Combustion of ethylamine, dimethylamine and diethylamine: Theoretical and kinetic modeling study

A quantum chemical and kinetics study on the unimolecular reactions of fuel radicals formed during the oxidation of n‐propylamine

“…Therefore, it is suggested that the β‐scission reactions, in which the CC and CN bonds around α ‐position carbon break, is more likely to occur than the β‐scission reaction of alkanes, and the β‐scission of the CC and CN bonds is more pronounced than that of alkanes. The observations are consistent with the conclusions disclosed by Li et al and others, that the CC bond around the α‐position carbon, weakened by the substituent effect of the amino group, preferentially contributed to the reaction 10–16, 20, 25 …”

“…However, since the rate constants for () and () proposed by Li et al are given as the inverse reaction, the rate constants for () and () were adjusted using equilibrium constants. The reaction rate constants for the CH 2 CH 2 NH 2 radical in CN bond scission and for the CH 3 CH 2 NH radical in CC bond scission are shown in Figure 9B,C 15, 25, 26 . As mentioned in section 2.2 above, a reasonable value for the average downward energy parameter of the n ‐propylamine fuel radical is not known in performing the RRKM/ME analysis.…”

“…The β‐scission of the dimethylamine CN bond was evaluated by CBS‐QB3 energy calculations and the Rice–Ramsperger–Kassel–Marcus (RRKM) / Master equation (ME) analysis method under their test conditions of 4 kPa pressure in Ar carrier gas 12 . Pappijn et al evaluated the reaction rate constants of the β‐scission reaction of fuel radicals, such as diethylamine, ethylamine, and dimethylamine, at the high‐pressure limit using the CBS‐QB3 method 25 . Mai et al used the RRKM/ME analysis method to evaluate the association reaction of ethylene and NH 2 radicals, and the unimolecular reaction of the product ethylamine radical 26 .…”

Theoretical Study of the Thermal Decomposition of Urea Derivatives

“…The construction of urea derivative kinetic models will need submechanisms for these two families of compounds. If detailed chemical kinetics models for the combustion of amines are available in the literature, − then this is not the case for isocyanates for which only HNCO submechanisms are available . Therefore, progress in the understanding and modeling of the kinetics of the combustion of isocyanates remains to be made to be able to develop detailed chemical kinetics models for urea derivatives’ combustion and pyrolysis.…”

Advanced kinetic calculations with multi-path variational transition state theory for reactions between dimethylamine and nitrogen dioxide in atmospheric and combustion temperature ranges

“…Li et al 5 and Shi et al 8 both investigated the combustion chemistry of DMA by measuring its ignition delay times in shock tubes and Shi et al 8 found that the H-abstraction reactions from DMA by NO 2 are important during the DMA autoignition. Recently, Pappijn et al 9 reviewed the combustion chemistries of several amines including DMA, and found that these amines are key precursors for HCN and NO x . These investigations indicate that NO 2 is a significant nitrogen-containing product during DMA combustion, and the reactions between DMA and NO 2 are important when amines are used as additives in engines.…”