Progress in Energy and Combustion Science 44 (2014) 40e102

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

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

Review

Alcohol combustion chemistry

S. Mani Sarathy a, *, Patrick Oßwald b, Nils Hansen c, Katharina Kohse-Höinghaus d
a
Clean Combustion Research Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
b
Institute of Combustion Technology, German Aerospace Center (DLR), Pfaffenwaldring 38-40, D-70569 Stuttgart, Germany
c
Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551, USA
d
Chemistry Department, Bielefeld University, Universitätsstraße 25, Bielefeld D-33615 Germany

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

Article history: Alternative transportation fuels, preferably from renewable sources, include alcohols with up to five or
Received 22 December 2013 even more carbon atoms. They are considered promising because they can be derived from biological
Accepted 14 April 2014 matter via established and new processes. In addition, many of their physical-chemical properties are
Available online 14 June 2014
compatible with the requirements of modern engines, which make them attractive either as re-
placements for fossil fuels or as fuel additives. Indeed, alcohol fuels have been used since the early years
Keywords:
of automobile production, particularly in Brazil, where ethanol has a long history of use as an automobile
Biofuel
fuel. Recently, increasing attention has been paid to the use of non-petroleum-based fuels made from
Combustion chemistry
Alcohols
biological sources, including alcohols (predominantly ethanol), as important liquid biofuels. Today, the
Kinetic modeling ethanol fuel that is offered in the market is mainly made from sugar cane or corn. Its production as a
Pollutant emissions first-generation biofuel, especially in North America, has been associated with publicly discussed
Internal combustion engines drawbacks, such as reduction in the food supply, need for fertilization, extensive water usage, and other
Flame speed ecological concerns. More environmentally friendly processes are being considered to produce alcohols
Ignition delay from inedible plants or plant parts on wasteland. While biofuel production and its use (especially ethanol
and biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicated
overview and summary of research on alcohol combustion chemistry is still lacking. Besides ethanol,
many linear and branched members of the alcohol family, from methanol to hexanols, have been studied,
with a particular emphasis on butanols. These fuels and their combustion properties, including their
ignition, flame propagation, and extinction characteristics, their pyrolysis and oxidation reactions, and
their potential to produce pollutant emissions have been intensively investigated in dedicated experi-
ments on the laboratory and the engine scale, also emphasizing advanced engine concepts. Research
results addressing combustion reaction mechanisms have been reported based on results from pyrolysis
and oxidation reactors, shock tubes, rapid compression machines, and research engines. This work is
complemented by the development of detailed combustion models with the support of chemical kinetics
and quantum chemistry. This paper seeks to provide an introduction to and overview of recent results on
alcohol combustion by highlighting pertinent aspects of this rich and rapidly increasing body of infor-
mation. As such, this paper provides an initial source of references and guidance regarding the present
status of combustion experiments on alcohols and models of alcohol combustion.
Ó 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2. Alcohol fuels e origins, sustainability, properties, and present use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.1. Origins and sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2. Alcohol fuel properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.3. Present use of alcohol fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

* Corresponding author. Tel.: þ966 2 808 4626 (work), þ966 (0) 544 700 142
(mobile).
E-mail address: Mani.Sarathy@kaust.edu.sa (S.M. Sarathy).

http://dx.doi.org/10.1016/j.pecs.2014.04.003
0360-1285/Ó 2014 Elsevier Ltd. All rights reserved.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 41

List of abbreviations MON motor octane number

MP-VTST multi-path variational transition state theory
ARAS atomic resonance absorption spectrometry MS mass spectrometry
BDE bond dissociation energy MS-VTST multi-structure variational transition state theory
CCD charge-coupled device NDIR non-dispersive infrared
CI compression ignition NMR nuclear magnetic resonance
CMOS complementary metal oxide semiconductor NOx nitrogen oxides
CN cetane number NTC negative temperature coefficient
CRDS cavity ring down spectroscopy NUIG National University of Ireland Galway
CRV constrained reaction volume PAH polycyclic aromatic hydrocarbon
DI direct injection PDPA phase Doppler particle anemometry
EAD electronic absorption detection PEPICO photoelectron photoion coincidence spectrometer
EI electron ionization PES potential energy surface
EPR electron paramagnetic resonance PI photon ionization
EVC exhaust valve closing PIV particle image velocimetry
FID flame ionization detector PM particulate matter
FTIR Fourier transform infrared spectroscopy RA resonance absorption
GC gas chromatography RCM rapid compression machine
HC hydrocarbon REMPI resonance enhanced multiphoton ionization
HCCI homogenous charge compression ignition RF resonance fluorescence
HPLC high-pressure liquid chromatography RON research octane number
IR infrared RRKM RiceeRamspergereKasseleMarcus
JSR jet-stirred reactor SAR structureeactivity relationship
LDV laser Doppler velocimetry SMPS scanning mobility particle sizer
LHV lower heating value SI spark-ignition
LIF laser-induced fluorescence ST shock tube
LS laser schlieren TCD thermal conductivity detector
LTC low-temperature combustion UV ultraviolet
mb/d million barrels of oil per day VUV vacuum ultraviolet
MBMS molecular beam mass spectrometry YSI yield sooting idex
mboe/d million barrels of oil equivalent per day

3. Fundamental combustion experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

3.1. Combustion properties in selected idealized experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2. Developments in experimental combustion research on alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.3. Methanol, ethanol, and isomers of propanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.4. Butanol isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.5. Higher alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4. Chemical kinetics of alcohol combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.1. The molecular structure of alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.2. Formulation of comprehensive chemical kinetic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.3. Reaction mechanism, reaction classes, and rate rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.4. Model testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.5. The combustion chemistry of methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.6. The combustion chemistry of ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.7. The combustion chemistry of propanol isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4.8. The combustion chemistry of butanol isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.9. The combustion chemistry of higher alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5. Insights into engine-relevant phenomena . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
6. Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95

1. Introduction increasing mobility of that population, the increasing production

and consumption of goods, and the transportation of those goods
Energy is among the most important factors influencing eco- are considerable concerns in future energy strategies. The need for
nomic and industrial development. Today, combustion of fossil clean, efficient, and affordable energy sources is often seen in
fuels accounts for more than two-thirds of the world’s primary contrast to the environmental and health issues connected with
energy utilization [1]. The growing global population, the fossil fuel use. Projections for the next two decades assume the
42 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

continued leading role of fossil fuel-based energy with a global Table 1

share of about 30% of primary energy to be needed and utilized in World fuel ethanol production in 2012 by region and country.

Asia, mainly China and India [1]. While many alternatives to coal, Region Millions of Gallons
petroleum, and natural gas are currently used or are being dis- North & Central America 13,768
cussed for power generation (e.g., hydroelectricity and nuclear, South America 5,800
solar, wind, geothermal, tidal or wave energy) transportation of Europe 1,139
people and goods depends on the availability of high-density en- Asia 952
Africa 38.31
ergy sources, primarily delivered to the market today as liquid fuels
derived from petroleum. Country Millions of Gallons
Because of associated greenhouse gas emissions, fossil fuel USA 13,300
combustion has been identified as a key factor in climate change. As Brazil 5,577
one example, Fig. 1 shows the sources of greenhouse gas emissions China 555
Canada 449
in the European Union (EU-27) in 2010. Around 80% came from
Australia 87.2
energy-related sources, with about 63% from direct combustion of
Data from Ref. [10].
fuels, including about 20% from fuel combustion for transportation
[2].
Emissions from petroleum combustion have also been impli-
International Energy Agency [8] suggest that biofuel use will triple
cated in the deterioration of air quality and, subsequently, of human
from 1.3 million barrels of oil equivalent per day (mboe/d) in 2010
health due to the formation of pollutants such as nitrogen oxides
to 4.5 mboe/d in 2035, driven primarily by blending mandates, with
(NOx), carbon monoxide (CO), particulate matter (PM) and soot, and
the fuel ethanol supply rising from 1 mboe/d in 2010 to 3.4 mboe/d
gaseous products from incomplete combustion. Because the
in 2035. To put this in perspective, global oil demand in the year
transformation to the use of alternative energy sources for trans-
2035 is projected to reach 99.7 million barrels of oil per day (mb/d),
portation is especially difficult, energy-efficient, clean combustion
up from 87.4 mb/d in 2011 [9].
processes remain an important research topic. With advances in
This article presents a comprehensive review of the combustion
the development of engine combustion systems, such as homoge-
chemistry of alcohol fuels. The article begins by providing infor-
nous charge compression ignition (HCCI) or related strategies that
mation on the history of alcohol production and use. Sustainability
can adapt to a variety of fuels, the use of biofuels as alternative neat
issues are addressed and important alcohol fuel properties are
fuels or fuel additives is possible [3e7]. Energy independence,
presented. As a prerequisite and background for the necessity of
possible decreases in CO2, soot, and unburned hydrocarbon (HC)
detailed combustion chemistry research, the combustion of alco-
emissions, and other factors are driving this possibility for trans-
hols and alcohol fuel blends in engines is addressed, with a focus on
formation, with biomass-related fuel sources preferably grown on
emission characteristics. The experimental and theoretical tools for
wasteland along with the use of agricultural residue, food waste,
addressing combustion chemistry of fuels are highlighted to pro-
woody plant parts, or algae biomass presenting important topics of
vide an understanding of desired information and observable
discussion and research [3].
quantities. With the stage thus set, the article aims to give an
Ethanol is the most widely used biofuel today. More than 7.3
extensive overview of fundamental combustion chemistry by
billion gasoline-equivalent gallons of ethanol were used as gasoline
considering studies of alcohol fuels in shock tubes, rapid
additives in 2009 in the USA. The increase in the use of biomass to
compression machines, jet-stirred and flow reactors, and laminar
more than 4% of total primary energy utilization in the USA was
flames. The value of information from such experiments is critically
therefore mainly due to ethanol production [3]. The largest pro-
discussed. Subsequently, alcohol combustion chemistry is dis-
duction of fuel ethanol was in the USA, followed by Brazil (see
cussed by presenting a large body of experimental and modeling
Table 1). In 2010, these two countries accounted for about 86% of
investigations covering the combustion of C1eC5 alcohols, with a
global fuel ethanol production [3]. Recent projections from the

Fig. 1. Sources of greenhouse gases in the European Union, 2010.

Reprinted from [2].
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
special emphasis on ethanol and the butanol isomers. Ignition,
flame propagation, qualitative species assignment, and full quan-
titative speciation, depending on the specific combustion regime,
are considered. The combustion kinetics and development of a
comprehensive mechanism relevant to alcohol combustion is pre-
sented. The article closes by presenting a summary of the dis-
tinguishing features of alcohol combustion chemistry and an
outlook toward future research in this area.
2. Alcohol fuels e origins, sustainability, properties, and
present use
Ancient civilizations converted grains to ethanol using
fermentation to produce low-alcohol-content wines and beers.
Archaeologists have discovered primitive forms of distillation
equipment dating back to antiquity [11], but these were used pri-
marily to purify plant essences for medicinal purposes [12] and to
make perfumes. Allchin [13] suggested that excavations in the In-
dian sub-continent together with ancient texts from the region
provide evidence that distillation of alcoholic beverages dates back
to c. 500 BCE. However, the first written account [14] of boiling wine
and observing flammable vapors is found in the writings of Jabir ibn
Hayyan (c. 721e815 CE). Al-Kindi (c. 801e873 CE) later described the
distillation of wine in his Kitab al-Taraffuq fi al-‘itr (The Book of the
Chemistry of Perfume and Distillations) [14]. This early knowledge
of wine distillation by Arab chemists was transmitted to the West,
and Latin texts from the medical schools of Salerno (c. 1100 CE)
mention the production of highly pure alcohol [15]. Up to the
present, distillation remains the industry standard for separation
and purification of alcohols.
Today, the primary source of ethanol continues to be microbial
fermentation of sugars and starches. It is envisaged that in the
future, lignocellulose will also be a source [4,7]. Historically,
methanol was produced from the destructive distillation of pyro-
lyzed wood, but more recently it has been made from natural gas or
coal via gasification to synthesis gas followed by methanol syn-
thesis. Industry-scale renewable routes to methanol exist in the
form of replacing coal with biomass in gasification processes [4].
The two isomers of propanol (n-propanol and iso-propanol) are
typically produced from petrochemicals, but novel biological routes
employing Escherichia coli are being explored at the laboratory
scale [16,17]. The production of butanol isomers from biomass
feedstock dates back to 1861 when Louis Pasteur first documented
the fermentation of sugars to n-butanol [18]. The early 1900s
witnessed a large growth in n-butanol production when Chaim
Weizmann, while attempting to produce n-butanol for synthetic
rubber production, discovered that Clostridium acetobutylicum
could convert sugars into a mixture of acetoneen-butanoleethanol
(ABE) [18]. This production process reached commercial scales in
the 1930s and 1940s, after which it lost market share to the more
economically viable petroleum-derived n-butanol. Nigam and
Singh [19] and Lee et al. [20] briefly reviewed the recent activities in
bio-butanol research and indicated that biological pathways exist
for the production of n-butanol, iso-butanol, and 2-butanol [16,21].
The fourth isomer of butanol, tert-butanol, is a petrochemical
product. The higher alcohols, including the isomers of pentanol and
hexanol, are currently derived from petrochemicals on relatively
small scales. The production of pentanol and hexanol isomers (e.g.,
3-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl-1-pentanol)
from biological sources has become an area of recent research ac-
tivity [16,22,23].
In their book “The Forbidden Fuel: A History of Power Alcohol”,
Bernton, Kovarik, Sklar et al. [24] provide a comprehensive history
of the production and use of alcohol fuels (primarily ethanol) in the
19th and 20th centuries, as well as the political and market factors
43
leading to the eventual rise of petroleum fuels. Methanol (i.e., wood
alcohol), derived from destructive distillation of wood, and ethanol
were commonly used as lamp fuels prior to the 19th century. The
first internal combustion engines developed in the 19th century,
including those by Samuel Morey, Nikolaus Otto, and George
Brayton, utilized ethanol as the fuel. Numerous engineers in the
early 20th century observed that ethanol and ethanol/gasoline
blends had anti-knock properties. The industrialist Henry Ford
(founder of Ford Motor Company) and research engineer Charles
Kettering (former Vice President of General Motors and former
President of the Society of Automotive Engineers) were strong
proponents of ethanol as a fuel for internal combustion engines in
the USA.
The internal combustion engine designer Sir Harry R. Ricardo
extensively studied the use of alcohol fuels in combustion en-
gines. In the Introduction to his 1931 book, “The High-Speed
Internal Combustion Engine”, Ricardo [25] advocated the use of
alcohol fuels. He explained, “It is perfectly well known that
alcohol is an excellent fuel, and there is little doubt, but that
sufficient supplies could be produced within the tropical regions
of the British Empire, yet little or nothing is being done to
encourage its development.” Ricardo then presented numerous
experimental results testing hydrocarbon fuels (e.g., paraffins,
aromatics, olefins, and naphthenes) and alcohol fuels in both
spark-ignition (SI) and compression ignition (CI) engines. His
pioneering early work on pre-ignition, which eventually led to
the development of fuel octane ratings, showed that ethanol
allowed for operation at a higher compression ratio due to its
decreased pre-ignition propensity. Ricardo also noted that
alcohol fuels had higher latent heats of vaporization and lower
flame temperatures than petroleum-based ones, and that these
properties could be exploited to increase power output and
decrease thermal losses.
2.1. Origins and sustainability
This review of research on alcohol fuel combustion chemistry
would be incomplete without at least a brief mention of the
intensely debated issues around biofuel sustainability. The highly
cited articles by Farrell et al. [26] and Goldemberg [27] demon-
strated that renewable ethanol fuel can be sustainably produced in
many countries. More recently, researchers [28,29] showed that
indirect land-use change (i.e., deforestation of Amazonian forests)
caused by biofuel plantations in Brazil needs to be critically
assessed to ensure sustainable production. A review on biofuels by
Koh and Ghazoul provides a unique perspective on the environ-
mental and societal impacts of biofuels [30]. The rapid policy-
driven growth of biofuel use has led to serious environmental
and food security concerns. Current biofuel technologies compete
with the food industry for feedstock, and the diversion of corn,
rice, and oilseeds to biofuel production is cited as the cause of
rising food prices and global food shortages. In addition, large
amounts of forested lands are being destroyed for biofuel feed-
stock production, leading to a loss in biodiversity and carbon-rich
sinks. The competition for fresh water resources presents an
additional barrier to widespread biofuel use. Despite these chal-
lenges, advances in biofuel feedstock and production technologies
may have the potential to ameliorate the negative impacts of
biofuels.
It is clear from the literature that conventional bio-alcohol
production from food crops, most notably corn, has limited po-
tential [28,31]. Reasons for this include competition from the food
industry [32], limited agricultural land for crop growth [31], and
high energy input requirements for agricultural chemicals and
harvesting [28]. For biofuels to live up to their potential as suitable
44 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

alternative fuels, lignocellulosic biomass must be considered.
Agricultural and forest residues as well as sources of lignocellu-
losic biomass offer advantages over food crop feedstock. These
advantages include the ability for lignocellulosic biomass to be
cultivated on marginal agricultural land, lower agricultural
chemical requirements, lower energy requirements, and the po-
tential for utilizing the lignin portion of the biomass as an energy
source for the production process. For these reasons, the projected
net energy gains from lignocellulosic alcohols are much higher
than those from corn-based alcohol production technologies, and
the resulting greenhouse gas emissions would then be much
lower. Despite these inherent advantages, the conversion of
lignocellulosic feedstock to fuels is not yet at commercial scale,
primarily because it is challenging to convert lignocellulosic
biomass to alcohols without offsetting some of the possible net
energy savings [28,31e33].
2.2. Alcohol fuel properties
Fuel property requirements for SI engine fuels are dictated by
ASTM D4814, Standard Specification for Automotive Spark-Ignition
Engine Fuels, and for CI engine fuels by ASTM D975, Standard
Specification for Diesel Fuel Oils. The physical and chemical prop-
erties of several alcohol, gasoline, and diesel fuels are presented in
Table 2. This limited data set includes some of the important
properties relevant to utilization of alcohol fuels in combustion
systems. The table includes all C1eC4 isomers, two C5 isomers, and
normal C6eC8 isomers of alcohols along with their molecular
structures. The following conclusions can be drawn from Table 2.
 An increase in the molecular weight of alcohol fuels corresponds
to a decrease in the oxygen content (wt%) and an increase in the
carbon and hydrogen content. This results in an increase in the

Table 2
Physical and chemical properties of alcohol, gasoline, and diesel fuels.

Fuel Structure MW O2 (wt%) LHVa (MJ/L) Stoichiometric Boiling RONd MONd DHvape (kJ/kg Solubility Specific gravityg,h
air/fuel ratiob Pointc ( C) from 25  C) in waterg at 20  C
at 25  C, wt%

Methanol 32.04 0.50 15.8 6.46 64.7 109 89 1168 Miscible 0.792

Ethanol 46.06 0.35 21.4 8.98 78 109 90 919.6 Miscible 0.794

n-Propanol 60.09 0.27 24.7 10.33 97 104 89 792.1 Miscible 0.804

iso-Propanol 60.09 0.27 24.1 10.33 83 117 95 756.6 Miscible 0.789

n-Butanol 74.11 0.22 26.9 11.17 118 98 85 707.9 7.4 0.81

2-Butanol 74.11 0.22 26.7 11.17 99 105 93 671.1 18.1 0.808

iso-Butanol 74.11 0.22 26.6 11.17 108 105 90 686.4 8.1 0.802

tert-Butanol 74.11 0.22 25.7 11.17 83 107 94 629.9 Miscible 0.789

n-Pentanol 88.14 0.18 28.5 11.74 138 80 74 647.1 2.2 0.816

3-Methyl-1-butanol 88.14 0.18 27.8 11.74 130 94 84 617.1 2.7 0.8

n-Hexanol 102.16 0.16 29.3 12.15 157 56 46 603.0 0.6 0.814

n-Heptanol 116.19 0.14 30.1 12.47 175 e e 575.0 0.2 0.822

n-Octanol 130.21 0.12 31.1 12.71 195 28 27 545.0 0.05 0.826

Gasoline Average C8H15 111.19 0.00 30e33 14.58 27e225 88e98 80e88 w351 Negligible 0.72e0.78
Diesel Average C14H30 198.4 0.00 35.66 14.95 125e400 <0 <0 w232f Negligible 0.81e0.89f
a
Lower heating values for methanol and diesel Agarwal [7]; values for tert-butanol, iso-pentanol, and larger alcohols are derived from DHC; all others from Christensen et al.
[37].
b
The mass basis air/fuel ratio is calculated using 28.97 g/mol as the average molecular weight of air and O2 composition of 21 mol%.
c
Gasoline boiling point range from Christensen et al. [37]; diesel from Agarwal [7]; all others are average values from a survey of the literature.
d
Volumetric blending research octane number (RON) and motor octane number (MON) values are from Christensen et al. [37] for n-pentanol and 3-methylbutanol; neat
RON and MON for methanol and ethanol are from Hunwartzen [39] and Bauer et al. [40], as presented in Anderson et al. [41]; neat RON and MON for tert-butanol and iso-
propanol is from Hamadi [42]; neat RON and MON for n-hexanol and n-octanol are from Graboski et al. [43]; neat RON and MON for n-propanol, n-butanol, 2-butanol, and iso-
butanol from Christensen et al. [37].
e
Heat of vaporization, DHvap, from Christensen et al. [37].
f
“Diesel Fuel Oils, 1987,” Petroleum Product Surveys, National Institute for Petroleum and Energy Research, October 1987.
g
CRC handbook of chemistry and physics, 87th edition. Handbook of Chemistry and Physics, 91st ed.; CRC Press: Boca Raton, FL, 2010/2011.
h
Specific gravity is defined as the ratio of the density of fuel to the density of water at 20  C.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
energy content, indicated by the fuel’s volumetric lower heating
value (LHV). C1eC3 alcohols have significantly lower LHVs than
gasoline and diesel. Use of C1eC3 alcohols therefore tends to
reduce fuel economy (i.e., miles per gallon). Alcohols with four
or more carbons have LHVs closer to that of gasoline, and are
thus beneficial for improving fuel economy [34].
 The presence of the hydroxyl moiety in alcohols causes them to
be liquid at room temperature and thus suitable fuels for trans-
portation applications. The lower alcohols (C1eC2) have lower
boiling points, which depresses front-end distillation when
blended with gasoline and diesel fuels. At present, US regulations
fix ethanol concentrations in gasoline, so refiners vary butane
concentrations in the fuel to meet summer and winter front-end
distillation specifications. In conventional carbureted SI engines,
this often leads to the problem of vapor lock, but recent de-
velopments in fuel injection (e.g., port fuel and direct injection)
are more tolerant of volatile fuels [34]. Nevertheless, altering the
distillation curve modifies fuel spray formation, vaporization,
and in-cylinder mixture stratification, which are important
design considerations for modern low-temperature combustion
(LTC) engines [35,36]. The C3eC8 alcohols tend to have boiling
points in the mid-point of the gasoline/diesel fuel range; they
can be blended with petroleum fuels at greater concentrations
with lesser impact on the fuel distillation curve.
 The latent heat of vaporization (DHvap) of alcohols is signifi-
cantly higher than those of petroleum gasoline and diesel fuels,
which negatively impacts the ability to start the engine under
cold conditions (i.e., cold-start). However, current advances in
fuel delivery systems are largely able to deal with this problem.
The higher molecular weight alcohols have less difficulty with
cold-start operation due to their lower specific latent heat of
vaporization. A fuel’s latent heat of vaporization can also affect
in-cylinder thermal stratification, which is important for con-
trolling excessive pressure rise rates in LTC engines [35,36].
 The hydroxyl moiety in alcohols introduces a dipole moment to
the non-polar hydrocarbon backbone. C1eC3 alcohols have short
hydrocarbon chains, so they are more polar and more soluble in
water than non-polar hydrocarbons. This fact lowers the upper
limit of blending in petroleum fuels without the use of a co-
solvent. Their water affinity also introduces challenges in their
distribution infrastructure, which must prevent water contam-
ination. Higher alcohols are increasingly less polar due to their
longer non-polar hydrocarbon chains. They are thus easier to
blend with non-polar hydrocarbons and they have lower affinity
for water.
 The ignition propensity (i.e., knock resistance, octane rating) of
alcohols is perhaps their most attractive feature for internal
combustion engine applications. A high octane rating correlates
with a lower propensity for ignition and allows the SI engine to
operate at a higher compression ratio without knocking.
Methanol, ethanol, and propanol isomers have high research
octane number (RON) and have long been used to improve the
octane number of SI engine fuels. Butanol isomers have octane
ratings similar to that of conventional gasoline and are thus
suitable for SI engines. C5- and larger alcohols have octane rat-
ings that are lower than that of gasoline, and hence decrease
knock resistance when blended with petroleum SI engine fuels
[37]. However, a decreased octane number correlates with an
increased cetane number (i.e., greater propensity for ignition),
making the larger alcohols suitable for CI engine applications.
Alcohol fuel branching such as methyl substitution tends to
decrease the ignition propensity (i.e., increase the octane num-
ber). Later sections of this paper provide fundamental expla-
nations of how chemical features such as hydroxyl moiety and
methyl substitution affect the ignition propensity.
45
 An interesting feature of alcohols is their high sensitivity,
defined as the research octane number minus the motor octane
number (S ¼ RON  MON). This unique fuel property can have
benefits in modern LTC engines and highly boosted direct in-
jection spark ignition (DI SI) engines that prefer high sensitivity
fuels [38].
2.3. Present use of alcohol fuels
Given the documented history of the use of alcohol fuels since
the internal combustion engine was developed and their favorable
physicalechemical properties, it is no surprise that alcohols
continue to be attractive fuels for today’s modern SI and CI engines.
The purpose of this study is to highlight the importance of alcohol
combustion in engines and thus to motivate the full investigation of
their combustion chemistry. The following articles give a compre-
hensive overview of the use of alcohol fuel in engines.
 Agarwal [7] reviewed a large body of literature to conclude that
ethanol can be blended with gasoline fuel to improve engine
performance and reduce emissions of CO and unburned HCs in
exhaust. Up to 20% of ethanol can be blended with diesel fuel to
reduce CO and NOx emissions. Hansen et al. [6] also discussed
the potential uses of ethanol-diesel fuel blends, highlighting
important blending characteristics and safety considerations.
 Giakoumis et al. [44] studied diesel engines running on blends
of ethanol or n-butanol with diesel fuel under transient condi-
tions. They concluded that alcohol/diesel blends decrease
engine-out PM and CO emissions, while increasing unburned HC
and oxygenated (e.g., carbonyl) emissions. A clear trend on NOx
emissions was not observed.
 n-Butanol was studied as a fuel or as a blending agent for use in
SI engines [34,45e52], CI engines [46,53e62], and motored
engines [63]. iso-Butanol has also received attention from en-
gine researchers with studies performed on SI engines [64e67]
and in CI engines [68,69]. Niass et al. [70] demonstrated that 2-
butanol and tert-butanol could be blended with gasoline fuel for
improved engine performance.
 In a series of papers, Gautam et al. studied combustion [34] and
emission [47] characteristics of C1eC5 normal alcohols blended
with gasoline. Their results indicated that there was substantial
knock resistance when using alcohol fuels blends as well as an
ability to reach higher compression ratio operation.
 Vancoillie et al. [71] recently demonstrated the use of methanol
as a fuel for SI engines at diesel-like efficiencies (up to 50%) and
emission levels comparable to or lower than those of gasoline.
In summary, these papers suggest that alcohols with various
molecular structures (i.e., carbon number and substitution) can be
used in today’s SI and CI engines with minor modifications to the
engine design. However, the details of the combustion chemistry of
alcohol fuels, including pathways to potential pollutants, are less
understood than are those of the hydrocarbons that constitute to-
day’s petroleum-derived transportation fuels [72]. Some aspects of
concern regarding their perceived “cleaner combustion” image are
the emissions of carbonyl species, such as formaldehyde (CH2O),
acetaldehyde (ethanal, C2H4O), acetone (C3H6O), acrolein (prope-
nal, C3H4O). These compounds present an air quality concern
because they are toxic and irritating, as well as being precursors to
urban smog (e.g., free radicals, ozone. and peroxyacyl nitrates) [73e
75]. Pang et al. [76] conducted carbonyl emissions measurements in
SI and CI engines using blends of ethanolegasoline and ethanole
biodieselediesel. Their results showed that ethanol blending
reduced tailpipe emissions of CO and PM, but increased total
46 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 2. Percentage of carbonyl compounds in engine-out emissions from E10 gasoline at six load levels under stable speed (2800 rpm). For (formaldehyde), Ace (acetaldehyde),
Arn (acrolein), Atn (acetone), Pro (propionaldehyde), Cro (crotonaldehyde), Mac (methylacrolein), But (butyraldehyde), Ben (benzaldehyde), Tol (m-tolualdehyde, p-tolualdehyde),
others include valdehyde, hexaldehyde, and 2,5-dimethylbenzaldehyde.
Reprinted from [76] with permission from Elsevier.
tailpipe carbonyl emissions. Engine-out emissions included high
concentrations of acetaldehyde (e.g., see Fig. 2), which is a product
of ethanol combustion.
Armas et al. [77] showed that ethanol and butanol blends with
diesel could reduce PM during warm engine start, whereas com-
bustion instabilities led to increases in unburned hydrocarbon and
CO emissions under cold-start conditions. Similarly, addition of n-
butanol was seen to decrease smoke density, CO, and NOx emis-
sions in diesel-n-butanol blends [57], but it increased (not further
specified) unburned hydrocarbon emissions. The use of increasing
amounts of n-butanol in gasoline in HCCI engines was seen to
significantly influence formaldehyde and acetaldehyde emissions
in a study by He et al. [78]. Formaldehyde levels increased with
increasing n-butanol addition, almost irrespective of engine speed.
The study concluded that formaldehyde, once formed, cannot be
further oxidized in the cylinder under the conditions tested
because n-butanol blending advanced ignition timing, reduced
combustion duration, and decreased in-cylinder temperatures
during the exhaust stroke. Emission of acetaldehyde were nearly
independent of engine speed under the conditions investigated,
but at any given exhaust valve closure timing, acetaldehyde levels
increased with the amount of n-butanol in the blend (Fig. 3). Such
effects were suggested to be a result of the different reaction
mechanisms of gasoline and n-butanol to form acetaldehyde [78].
Fig. 3. The effect of exhaust valve closing (EVC) timing on acetaldehyde emissions with
butanolegasoline blends.
Reprinted from [79] with permission from Elsevier.
Reviewing several earlier studies, the authors suggested the level of
aldehyde emission is a function of engine type, load, and com-
bustion mode in addition to different pathways that may lead to
their formation.
Aldehyde formation and emission from combustion sources
may cause underestimated health problems. A study by Jacobson
[79] concluded that widespread ethanol use may increase the risk
of cancer and ozone-related illnesses due to higher aldehyde
emissions and increased unburned ethanol emissions, which break
down to acetaldehyde in the atmosphere. Combustion chemistry
studies of alcohols can help to determine the importance of
oxygenated emissions by elucidating the role of fuel-bound oxygen
during combustion.
It is challenging to draw broad scientific conclusions from
vehicle engine studies, especially in terms of emissions character-
ization, because of the highly variable nature of tested boundary
conditions across studies (i.e., engine-out versus tailpipe, after-
treatment technologies, varying loads, speeds, engine types,
fueling methods, intake temperatures and pressures, and operating
conditions). Nevertheless, engine research demonstrates the utility
of alcohol fuels in practical applications and motivates the revision
of regulatory policies around fuel and emission standards. Work on
scientific approaches toward understanding the effects of alcohol
fuels on combustion is the focus of the remainder of this paper,
wherein fundamental chemical kinetic combustion experiments
and simulations with well-defined boundary conditions are
described. The fundamental combustion properties to be reviewed
for alcohol fuels are the premixed laminar flame speed, homoge-
nous ignition delay time, and product species distributions from
gas-phase oxidation/combustion.
3. Fundamental combustion experiments
Combustion in internal combustion engines is a complex pro-
cess involving fuel atomization, vaporization, fuel-air mixing,
ignition, and combustion. For example, Dec [80] has presented a
phenomenological description, or “conceptual model”, for diesel
combustion in a direct injected (DI) CI engine. As shown in Fig. 4,
liquid fuel is injected as a high-velocity spray into the combustion
chamber, where it vaporizes upon impingement with high-
temperature, high-pressure in-cylinder gases. Low-temperature
reactions spontaneously ignite portions of premixed fuel and air
at local equivalence rations of about 2e4 (i.e., fuel-rich conditions),
which results in rapid heat release. The remaining fuel spray is then
consumed in a high-temperature diffusion flame. Combustion
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 47

