Article

Cite This: Energy Fuels 2019, 33, 11781−11794 pubs.acs.org/EF

Reaction of Hydroperoxy Radicals with Primary C1−5 Alcohols: A

Profound Effect on Ignition Delay Times
Saleh E. Rawadieh,†,‡ Ibrahem S. Altarawneh,§ Mohammad A. Batiha,† Leema A. Al-Makhadmeh,#
Mansour H. Almatarneh,∥ and Mohammednoor Altarawneh*,⊥
†
Chemical Engineering Department, ‡Renewable Energy Research and Development Center, and #Environmental Engineering,
Al-Hussein Bin Talal University, Ma’an 71111, Jordan
§
Pharmaceutical and Chemical Engineering Department, German Jordanian University, Amman 11180, Jordan
∥
Department of Chemistry, University of Jordan, Amman 11942, Jordan
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

⊥
Department of Chemical and Petroleum Engineering, United Arab Emirates University, Sheikh Khalifa bin Zayed Street, Al-Ain
15551, United Arab Emirates
Downloaded via UNITED ARAB EMIRATES UNIV on May 20, 2023 at 10:28:26 (UTC).

*
S Supporting Information

ABSTRACT: Ignition delay times of primary alcohols often display a noticeable sensitivity to their initial reactions with HO2
radicals. In view of the transient nature of HO2 radicals, kinetic models on combustion of alcohols utilize theoretically obtained
constant parameters for the abstraction HO2 + alcohols reactions. Rate constants for the title reactions in pertinent kinetic
models are often extrapolated from analogous computed values for either alkanes + HO2 or n-butane + HO2 reactions. Even for
the simplest alcohol, methanol, literature values for the reaction rate constants considerably vary within one order of magnitude.
Herein, we compute reaction rate constants for H abstraction from the weakest sites in primary C1−5 alcohols by HO2
(methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, and i-pentanol). In most cases, our
reaction rate coefficients tend to slightly exceed corresponding values deployed in pertinent kinetic models. We have thoroughly
assessed the predictive performance of literature kinetic models in computing ignition delay times of these alcohols based on the
updated rate constants for HO2-abstraction reactions. In the case of methanol, updating kinetic parameters for the reaction
CH3OH + HO2 → CH2OH + H2O2 improves prediction of ignition delay times at lower temperatures in reference to original
literature kinetic models. Likewise, a modified kinetic model for n-butane and t-butanol affords better agreement with
experimental values of ignition delay times at low temperatures and high pressures. Kinetic parameters presented herein will be
useful to accurately account for salient oxidation features of alcohols in real combustion engines.

1. INTRODUCTION Reactions in Scheme 1 exhibit temperature- as well as

Hydroperoxy (HO2) radicals assume a key role in deriving the
low-temperature oxidation and auto-ignition of hydrocarbons
(typically between 600 and 1200 K).1 The commonly observed
“negative temperature coefficient, NTC” zone partly stems
from the combustion cycle of HO2.2−4 Formation of HO2 in
combustion medium initially ensues via the endothermic and
highly reversible O2-induced H abstraction reaction RH + 3O2
→ R· + HO2 where R· signifies a hydrocarbon radical. At
intermediate temperatures, reactions of hydrogen atoms with
oxygen molecules produce an appreciable concentration of
HO2. However, the HO2 radical predominantly forms via the
“cool-flame” reaction sequence depicted in Scheme 1 (RH
denotes an alkane species).5,6
Scheme 1. Cool-Flame Reaction
pressure-dependent behavior.7 HO2 radicals are mainly
consumed via H-abstraction reactions with hydrocarbons;
RH + HO2 → R· + H2O2. This reaction traps the relatively
active HO2 radicals into the stable hydrogen peroxide
molecules (H2O2) and thus underpins the reduction in
reactivity in the NTC region (around 650 K).3 As the
temperature increases, fragmentation of H2O2 into OH radicals
restores the oxidation capacity. As Scheme 1 portrays, HO2
radicals chiefly participate in all stages pertinent to the
development of ignition and the low-temperature oxidation.
Consequently, profiles of products and ignition delay times in
oxidation models of various hydrocarbons were found to be
highly sensitive to the kinetics of the abstraction reaction RH +
HO2 → R· + H2O2.8,9
Despite being highly transient species, sophisticated
experimental techniques provided direct identification and
quantification of HO2 radicals under atmospheric and
combustion conditions.10,11 Profiles of HO2 radicals were
qualitatively measured during oxidation of dimethylether12 and

