Combustion and Flame 218 (2020) 189–204

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Combustion and Flame

journal homepage: www.elsevier.com/locate/combustflame

Combustion of propanol isomers: Experimental and kinetic modeling

study
Gianluca Capriolo∗, Alexander A. Konnov
Division of Combustion Physics, Department of Physics, Lund University, P.O. Box 118, SE-221 00 Lund, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: In this work an experimental and kinetic modeling study on n-propanol and i-propanol combustion has
Received 5 October 2019 been performed. New burning velocity measurements were carried out using the heat flux method at 1
Revised 12 May 2020
atm over the temperature range of 323–393 K. Analysis of the temperature dependence was conducted
Accepted 14 May 2020
with to verify the data consistency of the new and available data from the literature. Important inconsis-
tencies were identified with the literature experiments performed using the spherical flame method and
Keywords: the nature of such inconsistencies was discussed. Moreover, a new kinetic mechanism, based on the most
Laminar burning velocity recent Konnov model and extended to include C3 alcohol isomers chemistry subset, was validated against
n-propanol new and all available literature data obtained at different combustion regimes. Rate constant parameters
i-propanol
were carefully selected by evaluating all experimental and theoretical sources. Moreover, Sarathy et al.
Modeling
(2014) detailed kinetic mechanism was also tested. Overall, both kinetic models reproduce experimental
data with good fidelity, but the presented model was found superior in representing ignition delay times
data performed at high-pressure conditions.
© 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction
The depletion of fossil fuels, combined with the contemporary
awareness that their use has a detrimental impact on climate and
air pollution, has led to a compulsive search for more sustainable
transportation fuels. In this regard, small aliphatic alcohols can be
valuable alternative fuels/fuel additives in SI engines, contributing
to improve engine combustion efficiency and performance as their
use increases antiknock index and burning velocities, if compared
to traditional gasoline. To this end, a recent review on alcohol com-
bustion chemistry performed by Sarathy et al. [1] provides a valu-
able explanation of C1 –C5 alcohols combustion characteristics and
why such hydroxylated compounds are suitable for internal com-
bustion engine (ICE) applications. Alcohol fuels can be manufac-
tured sustainably, i.e., through fermentation of biomass feedstocks,
waste, and also from new alternative routes, such as metabolically
engineered Escherichia Coli [2], which potentially would enable a
high yield and volumetric productivity.
Pyrolysis and oxidation kinetics of propanols has been exten-
sively studied in the literature, including static [3–6], flow [7–9],
and well stirred reactors [10,11], as well as shock tubes 12–17],
burners [18–24] and laminar burning velocity (LBV) measurement
apparatus 9–11,25–27]. Smith and Gordon [3] reported that, for n-
∗
Corresponding author.
E-mail address: gianluca.capriolo@forbrf.lth.se (G. Capriolo).
propanol and i-propanol the fastest reaction rates for primary rad-
ical decomposition are attributable to the Cα -H bond cleavage. The
following studies on propyl alcohols were mainly focused on py-
rolysis [4–6], leading to different conclusions. Barnard and Hughes
[4], and Barnard [5], ascertained that the chain-initiating step for
n-propanol and i-propanol pyrolysis occurred via the scission of
Cα –Cβ and Cα –H bonds respectively. On the contrary Trenwith [6],
investigating i-propanol pyrolysis with a static reactor at T = 721–
801 K and P = 10–100 Torr came to a different conclusion, namely
that the reaction was initiated by scission of Cα –Cβ bond.
Norton and Dryer [7] found out that the reactivity of n-
propanol was much higher than that of its isomer. The authors
[7] concluded that the difference between the two isomers was
strictly related to the diverse reactivity of the major intermediate
species derived from their oxidations, i.e., propanal and acetone,
in turn, related to the higher propensity of n-propanal to dehy-
drogenate than dehydrate. Assessment of the theoretical work of
Bui et al. [28] on the dehydration reaction rate of isopropanol was
made by Heyne et al. [8]. The experimental results revealed that
the dehydration reaction proceeds faster than the one predicted in
the study of Bui et al. [28].
Most recently, an experimental and kinetic work on C3 alcohols
was performed by Li et al. [9]. Results showed that the major oxy-
genated intermediates in n-propanol pyrolysis are C1 –C2 aldehy-
des and ethenol while, for i-propanol, C2 aldehydes, and ketones.
Model analysis unveiled that n-propanol mainly reacts via the H-