models. Finally, we demonstrate some examples of utilizing

detailed chemical kinetic modeling simulations to understand
alcohol fuel effects in internal combustion engines.

3.1. Combustion properties in selected idealized experiments

Investigating the combustion chemistry of alcohols requires

conditions under which chemical kinetic processes govern the
conversion of the fuel and oxidizer into products, and where mix-
ing processes are considered negligible or at least limited only to
gas-phase diffusion (e.g., perfectly mixed or slow mixing). These
requirements have led researchers to the use of idealized reactors
and flames for studying the global gas-phase combustion chemistry
Fig. 4. A conceptual model for diesel combustion in a DI CI engine. of alcohols at various temperatures, pressures, and mixture com-
Reprinted from Dec [80] with permission from SAE International. positions. These include, but are not limited to, homogenous gas-
phase batch reactors (e.g., shock tubes and rapid compression
machines), jet-stirred reactors, plug flow reactors (e.g., laminar flow
gases are produced throughout the expansion process with insuf-
and turbulent flow reactors), laminar premixed flames, and non-
ficient oxygen available to completely oxidize all the intermediates.
premixed diffusion flames. The fundamental combustion proper-
This unsteady, heterogenous, three-dimensional process is chal-
ties investigated using these experimental systems include the
lenging to model, and it is difficult to decouple physical mixing
homogenous ignition delay time, premixed laminar flame speed,
processes from chemical kinetic processes. A similar conceptual
and product species distributions from gas-phase oxidation and/or
model has recently been presented for partially premixed LTC
pyrolysis. The respective property can be monitored as a function of
diesel engines under low-load conditions by Musculus, Miles, and
time t, temperature T, pressure P, or a specific spatial coordinate x.
Pickett [81].
It has been demonstrated that a fuel’s homogenous ignition
Computer simulations are capable of combining fluid dynamics,
delay can be correlated with its octane rating [86,87], which is a
spray dynamics, chemical kinetics, and heat and mass transfer to
critical parameter for engine design and operation. Kalghatgi [88]
reproduce ignition behavior, pollutant formation, energy release,
notes that octane ratings are primarily determined by chemical
and other features of engine operation. Such simulations are widely
kinetics rather than physical fuel effects (e.g., latent heat of vapor-
used in the automobile industry to increase fuel economy and
ization, density, viscosity, physical mixing effects, etc.). The pre-
reduce emissions. Westbrook et al. [82] provided a thorough review
mixed laminar flame speed is a fundamental indicator of fuel
of computational combustion methods and their applications to-
reactivity at high temperature, and is also a critical parameter for
ward simulation of combustion in SI, CI, and HCCI engines. Typi-
determining the turbulent flame speed in engines. The emissions
cally, these engine simulations are computationally expensive, so
formed upon fuel oxidation and/or pyrolysis in ideal reactors are
simplifications in fluid dynamics, spray dynamics, and elementary
indicative of the species formed in engines under similar temper-
chemical kinetics are made to run them on present personal
ature, pressure, and equivalence ratio conditions. Thus, under-
computing technologies.
standing combustion in idealized systems can offer insights into a
Reducing the chemical fidelity in simulations would limit our
fuel’s performance in practical engines.
ability to understand the comprehensive combustion chemistry of
It is important to note that several researchers have had suc-
alcohols. Recent studies by Westbrook et al. [83,84] have shown
cess studying alcohol combustion chemistry in non-idealized
that an understanding of engine-relevant phenomena can be ob-
experimental setups. For example, Haas et al. [89] used an igni-
tained using detailed chemical kinetic models in simpler reacting
tion quality tester to study the ignition chemistry of butanol iso-
flow simulations, given the appropriate boundary conditions. For
mers in reacting sprays. By matching the physical properties of the
example, the effects of oxygenated hydrocarbons on soot emissions
fuels, they were able to attribute differences in ignition delay
from diesel engines were studied [83] using detailed kinetic
times to chemical kinetic processes rather than physical processes
modeling simulations of idealized rich premixed ignition and
(e.g., spray formation and droplet vaporization). In addition, HCCI
combustion of diesel surrogate fuels. The boundary conditions (e.g.,
engines have been used to study the combustion chemistry of
temperature, pressure, and equivalence ratios) were obtained from
alcohol fuels with reasonable levels of success. Some notable
Dec’s conceptual model for DI CI diesel engine combustion [80]. The
studies include investigations on interesting features such as HCCI
relative sooting tendencies of various fuels were then determined
engine low- and intermediate-temperature heat release and
by summing the concentrations of soot precursors (e.g., acetylene,
combustion phasing for ethanol [59,90e95], n-butanol [59,96],
benzene, ethylene, toluene, etc.) following the rich ignition event.
and iso-pentanol [97]. These studies offer insights into alcohol
In separate studies, Westbrook has shown that similar simulation
fuel/engine interactions, and describe engine-related phenomena
approaches can be used to the predict gasoline fuel octane ratings
that could be better understood with fundamental combustion
[85], HCCI engine pressure traces [85], and biodiesel fuel cetane
experiments at relevant temperature, pressure, and mixture
ratings [84].
fraction conditions.
The success of the aforementioned approach toward improving
The homogenous ignition delay is the time it takes for a ho-
an understanding of fuel effects in engines motivates us to first
mogenous gas-phase fuel/air mixture at a specified temperature
describe the study of alcohol fuel in idealized combustion systems
and pressure to reach an explosive state resulting in a rapid release
(e.g., reactors and flames). In this way, the fuel’s combustion
of heat and a rise in temperature and pressure. Ignition delay time
chemistry can be precisely modeled, such that the effects of the
measurements for fuel/air mixtures at high pressures (e.g., greater
molecular structure of the alcohol on combustion and emissions
than 10 bar) and low to intermediate temperatures (e.g., 600e
can be understood. We then delve deeper into the chemical kinetics
1000 K) tend to correlate well with fuel octane and cetane ratings,
and combustion chemistry mechanisms of alcohols, including
and thus are the most relevant to engine operating conditions.
simulation of idealized reactors using detailed chemical kinetic
Fuels with longer ignition delay times under the aforementioned
48 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
conditions tend to have higher octane numbers and lower cetane
numbers. Ignition delay time measurements at lower pressures,
higher temperatures, and/or on highly diluted mixtures are not
representative of real engine conditions, but still provide valuable
data for the testing and/or validation of chemical kinetic models.
Recent reviews on low-temperature ignition are available in this
journal by Battin-Leclerc [98] and by Zádor et al. [99]. Battin-Leclerc
[98] presents a comprehensive description of various experimental
setups used for measuring ignition delay times. For alcohols, these
properties have been largely measured using rapid compression
machines (RCMs) and shock tubes (STs). In both experiments, a test
gas mixture comprising fuel, O2, and a diluent (e.g., N2, Ar, etc.) is
rapidly raised to the desired temperature and pressure, and then
held under near-constant-volume conditions until an ignition
event occurs, typically measured as a rapid pressure rise or
chemiluminescence emission.
Fig. 5 presents typical ignition delay time measurements ob-
tained in shock tubes and RCMs. When interpreting and modeling
shock tube data, it is important to consider how the measurements
were performed [100,101] and the existence of pre-ignition pres-
sure rise [102,103]. Two approaches exist for handling pre-ignition
pressure rise in zero-dimensional homogenous batch reactor sim-
ulations: the volume-varying approach and the pressure-varying
approach. In the former method, the experimentally measured
pressure time-history is converted to a volume history [102]
(assuming isentropic compression) for use in the simulation,
whereas in the latter approach the measured pressure profile up to
the ignition time is used in the simulation to constrain the pressure.
RCM data also need to be carefully interpreted by evaluating the
compression time, compression ratio, heat losses before and after
the end of compression [104e106], and potential reactions during
the compression stroke. Ignition is a transient process of fuel
reacting with oxygen to form intermediate species that eventually
result in a radical chain-branching process [107]; experiments in
stirred reactors and flow reactors that measure the transient and/or
steady-state formation and destruction of low- and intermediate-
temperature species can also aid in understanding the ignition
chemistry of alcohols. Further details on the chemical mechanisms
Fig. 5. (Left) shock tube ignition delay time measurements performed at Stanford University on 2-butanol in 4% O2 diluted in Ar, f ¼ 1, T ¼ 1176 K, P ¼ 0.5 bar. Reprinted from
Stranic et al. [108] with permission from Elsevier. (Right) RCM ignition delay measurements performed at University of Connecticut on 2-butanol. P(t) is the pressure as a function of
time, and P0 (t) is the time derivative of the pressure, as a function of time.
Reprinted from Weber and Sung [105] with permission from Elsevier.
of low-temperature ignition unique to alcohol fuels are described in
Section 4.
The premixed laminar flame speed is simply defined as the
velocity at which a flame front propagates into an unburned gas
mixture at a fixed temperature, pressure, and mixture composition.
It is a fundamental combustion property that is employed in
describing more complex combustion phenomena existing in en-
gines, such as the turbulent flame speed, flame structure, flame
stabilization and instabilities, and flame extinction [109]. The
laminar flame speed is an idealized combustion property that
cannot be measured exactly. Therefore, experiments measuring
laminar flame speeds attempt to achieve near-ideal conditions and
account for non-ideal effects, such that they can be subtracted from
the experimental data [109]. Laminar flame speed measurements of
alcohols have been performed using a variety of experimental ar-
rangements, including counterflow diffusion flames, spherically
propagating flames, and burner-stabilized flames. The propagating
flame front is typically observed using direct photography of the
luminous zone, shadowgraphy, or schlieren imaging. A schematic
of the counterflow twin-flame configuration at the University of
Southern California [110], which has been used to measure the
laminar flame speeds of many C1eC5 alcohols, is shown in Fig. 6.
The effects of the molecular structure of alcohol fuels on laminar
flame speeds are discussed in Section 4.
Emissions are undoubtedly a chief concern in the use of com-
bustion technologies. Correlating the kind and quantity of
combustion-generated species with the molecular structure of the
fuel again requires experiments with idealized flames and reactors.
The distribution of species depends on the type of experimental
apparatus and its operating temperature, pressure, and mixture
composition. Species generated from alcohol fuel combustion have
been studied in shock tubes, RCMs, premixed flames, non-
premixed diffusion flames, flow reactors, and stirred reactors. The
species within the reacting gas and/or burnt gas mixture are
analyzed online by using optical diagnostics or offline by trans-
ferring gases into a chemical analyzer. Online diagnostic techniques
do not disturb the idealized flow conditions in the experiment, and
they preserve the chemical nature of the test gas being sampled.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 49

Fig. 6. Schematic of the experimental counterflow configuration used to measure laminar flame speeds of alcohol fuels at the University of Southern California.
Reprinted from Ref. [110] with permission from Elsevier.

These methods can measure a limited number of species present at
relatively high concentrations using a variety of absorption and
emissions spectroscopy techniques in the UV to IR wavelength
ranges [111,112]. Offline techniques offer the ability to measure a
larger number of species at lower concentrations than offered by
online techniques, but at the expense of perturbing the experiment
and test gas during the sampling process. The test gas is often
extracted to a gas chromatograph with various detectors (e.g., flame
ionization detector, thermal conductivity detector, mass spec-
trometer) or infrared spectrometers (e.g., Fourier transform
infrared detector, non-dispersive infrared detector). Fig. 7 displays a
flow reactor used at Ghent University to study the pyrolysis of
alcohol fuels using several offline GCs.
More recently, molecular-beam sampling into a differentially-
pumped mass spectrometer (MBMS) [113e117] has proven a
powerful tool for measuring a large number of stable and radical
species from alcohol combustion with minimal disturbance to the
reactive zone and/or sampled gases. In combination with
synchrotron-based vacuum ultraviolet (VUV) single photon ioni-
zation, the MBMS technique (PI-MBMS) is even able to provide
isomer-resolved quantitative species information from reactive
environments such as the reaction zone of a flame [118,119]. Most
recently, the technique was extended by the successful combi-
nation of a molecular-beam flame-sampling setup to a photo-
electron photoion coincidence spectrometer (PEPICO) [120]. This
technique adds an additional analytical dimension due to the
observation of molecule-specific transitions from the neutral to a
specific ionic state. First results show a high sensitivity for radical
detection in combination with highly reliable isomer identifica-
tion even for large species and multicomponent mixtures [120].
Table 3 presents a comprehensive summary of fundamental
combustion experiments conducted on C1 to C6 alcohols, along
with the diagnostic techniques employed in each, and the experi-
mental conditions (e.g., temperature, pressure, and mixture

Fig. 7. Schematic of the experimental pyrolysis setup at Ghent University used to study pyrolysis of alcohols. 1: butanol vessel, 2: water vessel, 3: electronic balance, 4: pump, 5:
valve, 6: evaporator, 7: mixer, 8: heater, 9: air cylinder, 10: pressure regulator, 11: mass flow controller, 12: nitrogen cylinder, 13: reactor, 14: nitrogen internal standard, 15: oven, 16:
GC for formaldehyde and water, 17: GC for C5 and higher, 18: cyclone, 19: condenser, 20: dehydrator, 21: GC for C4 and lower, and 22: data acquisition.
Reprinted from Harper et al. [121] with permission from Elsevier.
50 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 8. Number of refereed journal articles published per year on various alcohol fuels.
Alcohol isomers and alcohols larger than C5 are lumped together in the figure.
fraction). The remaining sub-sections in this section critically re-
view the large body of experimental data on alcohol fuels presented
in Table 3. The objectives of this review are as follows.
 To elucidate historical trends in on the combustion chemistry of
alcohol fuels. This is achieved by presenting a graph on the
number of papers published for each family of alcohols (e.g.,
methanol, ethanol, propanols, etc.) per year since 1970.
 To identify the variety of experiments and the range of tem-
peratures, pressures, and mixture fractions studied for each of
the alcohols, with an aim to highlight gaps on which future work
could focus.
 To identify exemplary experimental data sets that will aid in
testing the detailed chemical models for elucidating the com-
bustion chemistry of alcohols.
 To reveal peculiar and intriguing experimental phenomena that
require further investigation.
3.2. Developments in experimental combustion research on
alcohols
Fig. 8 presents a graph on the number of refereed journal articles
published each year (since 1930) that describe alcohol combustion
experiments. Accompanying the graph are 4-dimensional plots (see
Fig. 9aee) representing the approximate range of temperatures,
pressures, equivalence ratios, and years at which alcohol combus-
tion has been studied. Only premixed oxidation studies are pre-
sented in the 4-D plots (i.e., pyrolysis and non-premixed flame
studies are excluded). The earliest articles on alcohol combustion
actually date back to the 1930s when researchers [254e256] were
studying the “slow combustion” of methanol at low temperatures
(400e750  C) and sub-atmospheric pressures. These were the first
studies to show that methanol thermally decomposes in two stages
(CH3OH / H2 þ CH2O / 2H2 þ CO), as well as to measure the re-
action rates. Around the same time, Schultz and Kistiakowsky [257]
studied the thermal decomposition of tert-butanol and tert-iso-
amyl alcohol (1,1-dimethylpropan-1-ol) at 487e555  C and sub-
atmospheric pressures, identifying the low-lying molecular elimi-
nation pathways forming an alkene and water. From 1957 to 1960,
Barnard [189,201,202] continued to study the pyrolysis of alcohols
(iso-propanol, n-butanol, and tert-butanol), identifying the
presence of carbonyl products (e.g., ketones and aldehydes), eluci-
dating reaction mechanisms, and deriving kinetic rate coefficients.
These pioneering studies were motivated by the chemist’s fasci-
nation with various organic molecule reactions; there was no
mention of the relevance of such work to alcohol as a fuel for en-
ergy applications. Nevertheless, these early experimental works
contributed to laying foundations for understanding the combus-
tion chemistry of alcohols, including the development of experi-
mental methods, diagnostic techniques, reaction mechanisms, and
rate coefficient evaluations. Together with theoretical work by
Hinshelwood et al. [258] on chemical kinetics theory and by
Semenov [259] on chain reactions, a detailed understanding of the
combustion chemistry of alcohols was made possible. Indeed, the
water elimination pathways observed by Schultz and Kistiakowsky
[257] were recently shown to affect the ignition delay times at high
temperatures of tert-butanol [260], and the greater concentrations
of carbonyl products seen by Barnard [189,201,202] during alcohol
pyrolysis when compared with alkane pyrolysis explains why these
emissions are a source of concern in alcohol-fueled engines.
Articles published in the 1970s through the 1990s reported re-
sults from alcohol combustion in experimental systems similar to
those used in laboratories today (e.g., shock tubes, flow reactors,
and premixed flames). The early works state, as their motivations,
the need to understand the fundamental combustion chemistry of
alcohols because of their potential use as alternative sources of
fuels for internal combustion engines. The idea was then proposed
that fundamental combustion experiments, on such topics as the
ignition delay time and the premixed laminar flame speed, could
aid practical engine design. These experimental studies were
largely limited to methanol and ethanol, and there was less than
one article published per year over the 30-year period from 1970 to
2000.
In 2003, there was a sharp increase in the number of articles
published per year on these topics. From 2003 to 2013, the number
of articles published is more than double that of all prior years
combined. Ethanol became a topic of interest, while methanol and
propanol isomers studies averaged of one or two papers per year.
The significant growth in interest was in butanol isomers, on which
there have been numerous papers published since 2008. Histori-
cally, there has been a scarcity of fundamental combustion data on
higher alcohols (i.e., C5 and larger), as is also true for high molecular
weight hydrocarbons (e.g., alkanes, aromatics, etc.). These low va-
por pressure compounds complicate fuel vaporization and subse-
quent condensation in transfer lines, thus making it challenging to
achieve well-defined mixture compositions in the reactor/flame.
Experimentalists are overcoming these issues by using atomizers/
nebulizers to produce ultra-fine droplets/aerosols together with
various heating methods to promote vaporization and prevent
condensation (e.g., diluent gas pre-heaters, heated transfer lines,
heating jackets, etc.). Thus, the body of experimental data on higher
alcohols is expected to grow considerably over the next decade. The
recent interest in C4 and larger alcohols is a result of the industry’s
interest in using alcohols with higher energy densities in trans-
portation applications, the design of novel synthetic biological
routes to produce higher molecular weight alcohols, and the
combustion scientist’s ability to generate high-quality fundamental
combustion data rapidly.
3.3. Methanol, ethanol, and isomers of propanol
The summary of fundamental combustion experiments given in
Table 3 provides an overview of the available studies relevant for
development and testing of gas-phase reaction kinetics for the
respective alcohol fuel and its derived intermediates. The list in-
cludes data acquired for pure, gaseous combustion of the respective
Table 3
Fundamental experimental studies of alcohol combustion kinetics.