Received: July 2, 2019

Revised: October 7, 2019
Published: October 14, 2019

© 2019 American Chemical Society 11781 DOI: 10.1021/acs.energyfuels.9b02169

Energy Fuels 2019, 33, 11781−11794
Energy & Fuels
n-butane13 deploying optical approaches encompassing mid-
infrared Faraday rotation spectroscopy and fluorescence assay
by gas expansion (FAGE), respectively. Nonetheless, acquired
absolute HO2 concentrations were deemed to be “uncertain”
owing to sampling and calibration difficulties. Due to these
challenges and in view of the absence of a suitable HO2
precursor, direct measurement of the reaction rate constant for
H abstraction by HO2 is rather very limited. Jemi-Alade et al.14
measured the rate constant for the reaction HO2 + CH2O →
H2O2 + CHO in a flash photolysis experiment. Walker and co-
authors15,16 provided indirect measurements for H abstraction
from distinct C−H sites in alkanes, toluene, and benzene. Most
kinetics data on the abstraction RH + HO2 reaction stem from
quantum chemical calculations. For instance, theoretically
calculated reaction rate constants for H abstraction from
alkanes (up to butanes) by Aguilera-Iparraguirre et al.17 were
in accord with recommended analogous values by Walker.15
Likewise, we have utilized density functional theory (DFT)
calculations and chemistry models to compute rate constants
for H abstraction by HO2 from a large array of compounds
including methanol,18 benzene,19 mercaptans,20 and alkylated
benzenes.21,22 Despite the progress on the theoretical side, the
literature presents a rather limited account of kinetics data
germane to H abstraction by HO2 from an important fuel’s
category, that is, alcohols.
Alcohols are important non-petroleum fuels on their own
right or when blended with other hydrocarbon fuels.
Combustion chemistry of these alternative fuels (mainly up
to five carbon atoms) has been thoroughly investigated.23−27
Laboratory- and engine-scale studies presented focal combus-
tion properties of various types of alcohols with a prime focus
on pyrolysis and oxidation mechanisms, flame propagation,
and profiles of pollutant emission. Kinetic models on oxidation
of alcohols establish a noticeable sensitivity for the H
abstraction reaction by HO2.25,28 For instance, Sarathy et
al.29 found that the ignition time of 1-butanol was the most
sensitive to the reaction CH3CH2CH2CH2OH + HO2 →
CH3CH2CH2C•HOH + H2O2. Likewise, it was found that
20% of the reaction fluxes during 1-butanol combustion pass
via the former reaction at 950 K and 5 atm. Reaction rate
constants for H abstraction from butanol isomers were
extrapolated from a theoretical prediction by Zhou et al.30
for the system 1-butanol + HO2. Other theoretically calculated
rate constants encompass values for the systems ethanol +
HO231 and methanol + HO2.32 Reaction rate constants for the
latter reaction are scattered with one order of magnitude.
The significant importance of the H-abstraction reaction by
HO2 radicals in alcohol oxidation originates from the
formation of HO2 radicals and stable aldehyde species
following O2 addition to the alpha fuel radical of alcohol.29,33
The α-carbon site is defined as the one next to the OH moiety
and is typically the weakest C/O−H site in alcohols. Due to
the appreciable amount of HO2 produced in this pathway, the
H-abstraction reaction by HO2 is further promoted. To this
end, the aim of this study is to present thermal rate constants
for H abstraction by HO2 radicals from various distinct sites in
C1−C5 primary alcohols. Kinetic parameters provided herein
shall be useful in improving model prediction of ignition delay
times, especially at low temperatures and high pressures. The
performance of literature kinetic models in predicting ignition
delay times of primary alcohols is revisited in view of Arrhenius
coefficients for HO2-based reactions computed herein. The
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relative contribution of HO2 radicals in deriving the low-
temperature oxidation of these alcohols is thoroughly assessed.
2. COMPUTATIONAL METHODOLOGY
The Gaussian 0934 suite of programs performs geometry
optimizations, total energy computations, and vibrational
frequency calculations at the composite chemistry model
CBS-QB3.35 Transition structures retain a single imaginary
frequency along the designated reaction coordinate. The CBS-
QB3 methods locate optimized geometries at the B3LYP/
CBSB7 level of theory and employ successive single-point
energy calculations at higher theoretical levels. The satisfactory
performance of the cost-effective CBS-QB3 method in
predicting thermochemical and kinetic parameters for H
abstraction reactions is very well established. In a recent
paper,36 we compared reaction and activation energies
computed by the CBS-QB3 method (for H abstraction
reactions by NH2 radicals) against corresponding values
obtained with the more computation-intensive chemistry
models, G4 and CBS-APNO. It was found that CBS-QB3
and CBS-APNO values reside within 2.0 kJ/mol. The mean
unsigned errors for the difference in activation enthalpies
between CBS-QB3 and G4 values incur a value of 3.0 kJ/mol.
We also refer the reader to comprehensive thermochemistry
benchmarking of these three methods reported by Simmie et
al.37,38 The CBS-QB3 method is typically executed at a
significantly shorter time than other chemistry models. For this
reason, the CBS-QB3 method largely retains its position as the
most widely utilized cost-effective and accurate approach in
computing thermokinetics parameters pertinent to combustion
reactions. The multiplicity of all initial abstraction reactions
amounts to 2.
KiSThelP,39 a kinetic and statistical thermodynamic code,
computes reaction rate constants (fitted in the wide temper-
ature range 500−2000 K). It has been shown that variational
effects on the kinetics of HO2 + methanol/ethanol reactions
are rather very limited.31,40 Thus, reaction rate constants were
estimated based on the formalism of conventional transition
state theory (TST).41 To reflect the correct reaction
degeneracy, fitted pre-exponential A factors were multiplied
by the number of equivalent abstractable hydrogen atoms.
Plausible effects of quantum tunneling on reaction rate
constants were accounted for with the inclusion of a one-
dimensional Eckart functional as implemented in the KiSThelP
code.42 The CH3- and OH- internal rotations in reactants and
transition structures necessitate their rigorous treatment as
hindered rotors. The latter were obtained by performing partial
optimizations along the corresponding dihedral angles. In
addition to CH3 and OH internal rotations in reactants and
transition structures, we also treat the internal rotation of the
entire OH group in the HO2 moiety of the transition structures