https://doi.org/10.1016/j.combustflame.2020.05.012
0010-2180/© 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
190 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
abstraction and the Cα –Cβ bond dissociation reactions, while the
H2 O elimination and also the H abstraction reactions controlled the
i-propanol consumption.
Combustion characteristics of n-propanol and i-propanol were
experimentally studied, respectively, by Galmiche et al. [10] and
Togbé et al. [11] in a JSR and a spherical combustion chamber. Be-
sides, Galmiche et al. [10] also proposed a detailed kinetic mecha-
nism for the n-propanol oxidation, which showed good agreement
with their experimental results, but significant inconsistencies with
the LBV data from [24]. In the study of Togbé et al. [11], the per-
formed experiments were compared with numerical simulations
using the mechanism by Johnson et al. [13]. The model showed
poor performance in reproducing presented experimental data. Fi-
nally, both studies stated that the effect of pressure on LBVs was
coherent with previous literature works on C1 –C6 alcohols.
Wang and Cadman [12] focused their study on soot and PAH
formation during pyrolysis and oxidation of different hydrocar-
bons, including n-propanol. It was found that, among the consid-
ered fuels, n-propanol had a lesser sooting tendency. Johnson et
al. [13] investigated the ignition properties of propyl alcohols be-
tween 1350 and 20 0 0 K. A kinetic mechanism, based on Bourque
et al. [29] model and extended to include C3 alcohol isomers reac-
tion subset, was also proposed. The authors highlighted the impor-
tant role of low hydrocarbons and hydrogen chemistry on ignition
delay time (IDT) predictions. High-temperature ignition behavior
of i-propanol was also investigated by Akih-Kumgeh and Bergth-
orson [14]. Notable discrepancies were found when the model of
Johnson et al. [13] was assessed against the experimental results.
Noorani et al. [15] studied the ignition characteristics of C1 –C4
primary alcohols. The experimental results were compared with
different models from the literature. Particularly for n-propanol,
the IDTs data were compared with Johnson et al. [13] mechanism.
Model prediction failed in reproducing experiments, resulting in a
general underestimation of the n-propanol reactivity. Lately, Man
et al. [16] studied the IDTs of C3 alcohol isomers and also pro-
posed a new kinetic model based on a modified version of John-
son et al. [13] which was validated against new and literature data
[10,11,15,22]. Modeling results showed good agreement in simulat-
ing the IDTs and the JSR data, while tended to sensibly overpredict
the LBVs in rich mixtures. The model also showed that propanols
combustion is mainly sensitive to small hydrocarbon chemistry.
Jouzdani et al. [17] studied ignition and pyrolysis time scales of
propyl alcohols and the experiments were compared with several
literature models [1,13,16]. Investigations endorsed what stated in
other previous works, namely the highest reactivity of the primary
alcohol under the tested conditions. Moreover, among tested mod-
els, Sarathy mechanism [1] showed the closest agreement with the
experimental data.
A counterflow diffusion flame burner was employed by Sinha
and Thomson [18] to determine profiles of several C3 oxygenated
hydrocarbons and their products and stable intermediates. Partic-
ularly, for i-propanol, the product compositions were found sim-
ilar to those reported by the previous literature studies [3,7,28].
Lately, Li et al. [19] studied the combustion chemistry of acetone
and propyl alcohols flames using synchrotron photoionization and
molecular-beam mass spectrometry (MBMS); different structural
features of the oxygenated fuels were analyzed and discussed. Fur-
thermore, the production routes of known and newly observed in-
termediates were found or proposed. Kasper et al. [20] employed
two independent MSBM techniques, namely electron ionization
(EI) and vacuum UV light for single-photon ionization (VUV-PI), to
determine the products of n-propanol and i-propanol oxidation in
stoichiometric and rich low-pressure flat flames. Profiles of major
species were found very similar for the two isomers, while larger
differences were found for oxygenated intermediates. Flame struc-
tures of propyl alcohols were investigated by Frassoldati et al. [21].
A new kinetic model for propyl alcohols oxidation and pyrolysis
was also presented and assessed against new and literature ex-
perimental data [7,13,18,20] and it showed an overall satisfactory
agreement. An experimental and numerical study on extinction
and autoignition of C3 –C4 primary and secondary alcohols were
performed by Alfazi et al. [23]. The experimental results showed
that n-propanol had a higher propensity to auto-ignite and the
lower to extinguish; on the contrary, i-propanol exhibits the lowest
reactivity and extinction limits. Such behavior was attributed, sim-
ilarly to previous studies, to the less reactive intermediates formed
during the oxidation, such as acetone. Veloo and Egolfopoulos
[22] measured the LBV and the extinction strain rate of the two
propanol isomers at 343 K and at 1 atm and compared the results
with the prediction of the kinetic mechanism of Johnson et al. [13].
Numerical simulations were not able to reproduce experimental
data consistently. Authors [22] also attributed the higher reactiv-
ity of n-propanol to the differences in intermediate species’ forma-
tion between the two structural isomers. High-pressure measure-
ments of C1 –C4 primary alcohols LBV were performed by Beeck-
man et al. [25] and their experimental data were used to assess
the predictions of different models available from the literature.
Specifically for n-propanol, the accuracy of the model of Johnson
et al. [13] was tested; numerical simulations failed in reproduc-
ing experimental results resulting in an important underestimation
of the data over the whole investigated equivalence ratio range.
The authors [25] emphasized the need for additional studies of
the fuel-specific reactions that are pressure dependent. New LBV
measurements of several C3 oxygenated were provided by Gong et
al. [26] A new kinetic mechanism, based on an updated version of
Aramco mech. 1.3 [30] and extended to include then-propanol sub-
mechanism from [13], was also tested against the experimental re-
sults, resulting in a general overestimation of the experimental re-
sults for propanols+air mixtures. Li et al. [27] measured the LBVs
of C1 –C5 primary alcohol-isooctane blends and noted a monotonic
relationship between LBV and the alcohol mole fraction present
into the fuel mixture and an empirical relationship was suggested.
Katoch et al. [24] measured LBV at different temperatures and the
performance of six different models was also tested with the pre-
sented and the literature LBV measurements. Notable inconsisten-
cies among proposed and literature experimental data, as well as
among numerical simulations, were found. The authors concluded
on the need for further investigation to understand the nature of
model discrepancies among the tested mechanisms.
In addition to the mentioned experimental investigations, ded-
icated modeling studies were also performed. Ranzi et al. [31] de-
veloped a reaction scheme for hydrocarbon and oxygenated fuels
and used the LBV data from [22] to validate the propanol isomers
subset, achieving very good agreement between the model and ex-
periments. The detailed kinetic model of Man et al. [16] was em-
ployed by Liu et al. [32] to build a reduced PRF-alcohols mecha-
nism and validated against several literature datasets. With the in-
tent to deepen the knowledge of alcohol combustion properties,
Sarathy et al. [1] made a review on alcohol combustion chem-
istry, proposing also a new kinetic model for C1 –C5 alcohols. For
the propanol isomers, the model was tested against experimental
data from [16] and [22]. For the IDTs data, good fidelity was found,
while for the LBVs experiments there was a general trend in over-
predicting the experiments in rich conditions. Authors also stated
that the lower LBV and higher IDT of the branched alcohol stem
from the more stable form of its combustion intermediates.
In Table 1 are summarized the most recent kinetic works on
propyl alcohols pyrolysis, oxidation and combustion as well as
the literature data used for their validation. From the in-depth
analysis of the literature studies, it emerged as the existing LBV
and kinetic studies are somewhat contradictory. In virtue of the
above, the aim of this study was twofold. First, to propose a new
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
Table 1
Most recent kinetic models and experimental studies used for their validation.
detailed kinetic mechanism of C3 alcohol isomers combustion.
In this regard, new LBV measurements were also performed, for
the first time, with the heat flux method. This method ensures
robustness and reproducibility of the LBV measurements and
therefore is an extremely useful tool for the model validation.
Then, the proposed kinetic mechanism is also validated against
LBV existing data [9–11,14,24–26], obtained with other different
methods. Second, to try to elucidate the discrepancies that have
arisen between experimental and simulated LBV came out in
previous studies [10,11,14,24–26], by checking and comparing
the consistency of the different burning velocity measurements
performed with different experimental methods. Additionally, the
proposed new kinetic model was further assessed against a large
literature dataset (see Table 1). Finally, the proposed model was
compared with Sarathy et al. [1] kinetic mechanism predictions.
Sarathy mechanism, consisting of over 3600 reactions and more
than 680 species, was tested in the current study since its C3
alcohol isomers subsets are mainly based on the well-established
mechanism [16] to which important low-temperature chemical
reactions have been added. Moreover, the model of Sarathy et
al. [1] was also tested in several recent publications [1,17,23],
showing good performance and also because it was found superior
when compared with other kinetic models [23].
2. Experimental
In this work, the heat flux method was applied to determine
the LBVs of C3 alcohols at atmospheric pressure and over the
equivalence ratio range of  = 0.7–1.4. The low vapor pressure
of propyl alcohols did not allow performing measurements in the
gas phase at standard conditions; as a result, the unburned mix-
ture temperature was set to 323 K; higher temperatures, i.e., 343 K
and 393 K, were also explored. The test fuels were provided by
Alfa Aesar with stated high-purity (99+% for 1-propanol and 99.5%
for 2-propanol); the oxidizer was provided by AGA with the fol-
lowing composition: 21% O2 , 79% N2 . In the heat flux method
a flat premixed flame is stabilized on a perforated burner under
near-adiabatic conditions. The aforesaid conditions occur when the
heat losses needed to stabilize the flame on the burner plate are
191
equaled by the heat received by the inlet gasses flowing through
the preheated burner plate. The heat flux method provides flat
flame configurations free from the stretch effects, which are well
known to be one of the major issues in LBV determination per-
formed with other methods, i.e., spherical and counterflow flames.
Method description, as well as the experimental setup and the data
processing procedures, are extensively explained elsewhere [33],
while the associated measurement uncertainties are discussed in
[34]. New LBV of propyl alcohols +air mixtures, together with as-
sociated uncertainties, are available as Supplemental Material.
3. Kinetic mechanism
The present kinetic model, hierarchically structured, consists
of 1787 reactions and 161 species and is based on the most
recent Konnov mechanism provided by Capriolo et al. [35] with
some important modification introduced by Konnov [36] i.e., the
integration of the termolecular reactions associated to hydrogen
oxidation, namely, H + O2 + R suggested by Klippenstein and
Burke [37,38]; furthermore, the transport properties were updated
using calculations of Jasper et al. [39,40]. In this work, the mech-
anism has been extended to update and extend the chemistry of
propanol isomers. All of the most important reactions associated
with n-propanol and i-propanol oxidation and pyrolysis, along
with their Arrhenius coefficients, are listed in Tables 2 and3 and
discussed in this section. All the rate constant expressions adopted
in the propyl alcohols submodel were carefully selected to assure
a consistent modeling development; further details related to the
rate constants selections are available in the reaction datasheets in
the Supplemental Material. Some rate constants of the pressure-
dependent reactions are incorporated using PLOG formulation;
for these reactions only the rate constants at 1 atm are listed in
Tables 2 and 3. The prresent detailed reaction mechanism with
the thermodynamic and the transport properties, is also provided
in the CHEMKIN format as Supplemental Material.
According to the study of Oyeyemi et al. [41], performed using
multireference averaged coupled-pair functional (MRACPF2), the
hyperconjugated Cα -Cβ and Cα -H (see Fig. 1) bonds in C1 –C4 al-
cohols have the lowest bond dissociation energy values (BDEs). As
192 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204

