Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
6593855 | Combustion and Flame | 2018 | 10 Pages |
Abstract
The reaction of fulminic acid, HCNO, with NH2 radicals was studied using quantum chemical and theoretical kinetic methodologies. B3LYP/6-311++G(3df,2p) calculations combined with CCSD(T) energy calculations at the basis set limit reveal a complex potential energy surface, where only two entrance channels contribute significantly to the product formation. Transition state theory and RRKM master equation calculations find a rate coefficient ranging from 7.2â¯Ãâ¯10-12â¯cm3 moleculeâ1 sâ1 at room temperature, toâ¯>â¯1â¯Ãâ¯10â10â¯cm3 moleculeâ1 sâ1 at 3000â¯K. Despite a reduced efficiency in product formation due to fast redissociation of the adducts to the reactants at high temperatures, the title reaction can thus be an efficient sink for HCNO at combustion temperatures in nitrogen-rich environments. At 1â¯bar and below, H2NCOâ¯+â¯NO is the dominant product, with H2NCNâ¯+â¯OH and HCNâ¯+â¯NHOH contributing weakly. This work presents rate coefficients and product distributions for the temperature range 300-3000â¯K, and pressure range of 10â3-103â¯bar; a brute-force error analysis examines the expected uncertainty interval for these predictions.
Related Topics
Physical Sciences and Engineering
Chemical Engineering
Chemical Engineering (General)
Authors
Hue M.T. Nguyen, Trong N. Nguyen, Luc Vereecken,