as hindered rotors. Treatment of hindered rotors in the
KiSThelP package deploys the hindered rotor density-of-states
(HRDS) approach formulated by McClurg et al.43 The only
required input parameter in the HRDS formalism is the ratio of
the overall rotational barrier to the associated harmonic
frequency.
The Chemkin-Pro44 package predicts ignition delay times
using the commonly deployed constant-volume homogeneous
batch reactor model. The ignition delay times correspond to
the point of maximum temperature rise, max dT/dt, a point
that also reflects the maximum pressure rate rise. Simulations
are based on published chemical kinetic mechanisms and
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Energy & Fuels
thermodynamic data for the investigated C1−5 alcohols with
the inclusion of modified kinetic parameters for HO2-
abstraction reactions.
3. RESULTS AND DISCUSSIONS
Figure 1 depicts optimized geometries for the 10 considered
primary C1−C5 alcohols along with bond dissociation
Figure 1. Structures of the four considered C1−3 alcohols. Values
signify bond dissociation enthalpies in kJ/mol.25 Considered
abstraction sites are highlighted.
enthalpies (BDHs) for C/O−H bonds as reported by Sarathy
et al.25 Herein, we compute reaction rate constants for H
abstraction by HO2 radicals from the weakest sites. With the
noticeable difference in BDHs across the carbon skeleton of
C1−5 primary alcohols, it is anticipated that enthalpic factors
largely dominate entropic factors across the low to
intermediate temperatures intervals. These temperatures are
most pertinent to the auto-ignition window. To call attention
for a plausible competition between different abstractable H
sites, we highlight branching ratios for H abstraction from
distinct sites in selected primary alcohols with comparable
BDHs values (i.e., within 15−20 kJ/mol). C−H bonds in the
CH2 group attached (s/s1 sites) to the OH group in normal
alcohols are significantly weaker than other C−H sites. For
instance, BDH for the s1 C−H site in n-propanol is lower by 20
kJ/mol than the adjacent secondary C−H site, s2. BDH values
for tertiary C−H (t) in branched alcohols (i-butanol and i-
pentanol) are very close to analogous values of s1 sites. Thus,
these two sites were considered. The portrayed geometries for
transition structures in Figure 2 share very similar features. For
instance, the O···O bond in the HO2 radical is consistently
elongated by ∼8.0% in reference to the equilibrium distance in
HO2 radicals. Table 1 enlists fitted modified Arrhenius
parameters between 500 and 2000 K for H abstraction by
HO2 radicals from the highlighted sites in Figure 1.
In the following sections, we compare our calculated
reaction rate constants with analogous literature values, either
computed by DFT/ab initio methods or deployed in recent
kinetics models. The prime focus is to survey the performance
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of literature kinetics models in predicting ignition delay times
of C1−5 primary alcohols based on modified HO2-abstraction
reactions computed herein. The phrase “this work” in all tables
and figures denotes updated kinetic parameters for HO2-
abstraction reactions only in corresponding literature kinetic
models. While the error bar on experimental data is not
displayed in figures that report ignition delay times herein, it is
generally accepted that ignition delay times in shock tubes and
rapid compression machines typically incur uncertainties of
around 2045 and 15%, in that order.46 It is worth mentioning
that all abstraction reactions considered herein from secondary
sites are associated with negative entropies of activation in the
range of ∼110 to 150 J/mol K between 500 and 2000 K. As an
illustrative example, Figure S1 in the Supporting Information
plots entropy of activation for H abstraction by HO2 from the
secondary site in ethanol. Consequently, entropies of activation
reduce the A factors in all investigated bimolecular reactions.
3.1. Methanol (CH3OH + HO2 → CH2OH + H2O2).
Screening analysis by Klippenstein et al.32 demonstrated that
the reaction CH3OH + HO2 → CH2OH + H2O2 largely
dominates uncertainty in the predicted ignition delay of
methanol based on the kinetic model of Li et al.47 The
noticeable effect of the kinetics of this reaction on the ignition
delay times of methanol flames is more profound at high
pressures and low temperatures, relevant to real combustion
engines (>10 atm and 1000−1200 K). The literature provides
no direct experimental measurement for this reaction. A very
slow anticipated rate for this reaction (at low temperatures)
and rapid decomposition of HO2 radicals (at high temper-
atures) make experimental kinetics measurements very
challenging. As recently reviewed by Curran,9 the three
available theoretically derived rate constants18,32,40 for this
reaction significantly vary by almost an order of magnitude.
The noticeable difference in these estimates stems from the
adapted theoretical frameworks pertinent to the calculation
methodologies and treatment of anharmonicities in reactants
and transition states. Our computed reaction and activation
energies for this reaction amount to 38 and 63 kJ/mol,
respectively. These values compare very well with analogous
values (34 and 64 kJ/mol) reported by Klippenstein et al.32 (at
the UCCSD(T)/CBS//CASPT2/cc-pvtz level of theory). The
calculated activation energy by Alecu and Truhlar40 (based on
CCSD(T)/CBS formalisms) appears to exceed our computed
value in the range of 7−20 kJ/mol. Figure 3 contrasts our
computed rate constant for the CH3OH + HO2 → CH2OH +
H2O2 reaction with other theoretically derived and simulated
values.9,18,32,40,48 In Figure 3, rate coefficients by Rasmussen et
al.48 came from fitting of H2O2 concentration profiles from
methanol oxidation. At 1000 K, our computed rate constant
exceeds analogous values by Klippenstein et al.32 and Alecu
and Truhlar40 by factors of 7.4 and 27.6, respectively. As
pointed out by Curran,9 validation of the methanol oxidation
model against ignition delay times appears to agree better
when deploying our 201118 computed reaction rate coefficient.
Our recalculated reaction rate constant for this reaction in this
work remains close to our previously estimated value18 (a
difference by a factor of only 1.7). Such a difference partly
arises from a disparity of ∼15 kJ/mol in the estimated
activation energy (63 kJ/mol) calculated herein at the CBS-
QB3 level of theory and our previously estimated value of 78
kJ/mol18 computed at the BB1K/GTLarge theoretical
approach.
DOI: 10.1021/acs.energyfuels.9b02169
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Figure 2. Optimized structures for transition states. Distances are in Å.