Reference Fuels Experimental device Measured properties Diagnostic techniques T, P, mixture fraction

Methanol
Cooke et al., 1971 [122] Methanol, ethanol Shock tube Ignition delay Emission of OH, CH, C2, and CO2 1570e1870 K,
0.267e0.400 bar, f ¼ 1
Bowman, 1975 [123] Methanol Shock tube Species profiles O, OH, H2O, and CO emission 1545e2180 K,
and absorption f ¼ 0.75e6.0
Aronowitz et al., 1979 [124] Methanol Flow reactor Species profiles GC 950e1030 K, 1 bar,
f ¼ 0.03e3.16
Singh et al., 1979 [125] Methanol Jet-stirred reactor Species profiles (f) GC (FID þ TCD), commercial 1870 K, 0.93 bar f ¼ 0.7e1.4
analyzers
Natarajan and Bhaskaran, Methanol Shock tube Ignition delay Wideband emission 1300e1700 K,
1981 [126] 2.5e4.5 bar, f ¼ 0.5e1.5
Vandooren and van Methanol Laminar premixed flame Species profiles (x) EI-MBMS, 500e2100 K, 0.053 bar,
Tiggelen, 1981 [127] f ¼ 0.89, 0.36, and 0.21

S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Tsuboi and Hashimoto, Methanol Shock tube Ignition delay and Emission between 2.7 and 5.5 mm w1200e1800 K, f ¼ 0.2e2.0
1981 [128] species profiles CH3OH, H2O, CO2, CO, CH2O
Gülder, 1982 [129] Methanol, ethanol Constant volume bomb Laminar burning velocities Ionization probes w300e600 K,
iso-octane 1e8 bar, f ¼ 0.7e1.4
Metghalchi and Keck, Methanol, iso-octane, Constant volume bomb Laminar burning velocities Ionization probes 298e700 K,
1982 [130] indolene 0.4e50 bar, f ¼ 0.8e1.5
Pauwels et al., 1989 [131] Methanol Premixed flame Species profiles (x) GC and EPR 0.107 bar, f ¼ 1.0
Norton and Dryer, Methanol Turbulent flow reactor Species profiles (x, t) GC, infrared and thermo- w1000e1150 K,
1989 [132] magnetic detection 1 bar, f ¼ 0.6e1.6
Norton and Dryer, Methanol, ethanol, n-, Flow reactor Species profiles (x, t) GC 1020e1120 K (initial),
1991 [133] iso-propanol, 1 bar, f ¼ 1.18
tert-butanol,
MTBE
Bradley et al., 1991 [134] Methanol Premixed flames Burning velocities and GC and LDV (CH3OH, w400e2000 K,
species profiles O2, H2, CO2, and CO) 0.09e0.253 bar,
f ¼ 0.7e1.3
Cribb et al., 1992 [135] Methanol Shock tube pyrolysis Refractive index gradient LS and MS (CH3OH, CH2O, 1800e2800 K,
of incident shock and CO, C2H2, CH4, CH3, and H2O) 0.28e0.86 bar
species profiles of the
reflected shock
Cribb et al., 1992 [136] Methanol Shock tube Refractive index gradient LS and MS (CH3OH, CH2O, 1800e2800 K,
of incident shock and CO, C2H2, CH4, CH3, and H2O) 0.655e0.873 bar,
species profiles of the f ¼ 0.5e3
reflected shock
Egolfopoulos et al., 1992 [137] Methanol Counterflow premixed flame Laminar flame speed LDV Flame temperature,
1 bar, f ¼ 0.5e2.0
Lee et al., 1993 [138] Methanol, ethanol, Rapid compression machine Ignition delay Pressure 750e1000 K,
MTBE 20e40 bar, f ¼ 1
Aniolek and Wilk, 1995 [139] Methanol Constant volume reactor P,T, species time histories GC (FID þ TCD), FTIR 667e705 K, 1 bar,
(up to 900 s) f ¼ 0.5e1.5
Held and Dryer 1994 [140] Methanol Variable pressure flow reactor Species profiles Various spectroscopy 752e1043 K, 1e20 bar,
techniques f ¼ 0.4e2.6
Li and Williams, 1996 [141] Methanol Counterflow diffusion flame Species profiles (x), Microprobe-GC, PDPA 300e210 K, 1 bar,
velocity field strain rate 50/se100/s
Fieweger et al., 1997 [142] Methanol, iso-octane, MTBE Shock tube Ignition delay Pressure transducers w750e1250 K,
and CH-emission at 431 nm 13e40 bar, f ¼ 1.0
Alzueta et al., 2001 [143] Methanol, NO Flow reactor Species profiles (T) FTIR/NO analyzer 700e1500 K,
1 bar, f ¼ 0.1e2.70
Saeed and Stone, 2004 [144] Methanol Constant volume bomb Laminar burning velocities High-speed CCD 293e425 K,
0.5e3.5 bar,
f ¼ 0.8e1.6
Liao et al., 2006 [145] Methanol Constant volume bomb Laminar burning velocities High-speed CCD
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51
Table 3 (continued )

52
Reference Fuels Experimental device Measured properties Diagnostic techniques T, P, mixture fraction

358e480 K; 1 bar,
f ¼ 0.7e1.4
Dayma et al., 2007 [146] Methanol, NO Jet-stirred reactor Species profiles (T) GC(FID) 700e1000 K, 10 bar,
f ¼ 0.3e1
Rasmussen et al., 2008 [147] Methanol Flow reactor Species profiles (x, t) UV and IR 650e1350 K, 1 bar,
spectrophotometry, O2 1e16%
Zhang et al., 2008 [148] Methanol Constant volume bomb Laminar burning High-speed schlieren 373e473 K, 1e7.5 bar,
velocities photography f ¼ 0.8e1.2
Togbé et al., 2009 [149] Methanol, Jet-stirred reactor Species profiles (T) GC (FID), FTIR 770e1140 K, 10 bar,
M85 surrogate f ¼ 0.35e2
Noorani et al., 2010 [150] Methanol, ethanol, Shock tube Ignition delays CH-emission 1070e1760 K,
n-propanol, 2e12 bar,
n-butanol f ¼ 0.75 and 1.8
Veloo et al., 2010 [110] n-Butanol, methanol, Counterflow premixed flame Laminar flame speed, PIV 343 K, 1 bar,

S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
ethanol extinction strain rates f ¼ 0.7e1.5
Kumar and Sung, 2011 [151] Methanol Rapid compression machine Ignition delay times Pressure 7e30 bar, 850e1100 K,
f ¼ 0.25e2.0
Vancoillie et al., 2012 [152] Methanol Flat-flame burner Laminar flame velocities Heat-flux method Flame temperature,
1 bar, f ¼ 0.7e1.5
Aranda et al., 2013 [153] Methanol Flow reactor Species profiles (x, t) GC (FID and TCD) 600e900 K,
20e100 bar,
f ¼ 0.0625e4.0
Beeckmann et al., 2014 [154] Methanol, ethanol, Constant volume bomb Laminar flame speed High-speed schlieren 373 K, 10 bar,
n-propanol, photography f ¼ 0.7e1.3
n-butanol

Ethanol
Cooke et al., 1971 [122] Ethanol, methanol Shock tube Ignition delay Emission of OH, CH, 1570e1870 K,
C2 and CO2 0.267e0.400 bar,
f¼1
Gülder, 1982 [129] Methanol, ethanol, Constant volume bomb Laminar burning Ionization probes w300e600 K,
iso-octane velocities 1e8 bar, f ¼ 0.7e1.4
Rotzoll, 1985 [155] Ethanol Pyrolysis flow reactor Species profiles (T) MS (C2H5OH, C2H4, w1000e1300K 1.3 bar
CH3CHO,
H2, CH4)
Norton and Dryer, 1991 [133] Methanol, ethanol, n-, Flow reactor Species profiles (x, t) GC 1020e1120 K (initial),
iso-propanol, 1 bar, f ¼ 1.18
tert-butanol, MTBE
Dunphy and Simmie, 1991 [156] Ethanol Shock tube Ignition delay Pressure sensor 1060e1660 K, 1.8e4.6 bar,
and emission f ¼ 0.25e2
of CO þ O and OH
Curran et al., 1992 [157] Ethanol, iso-butene Shock tube Ignition delay Pressure transducer and 1100e1900 K,
and MTBE emission of OH or CO2 2e4.6 bar, f ¼ 0.25e1.5
Dagaut et al., 1992 [158] Ethanol Jet stirred reactor Species profiles (T) GC (CO, CO2, CH4, C2H4, w1000 K, 1 bar,
C2H6, CH3CHO, C2H5OH) f ¼ 0.2e2
Egolfopoulos et al., 1992 [159] Ethanol Counterflow premixed flame Laminar flame speed LDV Flame temperature,
1 bar, f ¼ 0.6e1.8
Norton and Dryer, 1992 [160] Ethanol Turbulent flow reactor Species profiles (x, t) GC w1100 K (initial),
1 bar, f ¼ 0.61e1.24
Lee et al., 1993 [138] Methanol, ethanol, MTBE Rapid compression machine Ignition delay Pressure 750e1000 K,
20e40 bar, f ¼ 1
Li et al., 2001 [161] Ethanol Flow reactor pyrolysis Species profiles (x, t) Online FTIR and 1045e1080 K,
offline GC 1.7e3.0 bar
Alzueta and Hernández, Ethanol, NO Flow reactor Species profiles (T) FTIR/NO Analyzer 700e1500 K,
2002 [162] 1 bar, f ¼ 0.1e2.70
Benvenutti et al., 2004 [163] Ethanol Low-pressure flame

Hidaka et al., 2005 [164] Ethanol
Ergut et al., 2006 [165] Ethanol, ethylbenzene
Kasper et al., 2007 [166] Ethanol
Liao et al., 2007 [167] Ethanol
Saxena and Williams, 2007 [168] Ethanol
Dagaut and Togbé, 2008 [169] Ethanol, E85 surrogate
Leplat et al., 2008 [170] Ethanol
Wang et al., 2008 [171] Ethanol, DME, propene
Bradley et al., 2009 [172] Ethanol
Cancino et al., 2010 [173] Ethanol
Noorani et al., 2010 [150] Methanol, ethanol,
n-propanol,
n-butanol
Veloo et al., 2010 [110] n-Butanol, methanol,
ethanol
Heufer and Olivier, 2010 [174] Ethanol
Eisazadeh-Far et al., 2011 [175] Ethanol
Konnov et al., 2011 [176] Ethanol
Leplat et al., 2011 [177] Ethanol
van Lipzig et al., 2011 [178] Ethanol, n-heptane,
iso-octane
Xu et al., 2011 [179] Ethanol, DME
Broustail et al., 2011 [180] Ethanol, butanol
iso-octane
Lee et al., 2012 [181] Ethanol
Varea et al., 2012 [182] Ethanol
Broustail et al., 2013 [183] Ethanol, butanol iso-octane
Tran et al., 2013 [184] Ethanol, methane
Varea et al., 2013 [185] Ethanol, iso-octane blends
Beeckmann et al., 2014 [154] Methanol, ethanol,
n-propanol, n-butanol
Herrmann et al., 2014 [186] Ethanol, DME
Mittal et al., 2014 [187] Ethanol
Temporal species Light emission Flame temperature,
profiles of OH, HCO, 0.355 bar, f ¼ 1
CH2O, CH and C2
Shock tube pyrolysis Species profiles GC þ IR absorption 1000e1700 K,
1.4e3.6 bar
Premixed flame Species profiles, PAH/soot absorption; w1800 K, 1 bar, f ¼ 2.5
PAH, soot (x) GC (MS, FID, TCD),
Low-pressure premixed flame Species profiles (x) EI- and REMPI eMBMS; w400e2400 K, 0.05 bar,
f ¼ 1.00 and 2.57
Constant volume bomb Laminar burning High-speed CCD 358e480 K; 1e10 bar,
velocities f ¼ 0.7e1.4
Partially premixed and Species profiles (x) GC w300e2000 K, 1 bar
non-premixed counterflow flame
Jet-stirred reactor Species profiles (T) GC (FID), FTIR 800e1100 K, 10 bar,
f ¼ 0.6e2
Low-pressure premixed flame Species profiles (x) EI-MBMS w600e2000 K,
0.05 bar, f ¼ 1.00
S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Laminar premixed flame Species profiles (x) MBMS (PI, EI), w500e2200 K,
0.04 bar, f ¼ 2
Constant volume bomb Laminar burning High-speed schlieren 300e393 K, 1e14 bar,
velocities photography f ¼ 0.7e1.5
Shock tube Ignition delays CH-emission 650e1220 K, 10, 30, and
50 bar, f ¼ 0.3
Shock tube Ignition delays CH-emission 1070e1760 K, 2e12 bar,
f ¼ 0.75 and 1.8
Counterflow premixed flame Laminar flame speed, PIV 343 K, 1 bar, f ¼ 0.7e1.5
extinction strain rates
Shock tube Ignition delay Pressure Down to 800 K,
13e40 bar, f ¼ 1.0
Cylindrical and spherical vessel Laminar burning speed Shadowgraph system 300e650 K, 1e5 bar,
with CMOS camera f ¼ 0.8e1.1
Flat-flame burner Laminar flame velocities Heat-flux method Flame temperature,
1 bar, f ¼ 0.7e1.5
Low-pressure premixed Species profiles (x) EI-MBMS, GC w500e1800 K, 0.05 bar,
flame and jet-stirred reactor f ¼ 0.75, 1, and 1.25;
890e1250 K, 1 bar,
f ¼ 0.25, 0.5, 1, and 2
Flat-flame burner Laminar burning velocities Heat-flux 298e338 K, 1 bar,
(thermocouples) f ¼ 0.6e1.5
Low-pressure premixed flame Species profiles (x) PI-MBMS w500e2000 K, 0.04 bar,
f ¼ 1.00
Constant volume bomb Laminar burning velocities High-speed 393 K, 1 bar,
Shadowgraph f ¼ 0.8e1.4
Shock tube and rapid Ignition delays Pressure, CH-emission, 775e1300 K, w80 bar
compression machine schlieren
Constant volume reactor Laminar flame speed High-speed laser 373 K, 1e5 bar,
tomography f ¼ 0.7e1.5
Constant volume bomb Laminar burning velocities High-speed 423 K, 10 bar,
Shadowgraph f ¼ 0.8e1.4
Low-pressure flame Species profiles (x) Microprobe-GC w300e2100 K,
(FID þ TCD þ MS) 0.066 bar, f ¼ 0.7e1.3
Constant volume reactor Laminar flame speed Mie scattering 373 K, 1e10 bar,
f ¼ 0.7e1.5
Constant volume bomb Laminar flame speed High-speed schlieren 373 K, 10 bar,
photography f ¼ 0.7e1.3
Flow reactor Species profiles (T) TOF-MS (EI) 400e1200 K, 1 bar,
f ¼ 0.8e1.2
Rapid compression machine Ignition delay times Pressure 10e50 bar, 825e985 K,
f ¼ 0.3e1.0
53
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Table 3 (continued )

54
Reference Fuels Experimental device Measured properties Diagnostic techniques T, P, mixture fraction

Knorsch et al., 2014 [188]
Barnard, 1960 [189]
Barnard and Hughes, 1960 [190]
Norton and Dryer, 1991 [133]
Sinha and Thomson, 2004 [191]
Li et al., 2008 [192]
Ethanol, n-, iso-butanol,
iso-octane, n-heptane
iso-Propanol
n-Propanol
Methanol, ethanol, n-,
iso-propanol, tert-butanol,
MTBE
iso-Propanol, dimethoxy
methane,
dimethyl carbonate
n- and iso-Propanol, acetone
Heat flux burner
Propanol isomers
Batch reactor pyrolysis
Batch reactor pyrolysis
Flow reactor
Counterflow diffusion flame
Laminar premixed flame
Laminar flame speed Heat-flux method 373e423 K, 1 bar,
f ¼ 0.5e1.5
Decomposition rate, Pressure, classical 797e888 K, 0.027e0.400 bar
products chemistry, GC
Decomposition rate, Pressure, classical 843e895 K, 0.020e0.400 bar
products chemistry, GC
Species profiles (x, t) GC 1020e1120 K (initial),
1 bar, f ¼ 1.18
Species profiles (x) Microprobe-GC(FID), 400e1800 K, 1 bar
HPLC (UV), NDIR-sensor;
Species profiles (x) MBMS(PI, EI) 500e2000 K, 0.02 and

S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
0.04 bar, f ¼ 0.75 and 1.8
Johnson et al., 2009 [193] n- and iso-Propanol Shock tube Ignition delay Pressure, CH-emission 1350e2000 K, 1 bar,
f ¼ 0.5e2
Kasper et al., 2009 [194] n- and iso-Propanol Laminar premixed flame Species profiles (x) MBMS(PI, EI) 500e2000 K,
0.033e0.047 bar,
f ¼ 1.0e1.9
Frassoldati et al., 2010 [195] n-Propanol, iso-propanol Counterflow diffusion flame Species profiles (x) Microprobe, GC(TDC) Flame temperature,
1 bar, strain rate 97.5 1/s
Noorani et al., 2010 [150] n-Propanol, methanol, Shock tube Ignition delays CH-emission 1070e1760 K, 2e12 bar,
ethanol, f ¼ 0.75 and 1.8
n-butanol
Akih-Kumgeh and Bergthorson, iso-Propanol, propanal, Shock tube Ignition delay CH-emission 1250e1700 K, 1 and
2011 [196] acetone, ethyl formate 12 bar, f ¼ 0.5e2
Galmiche et al., 2011 [197] n-Propanol Jet-stirred and batch reactor Species profiles (T) and FTIR, GC(FID, TCD, MS) 770e1190 K, 10 bar,
laminar flame speed f ¼ 0.35e2; Flame
speed: 323e473 K,
1e10 bar, f ¼ 0.7e1.4
Veloo et al., 2011 [198] n-Propanol, iso-propanol, Counterflow premixed flame Laminar flame speed Symmetric twin-flame 343 K, 1 bar,
propane f ¼ 0.7e1.5
Esarte et al., 2012 [199] Methanol, ethanol, Flow reactor pyrolysis and Species profiles (T) GC(FID þ TCD) 975e1475 K,
iso-propanol, oxidation with acetylene 1 bar, f ¼ 1
n-butanol
Man et al., 2014 [200] n-Propanol and Shock tube Ignition delay OH-emission 1100e1500 K,
iso-propanol 1e26 bar, f ¼ 0.5e2
Beeckmann et al., 2014 [154] Methanol, ethanol, Constant volume bomb Laminar flame speed High-speed schlieren 373 K, 10 bar,
n-propanol, photography f ¼ 0.7e1.3
n-butanol

Butanol isomers
Barnard, 1957 [201] n-Butanol Batch reactor pyrolysis Decomposition rate, Pressure, classical 846e902 K,
products chemistry, GC 0.027e0.667 bar
Barnard, 1959 [202] tert-Butanol Batch reactor pyrolysis Decomposition rate, Pressure, classical 760e893 K,
products chemistry, GC 0.027e0.533 bar
Tsang, 1964 [203] tert-Butanol, tert-butyl-chlonde, Single-pulse shock tube Decomposition rate GC 1050e1300 K,
-bromide, and -mercaptan pyrolysis 0.533e1.333 bar
Lewis et al., 1974 [204] tert-Butanol Single-pulse shock tube Decomposition rate GC 920e1175 K,
pyrolysis 0.5e2.1 bar
Choudhury et al., 1990 [205] tert-Butanol Shock tube pyrolysis Time histories (CO Absorption 1220e1620 K,
and H2O) spectroscopy 0.4e1.1 bar
Norton and Dryer, 1991 [133] Methanol, ethanol, n-, Flow reactor Species profiles (x, t) GC 1020e1120 K (initial),
iso-propanol, tert-butanol, 1 bar, f ¼ 1.18
MTBE
McEnally and Pfefferle, 2005 [206] n-,2-, iso- and tert-Butanol, Coflow methane flame Centerline species Microprobe-MS (EI, 1 bar
n-butane, iso-butane profiles (x) 118 nm PI)
Moss et al., 2008 [207]
Dagaut et al., 2009 [208]
Dagaut and Togbé, 2009 [209]
Gu et al., 2009 [210]
Sarathy et al., 2009 [211]
Black et al., 2010 [212]
Grana et al., 2010 [213]
Gu et al., 2010 [214]
Noorani et al., 2010 [150]
Togbé et al., 2010 [215]
Van Geem et al., 2010 [216]
Veloo et al., 2010 [110]
Broustail et al., 2011 [180]
Gu et al., 2011 [217]
Hansen et al., 2011 [218]
Harper et al., 2011 [121]
Heufer et al., 2011 [219]
Karwat et al., 2011 [220]
Obwald et al., 2011 [221]
Veloo and Egolfopoulos,
2011 [222]
Vranckx et al., 2011 [223]
Weber et al., 2011 [104]
Cai et al., 2012 [224]
Cai et al., 2012 [225]
Esarte et al., 2012 [199]
n-,2-, iso- and tert-Butanol Shock tube Ignition delay Pressure, OH-emission 1200e1800 K,
1e4 bar, f ¼ 0.25e1
n-Butanol Jet-stirred reactor Species profiles (T) GC (FID, TCD), FTIR 750e1100 K,
10 bar, f ¼ 0.5e2
n-Butanol/n-heptane mixture Jet-stirred reactor Species profiles (T) GC (FID), FTIR 530e1070 K,
10 bar, f ¼ 0.5 and 1
n-Butanol Batch reactor Flame speed High-speed schlieren 413- 473 K, 1.0 bar
photography and 2.5 bar,
f ¼ 0.8e1.6
n-Butanol Jet-stirred reactor, Species profiles (T and x), FTIR, GC (FID, TCD), 400e2000 K
counterflow diffusion flame speed Microprobe-GC (Flame),
flame, batch reactor (FID), NDIR, HPLC (UVeVis) 850e1250 K (JSR),
1 bar, f ¼ 0.25e2
n-Butanol Shock tube Ignition delay time Pressure, emission 1100e1800 K,
1e8 bar, f ¼ 0.5e2
n-,2-, iso- and tert-Butanol Counterflow diffusion flame Species profiles (x) Microprobe-GC (TCD) 400e1800 K,
1 bar, strain rate 100/s
S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
n-,2-, iso- and tert-Butanol Batch reactor Flame speed High-speed schlieren 428 K, 1e7.5 bar,
photography f ¼ 0.7e1.5
n-Butanol, methanol, ethanol, Shock tube Ignition delays CH-emission 1070e1760 K,
n-propanol 2e12 bar,
f ¼ 0.75 and 1.8
2- and iso-Butanol Jet-stirred reactor Species profiles (T) FTIR, GC (FID, TCD) 770e1250 K,
10 bar, f ¼ 0.275e4
n-,2- and tert-Butanol Flow reactor pyrolysis Species profiles (x, T) GC x GC (FID, TCD, MS) 880e1010 K,
1.5e1.7 bar
n-Butanol, methanol, ethanol Counterflow premixed flame Laminar flame speed, PIV 343 K, 1 bar,
extinction f ¼ 0.7e1.5
strain rates
n-Butanol, ethanol iso-octane Constant volume bomb Laminar burning velocities High-speed Shadowgraph 393 K, 1 bar,
f ¼ 0.8e1.4
tert-Butanol Batch reactor Flame speed High-speed schlieren 428e488 K,
photography 1e5 bar, f ¼ 0.8e1.5
n-Butanol, n-butanol/H2 Laminar premixed flame Species profiles (x) MBMS (PI) w500e1900 K,
0.020e0.033 bar,
f ¼ 1.0e1.4
n-Butanol Flow reactor pyrolysis Species profiles (T) GC x GC (FID, TCD, MS) 600e807 K,
1.7 bar
n-Butanol Shock tube Ignition delay Pressure, CH-emission 770e1250 K,
10e42 bar, f ¼ 1
n-Butanol Rapid compression machine Ignition delay, product Pressure, luminescence 920e1040 K,
speciation (reconstructed imaging, GC (FID, TCD) 2.90e3.39 bar
time histories)
n-,2-, iso- and tert-Butanol Laminar premixed flame Species profiles (x) MBMS (PI, EI) 500e2000 K,
0.040 bar, f ¼ 1.7
n-,2-, iso- and tert-Butanol Counterflow premixed flame Laminar flame speed, PIV 343 K, 1 bar,
extinction strain rates f ¼ 0.7e1.5
n-Butanol Shock tube Ignition delay Pressure, CH-emission 795e1200 K,
61e92 bar, f ¼ 1
n-Butanol Rapid compression machine Ignition delay Pressure 675e925 K,
15e30 bar,
f ¼ 0.5e2
tert-Butanol Flow reactor pyrolysis Species profiles (T) PI-MBMS 950e1850 K,
0.004e0.016 bar
n-Butanol Flow reactor pyrolysis and Species profiles (T, x) PI-MBMS 800e1500 K,
laminar premixed flame 0.007e1.013 bar;
Flame: 0.040 bar,
f ¼ 0.7e1.8
Species profiles (T) GC (FID þ TCD)
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55
Table 3 (continued )

56
Reference Fuels Experimental device Measured properties Diagnostic techniques T, P, mixture fraction

Methanol, ethanol, Flow reactor pyrolysis and 975e1475 K,

Karwat et al., 2012 [226]
Lefkowitz et al., 2012 [227]
Liu et al., 2011 [228]
Stranic et al., 2012 [108]
iso-propanol, n-butanol
n-Butanol/n-heptane blends
tert-Butanol
n-Butanol, iso-butanol,
methyl butanoate
n-,2-, iso- and tert-Butanol
oxidation with acetylene
Rapid compression machine
Flow reactor and counterflow
diffusion flame
Batch reactor and liquid
pool stagnation burner
Shock tube
1 bar, f ¼ 1
Ignition delay, product Pressure, luminescence 700 K, 9 bar, f ¼ 1
speciation imaging, GC (FID, TCD)
(reconstructed time
histories)
Species profiles (T, x), FTIR, NDIR, GC (FID) 675e950 K, 12
extinction and 5 bar f ¼ 1;
strain rate Flame: 1 bar, strain
rate 100/s
Laminar flame speed, High-speed schlieren 353 K, 1 and 2 bar, f ¼ 0.7e1.4
ignition photography
temperature
Ignition delay Pressure, OH-emission 1050e1600 K,

Stranic et al., 2012 [111]
Van Geem et al., 2012 [229]
Yasunaga et al., 2012 [230]
Broustail et al., 2013 [183]
Chung et al., 2013 [231]
Hansen et al., 2013 [232]
Merchant et al., 2013 [233]
Zhang et al., 2013 [234]
Stranic et al., 2013 [112]
Cai et al., 2013 [235]
Wu and Law, 2013 [236]
Camacho et al., 2013 [237]
Vasu and Sarathy, 2013 [238]
Yang et al., 2013 [239]
Zhu et al., 2014 [240]
Knorsch et al., 2014 [188]
Cai et al., 2014 [241]
Jin et al., 2013 [242]
Pan et al., 2014 [243]
S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
1.0e44 bar,
f ¼ 1 and 0.5
n-Butanol Shock tube pyrolysis Multi-species time Laser absorption (OH, H2O, 1250e1650 K,
histories C2H4, CO, and CH4) 1.3e1.9 bar
n-Butanol, acetone/ethanol/ Flow reactor pyrolysis Species profiles GC x GC (FID, TCD, MS) 880e1010 K,
butanol-mixture (conversion, T) 1.5e1.7 bar
n-,2-, iso- and tert-Butanol Single-pulse shock tube Speciation (T) GC (TCD) 1000e1800 K,
1e4 bar, f ¼ 0.25e1
Ethanol, n-butanol iso-octane Constant volume bomb Laminar burning velocities High-speed Shadowgraph 423 K, 10 bar,
f ¼ 0.8e1.4
n-, iso-Butanol and n-, iso-butene Premixed stagnation flame NO, velocity field NO-LIF, PIV Flame temperature,
1 bar, f ¼ 0.8e1.3
iso-Butanol Laminar premixed flame Species profiles (x) MBMS (PI) w500e1900 K,
0.015e0.03 bar,
f ¼ 1.0e1.5
iso-Butanol Flow reactor pyrolysis Species profiles (T) GC x GC (FID, TCD, MS) 550e1093 K,
1.7 bar
n-Heptane/n-butanol mixtures Shock tube Ignition delay Pressure, CH-emission 1200e1500 K,
2e10 bar, f ¼ 0.5 and 1
iso- and 2-Butanol Shock tube pyrolysis Multi-species time histories Laser absorption (OH, H2O, 1270e1640 K,
C2H4, CO, and CH4) 1.3e1.9 bar
2-Butanol Flow reactor pyrolysis and Species profiles (T, x) PI-MBMS 800e1500 K,
laminar premixed flame 0.007e1 bar; Flame:
0.04 bar, f ¼ 0.7e1.8
n-, 2-, iso- and tert-Butanol Constant volume bomb Laminar flame speed High-speed schlieren 353 and 373 K,
photography 1e5 bar, f ¼ 0.8e1.4
n-, iso-Butanol and n-, iso-butene Premixed stagnation flame Particle size distribution (x) SMPS 400e1800 K,
1.0 bar, f ¼ 2.25
n-Butanol Shock tube OH time histories Laser absorption of OH 1300e1550 K,
2 bar, f ¼ 1
n-Heptane/n-butanol mixtures Rapid compression machine Ignition delay Pressure 650830 K,
15e30 bar,
f ¼ 0.4e1.5
n-Butanol Shock tube Ignition delay Pressure, OH-emission, 716e1121 K,
IR-absorption 0.020 and 0.040 bar,
f ¼ 0.5e2
Ethanol, n-, iso-butanol Heat flux burner Laminar flame speed Heat-flux method 373e423 K,
iso-octane, n-heptane 1 bar, f ¼ 0.5e1.5
iso-Butanol Flow reactor pyrolysis Species profiles (T) PI-MBMS 950e1850 K,
0.004e0.016 bar
n-,2-, iso- and tert-Butanol Coflow diffusion flame Centerline species profiles (x) PI-Microprobe-MS w500e1700 K, 1 bar
iso-Butanol Shock tube Ignition delay Pressure, CH-emission 900e1700 K,
1.2e10 bar,
f ¼ 0.5e1
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 57

alcohol under well-defined conditions and provides properties

such as ignition delay times, laminar flame speeds, and species
concentration profiles. Beyond these kinetics-related in-