Table 2
Arrhenius parameters selected for n-propanol kinetic sub-mechanism. Units: A – cm3 mol−1 s−1 , Ea – cal mol−1 , T – K.

No Reaction A n Ea UF Ref.

Hydrogen abstraction
1 nC3 H7 OH + OH  C3 H7 O + H2 O 5.88E+02 2.82E+00 −5.85E+02 2 [1]
2 nC3 H7 OH + OH  C2 H5 CHOH + H2 O 3.61E+03 2.89 −2291.0 2 [1]
3 nC3 H7 OH + OH  CH3 CHCH2 OH + H2 O 1.54E+00 3.70 −3736.0 2 [1]
4 nC3 H7 OH + OH  CH2 CH2 CH2 OH + H2 O 5.28E+09 9.70E-01 1.59E+03 2 [13]
5 nC3 H7 OH + H  C3 H7 O + H2 5.36E+04 2.53E+00 4.405E+03 2 [13]
6 nC3 H7 OH + H  C2 H5 CHOH + H2 8.79E+04 2.68E+00 2.92E+03 2 [47]
7 nC3 H7 OH + H  CH3 CHCH2 OH + H2 1.11E+05 2.40E+00 2.01E+03 2 [13]
8 nC3 H7 OH + H  CH2 CH2 CH2 OH + H2 6.66E+05 2.54E+00 6.76E+03 2 [13]
9 nC3 H7 OH + O2  C3 H7 O + HO2 1.00E+13 0.00E+00 4.82E+04 2 [13]
10 nC3 H7 OH + O2  C2 H5 CHOH + HO2 2.00E+13 0.00E+00 4.95E+04 2 [13]
11 nC3 H7 OH + O2  CH3 CHCH2 OH + HO2 2.44E+12 0.22 4.98E+04 2 [13]
12 nC3 H7 OH + O2  CH2 CH2 CH2 OH + HO2 3.00E+13 0.00E+00 5.23E+04 2 [13]
13 nC3 H7 OH + HO2  C3 H7 O + H2 O2 2.50E+12 0.00E+00 2.40E+04 2 [13]
14 nC3 H7 OH + HO2  C2 H5 CHOH + H2 O2 3.50E-05 5.26E+00 8.27E+03 2.5 [49]
15 nC3 H7 OH + HO2  CH3 CHCH2 OH + H2 O2 7.51E-03 4.52E+00 1.47E+04 2.5 [49]
16 nC3 H7 OH + HO2  CH2 CH2 CH2 OH + H2 O2 8.80E-02 4.31E+00 1.73E+04 2.5 [49]
17 nC3 H7 OH + O  C3 H7 O + OH 1.46E-03 4.73E+00 1.73E+03 2 [50]
18 nC3 H7 OH + O  C2 H5 CHOH + OH 1.45E+05 2.47E+00 8.76E+02 2 [50]
19 nC3 H7 OH + O  CH3 CHCH2 OH + OH 1.44E+05 2.61E+00 3.03E+03 2 [13]
20 nC3 H7 OH + O  CH2 CH2 CH2 OH + OH 9.81+05 2.43E+00 4.75E+03 2 [13]
21 nC3 H7 OH + CH3  C3 H7 O + CH4 2.04E+00 3.57 7721.0 2 [13]
22 nC3 H7 OH + CH3  C2 H5 CHOH + CH4 1.993E+01 3.37 7634.0 2 [13]
23 nC3 H7 OH + CH3  CH3 CHCH2 OH + CH4 8.02E+00 3.23 6461.0 2 [13]
24 nC3 H7 OH + CH3  CH2 CH2 CH2 OH + CH4 4.53E-01 3.65 7154.0 2 [13]
25 nC3 H7 OH + C2 H5  C3 H7 O + C2 H6 1.00E+11 0.00E+00 9.20E+03 2 [13]
26 nC3 H7 OH + C2 H5  C2 H5 CHOH + C2 H6 2.00E+11 0.00E+00 1.10E+04 2 [13]
27 nC3 H7 OH + C2 H5  CH3 CHCH2 OH + C2 H6 7.66E+00 3.11E+00 1.22E+04 2 [13]
28 nC3 H7 OH + C2 H5  CH2 CH2 CH2 OH + C2 H6 4.62E-01 3.65E+00 9.14E+03 2 [13]
29 nC3 H7 OH + CH2 OH  C3 H7 O + CH3 OH 1.20E+02 2.76E+00 1.08E+04 2 [13]
30 nC3 H7 OH + CH2 OH  C2 H5 CHOH + CH3 OH 6.00E+01 2.95E+00 1.20E+04 2 [13]
31 nC3 H7 OH + CH2 OH  1.53E+01 3.11E+00 1.22E+04 2 [13]
CH3 CHCH2 OH + CH3 OH
32 nC3 H7 OH + CH2 OH  1.01E+02 2.95E+00 1.40E+04 2 [13]
CH2 CH2 CH2 OH + CH3 OH
33 nC3 H7 OH + CH3 O  C3 H7 O + CH3 OH 2.30E+10 0.00E+00 2.90E+03 2 [13]
34 nC3 H7 OH + CH3 O  C2 H5 CHOH + CH3 OH 1.50E+00 2.95E+00 4.50E+03 2 [13]
35 nC3 H7 OH + CH3 O  CH3 CHCH2 OH + CH3 OH 3.02E+00 1.80E-01 4.70E+03 2 [13]
36 nC3 H7 OH + CH3 O  CH2 CH2 CH2 OH + CH3 OH 2.17E+11 0.00E+00 6.46E+03 2 [13]
37 nC3 H7 OH + CH3 O2  C3 H7 O + CH3 O2 H 2.50E+12 0.00E+00 2.40E+04 2 [13]
38 nC3 H7 OH + CH3 O2  C2 H5 CHOH + CH3 O2 H 6.00E+12 0.00E+00 1.60E+04 2 [13]
39 nC3 H7 OH + CH3 O2  1.56E+03 2.81E+00 1.43E+04 2 [13]
CH3 CHCH2 OH + CH3 O2 H
40 nC3 H7 OH + CH3 O2  2.38E+04 2.55E+00 1.65E+04 2 [13]
CH2 CH2 CH2 OH + CH3 O2 H
41 nC3 H7 OH + HCO  C3 H7 O + CH2 O 3.40E+04 2.50E+00 1.35E+04 2 [13]
42 nC3 H7 OH + HCO  C2 H5 CHOH + CH2 O 1.00E+07 1.90E+00 1.70E+04 2 [13]
43 nC3 H7 OH + HCO  CH3 CHCH2 OH + CH2 O 5.16E+05 2.25E+00 1.68E+04 2 [13]
44 nC3 H7 OH + HCO  CH2 CH2 CH2 OH + CH2 O 1.02E+05 2.50E+00 1.84E+04 2 [13]
Unimolecular decomposition
45 nC3 H7 OH  C3 H7 O + H 7.03E+14 7.40E−02 1.05E+05 2 [13]
46 nC3 H7 OH  C2 H5 CHOH + H 1.78E+16 −1.73E−01 9.53E+04 2 [13]
47 nC3 H7 OH  CH3 CHCH2 OH + H 3.52E+18 −7.28E−01 1.00E+05 2 [13]
48 nC3 H7 OH  CH2 CH2 CH2 OH + H 1.84E+17 −3.56E−01 1.01E+05 2 [13]
49 nC3 H7 OH (+M)  C3 H6 + H2 O (+M) 3.53E+13 0.00E+00 6.73E+04 2 [13]
Low P limit 1.99E+81 −1.86E+01 7.92E+04
Troe a = 0.13 T3 = 1 T1 = 8.94E+09 T2 = 9.33e+09
50 nC3 H7 OH (+M)  CH3 + PC2 H4 OH (+M) 8.81E+23 −2.12 8.98E+04 2 [13]
Low P limit 2.20E+64 −13.39 9.53E+04
Troe a = 0.307 T3 = 1110 T1 = 9.33E+09 T2 = 9.33e+09
51 nC3 H7 OH (+M)  C2 H5 + CH2 OH (+M) 1.728E+26 −2.72 86,207.0 2 [45]
Low P limit 1.6771E+89 −20.364 99,453.0
Troe a = 5.5845E−03 T3 = 358.2 T1 = 4.9325E+07 T2 = 2.4761E+03
52 nC3 H7 OH (+M)  C3 H7 + OH (+M) 5.26E+20 −1.34 9.46E+04 2 [13]
Low P limit 8.92E+57 −11.78 99,410
Troe a = 0.355 T3 = 942 T1 = 9.92E+09 T2 = 9.92E+09
Radical decomposition
53 C2 H5 CHOH + O2  C2 H5 CHO + HO2 5.28E+17 −1.638 839 2 [53]a
54 CH3 CHCH2 OH + O2  C3 H5 OH + HO2 1.50E+12 0.00E+00 5.00E+03 2 [21]
55 CH3 CHCH2 OH + O2  C2 H5 CHO + HO2 1.50E+12 0.00E+00 5.00E+03 2 [21]
56 CH2 CH2 CH2 OH + O2  C3 H5 OH + HO2 1.50E+12 0.00E+00 5.00E+03 2 [21]
57 C3 H7 O  C2 H5 + CH2 O 2.46E+35 −7.69 1.92E+04 2 [51]a
58 C3 H7 O  C2 H5 CHO + H 1.72E+19 −3.41 1.80E+04 2 [51]a
59 C3 H7 O  CH2 CH2 CH2 OH 7.46E+09 6.18E−01 2.08E+04 2 [52]
60 C3 H7 O  C2 H5 CHOH 2.72E+11 6.35E−01 2.92E+04 2 [52]
(continued on next page)
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204 193