Table 1. Computed Reaction (ΔH) and Activation Enthalpies (ΔH#) for H Abstraction by HO2 from C1−5 Primary Alcohols
and Their Arrhenius Parameters (Fitted in the Temperature Range 500−200 K)a
alcohol TS reaction ΔH ΔH# A n Ea
−30
methanol TS1 CH3OH + HO2 → CH2OH + H2O2 (3) 38 63 1.23 × 10 5.85 32.0
ethanol TS2 C2H5OH + HO2 → CH3CHOH + H2O2 (2) 32 51 1.04 × 10−33 6.63 15.2
n-propanol TS3 n-C3H7OH + HO2 → n(s1)-C3H6OH + H2O2 (2) 32 48 8.67 × 10−33 6.26 15.8
TS4 n-C3H7OH + HO2 → n(s2)-C3H6OH + H2O2 (2) 52 59 3.63 × 10−35 6.77 20.3
i-propanol TS5 i-C3H7OH + HO2 → i(t)-C3H6OH + H2O2 (1) 27 40 4.70 × 10−31 5.69 9.2
n-butanol TS6 n-C4H9OH + HO2 → n(s1)-C4H8OH + H2O2 (2) 32 49 2.07 × 10−27 4.65 24.0
2-butanol TS7 2-C4H9OH + HO2 → 2(s1)-C4H8OH + H2O2 (2) 38 63 1.79 × 10−27 4.71 37.3
TS8 2-C4H9OH + HO2 → 2(t)-C4H8OH + H2O2 (1) 29 51 3.34 × 10−27 4.17 16.6
i-butanol TS9 i-C5H12OH + HO2 → i(s)-C5H11OH + H2O2 (2) 34 44 7.71 × 10−27 4.20 22.4
TS10 i-C5H12OH + HO2 → i(t)-C5H11OH + H2O2 (1) 45 46 9.53 × 10−26 3.76 28.2
t-butanol TS11 C(CH3)3OH + HO2 → C(CH3)3O + H2O2 (9) 74 81 2.09 × 10−23 3.34 59.9
TS12 C(CH3)3OH + HO2 → C(CH3)2CH2OH + H2O2 (1) 64 66 8.24 × 10−25 3.74 49.5
i-pentanol TS13 i-C5H12OH + HO2 → i(s1)-C5H11OH + H2O2 (2) 30 47 2.26 × 10−29 5.09 19.6
TS14 i-C5H12OH + HO2 → i(s2)-C5H11OH + H2O2 (2) 59 74 9.74 × 10−29 5.02 45.5
TS15 i-C5H12OH + HO2 → i(t)-C5H11OH + H2O2 (1) 40 48 6.56 × 10−27 4.49 24.1
n-pentanol TS16 n-C5H12OH + HO2 → n(s1)-C5H11OH + H2O2 (2) 33 44 1.71 × 10−27 4.40 21.1
TS17 n-C5H12OH + HO2 → n(s3)-C5H11OH + H2O2 (2) 49 58 1.66 × 10−26 4.45 34.2
a
All values of energies and A are in the units kJ/mol and molecule cm3 s−1, respectively. Numbers in parenthesis denote reaction’s degeneracies.