1.01 bar, strain rate 33/s

770e1220 K and 423 K,
vestigations, a substantial number of investigations focusing on the

1e2.6 bar, f ¼ 0.25e1

5e60 bar, f ¼ 0.35e4

530e1220 K, 10 bar,

10 bar, f ¼ 0.7e1.4
combustion properties of the liquid fuel (e.g. [261],) or the influence

10 bar, f ¼ 0.5e2

473 K, 1e7.5 bar,

600e1100 K and

of alcohol addition to hydrocarbon fuels (e.g. [262e266],) are not

9e30 bar, f ¼ 1

1100e1500 K,
7e23 bar, and
373 K, 10 bar,

423 K, 10 bar,

393, 433, and

considered herein. Similarly, studies on the “slow combustion” of
560e1030 K,

640e1200 K,

652e1457 K,

400e1800 K,
530e1800 K,
f ¼ 0.7e1.3

f ¼ 0.5e3.5

f ¼ 0.5e2.0

f ¼ 0.6e1.8
f ¼ 0.35e4

alcohols, meaning a reaction time of several seconds up to some

minutes conducted in the 1950’s (e.g. [267]), and studies on
oxidation of alcohols in supercritical water [268e271] are excluded
herein.
Cathonnet et al. [272,273] conducted a series of experimental
studies on the oxidation and pyrolysis of methanol. Ignition delay
time measurements are available for temperatures ranging from

Microprobe-GC (FID, TCD),

700 K to 2800 K, a stoichiometry range of f ¼ 0.2e6, and pressures

FTIR, GC (FID, TCD, MS),

GC (TCD, FID, MS) FTIR,

FTIR, GC (FID, TCD, MS)

GC (TCD, FID, MS) FTIR,

FTIR, GC (FID, TCD, MS)

High-speed schlieren

High-speed schlieren
up to 40 bar are reported. The majority of ignition delay data was

temperature (TC)
acquired from shock tubes in the 1970s and early 1980s. Extensive
Shadowgraphy

Shadowgraphy

PIV, pressure studies on shock tube ignition of methanol are provided by

photography

photography
CH-emission

Bowman [123] and Tsuboi et al. [128]. Both cover a temperature

Pressure

Pressure

range between 1500 and 2000 K and a wide stoichiometry range

and offer parameterized expressions of their results. Bowman [123]
additionally provides concentration time histories for some species.
More recent studies are scarce; RCM results [151] were obtained in
Species profiles (T), ignition
Species profiles (T), laminar

Species profiles (T), laminar

delay, laminar flame speed,

the low-temperature regime, while other studies focus on a wide

range of topics and provide just a limited number of conditions for
Laminar burning speed

extinction strain rate

Laminar flame speed

methanol [142,150,274].
Species profiles (T)

Species profiles (T)

Species profiles (x)

Ignition delay times for ethanol are available up to 1900 K and

Ignition delay

Ignition delay

Ignition delay

80 bar in the stoichiometry range of f ¼ 0.25e2. Studies in the

flame speed

flame speed

high-temperature regime date back the 1990s and earlier spanning

twenty-nine individual conditions, Dunphy and Simmie [275]
provide the largest dataset for ethanol ignition. The parameter-
Higher alcohols

ized ignition delay times are determined in a range of 1000e

1700 K, f ¼ 0.5e2.0, and pressures between 2 and 4.6 bar. More
Jet-stirred reactor, shock tube,

recent investigations (e.g. [173,181]) of ethanol ignition are focused

Counterflow diffusion flame
rapid compression machine

on the lower temperature region including results from RCMs.

Constant volume bomb

Overall, the amount of available ignition delay time measurements

compression machine

compression machine

is somewhat larger than for methanol.

Jet-stirred reactor,

Jet-stirred reactor,
Jet-stirred reactor

Jet-stirred reactor

Shock tube, rapid

Shock tube, rapid

cylindrical vessel

Propanol is the smallest alcohol existing in different isomeric

Spherical vessel
spherical vessel

structures (n- and iso-propanol). Nevertheless, the available exper-

Shock tube

imental data for both propanols are limited. Ignition delay time
measurements are just provided by four studies [150,193,196,200].
Johnson et al. [193] provide a direct comparison of both isomers, and
they report a higher reactivity of n-propanol compared to iso-prop-
anol. A comparative study of all normal alcohols (including meth-
Methanol, ethanol, n-propanol,

anol, ethanol and n-propanol) was recently provided by Noorani

n-Hexanol/jet A-1 mixtures

et al. [150] with ignition delay times measured under comparable

n-Pentanol, iso-pentanol,

conditions. They concluded that ignition delay times for the alcohols
n-Pentanol, n-hexanol

2-Methyl-1-butanol
2-methyl-1-butanol

(except for methanol) would be identical for a given stoichiometry

which, however, is not correctly reproduced by the kinetic models
tested in their study. A similar conclusion is drawn by Veloo et al.
iso-Pentanol

iso-Pentanol

iso-Pentanol
n-Pentanol
n-Hexanol

n-Hexanol
n-butanol

[110] when investigating laminar flame speeds in the lean-to-

stoichiometric regime of methanol, ethanol and n-butanol.
Laminar flame speeds for the C1eC3 alcohols are available for
the stoichiometry range of 0.7e1.5 and for pressures up to 10 bar.
Flame speed measurements are accessible by a broad variety of
experiments and are typically measured with air as the oxidizer. For
Mzé-Ahmed et al., 2012 [247]
Beeckmann et al., 2014 [154]

methanol and ethanol, several groups have measured experimental

Sarathy et al., 2013 [252]
Dayma et al., 2011 [245]

Heufer et al., 2012 [248]

data under comparable conditions. Recent results are available

Togbé et al., 2010 [244]

Togbé et al., 2011 [246]

Tang et al., 2013 [250]

Tsujimura, 2012 [249]

Yeung and Thomson,

using high-speed schlieren measurements in constant volume

Li et al., 2013 [251]

combustion chambers [145,148,167], from heat flux burner mea-

surements [152,176], and flow field determination by PIV (particle
2013 [253]

imaging velocimetry) in a counterflow premixed flame setup [110].

In general the database is a little larger for ethanol than for
methanol while for propanol just two papers report flame speeds
[197,198].
58 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Fig. 9. Four-dimensional plots representing the approximate range of temperatures, pressures, equivalence ratios, and years at which alcohol combustion has been studied. (a)
methanol, (b) ethanol, (c) propanol isomers, (d) butanol isomers, (e) higher alcohols. Only premixed oxidation studies are presented in the plots (i.e., pyrolysis and non-premixed
flame studies are excluded). The temperature of premixed flame studies are approximated as 2000 K.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Quantitative species profiles are the most challenging test case
for kinetic models. Speciation data of methanol combustion from a
variety of different flame and reactor experiments are available for
temperatures and pressures up to 2100 K and 100 bar. For meth-
anol, the quantitative data are primarily available from reactor
experiments for temperatures below 1000 K. Typically some or all
product and reactant species are traced, for example in the most
recent study of Aranda et al. [153] that extends the database up to
pressures of 100 bar. Additionally, concentrations of formaldehyde
and some other intermediate species (CH4, H2, CO) are determined
in most reactor studies. Compared to reactor experiments, quan-
titative data from higher temperature flame environments
[127,131,134] are surprisingly scarce for methanol. The most
detailed investigation from Vandooren and van Tiggelen [127]
dates back to 1981 and provides fourteen species profiles ob-
tained for three lean premixed flames.
Speciation data for ethanol is available for a wide range of
conditions and experiments. Pressures up to 10 bar and a temper-
ature range up to 2400 K have been covered. Several MBMS
[166,170,177,276e278] and other flame-sampling methods
[165,168,184] provide detailed insights to the high-temperature
regime. In contrast to methanol, higher molecular species (e.g.,
higher aldehydes such as acetaldehyde and soot precursors such as
benzene) are detectable in rich ethanol flames. This is related to
ethanol reaction pathways forming C2 hydrocarbons such as
ethylene or ethyl radicals. Lower temperatures are covered by a
similar number of various reactor studies. Even though no typical
low-temperature regime exists for ethanol, recent results confirm a
distinct reactivity even at temperatures below 800 K [186,279],
which is rarely covered by most kinetic models.
Again for the propanol isomers, only a limited number of
speciation studies are available. Conditions cover pressures up to
10 bar and temperatures up to 2000 K, while no speciation data was
reported below 750 K. Extensive studies are provided by Kasper
et al. [194] and Li et al. [192], both providing a large number of
stable and radical species for flames of both isomers measured
using MBMS setups with isomer-specific detection.
3.4. Butanol isomers
The four isomers of butanol are n-butanol, iso-butanol, 2-
butanol, and tert-butanol. Prior to the 1990s, literature studies on
the butanol isomers were limited to pyrolysis conditions. Inter-
estingly, the primary focus was to determine decomposition rate of
tert-butanol pyrolysis using batch reactors and shock tubes [202e
205]. Norton and Dryer [133] were the first to reveal species pro-
files evolving from the atmospheric-pressure oxidation of tert-
butanol in a flow reactor.
A growing interest in the combustion of butanol isomers began
in the mid-2000s with McEnally and Pfefferle’s [206] study on the
decomposition and hydrocarbon growth processes of non-
premixed co-flow diffusion methane flames doped with
3500 ppm of each of the four isomers of butanol. Gas samples
extracted from the flame revealed that the butanol isomers pro-
duce much higher concentrations of aldehydes and ketones than
normal alkane dopants. They also showed that the substituted
butanol isomers produce more propene and butene relative to n-
butanol, which forms more ethylene. Their flame study motivated
speciation studies in non-premixed counterflow diffusion flames of
n-butanol [211,213], iso-butanol, and tert-butanol [227]. Detailed
flame structures of low-pressure premixed burner-stabilized
flames of all four butanol isomers were measured by Obwald
et al. [221] using MBMS. Subsequent low-pressure premixed flame
studies with MBMS were conducted for n-butanol [218,225] and
iso-butanol [232]. These flame speciation studies provide
59
quantitative data and cross-comparisons of important aldehydes,
enols, and alkenes produced during the combustion of the four
butanol isomers. The premixed laminar flame speeds of the butanol
isomers have also been measured at a wide range of conditions
[110,150,210,214,217,228,236].
Other detailed speciation studies include experiments in ideal
reactors under oxidation and pyrolysis conditions. Jet-stirred
[208,211,215] and flow reactor [227] oxidation data is available at a
range of pressures, temperatures, and equivalence ratios for all
isomers of butanol. Atmospheric pressure pyrolysis flow reactor
data has also been presented for all butanol isomers
[216,224,225,233]. Species profiles during homogenous gas-phase
ignition have been obtained in RCMs [220] and STs [111,112,230].
The ignition delay times of the butanol isomers have also
received significant attention in the past 7 years. Moss et al. [207]
studied the high-temperature ignition characteristics of all four
butanol isomers in shock tubes, and concluded that tert-butanol is
the least reactive isomers while n-butanol is the most reactive.
These high-temperature results were later confirmed and extended
to wider ranges of pressures, temperatures, and equivalence ratios
[108,212,230,240]. Although of relevance to engines, data for low-
and intermediate-temperature ignition of the butanol isomers are
limited. Weber et al. [104,105] conducted RCMs studies of all
butanol isomers under high pressures and low temperatures of
direct relevance to reciprocating engines. Only n-butanol has been
studied under such conditions in STs [219,223,240] because igni-
tion delay times for the other butanol isomers exceed maximum
test times unless driver gas tailoring is employed.
3.5. Higher alcohols
As mentioned earlier, the experimental data available on higher
alcohols (C5 and larger) are limited. For the pentanol isomers, there
are data on n-pentanol [103,246], 3-methyl-1-butanol
[245,249,250,252] (i.e., iso-pentanol), and 2-methyl-1-butanol
[250,251]. Togbé et al. [246] studied n-pentanol and Dayma et al.
studied iso-pentanol combustion [245] in a jet-stirred reactor at
10 bar and a range of temperatures and equivalence ratios. n-
Pentanol produced 1-butene and pentanal, whereas iso-pentanol
produced more iso-butene and 3-methyl-1-butanal. Similar to their
other studies on butanol isomers, n-pentanol and iso-pentanol did
not show low-temperature reactivity under these experimental
conditions. Their data on various primary alcohols (namely,
ethanol, n-propanol, n-butanol, iso-butanol, n-pentanol, iso-pen-
tanol, and n-hexanol) revealed that they all produced similar in-
termediate molar fractions of formaldehyde, whereas secondary
alcohols (namely, iso-propanol and 2-butanol), yielded less form-
aldehyde. Ethanol was shown to produce more acetaldehyde than
the other tested alcohols, regardless of their structure. Similar JSR
experiments on n-hexanol by the same group [244] yielded similar
speciation results, except that hexanal was also observed. n-Hex-
anol exhibited low-temperature cool flame reactivity under the
tested conditions, which was not seen in smaller alcohols. Yeung
et al. [253] also measured species generated during combustion of
n-hexanol in a counterflow diffusion flame and noted appreciable
amounts of 1-pentene and 1-hexene.
To compare the various pentanol isomers, Tang et al. [250]
measured ignition delay times in shock tubes at temperatures
above 1100 K, pressures of 1.0 and 2.6 bar, and varying equivalence
ratios. Their results showed that the ignition delay times decreased
in the order of iso-pentanol, 2-methyl-1-butanol, and n-pentanol,
indicating that methyl substitution decreases reactivity. Heufer
et al. [103] measured ignition delay times for n-pentanol and n-
hexanol in a shock tube and RCM, spanning 9e30 bar and low to
high temperatures, and compared them to previous measurements
60 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
of alkanes. Their results showed that alcohol fuels ignite signifi-
cantly faster compared to alkanes in the high temperature regime,
whereas at low intermediate temperatures, the C5 and C6 alcohols
exhibit negative temperature coefficient (NTC) behavior similar to
C5 and C6 alkanes but with lower reactivity. In a recent premixed
laminar flame speed study on 2-methyl-1-butanol, Li et al. [251]
acquired data across a remarkable range of equivalence ratios
(f ¼ 0.6e1.8), initial temperatures (393, 433, and 473 K), and initial
pressures (1e7.5 bar), as shown in Fig. 10. Such a complete laminar
flame speed data set at the elevated temperatures and pressures
relevant to practical engines demonstrates the current state-of-the-
art in measuring this fundamental combustion property.
4. Chemical kinetics of alcohol combustion
Many combustion processes, including reactions in the flame
zone resulting in heat release, reactions controlling ignition, and air
pollutant formation mechanisms, occur at times when temperature
and pressure are changing rapidly. These processes depend on the
rate of each individual chemical reaction (i.e., the reaction kinetics),
which are governed by the temperature, pressure, and the con-
centration of reactants and products. A recent review by Simmie
[280] describes the development and application of chemical ki-
netics models of hydrocarbon fuel combustion. A chemical kinetic
model consists of a reaction mechanism, species thermochemical
data, and species transport data. The reaction mechanism describes
Fig. 10. Laminar flame speeds versus equivalence ratios at different temperatures and
pressures for 2-methyl-1-butanol/air mixtures.
Reprinted from Li et al. [251] with permission from Elsevier.
the molecular level transformation of reactants (i.e., fuel and air)
into products via a series of elementary steps. The chemical kinetic
model is coupled with a physical model describing the geometry
and operating regime of the specific combustion application. A
large number of differential conservation equations describing the
mass, momentum, energy, and species concentration are numeri-
cally integrated to generate species concentration and heat release
profiles [281]. The governing equations can be solved using a nu-
merical solver that evaluates the chemical kinetic, thermodynamic,
and transport properties of each differential element as time pro-
ceeds. A commonly used program for simulating chemically
reacting flow systems is Reaction Design’s CHEMKIN suite [282].
Other commonly used programs for simulating combustion include
CANTERA [283,284], OPENSMOKE [285,286], CMCL Innovations’
kinetics [287], and DETCHEM [288]. The CHEMKIN suite provides
modeling of a wide range of combustion instruments, including
shock tubes, premixed flames, diffusion flames, and partially and
perfectly stirred reactors. Chemical kinetic mechanisms are
coupled with thermochemical data on all the species in the
mechanism to calculate forward and reverse reaction rates based
on the principle of microscopic reversibility. Transport properties of
the species are also included when attempting to model a com-
bustion process in which mixing processes, such as diffusion, are
rate-controlling (e.g., premixed and non-premixed flames).
The process for developing and validating chemical kinetic
models was outlined by Frenklach et al. [289] and summarized by
Simmie [280]. Fig. 11 presents a flowchart of the model develop-
ment process. Chemical kinetic models are developed and tested
against experimental data from one or more well-characterized
combustion experiments, such as those described above. The
flowchart indicates that developing and validating a model is an
iterative process involving experiments and simulations, which are
combined to achieve a refined model. Computational chemistry
and reaction rate theory are important for the accurate determi-
nation of reaction rate, thermochemical, and transport data, while
sensitivity and reaction flux analysis help identify areas of the ki-
netic model that warrant further refinement.
The remainder of this section discusses the development of
chemical kinetic models for alcohols, specifically the formulation of
reaction mechanisms and selection of rate coefficients. Not dis-
cussed are methods for determining thermochemical properties
(e.g., group additivity [290e292] or ab initio calculations [293]), and
methods for determining transport properties (e.g., empirical cor-
relations) as described elsewhere [211,248,252,294e297]. Finally a
consistent chemical kinetic model for common C1eC5 alcohols (i.e.,
methanol, ethanol, both propanol isomers, all four butanol isomers,
and two pentanol isomers) is presented with the aim to improve
understanding of the combustion chemistry of alcohols.
4.1. The molecular structure of alcohols
Before considering comprehensive chemical kinetic models, we
should first understand the structural features of alcohols that
distinguish them from other fuels and that, in turn, affect their
molecular level transformations during combustion. Alcohols
contain a hydroxyl moiety connected to a hydrocarbon chain,
which results in unique thermochemical and reaction kinetics
properties in comparison to hydrocarbons. These effects include
phenomena such as weaker CeH bond strengths where the carbon
is bound to the hydroxyl moiety and hydrogen bonding interactions
when reacting with OH and HO2 radicals. These unique features
provide interesting discussion points in regard to the combustion
chemistry of alcohols.
The molecular structures of alcohols are routinely determined
using quantum chemistry software packages (e.g., Gaussian 09
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 61

Fig. 11. Flowchart for the development and validation of chemical kinetic models.

[298]) to identify the most stable conformers and then to
calculate bond dissociation energies (BDEs). The CBS-QB3, G3,
and G4 composite methods are usually selected for their reported
accuracies of 1.0 and 1.1 kcal mol1, respectively [248,252,299e
301]. Fig. 12 presents the results of such a calculation for n-
pentanol [248] and iso-pentanol (3-methyl-1-butanol) [252]
showing the lowest energy conformer and BDEs calculated us-
ing various levels of theory. Extensive discussions on these cal-
culations and comparisons amongst various levels of theory (e.g.,
G4 and CBS-QB3) are presented in Refs. [248,252]. Fig. 13 presents
CeH and OeH BDEs calculated at the CBS-QB3 level of theory for
methanol, ethanol, two propanol isomers, four butanol isomers,
n-pentanol, and iso-pentanol [248,252]. Even considering the
1 kcal mol1 uncertainty, there are some clear trends among the
various alcohols. The OeH BDEs are strong in all alcohols, making
it difficult to abstract the hydrogen atoms. The presence of the
hydroxyl moiety weakens the CeH bond at the adjacent a-site,
such that these hydrogen atoms are the easiest to abstract from
all alcohols. The a-site in methanol is a primary CeH bond with
the highest BDE (w96 kcal mol1) of all the a-C-H bonds in the
alcohols. The a-sites in ethanol, n-propanol, n-butanol, iso-
butanol, n-pentanol, and iso-pentanol are secondary CeH bonds
(BDE w95 kcal mol1), whereas iso-propanol and 2-butanol
contain tertiary a-sites with BDE w94 kcal mol1. The rate
coefficients for hydrogen abstraction on a per H-atom basis in-
crease in the order of primary a < secondary a < tertiary a. The
b-sites in the alcohols exhibit stronger than expected CeH BDEs,
which is a consequence of the weakened adjacent a BDEs. The b
CeH bonds are again ordered in decreasing strength for primary
(w103 kcal mol1) < secondary (w100 kcal mol1) < tertiary
(w98 kcal mol1) sites. The effects of the hydroxyl moiety are
diminished beyond the b site [302], wherein the subsequent g, d,
and ε CeH BDEs are identical to those of alkanes (e.g., primary
(w102 kcal mol1) < secondary (w99 kcal mol1) < tertiary
(w96 kcal mol1)). In the absence of any secondary effects (e.g.,
hydrogen bonding with OH radicals), hydrogen abstraction rates
from the g, d, and ε sites can be estimated from established rate
rules for alkane fuels [260].
4.2. Formulation of comprehensive chemical kinetic models
The comprehensiveness of a chemical kinetic model is
measured by its ability to describe combustion phenomena
extensively. A model is not considered comprehensive if it has only
been tested against a single experiment because the role of each
elementary reaction varies with temperature, pressure, and
composition. For example, reactions between hydrogen atoms and
fuel molecules are dominant in fuel-rich conditions, while