Table 2 (continued)

No Reaction A n Ea UF Ref.

61 C3 H7 O  CH3 CHCH2 OH 4.88E+10 5.62E−01 2.75E+04 2 [52]

62 CH2 CH2 CH2 OH  C2 H4 + CH2 OH 9.29E+38 −8.33 4.33E+04 2 [51]a
63 CH2 CH2 CH2 OH  C3 H5 OH + H 1.60E+12 0.427 4.08E+04 2 [52]
64 CH2 CH2 CH2 OH  C2 H5 + CH2 O 7.10E+41 −9.13 4.48E+04 2 [51]a
65 CH2 CH2 CH2 OH  C3 H6 + OH 3.16E+37 −8.17 4.19E+04 2 [51]a
66 C2 H5 CHOH  C2 H3 OH + CH3 5.67E+41 −8.8 4.19E+04 2 [51]a
67 C2 H5 CHOHC2 H5 CHO+H 1.03E+11 0.83 36,830 2 [52]
68 C2 H5 CHOH  CH3 CHCHOH + H 7.10E+41 −9.13 4.48E+04 2 [51]a
69 C2 H5 CHOH  CH3 CHCH2 OH 2.34E+10 8.38E-01 4.24 E+04 2 [52]
70 C2 H5 CHOH  C2 H5 + CH2 O 3.16E+37 −8.17 4.19E+04 2 [51]a
71 C2 H5 CHOH  CH2 CH2 CH2 OH 2.49E+09 8.79E-01 4.13 E+04 2 [52]
72 CH3 CHCH2 OH  C3 H6 + OH 1.51E+33 −6.46 3.24E+04 2 [51]a
73 CH3 CHCH2 OH  H+C3 H5 OH 1.36E+28 −5.24 3.83E+04 2 [51]a
74 CH3 CHCH2 OH  H + CH3 CHCHOH 1.79E+32 −6.51 3.84E+04 2 [51]a
Keto-enol isomerization
75 CH3 CHCHOH + HO2  C2 H5 CHO + HO2 1.49E+05 1.67E+00 6.81E+03 2 [57]
76 CH3 CHCHOH + HOCHO  2.81E−02 3.29E+00 −4.51E+03 2 [58]
C2 H5 CHO + HOCHO
a
Pressure-dependent reaction described using PLOG formulation.

Fig. 1. BDEs of n-propanol (right) and i-propanol (left) expressed in kcal/mol from [40], depicting the different labels used in this work.

a result, the expected routes for fuel decomposition and metathe- nC3 H7 OH + H  C2 H5 CHOH + H2 (R6)
sis reactions are dominated by the scission of the aforementioned
bonds. nC3 H7 OH + H  CH3 CHCH2 OH + H2 (R7)