The kinetic model by Burke et al.49 on methanol oxidation title reaction (CH3OH + HO2 → CH2OH + H2O2). The
utilized our previously computed kinetics parameters for the model reasonably predicted ignition delay times in reference to
11784 DOI: 10.1021/acs.energyfuels.9b02169
Energy Fuels 2019, 33, 11781−11794
Energy & Fuels
Figure 3. Comparison between calculated reaction rate constants for
H abstraction from the methyl group in methanol by HO2 with
analogous literature values. aRef 18, bref 32, cref 40, dref 48, and eref 9.
experimental measurements in shock tubes by Noorani et al.50
and others. Between 800 and 1600 K, Our calculated rate
constants herein surpass values of Altarawneh et al.18 by 1.74−
3.56. Thus, we focus our attention now to comparing the
performance of the model of Burke et al.49 in estimating
ignition delay times of methanol with the inclusion of updated
and slightly faster kinetics coefficients for the reaction CH3OH
+ HO2 → CH2OH + H2O2. Figure 4 contrasts simulated
Figure 4. Influence of the updated reaction rate constant for the
CH3OH + HO2 → CH2OH + H2O2 reaction on simulated ignition
delay times (based on the model of Burke et al.49) for methanol in
reference to analogous experimental data by Noorani et al. aRef 49
and bref 50.
ignition delay times of stoichiometric flames of methanol at a
dilution of D = 20 (in Ar) against experimental measurements
in a shock tube by Noorani et al.50 At 1068 and 1098 K, the
original model of Burke et al.49 overpredicts experimental
measurements by 58 and 27%, respectively. Considering the
updated kinetics for the title reaction calculated herein,
simulated values by the model of Burke et al.49 deviate by
only 1 and 19% from the analogous experimental measure-
ments. The original model by Burke et al.49 affords a better
comparison with experimental values at intermediate temper-
atures. Nonetheless, the role of HO2 in deriving auto-ignition
significantly diminishes as the temperature increases.
To attain further insight into the role of HO2 in controlling
ignition delay times of methanol, we plot in Figure 5a modeled
concentration profiles of OH and HO2 radicals from oxidation
of methanol. The predicted concentrations of HO2 signifi-
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Figure 5. (a) Profiles of HO2 and OH from oxidation of methanol
and (b) relative % consumption of methanol by OH and HO2
radicals. Concentrations and relative % consumption are obtained at
fixed temperatures between 800 and 1200 K at 10 atm.
cantly exceed those of OH radicals up to a temperature as high
as 1100 K, attesting to the central role of HO2 in the initial
oxidation stages of methanol. Higher HO2 concentrations at
low temperatures was also quantified by Blocquet et al.13
during oxidation of n-butane in Java specification requests
(JSR) based on the FAGE technique. Analysis of reaction
paths indicates prevalent contributions from the reactions
CH3OH + HO2 → CH2OH + H2O2 (∼800 K), HCO + O2 →
CO + HO2, CH2OH + O2 → CH2O + HO2 (∼850 K), and H
+ O2(+M) → HO2(+M) (>900 K) toward formation of HO2.
The relative consumption of methanol by OH and HO2
radicals is portrayed in Figure 5b between 800 and 1200 K
at 10 atm. At 900 and 1000 K, HO2 radicals account for 17 and
23% of the initial consumption of methanol. Following H
abstraction from methanol by oxygen molecules, the low-
temperature oxidative decomposition of methanol (i.e., 800−
850 K) is chiefly derived from HO2 radicals but approaches
zero at ∼1220 K. Across the low-temperature window, the
main exit channel for HO2 radicals ensues via their self-
combination along the reaction 2HO2 → O2 + H2O2.
Hydrogen peroxide radicals decompose into OH radicals,
thus initiating the auto-ignition. It is inferred from Figure 5
that auto-ignition of methanol takes place via the gradual
buildup of HO2 radicals and their subsequent decomposition
into OH radicals. The role of HO2 radicals in combustion of
methanol effectively diminishes after the onset of the auto-
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Energy & Fuels
ignition. The P/T-dependent contribution of HO2 radicals in
the initial oxidation of alcohols deserves further careful
scrutiny.
3.2. Ethanol (C2H5OH + HO2 → s-C2H4OH + H2O2).
Among C1−5 primary alcohols, combustion of ethanol is
arguably the most investigated system. Combustion character-
istics of ethanol (flame speeds, ignition delay times, and
profiles of species) were validated in numerous kinetic
models.51−54 A noticeable discrepancy among these models
in predicting ignition delay times of ethanol was often
attributed to considerable uncertainty in the kinetics of HO2
reactions, especially at low temperatures and high pressures.
Predicted ignition delay times in these models show a rather
moderate agreement with corresponding experimental meas-
urements. Kinetic parameters for the reaction C2H5OH + HO2
→ s-C2H4OH + H2O2 in these models are often extrapolated
by analogy to corresponding values computed for the n-
butanol + HO2 system by Zhou et al.30 Very recently, Zhao et
al.31 deployed the CCSD(T)/CBS//M062X/def-TZVP the-
oretical approach to compute rate constants for H abstractions
by HO2 radicals from the three distinct sites in ethanol. It was
found that H abstraction from the ethanol proceeds at slower
rates when compared with analogous values for the n-butanol +
HO2 system. For instance, H abstraction by HO2 from the
secondary site in n-butanol exceeds analogous values in ethanol
by factors within ∼37 to 23 between 800 and 1200 K. Zhao et
al.31 demonstrated that updating kinetics for ethanol + HO2
reactions displayed a rather limited effect on ethanol reactivity
at low temperatures and high pressures (in reference to models
that utilize values calculated for the n-butanol + HO2 system).
A further improvement could be potentially attained by
improving the acetaldehyde and vinyl alcohol submechanisms
and by reassessing kinetics for the other important initiation
C2H5OH + O2 reactions.
Among the various kinetic models on ethanol oxidation, the
detailed combustion chemistry model by Mittal et al.52
reasonably reproduced salient combustion features of ethanol.
The model by Mittal et al.52 is based on the C1−C2 mechanism
by Metcalfe et al.,55 (AramcoMech 1.3.). To improve the
performance of the model in predicting ignition delay times,
the A factor for the reaction C2H5OH + HO2 → s-C2H4OH +
H2O2 (extrapolated from the n-butanol + HO2 system) was
increased by a factor of 1.75. Barraza-Botet et al.54 utilized the
model of Mittal et al.52 to account for measured ignition delay
times of ethanol in a rapid compression facility. Likewise, in
the model by Barraza-Botet et al.,54 the A factor for the title
reaction was enhanced by a factor of 2.5 in order to improve
the predictive performance of the model against experimental
measurements of the ignition delay times. The 1.75/2.5 factors
were within the uncertainty limits of the calculations by Zhou
et al.30 on the n-butanol + HO2 system. Figure 6 compares our
computed Arrhenius plots for this reaction against correspond-
ing values used in the models of Mittal et al.52 and Barraza-
Botet et al.54 and calculated values by Zhou et al.30 and Zhao
et al.31
Our computed values depart from those of Zhou et al.30 at
the most relevant temperature to auto-ignition (800−1200 K)
by factors of 7.9−5.2. Consequently, our calculated rate
constants for this reaction exceed deployed values in the
models of Barraza-Botet et al.54 and Mittal et al.52 by 3.2−2.1
and 4.5−3.0, respectively (between 800 and 1200 K). As
Figure 6 portrays, our calculated k(T) values significantly
surpass corresponding values by Zhao et al.31 by almost an
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Figure 6. Comparison between calculated reaction rate constants for
H abstraction from a secondary C−H site in ethanol by HO2 radicals
with respective literature values. aRef 30, bref 31, cref 54, and dref 52.
order of magnitude. With a difference of only 5 kJ/mol in the
calculated ΔH# value (translates to a difference of only a factor
of 0.5 in k (1000 K) values), the noticeable difference in the
reaction rate constant must stem from the treatment of
anharmonicity. As stated in section 2, we have treated all
internal CH3/OH rotations in reactants and transition states
(including the internal rotation of the H−O bond in transition
states) as hindered rotors. For instance, Figure S2 in the
Supporting Information displays potential energy diagrams for
internal rotations of CH3 and OH groups in selected transition
structures. It is not clear from the description of methodology
by Zhao et al.31 if torsional modes in transition states were also
treated as hindered rotors. It is inferred from Figure 6 that
computed rate constants are higher than all other literature
values. Nonetheless, other theoretically obtained values by
Zhao et al.31 (for the ethanol + HO2 system) also differ from
analogous values by Zhou et al.30 (for the n-butanol + HO2
system) by a factor of ∼2 between 800 and 1200 K.
We next turn our attention to testing the predictive capacity
of the model by Mittal et al.52 with updated (and a markedly
faster) kinetic parameters for the C2H5OH + HO2 → s-
C2H4OH + H2O2 reaction. In Figure 7a, predicted ignition
delay times by our updated model of Mittal et al.52
underestimate analogous experimental values in comparison
to the original models of Mittal et al.52 and Barraza-Botet et
al.54 Values by the updated model of Mittal et al.52 approach
estimates of the updated model beyond 1000 K. On the
contrary and as Figure 7b shows, the updated model of Mittal
et al.52 affords an improved match with experimental values by
Noorani et al.50 in reference to the original models of Mittal et
al.52 and Barraza-Botet et al.54 In both cases (Figure 7a,b),
utilizing the recent calculated reaction constant parameters by
Zhao et al.31 results in a significant overprediction of the
ignition delay times in comparison to the three other models.
Figure 8 shows results of sensitivity analysis on formation of
OH and HO2 radicals during ignition of a stoichiometric
ethanol mixture at 1 atm under air dilution (D = 3.76). The
prominent role of HO2 radicals in controlling the ignition
delay times is clearly illustrated in Figure 8a,b. The most
important reactions for the consumption of HO2 radicals are
also the most prominent reactions in the formation of OH
radicals. HO2 radicals are mainly consumed through the two
reactions C2H5OH + HO2 → s-C2H4OH + H2O2 and
H2O2(+M) → 2OH(+M). These two reactions are also the
two most significant reactions toward production of OH
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Figure 7. Influence of updated reaction rate constants for the