Fig. 12. Schematic diagrams of the bond dissociation energies for n-pentanol (left) and iso-pentanol (right). The numbers in the brackets are G4 values, those in parenthesis are G3
values, and those without the brackets are the CBS-QB3 values. Blue values are CeH and black are CeC BDEs (kcal mol1 at 298 K). (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
Reprinted from [248,252] with permission from Elsevier and American Chemical Society.
62 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 13. CeH bond dissociation energies for fuel alcohols (kcal mol1) calculated at
CBS-QB3 level of theory.
reactions between hydroxyl radicals and fuel molecules dominate
in fuel-lean conditions. Many reactions are important only at low
temperatures, while others are dominant at high temperatures. In
early work on chemical kinetic mechanisms for hydrocarbon
combustion, Westbrook and Dryer [303] and Basevich [304]
explained that a comprehensive model must be compared against
experimental data covering chemically reacting flows at various
temperatures, pressures, and reactant compositions in shock tubes
and rapid compression machines, flow and stirred reactors, and
laminar flames. This approach presents a challenge for modelers
because experimental data spanning such a wide variety of con-
ditions are lacking for the higher molecular weight alcohols.
The development of a comprehensive model for alcohol fuels
requires a basic understanding of hydrocarbon oxidation in com-
bustion systems. This was first described by Semenov [259] in his
description of free radical chain reactions in combustion systems,
and led to the later descriptions by Lewis and von Elbe [305e307].
Westbrook and Dryer [303] and Basevich [304] applied these
methods to small hydrocarbons, Miller and Bowman [308] to ni-
trogen combustion chemistry, and Battin-Leclerc [98] to low-
temperature alkane oxidation. Comprehensive models for various
alcohols exist in the literature, including Westbrook and Dryer’s
early methanol model [309], Marinov’s [310] and Egolfopoulos
et al.’s [159] ethanol models, and Sarathy et al.’s [260] butanol iso-
mer model, to name a few. Following a recent review by Tran et al.
[311], Table 4 presents a summary of comprehensive chemical ki-
netic models currently available for alcohols along with their
experimental targets.
A single comprehensive model capable of elucidating similar-
ities and differences in the combustion of various C1eC5 alcohols is
not available in the literature; however, such a model is needed to
highlight differences in ignition delay times, premixed laminar
flame speeds, and important combustion products. We therefore
present a consistent C1eC5 alcohol model herein, but the reader
should not consider this a “new” modeling study. Instead, this is an
assembly of data on reaction mechanisms, rate coefficients, and
species thermodynamic and transport properties available in the
literature. The complete modeling files in CHEMKIN-PRO [282]
format are available as Supplementary Material to this publica-
tion and from the KAUST website cpc.kaust.edu.sa. The chemical
kinetic model was compiled and tested using a commercial version
of CHEMKIN-PRO [282], so researchers using older non-commercial
CHEMKIN versions or other simulation tools are encouraged to
contact the corresponding author when compatibility issues hinder
the models usage.
Compiling a comprehensive model for alcohol fuel combustion
first requires the election of a certain modeling methodology. At
present, there are various methods for building a comprehensive
chemical kinetic model, but most revolve around the same prin-
ciples. Essentially, a model should include a consistent set of re-
action classes and rate coefficient estimations or “rate rules”.
Battin-Leclerc et al. [315] recently reviewed automatic generation
methods for building chemical kinetic models, all of which have
been used to develop models for alcohol fuels (e.g., CNRS Nancy’s
EXGAS by Battin-Leclerc et al. [207,316], MIT’s RMG by Green et al.
[121,233], and Milano’s MAMOX by Ranzi et al. [317,318]). In this
study, we follow the manual generation methods employed by
Curran et al. [319,320] for large alkane combustion. Some key
points described by Basevich [304] and Westbrook and Dryer [303]
are considered, such as:
 The chemical kinetic model should reproduce quantitative
combustion properties, such as the rate of energy release, igni-
tion delay time, premixed laminar flame speed, and product
compositions.
 The model should be detailed enough to be useful for kinetics
investigations and explanations of combustion phenomena, for
which simple schemes are not suitable.
 The model should be developed in a hierarchical manner
because combustion sequentially fragments the fuel into
smaller intermediate species and eventually final products. For
example, the early work by Warnatz [321] and Dove and War-
natz [322] demonstrated that laminar flame speed simulations
of many hydrocarbons and methanol are primarily sensitive to
the small molecule reactions H þ O2 % O þ OH,
CO þ OH% CO2þH, and H þ O2(þM)% HO2(þM).
 A scarcity in fundamental kinetics data presents a concern
because rate coefficients for many important reaction rates for
alcohols are unknown. To resolve these concerns, one should
compile experimental data on measured rate coefficients, utilize
available quantum chemistry and theoretical rate calculations,
and rely on estimates when necessary.
 While this approach does present uncertainties, the objective is
to limit the tuning of rate coefficients to force agreement be-
tween experiment and model, and to preserve the generality of
the reaction mechanism. This approach is favorable because the
mechanism can be easily updated as new reaction pathways and
more accurate rate coefficients (measured or calculated)
become available.
4.3. Reaction mechanism, reaction classes, and rate rules
The detailed reaction mechanism for C1eC5 alcohols includes
both low-temperature and high-temperature kinetic schemes for
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Table 4
Comprehensive chemical kinetic models for combustion of alcohol fuels.
References
Westbrook and Dryer, 1979 [309]
Egolfopoulos et al., 1992 [137]
Held and Dryer, 1998 [312]
Li et al., 2007 [313]
Egolfopoulos et al., 1992 [159]
Marinov, 1999 [310]
Saxena and Williams, 2007 [168]
Leplat et al., 2011 [177]
Lee et al., 2012 [181]
Metcalfe et al., 2013 [314]
Frassoldati et al., 2010 [195] (n- and iso-propanol)
Dagaut et al., 2009 [208,211] (n-butanol)
Black et al., 2010 [212] (n-butanol)
Grana et al., 2010 [213] (four isomers of butanol)
Harper et al., 2011 [121] (n-butanol)
Sarathy et al., 2012 [260] (four isomers of butanol)
Merchant et al., 2013 [233] (iso-butanol)
Togbé et al., 2010 (n-hexanol)
Togbé et al., 2011 [246] (n-pentanol)
Heufer et al., 2012 [248] (n-pentanol)
Sarathy et al., 2013 [252] (iso-pentanol)
alcohol fuels. The mechanism is compiled in a hierarchical
manner, starting with the oxidation of small hydrocarbons and
alcohols, and then sequentially adding reaction mechanisms for
larger alcohols. The base C0eC2 hydrocarbon oxidation mechanism
used here is the recently published AramcoMech 1.3 developed at
the National University of Ireland Galway (NUIG) by Metcalfe,
Burke, and Curran with Ahmed from Saudi Aramco [314]. Their H2/
CO/O2 sub-mechanism is based on the work of Kéromnès et al.
[323]. The C4 and C5 alkane and alkene sub-mechanisms were
taken from Healy et al. [324]. The methanol and ethanol sub-
mechanisms are from the recent work of Metcalfe et al. [314]
and Mittal et al. [187], respectively. The n- and iso-propanol sub-
mechanism is from Johnson et al. [193] with several modifica-
tions explained by Man et al. [200] plus several important low
temperature reaction pathways. For the higher alcohols, including
the four butanol isomers and two pentanol isomers (n-pentanol
and 3-methyl-1-butanol), few models [233,248,249,252,260] are
comprehensive, such that they can be used to simulate both low-
temperature and NTC reactivity (e.g., ignition) and high-
temperature combustion phenomena (e.g., laminar flame
speeds). Thus, the mechanisms for butanol isomers by Sarathy
et al. [260], n-pentanol by Heufer et al. [248], and iso-pentanol (3-
methyl-1-butanol) by Sarathy et al. [252] are chosen for the pre-
sent analysis.
The important reaction classes are discussed in greater detail
below. As noted previously, these reaction classes follow from
methodologies initially established by Westbrook and Dryer
[303,309] and later applied to n-heptane modeling by Curran et al.
[319]. Several reaction classes that are not unique or important for
63
Experimental targets
Methanol
Shock tubes, flow reactors, and laminar flame speeds
Propagation speed and structure of premixed laminar flames, species
concentration evolutions in flow reactors, static reactors, and shock tubes
Static reactors, flow reactors, shock tubes, and premixed laminar flames
Static reactors, flow reactors, shock tubes, and premixed laminar flames
Ethanol
Premixed laminar flames, flow reactors, and shock tubes
Shock tubes, flow reactors, premixed laminar flames, counterflow
diffusion flames, and jet-stirred reactors
Shock tubes, premixed laminar flames, and counterflow diffusion flames
Shock tubes, flow reactors, premixed laminar flames, counterflow
diffusion flames, and jet-stirred reactors
Shock tubes, rapid compression machines, and premixed laminar flames
Shock tubes, flow reactors, premixed laminar flames, counterflow
diffusion flames, and jet-stirred reactors
Propanol isomers
Shock tubes, flow reactors, premixed laminar flames, and counterflow
diffusion flames
Butanol isomers
Premixed laminar flames, counterflow diffusion flames, and jet-stirred reactors
Shock tubes and jet-stirred reactors
Shock tubes, flow reactors, and counterflow diffusion flames
Shock tubes, flow reactors, coflow and counterflow diffusion flames, and
jet-stirred reactors
Shock tubes, rapid compression machines, premixed laminar flames, and
jet-stirred reactors
Shock tubes, flow reactors, premixed laminar flames, coflow and counterflow
diffusion flames, rapid compression machines, and jet-stirred reactors
Higher alcohols
Premixed laminar flames and jet-stirred reactors
Premixed laminar flames and jet-stirred reactors
Shock tubes, rapid compression machines, premixed laminar flames, and jet-stirred reactors
Shock tubes, rapid compression machines, jet-stirred reactors, premixed laminar
flames, and non-premixed counterflow diffusion flames
alcohol combustion are omitted in the present manuscript. Readers
are referred to the Supplemental Material of [260] for a more
detailed discussion. Fig. 14 presents a generalized scheme for the
primary mechanism of alcohol oxidation, to which the pyrolysis
reactions are added for a complete mechanism. Methanol and
ethanol do not exhibit low-temperature reactivity under typical
combustion conditions, so including comprehensive low-
temperature reaction pathways is not required. Table 5 presents
experimentally measured reaction rate coefficients available in the
literature for various alcohol-related reactions. This table is cited
along with references to theoretical studies to highlight important
rate coefficient studies, existing discrepancies, and areas for future
work. The reaction classes included for alcohol oxidation are shown
in Box 1, approximately in sequence along the oxidation reaction
from fuel to fully oxidized products.
4.3.1. Reaction class 1: unimolecular alcohol decomposition
At high temperatures (above 1500 K) and under fuel-rich or
pyrolysis conditions, the consumption of alcohols is dominated by
unimolecular decomposition. Such reactions are important for
correctly simulating soot emissions in fuel-rich combustion, igni-
tion delay times in highly diluted environments, and non-premixed
diffusion flame structures. In all alcohols, these reactions consist of
simple CeC and CeH bond scission reactions. Unimolecular water
elimination (i.e., dehydration) reactions are also important for al-
cohols. Moc et al. [325] explained that these reactions proceed via
stretching of the CeO bond with a concomitant stretching and
breaking of a CeH bond (a, b, g, d, etc.). They proceed via three-
center (a carbon), four-center (b), five-center (g), or larger
64 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 14. Simplified scheme for the primary mechanism of alcohol oxidation of alcohols.
Figure adapted from Battin-Leclerc [98].
transition state rings. The four-center reactions involving the b
hydrogen atoms are the most thermodynamically favored and
result in the formation of an alkene and water, as shown in Fig. 15.
The rates of these reactions can be determined experimentally, and
several important studies are presented in Table 5. The rate co-
efficients of four-center dehydration reactions vary with the extent
of substitution because this affects the number of abstractable b
hydrogen atoms and their BDEs (i.e., primary, secondary, or ter-
tiary). The structure of the product alkene affects the global reac-
tivity of the alcohol.
4.3.2. Reaction class 2: H-atom abstraction from the alcohol
H-atom abstraction reactions are the primary means by which
fuel alcohols are consumed in combustion environments. A variety
of small radical species can abstract hydrogen atoms from alcohols
(e.g., H, OH, HO2, O, CH3O2, CH3O, CH3, C2H5, etc.). The most
important radicals are OH and HO2 radicals at low and intermediate
temperatures and H radicals at high temperatures and/or under
fuel-rich conditions; only rate coefficients and branching ratios for
these will be discussed in this review. In alcohols, the H atoms can
be characterized as hydroxyl, a, b, g, etc., as well as primary, sec-
ondary, or tertiary (Fig. 13). These reactions are typically written in
the forward direction (i.e., H/OH/HO2 þ fuel), and the reverse rate
coefficients are calculated based on the principle of microscopic
reversibility. The rate coefficient for abstraction depends on the
radical species and the type of H atom being abstracted. As shown
previously, hydrogen bound in the OH moiety is the most difficult
to abstract, followed by primary H atoms, while tertiary H atoms
are the weakest and most easily abstracted. a CeH bonds are
weaker due to the nearby presence of the OH group, whereas b CeH
bonds are slightly stronger than analogous bonds in an alkane
molecule.
Accurate temperature-dependent rate coefficients and branch-
ing ratios for H-atom abstraction by OH radicals are especially
important for simulating alcohol reactivity from 500 to 1500 K. As
shown in Table 5 direct rate measurements of these reactions have
been performed either at low temperatures (e.g., <400 K), which
are of relevance to atmospheric chemistry, or at high temperatures
above 1000 K. H-atom abstraction reactions by HO2 radicals have
not been directly measured for any of the alcohols. The lack of
direct measurements across the range of combustion temperatures
thus requires application of computational theory and estimation
methods to determine the appropriate rate coefficients for reaction
mechanisms [326].
4.3.3. Reaction classes 3 and 4: alcohol radical decomposition and
alcohol radical isomerization
Fuel radicals can undergo unimolecular decomposition via b-
scission at high temperatures (e.g., above 900 K). In these reactions,
the bond once removed from the radical site (i.e., b to the radical
site) break to form an unsaturated species and another radical. b-
scission of CeC and CeH bonds leads to the formation of unsatu-
rated alcohols or alkenes (i.e., C]C bonds), whereas b-scission of
the OeH bonds results in the formation of an aldehyde (i.e., C]O
bond). Fuel radicals can also isomerize by transferring H-atoms
from any carbon/hydroxyl site to the radical site. The rate coeffi-
cient for these reactions depends on the nature of the CeH bonds
broken and formed (i.e., primary, secondary, tertiary, or hydroxyl)
and on the ring strain energy barrier. Typically, radical isomeriza-
tions involving 5-, 6-, or 7-member transition state rings are
considered due to their lower ring strain energies.
4.3.4. Reaction classes 5e9: reactions involving unsaturated
intermediates (enols and carbonyls)
Carbonyls are formed in appreciable quantities during alcohol
combustion. At high temperatures, H-atom abstraction and b-
scission of parent alcohols can result in the formation of alde-
hydes/ketones. At lower temperatures, the reaction of a-hydrox-
yalkyl radicals with O2 leads to the direction formation of
carbonyls. Typical carbonyl intermediates include formaldehyde
(methanal), acetaldehyde (ethanal), propionaldehyde (n-propa-
nal), acetone, butyraldehyde (butanal), and all possible isomers for
C3 and larger carbonyls. A thorough review of aldehyde/ketone
combustion is not available in the literature, and preparing one is
beyond the scope of this manuscript. Highlighted briefly are
several recent studies on carbonyl combustion experiments and
modeling. The destruction pathways of formaldehyde have been
extensively studied because all hydrocarbons are converted to CO
through formaldehyde. Li et al. [313] presented a comprehensive
chemical kinetic modeling study of formaldehyde combustion, and
also reviewed much of the previous experimental and theoretical
studies. Recent studies on combustion of propanal [327] and
butanal isomers [328] were conducted by Veloo et al., and they
present a complete discussion of previous works on these fuels. In
general, aldehydes are consumed via hydrogen atoms abstracted
from the weakly bound aldehydic HeC]O site, following by a-
scission to form CO and an alkyl radical. Larger aldehydes can
exhibit low-temperature reactivity via oxidation of their alkyl in-
termediates [327,328], as shown in Fig. 16.
Enols are common intermediates during the combustion of al-
cohols via dehydrogenation. The isomerization of enols to alde-
hydes or ketones (i.e., enoleketo tautomerization) are slow in the
gas-phase due to large energy barriers (w56 kcal/mol) [329];
however, these reactions occur rapidly in the condensed phase or
on surfaces [212]. The ketone/aldehyde tautomer is typically more
stable than the enol form, such that reaction mechanisms need to
include all realistic pathways for such tautomerization reactions.
Enoleketo tautomerizations and isomerizations catalyzed by H
radicals [218], as well as isomerizations catalyzed by HO2 [330] are
important. The H radical catalyzed isomerization can proceed via
an a-hydroxyalkyl intermediate species (e.g.,
C2H3OH þ H % sC2H4OH; sC2H4OH % CH3CHO þ H). Additionally,
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 65

Table 5
Overview of recent experimental studies of elementary reaction kinetics under conditions relevant to ignition and combustion of alcohols. Low-temperature atmospheric
studies below 400 K are included if they provide kinetic and/or mechanistic information. This table does not include experimental studies related to CH3OH and C2H5OH prior
to 2001, which have already been reviewed and presented by Baulch et al. [352]

References Reaction system Method of initiation Detection technique T, P range

Methanol
H-atom abstraction
Jimenez et al., 2003 [353] CH3OH þ OH Laser photolysis LIF 235e360 K
Baulch et al., 2005 [352] CH3OH þ OH Reviewed literature
prior to 2001
Dillon et al., 2005 [354] CH3OH þ OH Laser photolysis LIF 210e351 K
Srinivasan et al., 2007 [355] CH3OH þ OH Shock tube thermal EAD 1591e1710 K
Baulch et al., 2005 [352] CH3OH þ H Reviewed literature
prior to 2001. No recent
experimental work.
Lu et al., 2005 [356] CH3OH þ O Shock tube thermal ARAS 835e1777 K
Baulch et al., 2005 [352] CH3OH þ O Reviewed literature
prior to 2001
Carr et al., 2011 [357] CH3OH þ O Laser photolysis LIF 775 K
Baulch et al., 2005 [352] CH3OH þ CH3 Reviewed literature
prior to 2001
Park et al., 2012 [358] CH3OH þ phenyl Laser photolysis CRDS and MS 85e1777 K

Unimolecular decomposition
Baulch et al., 2005 [352] CH3OH to products Reviewed literature
prior to 2001
Srinivasan et al., 2007 [355] CH3OH to products Shock tube thermal EAD 1591e2865 K
Lu et al., 2010 [359] CH3OH to products Shock tube thermal ARAS 13591644 K
Lee et al., 2013 [360] CH3OH to products Shock tube thermal ARAS 304e767 K

Radical decomposition
Baulch et al., 2005 [352] CH2OH to products Reviewed literature
prior to 2001

Ethanol
H-atom abstraction
Meier et al., 1985 [361] C2H5OH þ OH Discharge flow reactor LIF 300e1000 K
Greenhill and Ogrady, C2H5OH þ OH Laser photolysis RA 255e459 K, 1.0133 bar
1986 [362]
Wallington and Kurylo, C2H5OH þ OH Laser photolysis RF 240e440 K, 0.0333e0.0666 bar
1987 [363]
Hess and Tully, 1988 [364] C2H5OH þ OH Laser photolysis LIF 293e750 K, 0.9333 bar
Bott and Cohen, 1991 [365] C2H5OH þ OH Shock tube thermal UV laser absorption w1200 K, 1.01325 bar
Jimenez et al., 2003 [353] C2H5OH þ OH Laser photolysis LIF 227e360 K, 0.0533 bar
Dillon et al., 2005 [354] C2H5OH þ OH Laser photolysis LIF 216e368 K, 0.1332 bar
Sivaramakrishnan C2H5OH þ OH Shock tube thermal EAD 857e1297 K
et al., 2010 [366]
Carr et al., 2011 [367] C2H5OH þ OH Laser photolysis LIF 298e900 K, 0.0067e0.1333 bar
Orkin et al., 2011 [368] C2H5OH þ OH Laser photolysis RF 220e370 K, 0.0133e0.2666 bar
Stranic et al., 2014 [369] C2H5OH þ OH Shock tube thermal UV laser absorption 900e1270 K, w1 bar
Sivaramakrishnan C2H5OH þ H Shock tube thermal ARAS 1054e1359 K
et al., 2010 [366]
Carr et al., 2011 [357] C2H5OH þ O Laser photolysis LIF 650e860 K
Park et al., 2012 [358] C2H5OH þ phenyl Laser photolysis CRDS and MS 835e1777 K

Unimolecular decomposition
Li et al., 2004 [370]
Baulch et al., 2005 [352]
Sivaramakrishnan
et al., 2010 [366]
Wu et al., 2011 [371]
C2H5OH to products Flow reactor FTIR 1045e1080 K, 1.7225e3.0398 bar
C2H5OH to products Reviewed literature
prior to 2001
C2H5OH to products Shock tube thermal ARAS 1308e1732 K, 0.20e0.709 bar
C2H5OH to products Shock tube thermal ARAS 1450e1760 K, 1e2 bar

Propanol isomers
Wallington and iso-C3H7OH þ OH Laser photolysis RF 240e440 K, 0.0333e0.0667 bar
Kurylo, 1987 [363]
Dunlop and Tully, 1993 [372] iso-C3H7OH þ OH Laser photolysis LIF 293e745 K, w1 bar
Yujing and Mellouki, n-C3H7OH þ OH Laser photolysis LIF 253e372 K, 0.0399e0.3999 bar
2001 [373]
Yujing and Mellouki, iso-C3H7OH þ OH Laser photolysis LIF 253e372 K, 0.0399e0.3999 bar
2001 [373]
Rajakumar et al., 2010 [374] n-C3H7OH þ OH Laser photolysis LIF 327e376 K, 0.1067e0.5333 bar
Rajakumar et al., 2010 [374] iso-C3H7OH þ OH Laser photolysis LIF 327e376 K, 0.1067e0.5333 bar
Orkin et al., 2012 [375] iso-C3H7OH þ OH Laser photolysis RF 240e370 K, 0.0399e0.1333 bar

Butanol isomers
H-atom abstraction
Wallington et al., 1988 [376] tert-C4H9OH þ OH Laser photolysis Fluorescence 240e440 K, 0.0333 and 0.0667 bar
Teton et al., 1996 [377] tert-C4H9OH þ OH Laser photolysis LIF 253e372 K, 0.1333 bar
(continued on next page)
66 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Table 5 (continued )

References Reaction system Method of initiation Detection technique T, P range

Yujing and Mellouki, n-C4H9OH þ OH Laser photolysis LIF 253e372 K, 0.0399e0.3999 bar
2001 [373]
Mellouki et al., 2004 [378] iso-C4H9OH þ OH Laser photolysis LIF 241e373 K, 0.1333 bar
Jimenez et al., 2005 [379] 2-C4H9OH þ OH Laser photolysis LIF 263e354 K, 0.0547e0.2573 bar
Vasu et al., 2010 [380] n-C4H9OH þ OH Shock tube thermal UV laser absorption 1017e1269 K, 2.279 bar
Pang et al., 2012 [381] n-C4H9OH þ OH Shock tube thermal UV laser absorption 900e1200 K, w1 bar
Pang et al., 2012 [382] iso-C4H9OH þ OH Shock tube thermal UV laser absorption 907e1147 K, w1 bar
Pang et al., 2012 [383] 2-C4H9OH þ OH Shock tube thermal UV laser absorption 888e1178 K, w1 bar
Stranic et al., 2013 [384] tert-C4H9OH þ OH Shock tube thermal UV laser absorption 900e1200 K, w1.1 bar
McGillen et al., 2013 [385] n-C4H9OH þ OH Laser photolysis LIF 221e381 K, 0.067e0.267 bar
McGillen et al., 2013 [385] 2-C4H9OH þ OH Laser photolysis LIF 221e381 K, 0.067e0.267 bar
McGillen et al., 2013 [385] iso-C4H9OH þ OH Laser photolysis LIF 221e381 K, 0.067e0.267 bar
McGillen et al., 2013 [385] tert-C4H9OH þ OH Laser photolysis LIF 221e381 K, 0.067e0.267 bar

Isomerization
Heiss and Sahetchian, 1-C4H9O Flow reactor thermal GC/MS 34e503 K, w1 bar
1996 [349]

Unimolecular decomposition
Tsang, 1964 [203]
Lewis et al., 1974 [204]
Kalra et al., 2004 [386]
Rosado-Reyes and
Tsang, 2012 [387]
Rosado-Reyes and
Tsang, 2012 [388]
Rosado-Reyes and
Tsang, 2013 [389,390]
tert-C4H9OH to products Shock tube thermal GC (detector not specified) 10501300 K, 0.1067e0.4667 bar
tert-C4H9OH to products Shock tube thermal GC (detector not specified) 9201175 K, 0.4933e2.0798 bar
tert-C4H9OH to products Shock tube thermal GC (detector not specified) 7091156 K, 0.07e1.6 bar
and static reactor and NMR
n-C4H9OH to products Shock tube thermal GC/FID/MS 11261231 K, 1.3e6.5 bar
2-C4H9OH to products Shock tube thermal GC/FID/MS 10451221 K, 1.5e6 bar
iso-C4H9OH to products Shock tube thermal GC/FID/MS 1090e1240 K, 1.5e6 bar

Higher alcohols
H-atom abstraction
Wallington et al., 1988 [391] 3-Methyl-2-butanol þ OH Laser photolysis RF 298 K, 0.0333e0.0667 bar
Wallington et al., 1988 [391] 2-Pentanol þ OH Laser photolysis RF 298 K, 0.0333e0.0667 bar
Wallington et al., 1988 [391] 3-Pentanol þ OH Laser photolysis RF 298 K, 0.0333e0.0667 bar
Wallington et al., 1988 [391] n-Hexanol þ OH Laser photolysis RF 298 K, 0.0333e0.0667 bar
Wallington et al., 1988 [391] 2-Hexanol þ OH Laser photolysis RF 298 K, 0.0333e0.0667 bar
Wallington et al., 1988 [391] n-Heptanol þ OH Laser photolysis RF 298 K, 0.0333e0.0667 bar
Mellouki et al., 2004 [378] 3-Methyl-1-butanol þ OH Laser photolysis LIF 241e373 K, 0.1332 bar
Mellouki et al., 2004 [378] 3-Methyl-2-butanol þ OH Laser photolysis LIF 241e373 K, 0.1332 bar
Jimenez et al., 2005 [379] 2-Methyl-2-butanol þ OH Laser photolysis LIF 263e354 K, 0.0547e0.2573 bar
Jimenez et al., 2005 [379] 2,3-Dimethyl-2-butanol þ OH Laser photolysis LIF 263e354 K, 0.0547e0.2573 bar

these reactions can be chemically activated, such that pressure
dependent rate coefficients are necessary [218,331,332].
Reactions of an enol þ HO2 forming an aldehyde þ HO2 are
based on the acetaldehyde/ethenol work of da Silva and Bozzelli
[330]. These reactions are faster pathways of enol-keto isomeriza-
tion given suitably high levels of HO2. These reactions are impor-
tant for enols (i.e., C]CeOH). Enol-keto isomerization catalyzed by
carboxylic acids (e.g., formic acid), which is an interesting reaction
mechanism recently proposed by da Silva [333], may also be
important in combustion systems. By means of theoretical calcu-
lations, he explains that formic acid reacts with vinyl alcohol (i.e.,
ethenol) to form acetaldehyde via a double hydrogen shift mech-
anism, as shown in Fig. 17. The proposed reaction is shown to be fast
at low temperatures and with low concentrations of formic acid
and is therefore important under atmospheric conditions [333].
Other important reactions for enols include H-atom abstraction
reactions, addition of H radicals to double bonds, unimolecular
decomposition of enols, and enol radical decomposition reactions
[334,335]
4.3.5. Reaction class 10: reaction of O2 to a-hydroxyalkyl radicals to
directly form an aldehyde/ketone þ HO2
The reaction pathway involving the reaction of molecular ox-
ygen to a-hydroxyalkyl radicals to directly form an aldehyde/ke-
tone and HO2 is known to occur rapidly in the atmosphere. Some
notable studies of this reaction include those in n-butanol
[336,337] and iso-butanol [338]. Despite the known importance of
this reaction pathway, there is very little information regarding
the rate coefficient at combustion relevant temperatures. Recently,
Zádor et al. [339] and da Silva et al. [340] conducted studies on the
a-hydroxyethyl þ O2 reaction system. They showed that the
aforementioned reaction proceeds through an activated a-hy-
droxy-ethylperoxy adduct that rapidly decomposes to
acetaldehyde þ HO2. Furthermore, the decomposition reaction
occurs with such a low barrier that conventional low-temperature
chain branching pathways are unimportant, as shown in Fig. 18.
This reaction pathway essentially inhibits the low-temperature
ignition behavior of alcohols. This reaction class should be
included at all temperatures because the reaction of a-hydrox-
yalkyl with O2 can be competitive with b-scission reactions up to
1000 K (e.g., premixed flames, intermediate-temperature shock
tube, etc.).
4.3.6. Reaction class 11: addition of O2 to alcohol radicals
(R þ O2 % ROO)
The addition of molecular oxygen to fuel radicals can form sta-
bilized hydroxyalkyl peroxy radicals (ROO), and thus initiate the
low-temperature chain branching process. These reactions are
important in C4 and larger alcohols, but their rates have not been
investigated in detail. From analogy with alkanes [319,320], the rate
of O2 addition to a fuel radical may depend on whether the radical
carbon is a primary, secondary, or tertiary site. Additional work is
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 67

Box 1
Reaction classes for alcohol oxidation

High-temperature reaction classes

1. Unimolecular alcohol decomposition

2. H-atom abstraction from the alcohol
3. Alcohol radical decomposition
4. Alcohol radical isomerization
5. H-atom abstraction reactions from unsaturated alcohols
(e.g., enols)
6. Enol-Keto tautomerizations and isomerizations
7. Addition of H radicals to unsaturated alcohols
8. Unsaturated alcohol radical decomposition
9. Unimolecular decomposition of unsaturated alcohols
10. Reaction of O2 to a-hydroxyalkyl radicals to directly
form an aldehyde/ketone þ HO2

Low-temperature reaction classes (R refers to a alcohol

_
radical such as CH3CHCH 2CH2OH)