3.1. Unimolecular decomposition nC3 H7 OH + H  CH2 CH2 CH2 OH + H2 (R8)

For reaction (R6), the kinetic parameters were taken from

For the unimolecular decomposition of n-propanol, the rate
constant expressions included in the current mechanism are taken
from Johnson et al. [13] recommendations, in turn based on the
earlier studies of Tsang [42–44], and from Sarathy et al. [45]. For
reactions (R100) and (R101), estimations from Man et al. [16] were
accepted and included here.
3.2. Metathesis reactions
Rate constant expressions needed to develop the C3 alcohol
isomers sub-model have been derived considering kinetic analo-
gies with published data for ethanol and butanol. Specifically, this
choice is made assuming that the H abstraction rates from the hy-
droxyl group and Cα carbon are analogous to the ones that occur
in ethanol. On the other hand, the H atom transfer from Cβ and
Cγ carbon to the specific radical is considered to be kinetically
identical to butanol. Such assumptions were made simply compar-
ing bond dissociation energy values of C1 –C4 alcohols calculated
in [41].
For n-propanol and i-propanol, most of the rate constant ex-
pressions involving metathesis reactions were largely based on
Johnson [13] C3 alcohol subsets, which are in turn based on the
previous detailed chemical mechanism proposed by Black et al.
[46]. For n-C3 H7 OH, hydrogen atom transfer with H atom proceeds
via four channels:
nC3 H7 OH + H  C3 H7 O + H2
the experimental and theoretical work of Sivaramakrishnan [47].
Channel-specific Arrhenius parameters were calculated using ab
initio TST and successively adjusted to fit experimental data from
their study and from Aders and Wagner [48], increasing the value
of each barrier by 0.8 kcal/ mol. The rate constants for reactions
(R5), (R7), and (R8) were adopted from the previous work on
propyl alcohols combustion of Johnson et al. [13].
For i-C3 H7 OH, the direct H abstraction by H atom from occurs
via three channels:
iC3 H7 OH + H  iC3 H7 O + H2 (R80)
iC3 H7 OH + H  tC3 H6 OH + H2 (R81)
iC3 H7 OH + H  iC3 H6 OH + H2 (R82)
Rate constants expressions related to the H abstraction from the
hydroxyl group, as well as from the CH3 group, were taken from
the experimental and theoretical study on C2 H5 OH [34]. For reac-
tion R81, the values recommended in the kinetic study of Johnson
et al. [13] on propyl alcohols were accepted here.
For metathesis reactions of HO2 radical, the kinetic similarity
with C4 H9 OH was applied for both C3 alcohol isomers. For (R14-
16), the expressions suggested in the theoretical study of Zhou
et al. [49], were adopted for the present model. Arrhenius parame-
ters in [49] were calculated using conventional TST with rigid-rotor
(R5) harmonic oscillator approximations, over the temperature range of
194 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204

Table 3
Arrhenius parameters selected for i-propanol kinetic sub-mechanism. Units: A – cm3 mol−1 s−1 , Ea – cal mol−1 , T – K.

No Reaction A n Ea UF Ref.

Hydrogen abstraction
77 iC3 H7 OH + OH  iC3 H7 O + H2 O 5.88E+02 2.82E+00 −5.85E+02 2 [16]
78 iC3 H7 OH + OH  tC3 H6 OH + H2 O 1.81E+03 2.89 −2611.0 2 [16]
79 iC3 H7 OH + OH  iC3H6 OH + H2 O 4.62E+00 3.70 −2946.0 2 [1]
80 iC3 H7 OH + H  iC3 H7 O + H2 9.45E+02 3.14E+00 8.70E+03 2 [47]
81 iC3 H7 OH + H  tC3 H6 OH + H2 2.30E+05 2.72 6260.0 2 [13]
82 iC3 H7 OH + H  iC3H6 OH + H2 5.31E+04 2.81E+00 7.50E+03 2 [47]
83 iC3 H7 OH + O2  iC3 H7 O + HO2 1.00E+13 0.00E+00 5.634E+04 2 [45]
84 iC3 H7 OH + O2  tC3 H6 OH + HO2 7.00E+12 0.00E+00 4.37E+04 2 [13]
85 iC3 H7 OH + O2  iC3H6 OH + HO2 4.20E+13 0.00E+00 5.20E+04 2 [13]
86 iC3 H7 OH + HO2  iC3 H7 O + H2 O2 2.50E+12 0.00 24,000.0 2.5 [49]
87 iC3 H7 OH + HO2  tC3 H6 OH + H2 O2 1.25E-05 5.26 7468.0 2 [16]
88 iC3 H7 OH + HO2  iC3H6 OH + H2 O2 2.26E-02 4.52 13,850.0 2 [1]
89 iC3 H7 OH + O  iC3 H7 O + OH 1.46E-03 4.73E+00 1.73E+03 2 [50]
90 iC3 H7 OH + O  tC3 H6 OH + OH 1.45E+05 2.47E+00 8.76E+02 2 [50]
91 iC3 H7 OH + O  iC3H6 OH + OH 9.70E+02 3.23 4660.0 2 [50]
94 iC3 H7 OH + CH3  iC3 H7 O + CH4 2.040E+00 3.57 −7721.0 2 [59]
93 iC3 H7 OH + CH3  tC3 H6 OH + CH4 9.56E−04 4.97 5710.0 2 [16]
94 iC3 H7 OH + CH3  iC3H6 OH + CH4 9.97E−12 7.05E+00 8.94E+03 2 [60]
95 iC3 H7 OH + CH3 O  tC3 H6 OH + CH3 OH 4.34E+11 0.00E+00 6.46E+03 2 [13]
96 iC3 H7 OH + CH3 O  iC3H6 OH + CH3 OH 3.00E+11 0.00E+00 7.00E+03 2 [13]
97 iC3 H7 OH + CH3 O2  tC3 H6 OH + CH3 O2 H 2.80E+12 0.00E+00 1.49E+04 2 [13]
98 iC3 H7 OH + CH3 O2  iC3H6 OH + CH3 O2 H 1.68E+13 0.00E+00 2.04E+04 2 [13]
Unimolecular decomposition
99 iC3 H7 O + H  iC3 H7 OH 1.00E+14 0.00E+00 0.00E+00 2 [45]
100 tC3 H6 OH + H  iC3 H7 OH 4.00E+13 0.00E+00 0.00E+00 2 [16]
101 iC3 H6 OH + H  iC3 H7 OH 4.00E+13 0.00E+00 0.00E+00 2 [16]
102 iC3 H7 OH (+M)  C3 H6 + H2 O (+M) 5.00E+13 0.00E+00 6.80E+04 2 [45]
Low P limit 4.82E+94 −22.464 8.35E+04
Troe a = 2.8246e-04 T3 = 362 T1 = 1.29E+04 T2 = 4.49E+03
103 iC3 H7 OH (+M)  CH3 + SC2 H4 OH (+M) 1.35E+24 −2.27E+00 8.70E+04 2 [13]
Low P limit 2.85E+69 −1.49E+01 9.47E+04
Troe a = 0.336 T3 =775 T1 =9.68E+09 T2 =8.21E+09
104 iC3 H7 OH (+M)  iC3 H7 + OH (+M) 6.43E+22 −1.865 9.62E+04 2 [45]
Low P limit 1.90E+78 −17.503 1.08E+05
Troe a = 8.6766e−05 T3 =2.93E+02 T1 =1.97E+04 T2 =1.67E+03
Radical decomposition
105 iC3 H7 O + O2  CH3 COCH3 + HO2 1.50E+12 0.00E+00 5.00E+03 2 [21]
106 tC3 H6 OH + O2  CH3 COCH3 + HO2 5.28E+17 −1.638 839 2 [53]a
107 iC3 H6 OH + O2  iC3 H5 OH + HO2 1.50E+12 0.00E+00 5.00E+03 2 [21]
108 iC3 H7 O  CH3 + CH3 CHO 8.10E+35 −7.88 1.89E+04 2 [51]a
109 iC3 H7 O  CH3 COCH3 + H 9.13E+21 −4.18 1.60E+04 2 [51]a
110 tC3 H6 OH  CH3 COCH3 + H 1.57E+40 −8.34 4.13E+04 2 [51]a
111 tC3 H6 OH  iC3 H5 OH + H 2.48E+38 −8.14 4.44E+04 2 [51]a
112 iC3 H6 OH  C3 H6 + OH 1.29E+35 −7.02 3.31E+04 2 [51]a
113 iC3 H6 OH  C2 H3 OH + CH3 2.27E+33 −6.63 3.58E+04 2 [51]a
Keto-enol isomerization
114 C2 H3 OH + HO2  CH3 CHO + HO2 1.49E+05 1.67E+00 6.81E+03 2 [57]
115 iC3 H5 OH  CH3 COCH3 6.957E+26 –4.138 57.344 2 [55]a , b
4.258E+56 –13.105 70.899 [55]a , c
116 iC3 H5 OH + HOCHO  CH3 COCH3 + HOCHO 2.81E-02 3.29E+00 −4.51E+03 2 [58]
117 iC3H5OH +HO2  CH3 COCH3 + HO2 1E−01+1.5E+00 3.1 + 3.0 16E+02+10E+03 2 [56]
a
Pressure-dependent reaction described using PLOG formulation.
b
Bath gas: N2.
c
Bath gas: Ar.