C2H5OH + HO2 → s-C2H4OH + H2O2 reaction on simulated
ignition delay times (based on the model of Mittal et al.52) in
reference to analogous experimental data by (a) Barazza-Botet et al.54
and (b) Noorani et al.50 aRef 54, bref 52, cref 30, and dref 50.

radicals. As Figure 8c depicts, the sharp decrease in the

concentration of HO2 radicals at the time of ignition
accompanies the sudden increase in the concentration of
OH radicals.
3.3. Isomers of Propanol (n-C3H7OH/i-C3H7OH). When
compared with methanol and ethanol, isomers of propanol
attain a higher energy density and reduced evaporative
emission profiles. As the simplest “next-generation” alcohols,
they mimic to a large extent the combustion property of real
biofuels. Several shock tube experiments reported ignition
delay times for the isomers of propanol.50,56−58 With a shorter
ignition delay time, n-propanol is more reactive than i-
propanol.25 This unique observation was mainly attributed to a
relatively weaker secondary C−H bond in the former and to Figure 8. Sensitivity coefficients for the 10 most important reactions
the formation of highly reactive formaldehyde in the flame of i- leading to formation/consumption of (a) OH and (b) HO2 during
propanol as opposed to the less reactive acetone in the case of combustion of ethanol. (c) Plots of the concentration of HO2 and
i-propanol. The literature presents no theoretical estimates for OH around the ignition window.
H abstraction from propanol isomers by HO2 radicals. In
simulating ignition delay times, kinetic models on combustion H abstraction from the s1 site in n-propanol and H abstraction
of i-propanol and n-propanol utilized reaction rate constants from the secondary site in ethanol ensue via very comparable
for HO2-based reactions from analogous values calculated for rates at all investigated temperatures.
n-butane and alkanes. The model of Man et al.56 updated the Figure 9 compares our computed rate constant for H
C3 chemistry in the study of Johnson et al.57 with a prime focus abstraction from secondary C−H and tertiary C−H sites in n-
on unimolecular initiation reactions and H abstraction propanol and i-propanol, respectively, with their analogous
reactions by the O/H radical pool. H abstraction from the t literature values.17,56 Between 800 and 1200 K, calculated rate
site in i-propanol exceeds that of H abstraction from the s1 site constants herein for n-propanol are within factors of ∼2.0 to
in n-propanol by factors within 8−2 between 500 and 1200 K. 1.17 from values deployed in the model of Man et al.56
Owing to similar activation enthalpies (51 versus 48 kJ/mol), Likewise, our computed values for H abstraction from i-
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propanol exceed values utilized in the model of Man et al56 by

Figure 9. Comparison between calculated reaction rate constants for
H abstraction from the secondary and tertiary sites in (a) n-propanol
and (b) i-propanol by HO2 radicals with corresponding literature
values. aRef 56 and bref 17.
factors of 11−4.6 between 800 and 1200 K. As illustrated in
the previous section on methanol, the difference in calculated
rate constants partially originates from the methodology of
treatment of anharmonicities. The noticeable difference with
values computed by Aguilera-Iparraguirre et al. 17 for
corresponding alkanes (n-C3H10 and i-C4H10) originates from
distinct activation energies. For instance, computed activation
energy for H abstraction from the tertiary site in i-butane
exceeds analogous values in i-propanol by 14 kJ/mol. Similarly,
activation energy for H abstraction from the s1 site in n-
propanol is lower by 16 kJ/mol if compared with H abstraction
from the secondary site in propane. Our calculated activation
energy for H abstraction from the s2 site in n-propanol
perfectly matches the corresponding value in the case of
propane (59 versus 60 kJ/mol). As such, calculated reaction
rate constants for H abstraction from the s2 site in n-propanol
remain within a factor of only ∼2 from analogous values
computed by Aguilera-Iparraguirre et al.17 for H abstraction
from the secondary site in n-propane.
In Tables 2 and 3, we compare the predictive performance
of the original model of Man et al.56 and the updated model of
Man et al.56 (in which the kinetics of HO2-based abstraction
reactions are modified based on current calculations) against
experimental measurements from different groups50,56,58 at
various combinations of temperatures and pressures. As shown
in Tables 2 (n-propanol) and 3 (i-propanol), the updated
model of Man et al.56 only slightly improves the overprediction
of ignition delay times in reference to the original model. At
temperatures above 1200 K, both models essentially yield very
similar values. The very similar performance of original and
updated models of Man et al.56 is clearly illustrated in Figure
10a,b with both models overpredicting experimentally fitted
values by Noorani et al.50 Nonetheless, both models still
outperform the model of Johnson et al.57 The updated model
correctly reproduces the confirmed lower reactivity of i-

Table 2. Comparison between Experimental and Simulated Values of Ignition Delay Times for n-Propanola
P (atm) T (K) Jouzdani et al.58 (exptl) Man et al.56 (exptl) Noorani et al.50 (exptl) this work Man et al.56 (model)
3.5 1152 2017 (122%) 4482 4590
2.4 1155 1724 (250%) 5597 5770
3.6 1163 2097 (80%) 3767 3840
1.28 1185 2181 (141%) 5370 5435
3.7 1206 1379 (47%) 2020 2050
3.8 1208 1271 (52%) 1940 1974
3.7 1210 1179 (39%) 1920 1944
3.7 1227 1005 (52%) 1520 1530
1.2 1230 1251 (130%) 2880 2898
2.3 1236 889 (50%) 1790 1800
3.5 1267 687 (33%) 914 918
1.17 1288 656 (140%) 1410 1320
3.3 1313 400 (31%) 522 523
2.2 1341 420 (12%) 470 472
3.3 1372 241 (7%) 258 262
2.1 1413 336 (37%) 212 174
1.25 1423 196 (34%) 262 262
3.3 1458 82 (26%) 103 104
3.1 1490 66 (19%) 78 78
1.28 1554 67 (18%) 79 77

a
ϕ = 1.0, D = 21(in Ar). Percentage values denote differences between experimental values and values calculated with our updated model (based
on the model of Man et al.56).

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Table 3. Comparison between Experimental and Simulated

Values of Ignition Delay Times for n-Propanola
Jouzdani Man et al.56 this Man et al.56
P (atm) T (K) et al.58 (exptl) (exptl) work model
17.29 1192 1014 (182%) 2910 3507
3.4 1240 2203 (65%) 3640 3938
3.1 1297 1206 2020 2097
4.13 1300 931 (71%) 1593 1661
3.5 1329 851 (48%) 1260 1297
3.9 1419 303 (32%) 399 403
17.52 1450 72 (67%) 120 123
3.2 1468 255 (1%) 254 254
3.6 1553 73 (33%) 97 98
1.23 1598 86 (41%) 121 119
a
ϕ = 1.0, D = 21 (in Ar). Percentage values denote differences
between experimental values and values calculated with the updated
model (based on the model of Man et al.56).