11. Addition of O2 to alcohol radicals (R þ O2 % ROO)

12. R þ ROO % RO þ RO
13. R þ HO2 % RO þ OH
14. R þ CH3O2 % RO þ CH3O
15. ROO radical isomerization (ROO % QOOH) including
Waddington type reaction mechanism
16. Concerted eliminations (ROO % unsaturated
alcohol þ HO2)
17. ROO þ HO2 % ROOH þ O2
18. ROO þ H2O2 % ROOH þ HO2
Fig. 15. Four-center dehydration reactions for alcohol fuels.
19. ROO þ CH3O2 % RO þ CH3O þ O2
20. ROO þ ROO % RO þ RO þ O2
21. ROOH % RO þ OH
needed to determine rate coefficients for this reaction class using 22. RO decomposition
quantum chemical potential energy calculations and master 23. Formation of epoxy alcohols via cyclization
equation methods. 24. QOOH % unsaturated alcohol þ HO2 (radical site b to
OOH group)
4.3.7. Reaction classes 12e14: R þ ROO % RO þ RO, 25. QOOH % alkene/unsaturated alcohol þ carbonyl þ OH
R þ HO2 % RO þ OH, and R þ CH3O2 % RO þ CH3O (radical site g to OOH group)
Reactions classes 12, 13, and 14 are grouped together because 26. Addition of O2 to QOOH (QOOH þ O2 % OOQOOH)
they are analogous reactions. Each reaction proceeds through a 27. Reaction of O2 with a-hydroxyalkyl hydroperoxy radi-
chemically activated ROOR0 adduct which decomposes to RO þ R0 O cals (e.g., CH3CH(OOH)CH2CHOH_ þ O2)
(where R0 ¼ R, CH3, H). The reactions are analogous to 28. Isomerization of OOQOOH and formation of carbonyl
CH3 þ HO2 % CH3O þ OH [341]. hydroxyalkyl hydroperoxides and OH, including
Waddington-type reaction mechanisms
4.3.8. Reaction class 15: ROO radical isomerization (ROO % QOOH) 29. Decomposition of carbonyl hydroxyalkyl hydroperox-
including Waddington type reaction mechanism ides to form carbonyl radical species and OH
The second step in the low-temperature radical chain branch- 30. Epoxy alcohols reactions with OH and HO2
ing process is the intramolecular H-abstraction of hydroxyalkyl
peroxy radicals (ROO) to form hydroxyalkyl hydroperoxy radicals
(QOOH). The most important isomerizations include 5-member, 6-
member, and 7-member transition state rings. For alcohols, the chain branching pathways, thereby inhibiting low-temperature
reaction rate coefficients for these reactions are not well studied, reactivity. Sun et al. [344] conducted theoretical calculations on
so estimations techniques are required. The rate coefficient de- these Waddington reactions for tert-butanol and iso-butanol sys-
pends on the nature of the broken CeH bond (i.e., primary, sec- tems. Their study suggests that the b-ROO radical almost
ondary, or tertiary) and on the ring strain energy barrier [260].
Waddington type reaction pathways [342,343] are known to be a
characteristic part of alkene oxidation, but are part of alcohol
oxidation too. These reactions involve the b-ROO radical under-
going a six-membered ring isomerization to abstract an H atom
from the hydroxyl moiety (i.e., forming an alkylhydroperoxide Fig. 16. Reaction path of propanal low-temperature oxidation in a JSR, 10 atm, 655 K,
alkoxy), followed by a rapid decomposition. These reactions are stoichiometric conditions.
chain propagating and compete directly with low-temperature Reprinted from Veloo et al. [327] with permission from Elsevier.
68 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 17. Transition-state structure for the double hydrogen shift reaction of vinyl
alcohol with formic acid to form acetaldehyde.
Reprinted from da Silva et al. [333] with permission from John Wiley and Sons.
exclusively reacts via the Waddington mechanism. Recently,
Welz et al. [345,346] described Waddington-type pathways
involving hydrogen transfer from the OH group as important for
the g-ROO and d-ROO radicals via 7- and 8-membered transition
state rings.
4.3.9. Reaction class 16: concerted eliminations
(ROO % enol þ HO2)
The concerted (direct) elimination of HO2 from the ROO radical
occurs via a 5-membered transition state and was first discovered
in alkanes by Quelch et al. [347]. The same type of reactions is
expected to occur in alcohols. Zádor et al. [99] explain that the OeO
moiety leaves the ROO molecule, and takes an H atom from the
adjacent C atom with it. This reaction pathway competes directly
with the ROO radical isomerization pathway to QOOH. Therefore
the concerted elimination path competes with the chain branching
path and reduces overall low-temperature reactivity. It is also
responsible for the majority of HO2 and enols formed in the low-
and intermediate-temperature regimes. The rate coefficient may
Fig. 18. Rate coefficients (k, cm3 mol1 s1) as a function of temperature and pressure
for formation of acetaldehyde þ HO2 (black lines), vinyl alcohol þ HO2 (gray lines), and
stabilized C2H5O3 radicals (white lines), in the reaction of a-hydroxyethyl þ O2.
Reprinted from da Silva et al. [340] with permission from ACS Publications.
depend on the nature of both the CeOO bond and the CeH bond
broken (i.e., primary, secondary, or tertiary) during the direct
elimination reaction; however, there is a lack of fundamental
experimental and theoretical rate parameters studies on this re-
action class for alkanes, let alone alcohols, to develop such a
rigorous rate rule.
4.3.10. Reaction classes 17e20: ROO þ HO2 % ROOH þ O2,
ROO þ H2O2 % ROOH þ HO2, ROO þ CH3O2 % RO þ CH3O þ O2,
and ROO þ ROO % RO þ RO þ O2
ROO can undergo bimolecular reactions with various radicals
(e.g., HO2, CH3O2, ROO) to form ROOH, which readily decomposes to
RO and OH radicals (i.e., class 21). ROO can also react with H2O2 to
form another stable species and a peroxy species. This reaction
sequence interconverts H2O2 to ROOH, which can decompose at
relatively lower temperatures to produce OH radicals. These re-
actions are discussed in further detail in the previous alkane work
of Curran et al. [319,320].
4.3.11. Reaction classes 21 and 22: ROOH % RO þ OH and RO
decomposition
The decomposition ROOH species leads to the formation of two
reactive radical species. This reaction pathway is generally unim-
portant because the pathways forming ROOH from RO2 (i.e., classes
17 and 18) are in competition with the RO2 % QOOH isomerization
reaction pathways (i.e., class 15). However, it cannot be completely
neglected because the concerted elimination pathway (i.e., class 16)
increases the HO2 concentration, which enhances the
ROO þ HO2 % ROOH þ O2 (i.e., class 17) pathway. The b-scission of
RO radicals leads to production of an alkyl/hydroxyalkyl radical plus
an aldehyde/ketone/acid.
4.3.12. Reaction class 23: formation of epoxy alcohols via
cyclization
The cyclization of a QOOH radical to form an epoxy alcohol (i.e.,
analogous to a cyclic ether in alkane oxidation) plus an OH radical is
an important pathway that competes with the critical chain
branching channel QOOH þ O2 % OOQOOH (i.e., class 25). The
activation energies and rate coefficients for these reactions are not
well known for alcohols, so alkane data [319] can be used as an
estimate. This particular reaction is minor, as cyclic epoxy alcohols
have not yet been measured in significant quantities during alcohol
combustion [345,346].
4.3.13. Reaction classes 24 and 25: QOOH % enol þ HO2 (radical
site b to OOH group) and QOOH % alkene þ carbonyl þ OH (radical
site g to OOH group)
The decomposition of a QOOH with a radical site b to the
hydroperoxy group leads to the formation of an enol plus HO2.
The decomposition of a QOOH when the radical site is g to the
OOH group forms an alkene, an aldehyde or ketone, and an OH
radical.
4.3.14. Reaction class 26: addition of O2 to QOOH
(QOOH þ O2 % OOQOOH)
The addition of molecular oxygen to hydroxyalkyl hydroperox-
ide radicals (i.e., QOOH) is the third step in the low-temperature
chain branching process. The rate of O2 addition to a QOOH
radical depends on whether the radical carbon is an a, primary,
secondary, or tertiary site.
4.3.15. Reaction class 27: reaction of O2 with a-hydroxyalkyl
_
hydroperoxy radicals (e.g., CH3CH(OOH)CH2CHOH þ O2)
The importance of molecular oxygen reaction with a a-
hydroxyalkyl radical to form an aldehyde/ketone and HO2 was
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
previously discussed (i.e., class 10). This reaction is important in
inhibiting the low-temperature reactivity of alcohols. It has been
shown experimentally under atmospheric conditions [348,349]
and theoretically [350,351] that an analogous reactions occurs
for O2 reaction to a-hydroxyalkyl hydroperoxy radicals (e.g.,
CH3CH(OOH)CH2CH.OH þ O2), thus forming a carbonyl hydroper-
oxide plus HO2. In the n-butanol system, the eventual products of
this reaction path are a hydroperoxide butyraldehyde plus HO2
[348,349]. The hydroperoxide butyraldehyde decomposes to give
back OH; therefore, this reaction path is a form of low-
temperature chain branching which produces one OH and one
HO2 radical.
4.3.16. Reaction class 28: isomerization of OOQOOH and formation
of carbonyl hydroxyalkyl hydroperoxides and OH including
Waddington type reactions mechanism
In this reaction class an OOQOOH radical isomerizes, releases an
OH, and then forms a carbonyl hydroxyalkyl hydroperoxide species
(i.e., analogous to carbonyl alkyl hydroperoxide in alkane oxida-
tion). This is the fourth step in the low-temperature chain
branching process. The rate coefficients for these reactions are
estimated based on analogous reaction in alkane combustion
[319,320]. An important underlying assumption in this methodol-
ogy is that the hydrogen atom being abstracted is bound to the
carbon atom bonded to the hydroperoxide (OOH) group, which has
a lower CeH bond strength than a normal CeH bond and makes it
easier to abstract.
4.3.17. Reaction class 29: decomposition of carbonyl hydroxyalkyl
hydroperoxides to form oxygenated radical species and OH
The decomposition of carbonyl hydroxyalkyl hydroperoxides
forms an OH radical, a smaller oxygenated radical, and a stable
oxygenate (i.e., aldehyde or ketone). This reaction pathway is the
final step in the low-temperature chain branching process because
it forms two radical species from one stable reactant.
4.3.18. Reaction class 30: epoxy alcohols reactions with OH and HO2
The epoxy alcohols formed via cyclization of a hydroxyalkyl
hydroperoxy radical (i.e., reaction class 23) have an oxygen atom
embedded within the ring. One can assume these species react via
H-atom abstraction by OH and HO2, which are the predominant
radicals at low and intermediate temperatures. The subsequent
epoxy alcohol radicals then undergo b-scission to form smaller
hydrocarbon and carbonyl species.
4.4. Model testing and analysis
Following the extensive discussion on reaction classes, testing of
the C1eC5 chemical kinetic model against experimental data is
necessary. Comparisons of each alcohol oxidation sub-mechanism
with experimental data are presented to demonstrate its perfor-
mance across a range of temperatures, pressures, and mixture
fractions of relevance to practical combustion devices. The goal
here is not to include comparisons against all available experi-
mental data for a specific alcohol fuel, but instead to follow
guidelines for selecting the targets to be presented in this review
article, which are as follows:
 Premixed laminar flame speed simulations are important for
flame propagation in SI engines; these are presented for all the
fuels. Comparisons are shown for a range of equivalence ratios
and, if data are available, at elevated pressures.
 Homogenous ignition delay time simulations are important for
SI, CI, and LTC engines; these are presented for all the fuels.
Comparisons are presented for data obtained temperatures
69
from 500 to 1500 K, pressures greater than 10 bar, and equiv-
alence ratios ranging from lean to rich (whenever available), as
these are the most relevant to internal combustion engines.
 Simulating the concentrations of intermediate and product
species is important for elucidating reaction pathways of alcohol
fuels and simulating (potentially harmful) emissions from
alcohol-fueled engines. Thus, comparisons are presented for
data obtained in premixed flames, stirred reactors, and/or flow
reactors at temperatures from 500 K and above, elevated pres-
sures, and a range of equivalence ratios.
 Data obtained in fuel/air (21% O2 and 79% N2) mixtures are
favored over data obtained with other diluents (e.g., Ar). Several
exceptions exist, such as premixed flame speciation studies
where Ar dilution is used as an internal standard for
calibration.
 Studies under non-premixed (e.g., counterflow flames, coflow
flames, etc.) and pyrolysis conditions are relevant to CI and
premixed charge compression ignition (PCCI) engine combus-
tion and pollutant formation. Experimental studies and model
simulations under such conditions are selectively presented to
develop a mechanistic understanding of alcohol combustion in
fuel-rich environments.
 When available, experimental data from newer studies are
favored over older data, unless the literature review has deemed
the newer data inaccurate.
 Comparing the combustion chemistry features across the
various alcohols is facilitated by utilizing data obtained from the
same experimental facilities under similar conditions.
 All the simulations were conducted in CHEMKIN-PRO [282]
using the appropriate reactor modules. Premixed laminar
flame simulations accounted for thermal diffusion (i.e., Soret
effect), assumed mixture-averaged transport, and the solutions
were highly resolved with approximately 200 grid points (GRAD
0.1, CURV 0.1). Burner-stabilized premixed flames were simu-
lated using the experimentally measured temperature profile as
a boundary condition.
4.5. The combustion chemistry of methanol
Methanol is the simplest alcohol and its oxidation mechanism
provides the basis for the oxidation of larger alcohols. In hydro-
carbon combustion, the recombination of methyl and hydroxyl
radicals forms methanol (e.g., CH3þOH%CH3OH), and many in-
termediate species important to methane combustion (e.g., CH2O,
CH3O, CH2OH, and HCO) are also relevant to methanol combus-
tion. Notable comprehensive reaction mechanisms described for
methanol are those by Westbrook and Dryer [309], Egolfopoulos
et al. [137], Held and Dryer [312], Li et al. [313], Ing et al. [392],
and Aranda et al. [153]. Table 5 lists manuscripts describing the
direct rate measurement of methanol decomposition and impor-
tant branching fractions. Srinivasan et al. [355] utilized the re-
flected shock tube technique with multipass absorption
spectrometric detection of OH radicals to measure the rate co-
efficients of important product channels between 1591 and
2865 K. More recently, Lee et al. [360] and Lu et al. [359]
measured methanol thermal decomposition rates behind re-
flected shock waves by atomic resonance absorption spectrometry
of H atoms from 1660 to 2050 K and 1359 to 1644 K, respectively.
Pressure-dependent rate coefficients using high-level ab initio
calculations and master equation simulations by Jasper et al. [393]
are in good agreement with the aforementioned direct experi-
mental measurements. Jasper et al. [393] found that the branching
ratio largely favors the (R1) channel (w80%) with the (R2) channel
(w20%) being the second most important. The important
70 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
reaction channels and pressure-dependent rate coefficients rec-
ommended by Jasper et al. [393] are utilized in the recent
methanol mechanisms proposed by Metcalfe et al. [314] and
Aranda et al. [153].
CH3OH % CH3 þ OH
CH3OH % 1CH2 þ H2O
CH3OH % CH2OH þ H
Hydrogen abstraction from methanol by H radicals have been
studied experimentally prior to 2001, as reviewed in detail by
Baulch et al. [352] (Table 5). Recent experimental studies have not
been found in the literature, but a detailed high-level direct dy-
namic variational transition state theory calculation has been per-
formed by Meana-Pañeda, Truhlar, and Fernández-Ramos [394].
The authors present good agreement of their calculated total rate
coefficient ((R4) þ (R5)) with the available experimental data.
Furthermore, their calculations indicate a variation in the branch-
ing ratio with temperature, wherein that (R4) contributes to 100%
at room temperature and w75% at 2500 K.
CH3OH þ H % CH2OH þ H2
CH3OH þ H % CH3O þ H2
Hydrogen abstraction by OH radicals is the primary consump-
tion pathway for methanol in lean and stoichiometric environ-
ments. Baulch et al. [352] reviewed the large body of experimental
rate coefficient measurements prior to 2001. In 2003 and 2005,
these reactions were studied at atmospheric conditions (<400 K)
by Jiménez et al. [353] and Dillon et al. [354]. Srinivasan et al.
[355] recently conducted high-accuracy experiments at high
temperatures. The rate coefficients for (R6) þ (R7) and its
branching ratios were studied theoretically by Xu and Lin [395]
using high-level computational theory. Their study noted the
importance of characterizing pre-reaction complexes in this class
of reactions. Their proposed rate coefficient in the temperature
range of 200e3000 K is in good agreement with the available
experimental data. Their calculations indicate a branching ratio
that is largely independent of temperature; (R6) contributes to
96e89% of the total rate coefficient across the entire temperature
range, which is in agreement with the recent combustion exper-
iments of Rasmussen et al. [147]
CH3OH þ OH % CH2OH þ H2O
CH3OH þ OH % CH3O þ H2O
Hydrogen abstraction from methanol by HO2 has never been
measured experimentally. Metcalfe et al. [314] utilized brute-force
sensitivity analysis to show that high pressure (30 bar) shock tube
ignition delay times are sensitive to the rate coefficient for (R8). In
studies of RCM, Kumar and Sung [151] and Aranda et al. [153] also
highlighted the importance of this reaction’s rate coefficient for
accurately simulating RCM ignition delay measurements. The
recent theoretical investigations include those by Altarawneh et al.
[335], Klippenstein et al. [396], and Alecu and Truhlar [397,398].
Metcalfe et al. [314] compared the rate coefficients determined in
various studies, including estimations based on analogies and/or
comparison with experimental combustion data and theoretically
calculated values. From 900 to 1000 K, the theoretically calculated
values from Klippenstein et al. [396] and Alecu and Truhlar
[397,398] deviated by a factor of w3.5e4. Aranda et al. [153]
explained that the discrepancy between the high-level calcula-
tions is attributed to the different treatment of anharmoncity. As
will be shown later, a definitive direct experimental measurement
is needed to provide further guidance in reaction mechanism
(R1)
development.
(R2)
CH3OH þ HO2 % CH2OH þ H2O2 (R8)
(R3)
CH3OH þ HO2 % CH3O þ H2O2 (R9)
The hydroxymethyl (CH2OH) and methoxy (CH3O) produced
by hydrogen abstraction from methanol are primarily consumed
via thermal decomposition (i.e., b-scission reactions), leading to
the products of both reactions being formaldehyde and H radi-
cals. The hydroxymethyl radical can also react with molecular
oxygen to produce formaldehyde and H radicals. The methoxy
radical is primarily consumed via thermal decomposition (R10).
Rasmussen et al. [147] reviewed rate coefficients for (R10), and
the preferred rate coefficient is based on the work of Hippler et al.
[399]. Baulch et al. [352] reviewed the various rate coefficients
proposed for R11, including those by Bowman [123], Tsuboi and
Hashimoto [128], Cribb et al. [135,136], Greenhill and Ogrady
(R4)
[362], and Held and Dryer [312]. Baulch et al. [352] noted large
discrepancies in the aforementioned rate coefficient recommen-
(R5)
dations. No detailed study of the pressure dependence of this
reaction has been made, even though Greenhill and Ogrady [362]
showed that fall-off effects are important. Baulch et al. [352]
recommended using the rate coefficient for (R10) proposed by
Held and Dryer [312], and this is the one most commonly used in
recent methanol combustion models [147,314]. Baulch et al. [352]
also reviewed the proposed rate coefficients for oxidation of
hydroxymethyl by O2 (R12), and they noted an excellent agree-
ment across experimental studies at low temperatures. The high
temperature rate coefficient extrapolation from the work of
Grotheer et al. [400] (at 298e684 K) shows good agreement with
flame studies by Vandooren and van Tiggelen [127]. Baulch et al.
[352] recommended a rate coefficient for this reaction by fitting
the mean of the low-temperature data with the high-temperature
measurements, resulting in a rate coefficient valid in the range
298e1200 K.
CH3O % CH2O þ H (R10)
CH2OH % CH2O þ H (R11)
(R6)
CH2OH þ O2 % CH2O þ HO2 (R12)
(R7)
The methanol mechanism utilized in this study is that devel-
oped recently by Metcalfe et al. [314], namely AramcoMech 1.3.
This mechanism is chosen due to its comprehensive development
and testing for methanol, as well as for hydrogen [323], hydrogen/
CO mixtures [323], methane, and formaldehyde, which are all
relevant to methanol combustion. In their paper [314], the au-
thors present methanol model comparisons against shock tube
ignition delay data from Bowman [123] (>1500 K, 1e11 bar,
f ¼ 0.75e6.0) and from Fieweger et al. [142] (750e1250 K, 13e
40 bar), flow reactor speciation data from Norton and Dryer
[132,133] and Held and Dryer [140], and premixed laminar flame
speed data from Veloo et al. [110] and Vancoillie et al. [152] (1 bar,
f ¼ 0.7e1.5).
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Atmospheric pressure methanol/air premixed laminar flame
speeds were recently measured by Veloo et al. [110] and Vancoillie
et al. [152] near 343 K. The former utilized the counterflow twin
premixed flame technique, whereas the latter employed the heat
flux burner method. Egolfopoulos et al. [137] also utilized the
counterflow twin flame technique to measure methanol/air flame
speeds near 340 K, although they used a linear extrapolation to
account for flame stretch, whereas Veloo et al. [110] utilized a more
accurate non-linear extrapolation to zero stretch. Fig. 19 presents
the experimental data obtained in the aforementioned studies. The
recent data sets from Veloo et al. [110] and Vancoillie et al. [152]
agree well for lean and stoichiometric mixtures, but rich mixtures
are notably faster in the latter data set. The model from Metcalfe
et al. agrees with both data sets under lean conditions and partic-
ularly concurs with the data of Vancoillie et al. [152] on the rich
side, albeit there is only a single measurement at this condition.
Additional experiments for methanol/air mixtures under rich
conditions are needed to better validate the chemical kinetic
mechanisms.
The homogenous ignition delay of methanol has been well
studied under Ar dilution at high temperatures above 1200 K
(refer to Table 3). Kumar and Sung conducted RCM measurements
at elevated pressures and intermediate temperatures of greater
relevance to internal combustion engines (7e30 bar, 850e1100 K,
f ¼ 0.25e2.0), again under Ar dilution (O2/Ar : 1/3.76). Their RCM
data [151] in Fig. 20 displays methanol’s Arrhenius-type mono-
tonic decrease in the ignition delay time with increasing temper-
ature. Simulations are also presented using the chemical kinetic
model of Metcalfe et al. [314] (dashed gray line) and employing a
volume-varying history to account for heat losses after the end of
compression [104,106,401,402]. The model is able to simulate the
qualitative Arrhenius behavior that is observed experimentally,
but the simulated ignition delay times are quantitatively lower
than those measured experimentally. Rate coefficients responsible
for the discrepancy are discussed later. Fieweger et al. [142]
measured shock tube ignition delay times for methanol/air and
conditions comparable to SI engine conditions (i.e., 750e1250 K,
Fig. 19. Laminar flame speeds for methanol/air mixtures at 1 bar and 343 K. Symbols
are experimental measurements by Veloo et al. [110], Vancoillie et al. [152], and
Egolfopoulos et al. [137] and the line is a simulation.
71
1.0E+00
13 bar ST
var V
var V (CH3OH+HO2)
30 bar RCM
1.0E-01
var V
var V (CH3OH+HO2)
Ignition Delay Time (s)
40 bar ST
var V
1.0E-02
const V
1.0E-03
1.0E-04
1.0E-05
0.7 0.8 0.9 1 1.1 1.2 1.3 1.4
1000 K / T
Fig. 20. Methanol ignition delay times at stoichiometric conditions. Symbols are
experimental data from Fieweger et al. [142] (shock tube, methanol/O2/N2, 13 and
40 bar) and from Kumar and Sung [151] (RCM, methanol/O2/Ar, 30 bar). Open symbols
represent shock tube measurements affected by deflagration. Lines are simulations
under various conditions (see text).
13e40 bar, f ¼ 1.0). Fig. 20 presents their experimental results
along with simulations using the chemical kinetic model of Met-
calfe et al. [314]. Methanol/air mixtures display long ignition delay
times at high pressures and intermediate temperatures (i.e., 10e
100 ms), which agrees with its high RON value (i.e., 112). Constant
volume simulations (Fig. 20 thin dashed blue line) are presented at
40 bar, and the model displays the linear trend of decreasing
ignition delay time with decreasing temperature. The data suggest
significantly shorter ignition delay times at lower temperatures,
but Fieweger et al. [142] attributed this discrepancy to the exis-
tence of a pronounced deflagration phase that causes the post-
compression pressure to double prior to the main ignition event.
The result is up to an order of magnitude decrease in ignition
delay times for experiments affected by deflagration (e.g., open
symbols in Fig. 20). Increasing pressure during the ignition delay
time period is not ideal, and such phenomena can be modeled
using volume-varying simulations, as explained by Chaos and
Dryer [102] or pressure-varying simulations as explained by Zhu
et al. [240]. When the former methodology (denoted as “vol hist
sim” in Fig. 20) is implemented using a 10%/ms pressure rise rate
(Fig. 20, thick dashed blue line and solid red line), the model
simulations are in much better agreement with the experimental
data.
The oxidation of methanol in stirred and flow reactors has
been studied to measure the global reactivity and to identify
intermediate and product species distributions. A list of pub-
lished studies is presented in Table 3, with the most notable ones
being those at elevated pressures by Held and Dryer [312], Dayma
et al. [146], and Aranda et al. [153]. Metcalfe et al. [314] presented
comprehensive comparisons of their methanol model against the
data of Held and Dryer [312]. Here the model is compared with
JSR data at 10 bar [146] because the same facility and experi-
mental methodology has also been used to study many other
alcohol fuels. The data in Fig. 21 indicate that methanol is
unreactive below 800 K and no intermediate or product species
are measured. Above 800 K, methanol reacts to produce
72 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Fig. 21. Jet-stirred reactor speciation profiles for methanol oxidation at 10 bar, f ¼ 0.6,
s ¼ 1 s, 8000 ppm CH3OH, 20000 ppm O2, 800 ppm H2O, and balance N2. Symbols are
experimental data from Dayma et al. [146]. Lines are simulations.