50 0–20 0 0 K with an estimated uncertainty factor of 2.5. Product carbon is the dominant one at T<600 K (96%), while at T>2300 K,
branching ratio analysis showed that H abstraction from Cα car- H abstraction from Cβ becomes the most prominent (44%).
bon is the most favorable along the investigated temperatures, go-
ing from ~96% at 20 0 0 K to ~ 47% at 500 K. Note that for (R14),
3.3. Radical decomposition
as also suggested by Man et al. [16], a factor of 2.5 was applied
to the rate constant. For (R13), recommendations from [11] were
N-propanol and i-propanol H abstraction lead to the formation
adopted.
of metastable radical isomers (4 and 3, respectively) which in turn
For reactions (R17), (R18), and (R89-91), the kinetic similarity
mainly decompose via β -scission. For thermal decomposition of
with the lower alcohol homologous C2 H5 OH led to accept Wu et al.
the alkyl/alkoxy radicals, pressure and temperature-dependent rate
[50] recommendations. Rate constant expressions in [50] were de-
parameters were only evaluated by Zador et al. [51]; such values
rived using CVT/SCT over a temperature range of 30 0–30 0 0 K and
were accepted and included in the current mechanism; however,
compared with experimental results obtained using a diaphragm-
for reaction (R63) and (R67), the recent recommendations from
less shock tube over the temperature range of 782–1410 K. Authors
the theoretical study of Ferros-Costas et al. [52] were included,
observed that in the branching ratio analysis H abstraction from Cα
since that allowed to have a better agreement with LBV and IDT
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204 195

experimental data. Calculations of dissociation and isomerization

of primary radicals of propyl alcohols were made using the RRKM-
based energy-resolved master equation (ME) using Variflex 2.03
[51]. Zador et al. [51] also found out that the preferred dissociation
route for tC3 H6 OH radical is the cleavage of OH bond, since its
activation energy was found 4.6 kcal/mol lower than the one for
the β -scission channel. Isomerization channels of propoxy radical,
as well as H-migration from α -hydroxypropyl radical are not
included in [51] study; however, at high temperatures, their con-
tribution becomes non-negligible, hence rate constants reported
in [52] were included in the current mechanism. Two different
approaches of variational transition-state theory (VTST) were used
in [52] to calculate thermal rate constants, namely one-well (1 W)
and the more accurate multipath (MP) formulation. The present
study accepted the rate constant values obtained using the MP
formulation of VTST.
For oxidation of hydroxypropyl/propoxy radical by O2 , kinetic
analogies with oxidation of α -hydroxyethyl were applied. The ex-
pressions recommended in the work on ethanol oxidation of Da
Silva et al. [53], also lately endorsed by Sarathy et al. [45] for butyl
alcohol isomers, were adopted for reaction (R53) and (R106), while
for all the other oxidation pathways, Arrhenius coefficients from
[21] were accepted.

3.4. Enol-keto isomerization

Enols are formed due to radical decomposition of propyl

alcohols and therefore play an important role in the pyrolysis
and oxidation of C3 alcohols. However, they tend to tautomerize
into more stable structures in the condensed phase [54], i.e.,
to ketones (R115-117) or aldehydes (R75-76, R114). For reaction
R117, recommendations from Grajales-González et al. [55] were
accepted here. Rate constant calculations were performed using
System-Specific Quantum Rice-Ramsperger-Kassel (SS-QRRK) the-
ory, over the temperature range of 20 0–30 0 0 K and pressure of
0.1 − 108 kPa. Authors [55] also found that, as generally expected,
keto form is largely dominant at the equilibrium under aforemen-
tioned temperature conditions. For reaction (R117), the only study
in the literature refers to the recent investigation performed by
Monge-Palacios et al. [56], and the suggested Arrhenius parame-
ters included in the proposed model. Calculations were performed
using CCSD(T)/aug-ccpVTZ//M06-2X/cc-pVTZ ab initio together
with the MS-VTST over the temperature range 20 0–30 0 0 K.
Regarding the other uncatalyzed reactions, kinetic parallelism
with the tautomerism occurring between vinyl alcohol and ac-
etaldehyde was applied. In the light of the above, recommenda-
tions of Da Silva [57,58] were accepted when enol-keto tautomer-
ization were catalyzed by perhydroxyl radical (R75, R114) and by
formic acid (R76, R116).

4. Modeling details

Cantera software [61] was used to model adiabatic, one dimen-

sional and freely propagating flames of propanols + air mixtures
at atmospheric pressure. Multicomponent transport and thermal
diffusion (Soret Effect) were enabled for the calculations; conver-
gence was achieved for adaptive grid parameters GRAD = 0.015
and CURV = 0.1, which allowed generating grid-independent so-
lutions consisted of 850–1200 points.
In the work of Man et al. [16], IDT was defined as the time
from the arrival of the reflected shock wave at the endwall and
the ignition onset. This latter was calculated by extrapolating the
maximum rate of change of OH∗ emission to the baseline, while
their modeled IDT was defined as the time when the maximum
dT/dt is reached. These experimental datasets in the present work
were modeled adopting the same modeling criterion applied in
Fig. 2. Laminar burning velocities of propanols + air flames. n-propanol: black;
i-propanol: light blue. Symbols: experiments, line: modeling. Open diamonds:
present work; half right-solid circles: [22]; half right-solid down triangles: [26];
solid spheres [24]. Solid line: present model; dash line: prediction from Sarathy
et al. [1].
[16] and also in the later work of Sarathy et al. [1]. Shock tube
experiments were modeled using a homogeneous reactor under
constant volume and adiabatic condition. JSR and flow reactor data
were modeled, respectively, using a perfect stirred reactor and
closed homogeneous configuration. Finally, flame structure data
were simulated using a premixed burner configuration adopting
196 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
Fig. 3. Laminar burning velocities of n-propanol + air as a function of inlet gas temperature at atmospheric pressure plotted in log-log scale. Symbols: experimental data,
line: present model.
the provided flame temperature profile, while the pyrolysis exper-
iments were modeled using the same criteria adopted in [9], i.e.,
using the plug flow reactor module.
5. Results and discussion
5.1. Laminar burning velocity
Figure 2 depicts new and available literature LBVs measure-
ments for n-propanol and i-propanol + air flames at P = 1 atm
and at T = 323–393 K; other literature data are compared with the
modeling in Fig. S1 in the Supplemental Material. Overall uncer-
tainties in LBVs determination related to this work were evaluated
adopting Alekseev et al. [34] procedure and are represented with
error bars and typically restricted in a range of less than ±1 cm/s.
Whenever possible, present LBV results were compared with litera-
ture data performed with a different experimental method, i.e. the
counterflow technique [22] and the externally heated mesoscale
diverging channel (MDC) [24] at 343 K and spherical flames ap-
proach [9,10,26] at 393 and 423 K. For both fuels, the LBV peak
lies around =1.10, appearing in agreement with what was found
with lower alcohol homologous; the higher values of LBVs result-
ing for the oxidation of n-propanol + air mixtures, are related to
the higher flame temperatures (~12 K) reached for the oxidation
of the primary alcohol. When compared to i-propanol, the higher
reactivity of n-propanol is due to the propensity to form more re-
active intermediates during its combustion process, as also stated
in Veloo and Egolfopoulos study [22].
To check data consistency, the analysis of the temperature de-
pendence of LBV of n-propanol + air mixture was performed at
different  for present and literature data; the influence of the
initial gas temperature was analyzed in logarithmic coordinates
as shown in Fig. 3 and in Fig. S2 . An excellent congruity of the
presented data is observable at all the temperatures tested and,
more generally, strong methods consistency were found between
the heat flux, MDC and with data from [9] performed using spher-
ical flames configuration, as well as with counterflow technique
up to =1.10 (Fig. 3), after which important deviations were en-
countered (8–27%). When compared with the data from [26], the
present LBV measurements were found higher by approximately
11%; a similar trend was observed in our recent study on propanal
kinetic and oxidation [35] when the two experimental methods
were compared. Important deviations were also found with the
other measurements performed in spherical flames [10,27].
Overall, it appears rather evident from Fig. 3 and Fig. S2 that
the experiments carried out with the spherical flames approach
[9,10,26,27] are inconsistent with each other. In this regard, fur-
ther investigations are needed to comprehend the reasons for
such inconsistencies. As previously stated [35], one of the possible
explanations might lies in the longer residence time required to
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204 197