propanol in reference to n-propanol (Figure 10c). Matching

the experimentally reported ignition delay times for both
isomers of propanol necessitates significantly faster HO2-
abstraction reactions and improving the C3 submechanism.
3.4. Isomers of Butanol (n-C4H9OH/2-C4H 9OH/i-
C4H9OH/t-C4H9OH). The seminal paper by Sarathy et al.29
presented a detail combustion chemistry model for the four
isomers of butanol. The model satisfactorily accounts for the
species profile, ignition delay times, and laminar flame speeds
under a wide range of operational conditions (temperatures,
pressures, dilution extent, and equivalence ratios) encountered
in various combustion devices (rapid compression machines,
shock tubes, JSR, and low-pressure premixed flames). The
model is based on the hierarchical nature of the combustion
chemistry starting from the H2/CO/O2 submechanisms while
comprehensively updating and improving the C1−C3 mecha-
nisms. The model distinguishes between reactions prevailing in
the low-temperature window from that dominating in high-
temperature oxidation. As expected, ignition delay times were
the most sensitive to HO2-abstraction reactions based on brute
force sensitivity analysis. HO2 radicals accounted for 20%
consumption of n-butanol at 950 K and 5 atm under
stoichiometric conditions. In the model of Sarathy et al.,29
rate constants for n-butanol + HO2 reactions were adapted
from the study of Zhou et al.30 (with the A factor multiplied by
2.5). For the other butanol isomers, reaction rate constants
were extrapolated from the n-butanol + HO2 system based on Figure 10. Ignition delay times for (a) n-propanol and (b) i-propanol
an Evans−Polanyi-type correlation. For the t-butanol molecule and (c) comparison between them. Our calculated values are based
on the model of Man et al.56 with a modified rate constant for H
in particular, the Evans−Polanyi correlation yields a reaction abstraction by HO2. aRef 57, bref 56, and cref 50.
rate constant that resulted in very long ignition delay times.
Thus, rate constant for H abstraction from the primary site in
t-butanol by HO2 radicals was assigned with the same A factor
computed in the case of n-butanol. times of n-butanol when compared with experimental
In Figure 11, we compare our computed reaction rate measurements by Noorani et al.50 between 1150 and 1500 K
constants for H abstraction from the weakest C−H sites in the and 8.8−11.7 atm. However, at low to intermediate temper-
four butanol isomers with corresponding values deployed in atures (∼800 to 1000 K), our calculated rate constants for H
the model of Sarathy et al.29 For abstraction from the s1 site in abstraction from the s1 site in n-butanol exceed values deployed
n-butanol, the two sets of values fall within factors of 1.3−1.0 in the model of Sarathy et al.29 by factors between ∼3 and 2.
between 1200 and 1500 K. As such, updating the reaction rate This noticeable difference causes the updated model of Sarathy
constant for the reaction n-C4H9OH + HO2 → n(s1)-C4H8OH et al.29 to perform better at low temperature in predicting
+ H2O2 in the model of Sarathy et al.29 derives a minimal ignition delay times. In Figure 12b, the original model by
difference in predicted ignition delay times at temperatures Sarathy et al.29 significantly over predicts ignition delay times
above ∼1150 K. As Figure 12a shows, the original and updated measured by Zhu et al.59 at low temperatures and high
model by Sarathy et al.29 slightly overpredicts ignition delay pressures. Simulated values based on the modified model by
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Figure 11. Comparison between calculated reaction rate constants in this work with analogous literature values for (a) n-butanol, (b) 2-butanol,
(c) i-butanol, and (d) tetra-butanol. aRef 30 and bref 29.
Sarathy et al.29 reside within 20−50% of the corresponding
experimental values.
Inspection of values in Figure 11b for 2-butanol reveals a
fundamental difference between our computed reaction rate
constants herein and values deployed in the model of Sarathy
et al.29 Between 800 and 1200 K, the contribution of H
abstraction from the tertiary site decreases from 0.53 to 0.24.
In the model of Sarathy et al.,29 abstraction from the tertiary
site largely dominates that of the secondary site with branching
ratios in the range of 0.96 (800 K) to 0.87 (1200 K). For the i-
butanol isomer, the tertiary C−H bond is stronger than the
secondary C−H bond by 9 kJ/mol. Thus, it is expected that
abstraction from the secondary site proceeds at a faster rate.
Indeed, this is the trend that Figure 11c illustrates. The
branching ratio for abstraction from the secondary site remains
consistently high at ∼0.78 (800−1200 K). On the contrary,
abstraction from the tertiary site dominates the i-butanol +
HO2 reactions in the model of Sarathy et al.29 with a branching
ratio at 0.97 (800−1200 K). Finally, our calculated rate
constants for abstraction from the primary site in t-butanol are
approximately one order of magnitude slower than analogous
values utilized in the model of Sarathy et al.29 However, values
deployed in the model of Sarathy et al.29 exceed corresponding
values for H abstraction from primary sites in alkanes by a
factor of 4 at 1000 K. Calculated reaction constants herein
improve the predictive performance for the model of Sarathy et
al.29 for t-butanol at low temperatures (800−860 K) and high
pressures (15 atm) as Figure 13a portrays, in reference to
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experimental measurements by Weber and Sung.60 Nonethe-
less, the original model by Sarathy et al.29 retains a better
predictive performance for i-butanol as Figure 13b shows.
With these striking differences in absolute values of reaction
rate constants and relative importance for specific abstractable
sites, it is insightful to compare the overall predictive
performance of the original model of Sarathy et al.29 with an
updated model that includes modified rate constants for HO2-
abstraction reactions. Ignition delay times for the four isomers
depicted in Figure 14 (based on the updated HO2 rate
constants) reflect to a large extent the trend deduced from the
original model of Sarathy et al.29 Above 850 K and at 15 atm
(φ = 1.0 with air dilution), the original model of Sarathy et
al.29 predicts n-butanol to be the most reactive isomer with the
shortest ignition delay times. The t-butanol isomer exhibits the
least reactivity, while 2-butanol and i-butanol isomers incur
very comparable reactivity.
3.5. Isomers of Pentanol (n-C5H11OH/i-C5H11OH). With
similar physiochemical properties to gasoline, i-pentanol (3-
methyl-1-butanol) has emerged as a potential bioderived fuel.
Tsujimura et al.61 investigated the auto-ignition character of i-
pentanol in shock tube and rapid compression machine
experiments under a wide range of equivalence ratios,
temperatures, and pressures. The deployed kinetic model is
largely based on existing models for C1−C4 alcohols with the
inclusion of updated reactions rate constants for a concerted
HO2 elimination step from ROO-type radicals along the
reaction scheme proposed by da Silva et al.62 for ethanol. The
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Figure 12. Comparison between computed ignition delay times for n-