Fig. 22. Reaction path diagram for methanol combustion.

formaldehyde (CH2O), which has a peak concentration near
Figure adapted from Ref. [153].
825 K, and is then oxidized to form CO and subsequently CO2. The
model of Metcalfe et al. [314] qualitatively agrees with the con-
sumption of methanol, the production and consumption of and 21. Adopting the recent theoretically calculated rate co-
formaldehyde, and the generation of major product species (CO, efficients from Alecu and Truhlar [397,398] slows down ignition
CO2, and H2O). However, the simulated reactivity is shifted to delay times under RCM conditions and simulations are in better
lower temperatures (w50 K) than measured experimentally. As agreement with the experimental data. Their slower rate coeffi-
will be discussed later, this is attributed to the selected rate co- cient also slows the reactivity of methanol in the JSR bringing it into
efficient for CH3OH þ HO2 % CH2OH þ H2O2. better agreement with the experimental profile and also improving
The general reaction scheme for methanol combustion in pre- formaldehyde agreement. However, the proposed rate coefficient
mixed flames, batch reactors, and stirred and flow reactors is pre- also slows ST ignition delay times, resulting in an under agreement
sented in Fig. 22. Methanol consumption is initiated by hydrogen of the data from Fieweger et al. [142], which is consistent with the
abstraction by OH, HO2, and H radicals. As mentioned earlier, the findings of Metcalfe et al. [314] when using the aforementioned
branching ratio of hydrogen abstraction by OH strongly favors the rate coefficient to simulate ST data from Noorani et al. [150]. The
formation of CH2OH with CH3O being a minor channel. Both these various combustion modeling studies [147,153,313,314] and theo-
radical intermediates share their fate in the formation of formal- retical calculations [335,396,398] have not yet converged upon a
dehyde, and once formed this species controls the reactivity of the
system. Hydrogen abstraction from formaldehyde yields the HCO
radical (formyl), eventually leading to the formation of CO and CO2
via the sequence CH2O / HCO / CO / CO2.
Both Veloo et al. [110] and Metcalfe et al. [314] have shown that
the laminar flame speed of methanol displays a strong positive
sensitivity to the ubiquitous radical chain branching
H þ O2 % O þ OH and the reaction HCO(þM) % H þ CO(þM). The
latter reaction produces the H radicals needed to drive the former
reaction. The reaction of HCO þ O2 % CO þ HO2 has been shown to
inhibit laminar flame speeds because it competes directly with the
HCO decomposition channel and traps H-atoms in the hydro-
peroxyl radical.
Fig. 23 from Kumar and Sung [151] presents a sensitivity analysis
on ignition delay times measured in the RCM at 30 bar, 905 K, and
under stoichiometric conditions, which is one of the points plotted
in Fig. 20. The ignition delay is strongly promoted by the reactions
CH3OH þ HO2 % CH2OH þ H2O2 and H2O2(þM) % OH þ OH(þM).
The former reaction produces the hydrogen peroxide (H2O2) that
Fig. 23. Sensitivity figures of merit obtained by applying Morris analysis on RCM
decomposes to form reactive OH radicals in the latter reaction. The ignition experiments conducted at 30 bar, 905 K, under stoichiometric conditions, on
importance of the reaction CH3OH þ HO2 % CH2OH þ H2O2 under methanol/O2/Ar mixtures.
combustion-relevant conditions is further highlighted in Figs. 20 Reprinted from Kumar and Sung [151] with permission from John Wiley and Sons.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
agreeable rate coefficient for CH3OH þ HO2 % CH2OH þ H2O2, and
thus a direct experimental measurement is greatly needed.
4.6. The combustion chemistry of ethanol
Ethanol is the most widely used alcohol fuel in transportation
applications. Its oxidation mechanism is also an important sub-
component of ethane and propane combustion models. Detailed
chemical kinetic models for ethanol have been presented and
tested against experimental data. Notable models include the first
by Natarajan and Bhaskaran in 1981 [126]; the models by Egolfo-
poulos et al. [159] and Marinov [310] in the 1990s that were
compared against data from shock tube ignition delay, laminar
flame speeds, and chemical species concentration measurements in
a jet-stirred reactor; and the comprehensively developed model by
Frassoldati et al. [403] for ethanol and ethanolegasoline mixtures.
Other recent ethanol oxidation models that are widely tested (i.e.,
shock tube, jet-stirred reactor, flow reactor, flame speed, and flame
speciation) include AramcoMech presented by Metcalfe et al. [314]
and Mittal et al. [187] and the ethanol model by Leplat et al. [177]. A
number of other models have also been presented for ethanol
oxidation, but they tend to present comparisons against a limited
set of experimental data [110,160,169,173,176,179,181,184,404].
The unimolecular thermal decomposition of ethanol proceeds
primarily via a dehydration reaction (R13), CeC bond scission (R14),
or CeO bond scission (R15). Baulch et al. [352] reviewed the limited
number of related experimental studies (e.g., the direct measure-
ment of (R13) by Herzler et al. [405]), but noted that none provided
detailed temperature and pressure-dependent rate coefficients.
More recently, Li et al. [370] measured the rate coefficient of (R13)
by monitoring ethanol decay and ethylene production in a pyrolysis
flow reactor with online FTIR sampling. Their experimentally
determined rate coefficient agreed with that of Herzler et al. [405].
Tsang [406] conducted a master-equation analysis, concluding that
R13 is the main reaction with CeC and CeO bond scissions being
secondary processes, and assigned a rate in creditable agreement
with the aforementioned experimental measurements [370,405].
Park et al. [407] employed ab initio molecular orbital theory and
RiceeRamspergereKasseleMarcus (RRKM) calculations to deter-
mine pressure and temperature-dependent rate coefficients and
branching ratios, but their calculated rate for (R13) was 3.2 times
higher than that of Tsang [406]. Sivaramakrishnan et al. [366]
recently conducted a definitive experimental and theoretical
analysis using a high-temperature shock tube with ab initio variable
reaction coordinate transition state theory-based master equation
calculations. The rate coefficient of (R15) was measured directly
using OH optical absorption, the total rate coefficient and that of
(R13) þ (R14) was measured by H-atom ARAS detection, and the
difference gave the rate coefficient of (R13). They highlighted the
sources of disagreement with previous theoretical calculations,
noting that Park et al. [407] did not correctly account for the bar-
rierless potential of (R13), while Li et al. [370] artificially lowered
their transition state frequencies to match experimental data. In
addition, the variations in pressure fall-off treatment from the use
of different energy transfer models led to discrepancies in theo-
retical rate coefficient calculations. The branching ratios from
Sivaramakrishnan et al. [366] favor the dehydration reaction (R13)
below 1400 K (ranging from 90 to 70% from 500 to 1400K), while
CeC bond scission (R14) becomes increasingly important at high
temperature (w45% at 2000 K). The CeO bond scission (R15) in
ethanol is negligible because its bond strength is significantly
higher than that of a CeC bond. A recent shock tube study by Wu
et al. [371] on ethanol decomposition using H-atom ARAS detection
are in good agreement with previous works; however, the pressure
73
dependence of the branching fraction is smaller than previous
theoretical calculations suggest.
C2H5OH % C2H4 þ H2O (R13)
C2H5OH % CH3 þ CH2OH (R14)
C2H5OH % C2H5 þ OH (R15)
H-atom abstraction reactions from ethanol proceed from the a,
b, or hydroxyl sites. The total rate coefficient for H-atom abstraction
by H radicals ((R16) þ (R17) þ (R18)) was first studied by Aders and
Wagner in 1973 [408] in the temperature range of 295e700 K. The
only other direct experimental measurement was recently per-
formed by Sivaramakrishnan et al. [366] at temperatures of 1054e
1359 K, wherein the total rate coefficient was measured and indi-
vidual rate coefficients were calculated from theory. The theoreti-
cally calculated rate coefficients from Sivaramakrishnan et al. [366]
and Park et al. [409] are in excellent agreement with the afore-
mentioned direct measurements. The branching ratios are also in
agreement, with (R17) being the dominant channel (w99% at 500 K
and w64% at 2000 K), (R18) contributing a maximum of 38% at
2500 K, and (R16) being negligible (7% at 2500 K) [366].
C2H5OH þ H % C2H5O þ H2 (R16)
C2H5OH þ H % CH3CHOH þ H2 (R17)
C2H5OH þ H % CH2CH2OH þ H2 (R18)
OH radicals are the most important abstractors of hydrogen
atoms from ethanol. Table 5 lists experimental measurements for
the total rate coefficient ((R19)-(R21)) across a range of tempera-
tures. Early works in the 1980s [361,362,376] studied this reaction at
low temperatures of relevance to atmospheric chemistry, except for
the study of Hess and Tully, who conducted measurements up to
750 K [364]. Bott and Cohen later performed higher temperature
measurements (1200 K) [365] using a shock tube with laser ab-
sorption spectroscopy. In the past decade, the rate coefficient was
again measured by Jiménez et al. [353] and Dillon et al. [354] in at-
mospheric temperature ranges and by Carr et al. [367] and Sivar-
amakrishnan et al. [366] at combustion-relevant temperatures. The
consensus among experimental studies is that the total rate coeffi-
cient is well established from 200 to 2500 K, but the proposed
branching ratios vary greatly between studies. One challenge is that
the individual rate coefficient of (R21) cannot be measured by
monitoring OH radical concentrations because the b CH2CH2OH
radical quickly decomposes to C2H4 plus OH above 600 K. Carr et al.
[367] utilized isotopic labeling to measure individual rate co-
efficients of (R21) and (R22) below 550 K, but these temperatures
were not directly relevant to combustion. Thus, theoretical calcu-
lations and/or estimations are necessary to better determine the
individual rate coefficients. Such theoretical calculations have been
performed by Xu and Lin [395], Zheng and Truhlar [410], and
Sivaramakrishnan et al. [366]. In general, all these studies present
total rate coefficients that can reproduce the aforementioned
experimentally measured data. However, Sivaramakrishnan et al.
[366] had to adjust their theoretical calculations to obtain good
agreement with data, whereas Zheng and Truhlar [410] noted that
their lower level potential energy surface calculations (MS-VTST
with M08-SO/6-31 þ G(d,p)) agreed with experimental data better
than did their state-of-the-art multi-path variational transition state
theory calculations (MP-VTST with M08-HX/6-31 þ G(d,p)).
Table 6 presents branching ratios determined in several recent
studies. The theoretical calculations of Xu and Lin [395], Zheng and
74 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Table 6
Branching ratios for hydrogen abstraction by OH radicals from ethanol’s a, b, and OH sites at 900 K.

Sivaramakrishnan et al. [366] Xu and Lin [395] Zheng and Truhlar [410] Carr et al. [367] Tran et al. [184]

% of total rate a 93 83 74 39 79
b 4 13 15 10 21
OH 3 4 11 51 3

Truhlar [410] (MP-VTST calculations), and Sivaramakrishnan et al.
[366] (adjusted theoretical calculations), and the estimate from
Tran et al. [184] (EvansePolanyi correlation with ethane) all suggest
that abstraction from the a site (R20) is dominant followed by the b
channel (R21). The rate coefficients proposed by Carr et al. [367]
suggest that (R19) is the dominant channel, which is unexpected
given the high BDE of the OeH bond, and in disagreement with the
other studies. The branching ratio of (R20) varies by about 20%
between Zheng and Truhlar [410] and Sivaramakrishnan et al.
[366], wherein the former places more importance on (R19) and
(R21). Zheng and Truhlar [410] have identified inaccuracies in
previous studies [366,395], such as unexpectedly high saddle point
energies for transition states with hydrogen bonded structures in
(R21), which explains why Sivaramakrishnan et al.’s [366]
branching ratio for (R21) is lower than others. The MP-VTST cal-
culations by Zheng and Truhlar [410] are the state-of-the-art in
computational chemistry. It seems reasonable that their branching
ratios would therefore be the most accurate given the high-level of
theory employed. However, we recall that their total rate coefficient
could not accurately reproduce experimental data. They [410]
concluded that advances in computational chemistry are needed
to make rate calculations more predictive, especially for reactions
with stabilized pre-reaction complexes and hydrogen bonding in
the transition states.
C2H5OH þ OH % C2H5O þ H2O
C2H5OH þ OH % CH3CHOH þ H2O
C2H5OH þ OH % CH2CH2OH þ H2O
n-butanol by hydroperoxyl radicals showed that hydrogen bonds in
the transition state lead to ring structures. These were found to be
important for the b and g sites of n-butanol, resulting in lower
energy barriers and higher entropy loss (i.e., lower activation en-
ergies and lower A-factors). Sarathy et al. [260] found that the rate
coefficients determined by Zhou et al. [326] for n-butanol were
suitable for combustion modeling; however, an increase in the a
channel rate by a factor of 2.5 (within the uncertainty specified by
Zhou et al. [326]) was needed to obtain better agreement with the
results of intermediate temperature shock tube ignition delay ex-
periments. Metcalfe et al. [314] and Mittal et al. [187] expected that
such hydrogen bonding effects would also be important in ethanol.
Mittal et al. [187] assigned (R23) a rate coefficient 1.75 times greater
than the a channel rate recommended by Zhou et al. [326] for n-
butanol. Their rate coefficient for abstraction from the hydroxyl
moiety (i.e., (R22)) was that calculated by Zhou et al. [326] for the
analogous reaction in n-butanol. Abstraction from the b carbon was
estimated as the average of Zhou et al.’s [326] calculated rate co-
efficients from the d and b channels in n-butanol.
C2H5OH þ HO2 % C2H5O þ H2O2 (R22)
C2H5OH þ HO2 % CH3CHOH þ H2O2 (R23)
C2H5OH þ HO2 % CH2CH2OH þ H2O2 (R24)
(R19)
At high temperatures, the ethoxy (C2H5O), a-hydroxyethyl
(R20) (CH3CHOH), and b-hydroxyethyl (CH2CH2OH) radicals produced by
hydrogen abstraction from ethanol are consumed via thermal
(R21) decomposition (i.e., b-scission reactions) and unimolecular

Hydrogen abstraction from ethanol by HO2 has not yet been

measured experimentally or calculated using theoretical chemistry.
As shown previously for methanol and later for ethanol, ignition
delay times of ethanol/air mixtures are sensitive to the total reac-
tion rate and its branching ratios. One would expect the abstraction
to favor the a site given its low BDE and the abstraction from the
hydroxyl moiety to be negligible. Recent chemical kinetic models
vary widely in their choice of rate coefficients for (R22), (R23), and
(R24). Several proposed rate coefficients for (R23) (a) and (R24) (b)
are shown in Fig. 24. All studies suggest that abstraction from the a
site is dominant at all temperatures, but the temperature depen-
dence varies across studies. Estimates of (R24) by Marinov [310]and
Tran et al. [184] agree with each other at 1000 K, whereas that of
Mittal et al. [187]is nearly a factor of 3 higher. Leplat et al. [177] and
Lee et al. [181] used the proposed rate coefficient from Marinov
[310]. He assumed that (R23) had a rate coefficient similar to
methanol’s (R8) (CH3OH þ HO2 % CH2OH þ H2O2) and that the rate
coefficient of (R24) was based on the derived rate expression of
(R23). Marinov [310] assigned large error bars to his proposed rate
coefficients and stated that they were highly uncertain. Recently,
Tran et al. [184] proposed rate coefficients for (R23) and (R24) using
EvanePolanyi correlations proposed by Dean and Bozzelli [411]
with ethane as a reference. This methodology accounts for varia-
tions in BDEs between ethanol and ethane, but not for secondary
Fig. 24. Comparison of rate coefficients for C2H5OH þ HO2 from a and b sites. Rate
effects such as hydrogen bonds formed in transition states. A recent coefficients are plotted from the studies of Mittal et al. [187], Marinov [310], and Tran
theoretical study by Zhou et al. [326] on hydrogen abstraction from et al. [184].
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 75

isomerization reactions. Xu et al. [412] recently conducted a theo-

retical study on the decomposition and isomerization of C2H5O
radicals. Senosiain et al. [413] also performed high-level quantum
chemistry calculations for all the low-energy pathways of the re-
action of ethylene with OH radicals. These included all C2H5O iso-
mers following OH addition to the double bond in ethylene and
subsequent isomerization reactions. Both studies noted that very
few direct measurements have been made at combustion-relevant
temperatures. The ethoxy radical (C2H5O) undergoes decomposi-
tion either by CeC bond scission (R25) to formaldehyde and methyl
radical or CeH bond scission (R26) to acetaldehyde and H radical,
with isomerization reactions being negligible. At 1 bar and 1000 K,
the branching ratio of R25:R26 is approximately 73:27 [412]. The a-
hydroxyethyl (CH3CHOH) also favors thermal decomposition at
combustion-relevant conditions. The OeH bond scission forming
acetaldehyde (R27) is in competition with the CeH bond scission
leading to ethenol (R28) [413]. Both channels are thus important,
but the path leading to acetaldehyde is favored according to cal-
culations by Dames [414]. CeC bond scission to ethylene and OH
radical (R30) accounts for about 90% of the destruction of b-
hydroxyethyl (CH2CH2OH), with 10% going to form ethenol (R31)
[412].

C2H5O % CH2O þ CH3 (R25)

C2H5O % CH3CHO þ H (R26)

CH3CHOH % CH3CHO þ H (R27)

CH3CHOH % C2H3OH þ H (R28) Fig. 25. Stationary points on the (a) CH3CHOH þ O2 and on the (b) CH2CH2OH þ O2
potential energy surfaces.
Reprinted from Zádor et al. [339] with permission from Elsevier.
CH2CH2OH % C2H4 þ OH (R29)

CH2CH2OH % C2H3OH þ H (R30)

At lower temperatures (below 1000 K) the reactions between a-
and b-hydroxyethyl and O2 are important because the aforemen-
tioned decomposition channels are slow. Rate coefficients for these
reactions were studied experimentally at low pressures (<10 mbar)
by Miyoshi et al. [415] at room temperature using the laser flash
photolysis-photoionization mass spectrometry method, and by
Grotheer et al. [416] in the temperature range of 300e682 K using a
discharge flow reactor with a low electron energy mass spec-
trometer. Zádor et al. [339] recently conducted a theoretical anal-
ysis and experimental product study of the reaction of
hydroxyethyl radicals with O2. Their experiments studied the pri-
mary products of the reaction (not rate coefficient measurements)
initiated by an excimer laser in a heated flow reactor coupled with
tunable synchrotron photoionization mass spectrometry. Pressure-
dependent rate coefficients and branching ratios were computed
(and not measured) in the temperature range of 255e1000 K using
high-level ab initio potential energy surface calculations and state-
of-the-art master equation methods. Around the same time as
Zádor et al. conducted their work, the reactions of a-hydroxyethyl
with O2 were also studied theoretically by da Silva et al. [340]. The
potential energy surfaces of these reactions are complex, as shown
in Fig. 25 from Zádor et al. [339], but theoretical studies help to
identify the dominant pathways. Both theoretical studies are in
excellent agreement regarding the CH3CHOH þ O2 reaction,
concluding that it proceeds through an activated a-hydroxy-eth-
ylperoxy adduct that rapidly decomposes to acetaldehyde þ HO2
(R31). The predominance of (R31) was confirmed experimentally
by Zádor et al. [339]. Furthermore, the decomposition reaction
occurs with such a low barrier that conventional low-temperature
chain branching pathways are unimportant. The potential energy
surface (PES) for the b-hydroxyethyl þ O2 reactions (Fig. 25) is also
complicated, but Zádor et al.’s [339] theoretical and experimental
results indicate two pathways as dominant. First, as previously
discussed, the Waddington pathway is shown to be important,
wherein a b-RO2 radical is stabilized and then quickly decomposes
to two formaldehyde and one OH radical (R32). The second
important reaction is a concerted elimination reaction leading to
the formation of ethenol and HO2 radicals (R33). The branching
ratio between (R32) and (R33) is still uncertain due to the multi-
reference character of the transition states
CH3CHOH þ O2 % CH3CHO þ HO2 (R31)
CH2CH2OH þ O2 % OOCH2CH2OH % 2 CH2O þ OH (R32)
CH3CHOH þ O2 % C2H3OH þ HO2 (R33)
The present analysis utilizes the ethanol mechanism by origi-
nally presented by Metcalfe et al. [314] and recently modified by
Mittal et al. [187]. This mechanism is chosen due to its compre-
hensive development and testing for ethanol combustion. In their
papers [187,314], the authors present ethanol model comparisons
against RCM ignition delay data, (825e985 K, 10e50 bar, and
f ¼ 0.3e1.0) shock tube ignition delay data by Heufer and Olivier
[174] (down to 800 K, 13e40 bar, f ¼ 1.0); JSR speciation data from
LePlat et al. [177] (890e1250 K, 1 bar, f ¼ 0.25e2) and Dagaut and
Togbé [169] (770e1220 K, at 10 bar, f ¼ 0.6e2); flow reactor
speciation data from Li et al. [161] (1045e1080 K, 1.7e3.0 bar) and
Norton and Dryer [133] (1020e1120 K initial, 1 bar, f ¼ 1.18); pre-
mixed laminar flame speeds from Egolfopoulos et al. [159] (1 bar,
f ¼ 0.6e1.8), van Lipzig et al. [178] (1 bar, f ¼ 0.6e1.5), and Gülder
76 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
[129] (1e8 bar, f ¼ 0.7e1.4); and premixed laminar flame speciation
data from Leplat et al. [177] (500e1800 K, 50 mbar, f ¼ 0.75e1.25).
The laminar flame speeds of ethanol/air mixtures have been
measured in a number of studies, as noted in Table 3, and there is
reasonably good agreement across the various measurements ob-
tained at atmospheric pressure and a range of unburned gas tem-
peratures. Metcalfe et al. [314] and Mittal et al. [187] have shown
that their ethanol model can accurately reproduce laminar flame
speeds data at 298 K [129,159,178], 338 K [178], 363 K [159,178],
428 K [159], and 453 K [159]. Not presented in their paper is the
performance of the model at elevated pressures. Fig. 26 presents
the experimental data from Bradley et al. [172], which covers
pressures from 1 bar up to 14 bar and a range of equivalence ratios.
Their maximum equivalence ratio achievable at higher pressures
was constrained by the safe operating pressure limit of their
combustion vessel. The data indicates a decrease in flame speed as
pressure increases, a qualitative trend that is accurately reproduced
by the model. The quantitative agreement between the simulations
and measurements are in need of improvement. At 1 bar, the pre-
sent model simulates higher flame speeds than the measured data,
which is a discrepancy not observed when comparing with data
from other facilities [159,314]. At 2 bar, the model simulates higher
flame speeds than the data by up to 10 cm/s, whereas at higher
pressures the model simulations are generally within 5 cm/s of the
experimental data. The sensitive reactions controlling the model
simulations are small molecular reactions [314] and not specific to
ethanol chemistry. It should be noted that the ethanol model pro-
posed by Leplat et al. [177] provides much better quantitative
agreement with the data from Ref. [172] at all pressures.
The homogenous ignition delay of ethanol/air has been studied
at a range of pressures and temperatures of relevance to internal
combustion engines using both shock tubes and RCMs. A recent
shock tube ignition study by Lee et al. [181] utilized schlieren im-
aging to show that pre-ignition reactions cause significant pressure
rises prior to the main ignition event, and these pressure rises must
be well characterized for comparison against chemical kinetic
modeling simulations. Fig. 27 presents experimentally measured
Fig. 26. Laminar flame speeds for ethanol/air mixtures at 1e14 bar pressures and
358 K. Symbols are experimental measurements by Bradley et al. [172] and lines are
simulations.
Fig. 27. Ignition delay times of ethanol/air mixtures at stoichiometric conditions.
Symbols are experimental data from Cancino et al. [173] (shock tube at 10, 30, and
50 bar) and Lee et al. [181] (RCM at 40 bar and ST at 80 bar) and lines are simulations.
Shock tube simulations account for pre-ignition pressure rises.
ethanol/air ignition delay times at a range of pressures using shock
tubes [173,181] and RCMs [181] along with chemical kinetic
modeling simulations that account for shock tube pressure rises
prior to ignition. The RCM measurements at 30 bar exhibit Arrhe-
nius behavior below 1000 K, which is extended to higher temper-
atures in the shock tube measurements. The discrepancy between
measured ignition delay times in the temperature region covering
both RCM and shock tube experiments is attributed to the afore-
mentioned pre-ignition pressure rise phenomenon in shock tubes.
The model is able to well reproduce both RCM and shock tube when
facility effects are included, along with the experimentally
observed decreasing ignition delay times with increasing pressure.
The lack of NTC behavior in ethanol is consistent with its high
research octane number. The combustion chemistry contributing to
these features is discussed later.
Speciation measurements during oxidation of ethanol have
been studied extensively in flow reactors, stirred reactors, non-
premixed flames, and premixed flames using a variety of diag-
nostic techniques (refer to Table 3). Here, the ethanol kinetic model
is compared with JSR data at 10 bar from Dagaut and Togbé [169]
and low-pressure premixed flame speciation measurements using
MBMS by Leplat et al. [177]. Only selected species profiles are
presented in Fig. 28 to highlight some important features of ethanol
oxidation and the model’s performance. The low-pressure pre-
mixed flames are burner stabilized, allowing the experimentally
measured temperature profile to be used as a boundary condition
for the simulation. In both the JSR and low-pressure flame, ethanol
is oxidized to form acetaldehyde and ethylene, which are primary
b-scission products. The model accurately reproduces the qualita-
tive formation of these intermediates in the JSR and their con-
sumption, but ethanol reacts at lower temperatures to form
acetaldehyde in the model than in the experiments. Ethylene
concentrations are correctly simulated in both the JSR and with the
low-pressure premixed flame. Later, we highlight some of the
important reactions controlling these products, namely hydrogen
abstractions by OH and HO2 radicals. Ethenol (C2H3OH) is an
interesting species that was not measured in the JSR or ethanol
low-pressure flames due to experimental limitations; however, Xu
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 77

Fig. 28. (Left) Jet-stirred reactor speciation profiles for ethanol oxidation [169] at 10 bar, f ¼ 1.0, s ¼ 0.7 s, 2000 ppm C2H5OH, 6000 ppm O2, and balance N2. (Right) Low-pressure
flame speciation profiles [177] for ethanol/O2/Ar at 50 mbar and f ¼ 0.75. Lines are simulations. Simulated flame profiles are shifted by 0.5 mm away from the burner surface.

et al. [179] recently acquired speciation measurements using mo-
lecular beam flame-sampling photoionization mass spectrometry.
Ketene (CH2CO) has also been measured in low-pressure flames
[177,179]. Simulations of ethenol and ketene under the low-
pressure premixed flame conditions of Xu et al. [179] were not
possible because their experimentally measured temperature
profiles are not in agreement with those used for their simulations,
and no discussion of this discrepancy is offered in their paper.
Therefore, simulations of ethenol and ketene are presented under
the flame conditions of Leplat et al. and presented in Fig. 28. The
chemistry contributing to the formation of these intermediates is
discussed later.
The general reaction scheme for ethanol combustion in pre-
mixed flames, batch reactors, and stirred and flow reactors is pre-
sented in Fig. 29. Ethanol consumption is initiated by hydrogen
abstraction by radicals (denoted as R), such as OH, HO2, and H. As
mentioned earlier, the branching ratio of hydrogen abstraction by
OH favors the formation of CH3CH2OH with CH3O and CH2CH2OH
being less important channels. At high temperatures, these radicals
undergo b-scission wherein CeC and CeO bonds are favored,
leading to the formation of stable intermediates, including
ethylene, acetaldehyde, and formaldehyde. Highlighted in the
figure is also the b-scission of a CeH bond in CH3CHOH leading to
the formation of ethenol, a pathway responsible for producing this
compound in premixed ethanol/O2 flames (Fig. 28). The acetalde-
hyde intermediate is primarily consumed via hydrogen abstraction
from the aldehydic carbon; the subsequent radical then de-
composes to form carbon monoxide. A minor pathway of acetal-
dehyde consumption proceeds via abstraction from the methyl
group leading to ketene production. This is the primary route to
ketene and explains why its maximum concentration in flames
(Fig. 28) occurs after the acetaldehyde maximum. As shown earlier,
ethylene concentrations are correctly simulated in the JSR and in
premixed flames (Fig. 28). This agreement is due to the branching