Fig. 4. IDTs for n-propanol + O2 + Ar from [16]. Symbols: experiments, lines: mod- Fig. 5. IDTs for i-propanol + O2 + Ar from [16]. Symbols: experiments, lines: mod-
eling. Solid lines: present model; dash lines: Sarathy mechanism [1]. eling. Solid lines: present model; dash lines: Sarathy mechanism [1].

perform some of the experiments using spherical flames con-
figuration, which could result in a partial oxidation of the fuel
prior to its ignition. Moreover other possible error sources in the
LBV determination could be due to stretch extrapolation of the
expanding flame, as well as radiation losses and compression
effects dependent on the chamber size, both reducing the flame
speed propagation and so the LBV values.
At all tested conditions from this study, i.e. 323 K, 343 K and
393 K, the general trend of LBV of n-propanol + air mixtures is
well captured by the present and Sarathy et al. [1] models, while

Fig. 6. Sensitivity analysis of the ignition of n-propanol (black) and i-propanol (gray) at T = 1428 K, P = 1.2 bar and at =2.0.
198 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
Fig. 7. Mole fraction profiles of reactants and major products of n-propanol oxidation in a JSR at P = 10 atm and τ = 0.7 s. Symbols: experiments [10], lines: modeling. Solid
line: present model; dash line: Sarathy mechanism [1].
both slightly underestimate (~5%) the LBV of i-propanol + air mix-
ture near stoichiometric conditions. One may note that both model
behaviors are close to each other. When compared with the liter-
ature results, the models show satisfactory performance in repro-
ducing data from [9,11,24], while discrepancies arise when com-
pared with [10,25,26,27] studies. Particularly, where simulations
overestimate the experimental data, namely in [10,26,27] studies,
the inconsistencies can be related to the abovementioned oxidative
and thermal stability issues of the reactant mixture; a similar de-
viation from data of [18] is also observed at 3 bar (Fig.S1 ). On the
contrary, at high-pressure conditions, models considerably under-
predict values from [25] up to 20% (Fig.S1 ), while less noticeable
differences are found when the models are compared with Li et
al. [9] data. Such discrepancies might be explained, on the exper-
imental side, with the possible presence of Darrieus-Landau insta-
bilities, resulting in higher values of the LBV, and/or, on the model
side, to the deficiencies of fuel-specific pressure-dependent reac-
tions, as also suggested in [25], resulting in an underestimation of
the experimental values.
5.2. Ignition delays
In Figs. 4 and 5 the ignition characteristics of n- and i-
propanol + O2 + Ar mixtures from Man et al. [16] are compared
with the numerical simulations performed with the present and
Sarathy model. The IDTs measurements were carried out behind
reflected shock waves with P = 1.2, 4 and 16 atm, T = 1100–
1500 K, at = 2.0; for both investigation the fuel concentration
was set to 0.75%. Overall, both mechanisms exhibit good perfor-
mances in reproducing the experimental results. However, for n-
propanol-based experiments, the proposed mechanism was found
superior to the Sarathy model at 4 and 12 bar, while this latter
shown a closer agreement to the experiments at 1.2 bar. It has to
be noted that both models sensibly overpredict the fuel mixture
reactivity under rich conditions. When compared to i-propanol
IDTs data, the present mechanism exhibits better performance in
comparison to the Sarathy model [1] at 1.2 and 16 bar while it
tends to underpredict the fuel mixture reactivity at 4 bar.
To emphasize the difference between the models’ behavior,
brute-force sensitivity analysis of the simulated IDT’s was per-
formed with both models at T = 1428 K, P = 1.2 atm and at
=2.0 and the most sensitive reactions were ranked and de-
picted in Fig. 6. A negative value indicates that a reaction de-
creases the temperature of the system, causing a longer ignition
delay time. For the ignition of n-propanol, the reaction (R8) is a
reactivity-inhibiting step for the present model, while it enhances
the propensity to ignite the primary alcohol in the Sarathy mecha-
nism, resulted of the different branching ratio for the nC3 H7 OH+H
reaction present in the two models. For the ignition of i-propanol,
the only difference between the two models is related to the re-
action CH3 COCH3 C2 H6 +CO, which inhibits the reactivity of the
branched isomer and is not present in Sarathy mechanism.
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204 199

Fig. 8. Mole fraction profiles of reactants and major products of i-propanol oxidation in a JSR at P = 10 atm and τ = 0.7 s. Symbols: experiments [11], lines: modeling. Solid
line: present model; dash line: Sarathy mechanism [1].