butanol with corresponding experimental values at (a) high and (b)
low temperatures. aRef 50, bref 29, and cref 59. Computed ignition
delay times herein are based on the model of Sarathy et al.29 with
modified rate constants for HO2 reactions with the four isomers. Figure 13. Influence of updated reaction rate constants for H
abstraction from (a) t-butanol and (b) i-butanol on simulated ignition
model satisfactorily describes the monotonous decrease in delay times (based on the model of Sarathy et al.29) in reference to
respective experimental data by Weber and Sung.60 aRef 60 and bref
ignition delay times with temperature. Rate coefficients for
29.
abstraction reactions by HO2 radicals were adapted from
analogous values calculated by Aguilera-Iparraguirre et al.17 for
alkanes. To improve comparison with experimental measure-
ments of ignition delay times, the A factor in these reactions
was multiplied by a factor of 3.0. In another study, Tang et al.63
investigated high-temperature ignition delay times for C5
primary alcohols (i-pentanol, n-pentanol, and 2-methyl-1-
butanol). Ignition delay times were simulated based on kinetic
models developed by Dagaut and co-authors.64,65
Figure 15 contrasts our computed rate constants for H
abstraction by HO2 radicals from distinct sites in i-pentanol
and n-pentanol with analogous values deployed in the model of
Tsujimura et al.61 Our calculations indicate that abstraction
from the tertiary site prevails over abstraction from the s1 site
in i-pentanol at all temperatures. The branching ratio for
abstraction from the s1 site remains constant at ∼0.26 between Figure 14. Ignition delay times for the four butanol isomers.
800 and 1200 K. In the model of Tsujimura et al.,61 abstraction
from the s1 sites dominates the overall i-pentanol + HO2
reactions at a branching ratio of ∼0.70 between 800 and 1200 models satisfactorily reproduce experimentally measured
K. Despite these differences, our computed rate constants for ignition delay times at 7 and 20 atm between 800 and 1600 K.
the overall reaction i-pentanol + HO2 reside within factors of Overall, we envision that the difference between simulated
2.5−1.3 between 800 and 12 00 K from corresponding values and experimental values is underpinned by the anticipated
deployed in the model of Tsujimura et al.61 Consequently, the uncertainties in experimental values of ignition delay times
updated model of Tsujimura et al.61 yields very similar ignition (typically within 15−20%) and by the expected aced accuracy
delay times to the original model. As Figure 16 shows, both margin of reaction rate constants calculated herein (i.e., a
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Energy & Fuels
Figure 15. Comparison between calculated Arrhenius plots for the
abstraction channels from i-pentanol and their corresponding values
used in the model of Tsujimura et al.61 aRef 61. s1, s2, and t signify
abstraction from these distinct sites (shown in Figure 1 for i-
pentanol). Solid lines refer to values calculated herein, while dashed
lines refer to values deployed in the model of Tsujimura et al.61
Figure 16. Comparison between computed ignition delay times for i-
pentanol with matching literature values. Computed values are based
on the model by Tsujimura et al.61 with modified reaction rate
constants for HO2-abstraction reactions. aRef 61.
factor of 3−5). A systematic benchmarking of ignition delay
times against HO2-derived rate constants by other chemistry
models (most notably, G4 and CBS-APNO) may improve the
agreement between computed and measured ignition delay
times. Nonetheless, the ignition delay times in the investigated
alcohols might be sensitive to other sets of reactions. For
instance, a further improvement could be potentially attained
by improving the acetaldehyde and vinyl alcohol submechan-
isms and by reassessing the kinetics for the other important
initiation alcohols + O2 reactions.
4. CONCLUSIONS
Reaction rate parameters are provided herein for H abstraction
from the weakest sites in C1−5 primary alcohols. Computed
activation enthalpies positively correlate with values of bond
dissociation enthalpies for the respective abstractable C−H
sites. For instance, a difference in bond dissociation enthalpies
for the C−H bond in methanol and C−H in ethanol (the s
site) of 16 kJ/mol translates into a difference of 12 kJ/mol in
computed enthalpies of activation. The computational
methodology comprises CBS-QB3 energy estimation, hindered
rotor treatment, and a one-dimensional Eckart functional. We
found that HO2 radicals account for 17−23% of the initial
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decomposition of methanol between 900 and 1000 K at 10
atm. Slightly higher rate constants for the CH3OH + HO2
reaction improves prediction of ignition delay of methanol at
low temperatures and high pressures. Our calculated rate
constants for the reaction C2H5OH + HO2 → s-C2H4OH +
H2O2 significantly exceed very recent theoretical calculations.
Nonetheless, predicted ignition delay times of ethanol based
on our updated kinetic parameters for the former reaction
afford an improved match with analogous experimental
measurements, especially at high pressures and high dilution.
The role of HO2 in controlling ignition delay times of ethanol
manifests itself by the fact that the most important reactions in
depletion of HO2 radicals are also the most prominent reaction
in the formation of OH radicals. Calculated rate constants for
the reactions of HO2 with n-propanol/i-propanol slightly
improve the overprediction of their ignition delay times in
reference to the original literature kinetic model. While
computed rate constants for reactions of the butane isomers
with HO2 differ from deployed values in literature kinetic
models in absolute values and the nature of preferred
abstraction sites, our updated model accurately reproduces
ordering of the butane isomers reactivity. For i-pentanol, we
found that abstraction from the tertiary site prevails over that
of the secondary site. Ignition delay times of i-pentanol (based
on modified rate constants for HO2-abstraction reactions
herein) are very similar to values computed in the original
literature model. It is interesting from the perspectives of
modelers to compare the rate constants of various alcohols and
to compare the impact of chain length and branching
structures on these values. Such interesting aspects will be
addressed in due course.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.energy-
fuels.9b02169.
Cartesian coordinates for transition structures (in Å)
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: mn.altarawneh@uaeu.ac.ae.
ORCID
Mansour H. Almatarneh: 0000-0002-2863-6487
Mohammednoor Altarawneh: 0000-0002-2832-3886
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Australian Research Council
(ARC). We acknowledge the Pawsey Supercomputing Centre
in Perth as well as the National Computational Infrastructure
(NCI) in Canberra, Australia, for providing the grants of
computational resources.
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11794 DOI: 10.1021/acs.energyfuels.9b02169

Energy Fuels 2019, 33, 11781−11794