Including Nitrogen as a
ALON GRINBERG DANA, BEAT BUESSER, SHAMEL S. MERCHANT, WILLIAM H. GREEN
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, 02139, United States
Received 18 October 2017; revised 29 December 2017; accepted 4 January 2018
Published online 5 February 2018 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: The open source rate-based Reaction Mechanism Generator (RMG) software and
its thermochemical and kinetics databases were extended to include nitrogen as a heteroatom.
Speciﬁc changes to RMG and the mining of thermochemistry and reaction kinetics data are
discussed. This new version of RMG has been tested by generating a detailed pyrolysis and
oxidation model for ethylamine (EA, CH
)atß1400 K and ß2 bar, and comparing
it to recent shock tube studies. Validation of the reaction network with recent experimental
data showed that the generated model successfully reproduced the observed species as well
as ignition delay measurements. During pyrolysis, EA initially decomposes via a C
scission, and the CH
product subsequently produces the ﬁrst H radicals in this system via
β-scission. As the concentration of H increases, the major EA consuming reaction becomes H
abstraction at the α-site by H radicals, leading to a chain reaction since its product generates
more H radicals. During oxidation, the dominant N
-producing route is mediated by NO and
O. The observables were found to be relatively sensitive to the C
N EA bond
scission reactions as well as to the thermodynamic values of EA; thermodynamic data for EA
were computed at the CBS-QB3 level and reported herein. This work demonstrates the ability of
RMG to construct adequate kinetic models for nitrogenous species and discusses the pyrolysis
and oxidation mechanisms of EA.
2018 Wiley Periodicals, Inc. Int J Chem Kinet 50: 243–258,
Nitrogen chemistry attracts great attention, especially
in combustion science, because of the abundance of
Correspondence to: William H. Green; e-mail: whgreen@mit.
Present address of Beat Buesser: IBM Research, Dublin, Ireland.
Supporting Information is available in the online issue at
2018 Wiley Periodicals, Inc.
bound nitrogen in various conventional and alternative
fuel sources. Despite decades of research on nitrogen
reaction kinetics, summarized in seminal reviews by
Miller and Bowman  and by Dean and Bozzelli
, detailed reaction mechanisms of many nitrogen-
containing species remain a largely unexplored ﬁeld.
Coal and crude oil contain signiﬁcant amounts
of fuel-bound nitrogen [3–5], which, unless entirely
removed prior to combustion, leads to NO
tion (predominantly NO and NO
) that are subject to