5.3. Well stirred reactor

Figures 7 and 8 represent, respectively, experimental and pre-

dicted mole fraction profiles of the major species in stoichiometric
and rich n-propanol+O2 +N2 and i-propanol+O2 +N2 mixtures from
[10,11], together with some key intermediates involved in their
oxidation process. Similar comparisons for other mixtures studied
in the well-stirred reactor [10,11] are shown in Figs. S5 – S10 of
the Supplemental Material. Generally, as for the previous compar-
ison made at different regimes, both models reveal similar perfor-
mances. Particularly, the fuel reactivity and also the major species
formation is well reproduced by both models at all investigated
conditions, while some discrepancies arise in representing minor
species chemistry. However, for the oxidation of n-propanol fuel
mixtures, the proposed model shows a closer fidelity in reproduc-
ing the concentrations of H2 and C1 –C2 saturated and unsaturated
hydrocarbons, while the formaldehyde formation is systematically
underpredicted. For the oxidation of i-propanol fuel mixtures, in-
termediates like acetone, 2-propenal, propene, and ethylene forma- Fig. 9. Mole fraction profiles of major products of n-propanol oxidation in a flow
tions are well reproduced by the present model, and good predic- reactor at P = 1 atm, T = 1084 K, and = 0.64. Symbols: experiments [7], lines:
tions are even shown for CO2 product; however, numerical simu- modeling. Solid line: present model; dash line: Sarathy mechanism [1].
lation from the present model tends to underestimate H2 O con-
centration in the high-temperature region. A tendency to underes- 5.4. Flow reactor
timate the formation of non-oxygenated compounds is shown by
both models; such difference becomes more relevant as the exper- In Figs. 9 and 10 the experimental mole fraction profiles dur-
imental conditions become richer. ing flow reactor oxidation of C3 alcohols experimentally studied by
200 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
Fig. 10. Mole fraction profiles of major products of i-propanol oxidation in a flow
reactor at P = 1 atm, T = 1121 K, and = 0.78. Symbols: experiments [7], lines:
modeling. Solid line: present model; dash line: Sarathy mechanism [1].
Fig. 11. Mole fraction profiles of the major and minor species for and 3% n-propanol
pyrolysis at 1atm. Symbols: experiments [9], lines: modeling. Solid line: present
model; dash line: Sarathy mechanism [1].
Fig. 12. Mole fraction profiles of the major and minor species for and 3% i-propanol
pyrolysis at 1atm. Symbols: experiments [9], lines: modeling. Solid line: present
model; dash line: Sarathy mechanism [1].
Norton and Dryer [7] are compared with the present and Sarathy
model predictions. As for many fuel oxidation studies, to match
the point of 50% experimental fuel consumption, model predictions
were adjusted using time-shifting. For n-propanol oxidation, both
models show good agreement with experimental results; however,
in the present model simulations, CO and CO2 maxima are sensi-
bly shifted in time by ~20 ms. For i-propanol oxidation both mod-
els shown similar predictions, i.e., they tend to underestimate fuel
reactivity under the investigated conditions as well as some mi-
nor species formations, such as CO, C2 H4 and C3 H6 . On the con-
trary, CH4 formation is instead constantly overpredicted under the
all simulation condition range.
The effect of temperature on n-propanol and i-propanol py-
rolysis [9] is represented in Figs. 11 and 12; the experimental
mole fraction profiles of the major species are compared with
the present and Sarathy kinetic model predictions. Experiments
were performed in a flow reactor with 3% fuel in argon, at a
stated flow rate of 10 0 0 sccm. Comparison of the n-propanol ex-
perimental data with models predictions show that both models
well capture n-propanol conversion and formation of some ma-
jor species, such as H2 O, CH4 , CO, and C2 H4 . However, they tend
to underestimate the formation of some minor species profiles
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
Fig. 13. Sensitivity analysis of the pyrolysis of n-propanol (black) and i-propanol (gray) at 50% of fuel consumption.
such as CH3 CHO and C2 H5 CHO; while C3 H6 concentration is bet-
ter represented by the present model. Regarding i-propanol pyrol-
ysis, models show a satisfactory performance in reproducing fuel
conversion and formation of major species while some discrep-
ancies arise with the CH3 COCH3 profile, where experimental data
are overestimated and maxima shifted to higher temperature (by
~100 K).
Figure 13 shows sensitivity analyses performed at 50% fuel
decomposition point for both C3 alcohols pyrolysis; reactions
with negative sensitivity coefficients promote fuel depletion.
Both models show that the main contribution in promot-
ing/inhibiting n-propanol decomposition is due to the fall-off
reactions CH2 OH(+M)CH2 O+H(+M) and (R51), respectively.
For the present model an important contribution to decreas-
ing fuel depletion is also given by the recombination reaction
C2 H5 CO+CH3 O CH2 O+C2 H5 CHO, which is not included in the
Sarathy mechanism, whereas in this latter, the reactions (R8)
and CH2 OH+CH2 O=CH3 OH+HCO show a higher relevance than
in the present model. For the pyrolysis of i-propanol, no major
differences are appreciable between the tested models for the
most sensitive reactions.
201
5.5. Flame structure
In Figs. 14 and 15 and S11 –S12 are depicted the experimental
mole fraction profiles of major intermediates measured in low-
pressure flames of C3 alcohol isomers [20], together with the
present and Sarathy model predictions. As previously mentioned,
experiments were carried out using 2 different MBMS techniques,
i.e., EI and VUV-PI, at the experimental condition of P = 3333–
4666 Pa and =1.00–1.94. In this work, experiments conducted
using EI are compared with model predictions. Simulation pro-
files were shifted by ~2 mm to better represent experimental data
from [20]; a similar approach was also employed by Frassoldati et
al. [21]. Once more, present and Sarathy mechanisms show sim-
ilar performances, and major species profiles of n-propanol and
i-propanol are well captured by both; on the contrary, simulated
CO and H2 concentration profiles systematically underestimate ex-
perimental data. It has to be noted that simulations were per-
formed using the unperturbed flame temperature profiles provided
by Kasper et al. [20], since in their work the nozzle effect of the
sample probe on the flame temperature profile was not quantified
and this might sensibly affect the measured species profiles [62].
202 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204

Fig. 14. Mole fraction profiles of major products of n-propanol oxidation in a low- Fig. 15. Mole fraction profiles of major products of i-propanol oxidation in a low-
pressure burner at P = 0.033 atm, and = 1.03. Symbols: experiments [20], lines: pressure burner at P = 0.033 atm, and = 1.00. Symbols: experiments [20], lines:
modeling. Solid line: present model; dash line: Sarathy mechanism [1]. modeling. Solid line: present model; dash line: Sarathy mechanism [1].

The selection of the rate constants employed to build the n-

6. Conclusions
propanol and i-propanol subset was also presented. Models com-
parison shows that both kinetic mechanisms successfully repro-
This study provides a new kinetic model for propyl alcohols py-
duce new and literature data. However, the newly developed
rolysis and oxidation, together with new LBV measurements car-
model shows a closer fidelity in representing IDTs data obtained
ried out with the heat flux method at T = 343–393 K, P = 1 atm
at high-pressure conditions.
and =0.7–1.4. Moreover, all the available LBV data from the lit-
erature are used to validate the proposed model and the litera-
ture model from [1], as well as to check experimental data consis-
tency. In addition, the kinetic models were also tested against the Acknowledgments
literature experiments performed at different combustion regimes
(IDT, well-stirred and flow reactors, flame structure). Excellent The authors would like to acknowledge the financial support
agreement was found with experiments performed with the MDC from the Swedish Energy Agency through the centre for Combus-
method, as well as with the data from [9] obtained using spher- tion Science and Technology (Project KC-CECOST 22538-4), and the
ical flame configuration and with counterflow technique up to Swedish Research Council (VR) via project 2015-04042. The au-
slightly rich conditions. Important inconsistencies appeared with thors further acknowledge the valuable discussions with Dr. V. A.
other experiments performed in spherical flames, as also previ- Alekseev and Dr. T. Methling.
ously observed in our recent work [35] and, more generally, spher-
ical flame measurements were found inconsistent with each other.
Once again such differences were attributed to the possible oxida- Declaration of Competing Interest
tive phenomena occurring to the combustible mixture prior to its
ignition. None.
 G. Capriolo and A.A. Konnov / Combustion and Flame 218 (2020) 189–204
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.combustflame.2020.
05.012.
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