brown Univ, Sch Engn, Providence, RI 02912 USA

来源：

REACTION CHEMISTRY & ENGINEERING | 2019年 / 4卷 / 02期

基金：

美国国家科学基金会;

关键词：

MULTIREFERENCE PERTURBATION-THEORY; TRANSITION-STATE THEORY; MASTER EQUATION; RATE CONSTANTS; MULTISCALE INFORMATICS; NITROGEN CHEMISTRY; ADDITION-REACTIONS; RATE COEFFICIENTS; TEMPERATURE; COMBUSTION;

D O I：

10.1039/c8re00201k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This work presents a detailed investigation into the isomerization and decomposition of HONO and HNO2. State-of-the-art electronic structure theory is used to compute the HNO2 potential energy surface. Temperature and pressure dependent rate coefficients are computed using microcanonical rate theory and the master equation. The electronic structure theory properties are optimized against the relevant experimental data. A novel strategy was developed to incorporate uncertainty in the minimum energy pathway into the optimized mechanism. The new mechanism is in excellent agreement with all available experimental data for H + NO2 OH + NO and OH + NO HONO. The calculations identify OH + NO as the dominant products for HNO2, which were neglected from all previous mechanisms in the literature.

引用

页码：323 / 333

页数：11

共 57 条

[1] Computational Study of NOx Formation at Conditions Relevant to Gas Turbine Operation, Part 2: NOx in High Hydrogen Content Fuel Combustion at Elevated Pressure [J].