Fig. 29. Reaction path diagram for ethanol combustion. R denotes a radical, such as OH, HO2, and H. Low-temperature pathways are shown in green. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
78 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
ratio of hydrogen abstraction by OH. The model by Metcalfe et al.
[314] utilizes rate coefficients from Sivaramakrishnan et al. [366],
which strongly favors the formation of a-hydroxyethyl (CH3CH2OH)
(Table 6), while Mittal et al. [187] reduced the branching ratio to a-
hydroxyethyl by 25% and increased the branching to b-hydrox-
yethyl radical by 25%. Calculations by Zheng and Truhlar [314,410]
give lower weighting to the formation of b-hydroxyethyl
(CH2CH2OH). Fig. 28 presents simulations using the C2H5OH þ OH
rate coefficients proposed by Tran et al. [184] that have total rate
coefficients in agreement with experimental results and branching
ratios similar to Zheng and Truhlar [410]. The decreased branching
ratio assigned to the b-site decreases ethylene production and in-
creases acetaldehyde formation. Simulations were also conducted
to determine the importance of ethenol under the JSR and flame
conditions in Fig. 28. Ethenol was simulated in very low concen-
trations in the JSR, but simulated low-pressure flame concentra-
tions were found to be above 1000 ppm. A reaction path analysis
showed that under the 10 bar JSR conditions, the decomposition of
CH2CH2OH is primarily to C2H4 þ OH, whereas in the low-pressure
flame, the pathway to C2H3OH þ H equally as important. Thus, the
pressure dependence of these reactions alters the branching ratio
of CH2CH2OH decomposition, which is a phenomenon that has not
been studied in great detail to date.
At low temperatures (i.e., below 1000 K), the a- and b-hydrox-
yethyl radicals can react with O2 to form products. As mentioned
previously, the primary product from the a-hydroxyethyl channel is
acetaldehyde þ HO2. These reactions control the low-temperature
ignition behavior of ethanol/O2 mixtures, especially at elevated
pressures. The low energy barrier for the chemically activated a-
hydroxyethyl þ O2 channel precludes conventional peroxy stabili-
zation and isomerization channels that eventually lead to chain
branching processes in alkanes (e.g., ethane, propane, etc.) [340].
The b-hydroxyethyl þ O2 channel proceeds through stabilization of
a b-peroxy (b-RO2) radical that either undergoes a concerted
elimination to form ethenol þ HO2 or a Waddington isomerization
and decomposition channel to form two formaldehydes þ an OH
radical. The b-channels are of minor importance in combustion
systems because initial hydrogen abstractions by OH radicals
strongly favor the a site at lower temperatures. The absence of an
OH radical chain branching route in ethanol explains its lack of low-
Fig. 30. ‘Brute force’ sensitivity of ignition delay times at 25 bar, three temperatures, and three equivalence ratios.
Reprinted from Mittal et al. [187] with permission from Elsevier.
temperature reactivity, and this phenomenon will be shown to be
important in larger alcohols as well.
Fig. 30 from Ref. [187] presents a ‘brute force’ sensitivity analysis
on shock tube ethanol/air ignition delay times at 30 bar, 1050 K, and
stoichiometric conditions. These results are consistent with the
sensitivity analysis conducted in other studies in shock tubes,
RCMs, and JSRs [177,181,279]. The ‘brute force” sensitivity analysis
quantifies the change in ignition delay time from a doubling and
halving of each reaction rate coefficient. Similar to those previously
shown for methanol/air mixtures, the ignition delay is strongly
promoted by the hydrogen abstraction by HO2 radicals and H2O2
decomposition. The importance of the reactions involving
C2H5OH þ HO2 under combustion-relevant conditions is further
highlighted in Figs. 27 and 28, wherein the rates for abstraction
from the hydroxyl, a, and b sites are replaced by those proposed by
Tran et al. [184]. Recall from Fig. 24 that the total rate coefficient
employed by Mittal et al. [187] is approximately a factor of 2 higher
than that proposed by Tran et al. [184]. Utilizing the latter rate
coefficient slows the reactivity of ethanol in the JSR and improves
agreement with the experimental data. However, the slower rate
coefficient worsens the agreement of ignition delay times at 10 bar
(Fig. 27) and higher pressures. Thus, direct experimental mea-
surements and/or high-level theoretical calculations are needed to
constrain this rate coefficient.
4.7. The combustion chemistry of propanol isomers
The two isomers of C3 alcohols are n- and iso-propanol. These
fuels have received little attention from the combustion chemistry
community with few experimental and kinetic modeling studies
available in the literature (refer to Table 3). This lack of combustion
data together with a scarcity of fundamental mechanistic and ki-
netic rate coefficient studies (refer to Table 5) has hindered progress
in the development of comprehensive chemical kinetic models for
the propanol isomers. Frassoldati et al. [195] and Man et al. [200]
have presented kinetic models for the propanol isomers using
primarily analogies with ethanol and the butanol isomers to assign
rate coefficients. For the present analysis, we use the sub-
mechanism recently proposed by Man et al. [200], which is
essentially an updated version the propanol isomers kinetic model
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
presented by Johnson et al. [193]. We also added several important
low temperature reaction pathways based the reaction classes
explained previously and rate rules derived from the modeling of
butanol isomers [260].
Comparing the bond dissociation energies for n- and iso-prop-
anol with those of other alcohols allow the estimation of rate co-
efficients for unimolecular decomposition reactions. The water
elimination channels are important routes of fuel consumption at
high temperatures, and the rate coefficients for these reactions are
estimated based on analogies to n-butanol and 2-butanol
[200,260]. Similarly, other CeC bond scissions in the propanol
isomers can be assigned rates based on analogous reactions for the
butanol isomers. The rate coefficients of H-atom abstraction re-
actions from the propanol isomers are not well studied. Abstrac-
tions from n-propanol proceed from the hydroxyl site (R34), a
(secondary, (R35)), b (secondary, (R36)), or g (primary, (R37)). Ab-
stractions from iso-propanol proceed from the hydroxyl site (R38),
a (tertiary, (R39)), or two b sites (primary, (R40)). As shown in
Table 5, there is only one rate coefficient measurement of
abstraction by OH radical at combustion relevant temperatures,
performed by Dunlop and Tully [372]. Theoretical reaction rate
studies for hydrogen abstraction from the propanol isomers are
lacking. Thus, the site-specific rate coefficients for abstraction re-
actions by important radicals (e.g., H, OH, and HO2) must be derived
using analogy with reaction rate coefficients established for n-
butanol and 2-butanol [200,260]. This approach is tested for the
case of iso-propanol þ OH in Fig. 31, wherein experimental mea-
surements of the total rate coefficients from Dunlop and Tully [372]
are compared with estimates based on analogy with 2-butanol
[200,260]. The method of estimation using EvansePolyani corre-
lations [411] is within 25% of the experimentally measured values,
which indicates the appropriateness of such techniques for esti-
mating rate coefficients.
nC3H7OH þ R % C3H7O þ RH (R34)
nC3H7OH þ R % CH3CH2CHOH þ RH (R35)
Fig. 31. Comparison of measured (symbols) and estimated (line; see main text for
source) total reaction rate coefficients for hydrogen abstraction from iso-propanol by
OH radical. Measurements are from Dunlop and Tully [372].
79
nC3H7OH þ R % CH3CHCH2OH þ RH (R36)
nC3H7OH þ R % CH2CH2CH2OH þ RH (R37)
iC3H7OH þ R % C3H7O þ RH (R38)
iC3H7OH þ R % (CH3)2COH þ RH (R39)
iC3H7OH þ R % CH3(CH2)CHOH þ RH (R40)
The laminar flame speeds of the propanol isomers in air have
been measured in a few studies. Beeckmann et al. [154] noted that
the n-propanol chemical kinetic model proposed by Johnson et al.
[193] could not well reproduce laminar flame speeds measure-
ments by Veloo et al. at 1 bar [198] or their own 10 bar data [154].
Fig. 32 displays experimental [198] and simulated laminar flame
speeds for n-propanol/air and iso-propanol/air mixtures at 1 bar.
The present chemical kinetic model well reproduces experimen-
tally measured values for both fuels across the entire range of
tested conditions. The simulations and experiments indicate that
iso-propanol is significantly less reactive than n-propanol, which
indicates that methyl substitution decreases flame speeds. This
effect of branching on flame speed is well established in alkane
combustion; increased branching decreases formation of reactive
H radicals and increases formation of stable allyl radicals [109,417].
The homogenous ignition delay times of n-propanol/air and iso-
propanol/air mixtures have been studied at a limited number of
conditions, primarily at higher temperatures and lower pressures
[150,193,196,200]. Ignition studies at engine-relevant conditions
(e.g., lower temperatures and higher pressures) are not available for
testing chemical kinetic models. Fig. 33 presents comparisons of
kinetic modeling simulations and experimentally measured shock
tube ignition delay times for n-propanol/air and iso-propanol/air
mixtures at pressures ranging from 1.2 to 16 bar, temperatures above
1100 K [200], and equivalence ratios ranging from lean to rich. The
shock tube measurements display Arrhenius behavior across the
Fig. 32. Laminar flame speeds for n-propanol/air and iso-propanol/air mixtures at
1 bar and 343 K. Symbols are experimental measurements by Veloo et al. [198] and
lines are simulations.
80 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Fig. 33. Ignition delay times of n-propanol/air (left) and iso-propanol/air (right) mixtures at stoichiometric conditions. Symbols are shock tube ignition delay data from Man et al.
[200] (shock tube at 1.2, 4, and 16 bar) and lines are simulations.

entire range of conditions. iso-Propanol is notably slower to ignite
(i.e., less reactive) that n-propanol at the same conditions. These
features, as well as equivalence ratio effects, are well reproduced by
the kinetic modeling simulations. The present set of tested condi-
tions does not allow us to draw conclusions on the lower tempera-
ture (i.e., below 1000 K) reactivity of the propanol isomers.
The general reaction scheme for n-propanol and iso-propanol
combustion in premixed flames and batch reactors is presented in
Figs. 34 and 35, respectively. The combustion of the propanol iso-
mers is initiated by hydrogen abstraction by radicals (e.g., OH, HO2,
H, CH3, etc.). As in the case of ethanol, the hydrogen abstraction
reactions favor the formation of a-hydroxypropyl radicals. At high
temperatures, the b-scission products of fuel radicals from n-
propanol are ethylene, propene, ethenol, propanal (i.e., propion-
aldehyde), and formaldehyde. Propanal further decomposes to
form CO and ethyl radical (C2H5). The b-scission products of fuel
radicals from iso-propanol are propene, ethanol, acetaldehyde, and
acetone. Subsequent decomposition of propene and acetone both
form resonantly stabilized radicals, which inhibit reactivity.
Therefore, iso-propanol exhibits lower flame speeds and longer
high temperature ignition delay times that n-propanol because a
larger concentration of stable intermediates are formed. At low
temperatures (i.e., below 1000 K), the fuel-derived radicals react
with O2 to form a range of products. The primary product from n-
propanol’s a-hydroxypropyl channel is propanal þ HO2, while iso-
propanol’s a-hydroxypropyl channel yields acetone þ HO2. For both
propanol isomers, the b-hydroxypropyl þ O2 channel proceeds
through stabilization of a b-peroxy (b-RO2) radical that undergoes a
Waddington isomerization and decomposition channel to form one
formaldehyde, one acetaldehyde, and an OH radical.

n-

Fig. 34. Reaction path diagram for n-propanol combustion. R denotes a radical, such as OH, HO2, and H. Low-temperature pathways are shown in green. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 35. Reaction path diagram for iso-propanol combustion. R denotes a radical, such as OH, HO2, and H. Low-temperature pathways are shown in green. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
4.8. The combustion chemistry of butanol isomers
The combustion chemistry of butanol isomers has been an area
of intense research activity in the recent six years. The primary
focus of this work has been on n-butanol because industrialists
have targeted it as an alternative fuel for deployment in the fore-
seeable future [418]. Nevertheless, the other butanol isomers are
also gaining industry attention, and studying all the butanol iso-
mers as a family of fuels can elucidate unique structural effects (e.g.,
methyl and OH substitution) on the global combustion properties
and combustion emission profiles of alcohols.
The first chemical kinetic model for n-butanol combustion was
developed by Dagaut and coworkers [208,419] with comparisons
against JSR speciation data (800e1100 K and 10 bar). Around the
same time, Moss et al. [207] conducted high-temperature shock
tube ignition delay measurements (1200e1800 K and 1e4 bar) and
proposed a chemical kinetic model for all the four isomers of
butanol using the EXGAS software [207,316]. Later, Sarathy et al.
[211] extended the comparisons of Dagaut et al.’s butanol model
[208,419] to atmospheric pressure measurements of JSR speciation,
premixed laminar flame speed, and counterflow diffusion flame
speciation. Black et al. [212] also proposed an n-butanol chemical
kinetic model that was compared against Dagaut and coworker’s
JSR data [208] and their own shock tube measurements (1100e
1800 K, 1e8 bar). The aforementioned n-butanol combustion
studies laid important foundations, but all were limited in their
targets because of the unavailability of data in various reactive
environments. The first attempts to model a large set of experi-
mental data for n-butanol were made by Harper et al. [121] and
Grana et al. [213]. Harper et al. [121] utilized the automatic Reaction
Mechanism Generator (RMG) software [420,421] to generate an n-
butanol combustion model capable of reproducing JSR speciation,
81
iso-propanol
iso-propoxy
counterflow diffusion flame species profiles, high-temperature
shock tube ignition delay times, doped methane diffusion flame
species profiles, and n-butanol pyrolysis experiments. Subse-
quently, the RMG software was utilized by Van Geem et al. [216] to
develop chemical kinetic models for all four butanol isomers. Grana
et al. [213] also developed a hierarchical chemical kinetic model
with detailed sub-mechanisms for all four butanol isomers. Their n-
butanol model was also widely compared against experimental
speciation data from JSRs and counterflow diffusion flames, pre-
mixed laminar flame speeds, and high-temperature shock tube
ignition delay times. Furthermore, Grana et al. [213] also included
models for the other butanol isomers with comaparisons presented
for all four isomers against high-temperature shock tube ignition
delay data [207], iso-butanol species profiles in counterflow diffu-
sion flames, and tert-butanol oxidation in a flow reactor [133].
Despite the noteworthy modeling studies prior to 2011, the
models did not include the low-temperature peroxy chemistry
needed to simulate ignition at engine-relevant conditions (e.g., low
temperatures and high pressures). Again, the limiting factor was
the lack of experimental data at such conditions to motivate such
modeling studies. Heufer et al. [219] were the first to conduct shock
tube ignition delay measurements of n-butanol at low tempera-
tures and high pressures (10e42 bar and 770e1250 K). Weber et al.
[104] later studied the ignition of n-butanol in an RCM at elevated
pressures and low to intermediate temperatures (15 and 30 bar,
675e925 K, and f ¼ 0.5, 1.0, and 2.0). Both these studies demon-
strated that butanol models simulated longer ignition delay times
(by more than a factor of 10) at temperatures below w950 K,
suggesting that important reaction pathways were missing from
the models. Shortly thereafter, Vranckx et al. [223] obtained addi-
tional n-butanol shock tube ignition data near 80 bar (795 Ke
1200 K). Their experimental results showed that n-butanol exhibits
82 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
NTC behavior at elevated pressures similar to alkanes, thus moti-
vating the researchers to develop a simplified sub-mechanism for
butylperoxy formation capable of simulating their experimental
data. This simplified peroxy mechanism was later revised in a
comprehensive modeling study by Sarathy et al. [260], which
included detailed low-temperature reaction pathways for all
butanol isomers. The model by Sarathy et al. [260] is capable of
accurately simulating ignition of n-butanol, iso-butanol, 2-butanol,
and tert-butanol at low temperatures and elevated pressures, as
will be demonstrated later. For the iso-butanol isomer, Merchant et
al. have published models of comparable accuracy [232,233] that
also includes species and reactions leading to formation of aromatic
byproducts. Furthermore, the model developed by Merchant et al.
was developed independently yet well predicts a wide range of
experimental data, and thus demonstrates the ability to formulate a
predictive model a priori.
The above background discussion exhibits the data-driven
methodology that led to improved models for low-temperature
combustion of the butanol isomers. As mentioned previously, the
low-temperature ignition behavior of methanol, ethanol, and
propanol isomers can be modeled successfully without the need for
alkane-like peroxy chemistry. The following sections further
describe the important reactions in the oxidation of the butanol
isomers, including thermal decomposition, hydrogen abstractions,
and low-temperature reaction pathways.
The unimolecular thermal decompositions of the butanol iso-
mers proceed primarily via dehydration reactions and CeC bond
scissions. CeO bond scissions are however negligible because their
BDEs are approximately 10 kcal higher than those of CeC bonds.
Rosado-Reyes and Tsang [387] used a single pulse-shock tube to
perform the first direct measurement of n-butanol dehydration.
The authors also estimated CeC bond scission rate coefficients
using their measured GC-FID/MS results. They showed that previ-
ous estimates used in combustion models [207,208,213] for these
reactions were not in agreement with their rate coefficients. A
notable conclusion from their work was the lack of pressure
dependence observed for these reaction rate coefficients (1.5e
6.5 bar), which they verified by master equation calculations. Thus,
these reactions are at their high-pressure limit in practical com-
bustion environments. Cai et al. [225] recently performed a theo-
retical study on the unimolecular decomposition of n-butanol using
variational transition state theory with master equation modeling
to provide temperature- and pressure-dependent rate coefficients.
At atmospheric pressure and in the temperature range of 850e
1150 K, the rate coefficients for n-butanol dehydration calculated by
Cai et al. [225] are a factor of 2e4 greater than those measured by
Rosado-Reyes and Tsang [387].
The rates for thermal decomposition of iso-butanol [390], 2-
butanol [388], and tert-butanol [203,204,386] have also been
measured experimentally in single-pulse shock tubes. Rosado-
Reyes et al. [390] showed that the dehydration rate coefficients
of iso-butanol calculated by themselves and by Zhou et al. [422]
were within a factor of 2 of experimental measurements, and
that the pressure effects were minimal. The decomposition rate
coefficient for 2-butanol was measured by Rosado-Reyes and
Tsang [388], and their measured dehydration rate coefficients
were in good agreement with the ab initio calculations of El-Nahas
et al. [423]; however, the measured CeC bond scission rate co-
efficients were notably different than those from calculations
[423]. The measured rate coefficients for tert-butanol dehydration
by Tsang [203] were in excellent agreement with the experimental
measurements of Lewis et al. [204] and the rate coefficients
calculated from theory [386]. Rosado-Reyes et al. [390] also
concluded that the rate coefficient of fuel alcohol dehydration
reactions is controlled primarily by the available number of
hydrogen atoms for water elimination, and not by the position of
the OH group (primary, secondary, or tertiary). Shock tube species
time-history experiments by Stranic et al. [111,112] provide
experimental data under pyrolysis conditions that are sensitive to
unimolecular decomposition rates. A recent modeling study by
Vasu and Sarathy [238] showed that the majority of data from
Stranic et al. could by accurately simulated by adopting the
aforementioned unimolecular decomposition rate constants pro-
posed by Rosado-Reyes et al.
H-atom abstraction reactions from n-butanol proceed from one
of five sites (a, b, g, d, or hydroxyl). 2-butanol (sC4H9OH) also has
five unique abstraction sites with a hydroxyl site (R41), a site
(secondary, (R42)), two unique b sites (a primary, (R43), and sec-
ondary, (R44)), and a g site (primary, (R45)). iso-Butanol has three
unique abstraction sites (a, b, g, and hydroxyl), whereas tert-
butanol has two (three bs and a hydroxyl).
sC4H9OH þ R % C4H9O þ RH (R41)
sC4H9OH þ R % CH3CH2C(CH3)OH þ RH (R42)
sC4H9OH þ R % CH3CH2CH(CH2)OH þ RH (R43)
sC4H9OH þ R % CH3CHCH(CH3)OH þ RH (R44)
sC4H9OH þ R % CH2CH2CH(CH3)OH þ RH (R45)
The H-atom abstraction rate coefficients by H radicals from the
butanols have not been measured experimentally. Ratkiewicz et al.
[424] and Carstensen and Dean [302] presented ab initio calcula-
tions for all four isomers of butanol. The latter authors explained
that the OH group does not affect the rate coefficients of H-atom
abstraction by H radical atoms after the b CeH site, and the rate rule
converges to that for hydrocarbons. Based on this assumption,
Sarathy et al. [260] assigned the H-atom abstraction rate coefficient
by H radicals from the a carbon and hydroxyl moiety based on the
ethanol þ H work of Sivaramakrishnan et al. [366]. The b-carbon Ce
H BDE in n-butanol is between that of a secondary and primary Ce
H BDE of n-butane; the rate of abstraction was therefore calculated
as the average of the two [212]. The abstraction rates for sites more
than two carbons away from the hydroxyl group (e.g., g and d car-
bon atoms in n-butanol) were taken to be equal to analogous
abstraction rates from secondary and primary carbon sites of n-
butane [425].
Experimentalists and theoreticians have recently studied
hydrogen abstraction by OH radicals in all the butanol isomers. The
rate coefficients for all these isomers have been measured from low
to high temperatures, as shown in Table 5. The total rate of n-
butanol þ OH at high temperatures (above 900 K) measured by
Vasu et al. [380] and Pang et al. [381] are in good agreement with
each other. Subsequent high-temperature studies (above 900 K) by
Pang et al. on iso-butanol þ OH [382] and 2-butanol þ OH [383]
have also confined these total rate coefficients within narrow un-
certainty limits. Atmospheric chemistry researchers have also
studied butanol þ OH reactions at temperatures generally below
400 K. McGillen et al. [385] recently measured rate coefficients of
hydrogen abstraction by OH radicals for all four butanol isomers at
low temperatures, and their results showed excellent agreement
with previous measurements [373,376e379]. Thus, it has become
possible to estimate the total rate coefficient for all butanol isomers
across low to high temperatures (220e1800 K), including the in-
termediate range of 400e1000 K where no measurements are
available. However, less certain are the branching ratios of
hydrogen abstraction reactions from the a, b, g, and d CeH sites and
the hydroxyl moiety, because direct measurements are not
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
available. Theoretical calculations [426e429] have been performed
to determine these branching ratios, but they are often unreliable
because their total rate coefficients do not match experimental data
[260,385]. These reactions are particularly challenging to calculate
due to very low energy barriers, the large number of butanol con-
formers, pre- and post-reaction complexes, and the theoretical
treatment of the various hindered rotors. For this reason, Sarathy
et al. [260] indirectly estimated site-specific rate coefficients by
combining previous theoretical calculations, analogies with al-
kanes, and EvansePolyani correlations [411]. Their estimated rate
coefficients were shown to agree (i.e., within a factor of 2) with low-
and high-temperature rate coefficient measurements, and they
enabled accurate simulations of low-temperature ignition delay
times sensitive to butanol þ OH reactions [260]. Recently, McGillen
et al. [385] (Fig. 36) employed an elegant approach of combining
experimental rate coefficient measurements, room temperature
end-product yields, and modified structureeactivity relationships
(SAR) of Bethel et al. [430] to derive self-consistent, site-specific
rate coefficients for all four butanol isomers. The rates recom-
mended by McGillen et al. [385] are yet to be tested in compre-
hensive combustion models of the butanol isomers. Future
modeling studies should therefore make an effort to utilize them.
Hydrogen abstraction from butanol isomers by HO2 has never
been measured experimentally. Sarathy et al. [260] used a combi-
nation of theoretical calculations and estimations to determine
these rates. The H-atom abstraction rates by HO2 radicals were
based on the ab initio calculations (CCSD level of theory) for n-
butanol þ HO2 by Zhou et al. [326]. Their calculations considered
primary effects (e.g., CeH BDEs) and secondary effects (e.g., pre-
reaction complexes and transition states exhibiting hydrogen
bonding) on the rate coefficient. Sarathy et al. [260] multiplied the
a-channel rate coefficient by a factor of 2.5, to obtain better
agreement with intermediate shock tube ignition delay experi-
ments. EvansePolanyi type correlations with the n-butanol þ HO2
Fig. 36. Total and site-specific rate coefficients for butanol þ OH reactions proposed by McGillen et al. [385]. Black circles are low-temperature experimental measurements from
McGillen et al. [385] and red circles are high-temperature experimental data from Pang et al. [381e383]. Blue, green, and magenta circles represent end-product yields from various
studies, as described by Ref. [385].
Reprinted from McGillen et al. [385] with permission from ACS Publications.
83
system were used to estimate abstraction rates for the other
butanol isomers. Their estimations derive abstraction rate co-
efficients based on the proximity of CeH sites to the hydroxyl
moiety (e.g., a, b, g, etc.). In this way, the effects of hydrogen-
bonded transition state complexes on the rate coefficients (e.g.,
entropy effects) are indirectly captured. The authors [260] found
this approach to work well for iso- and 2- butanol, but not for tert-
butanol, wherein the rate expression for H-atom abstraction by
HO2 from a primary CeH bond of n-butane was used with the A-
factor modified to account for reaction path degeneracy. The rates
of hydrogen abstraction from the butanol isomers by HO2 were
consistent with those previously mentioned for methanol, ethanol,
and n-propanol, showing that abstraction from the a-site is
predominant.
At high temperatures, the various C4H9O radicals formed from
n-, 2-, iso-, and tert-butanol react via thermal decomposition (i.e.,
b-scission reactions) and unimolecular isomerization reactions.
Isomerization reactions are favored for 5- and 6-member transition
state rings, which limits their importance to H-atom migration
reactions between the g or d site and the hydroxyl site (i.e., g-rad or
d-rad to O-rad). Isomerization reactions have been studied theo-
retically in n-butanol’s C4H9O radicals by Zheng and Truhlar [431],
Xu et al. [432], and Zhang et al. [433], with reasonable agreement
between the studies. Experimental or theoretical studies of isom-
erization reactions involving C4H9O radicals from 2-, iso-, and tert-
butanol were not found. Studies on b-scission reactions for various
C4H9O radicals are also limited to the n-butanol system. Simmie
and Curran [434] theoretically studied the decomposition of bu-
tanol’s a-hydroxybutyl decomposition to ethenol þ ethyl,
butanal þ H, or butanol þ H. Recently, Zhang et al. [433] performed
a comprehensive theoretical study of the decomposition and
isomerization of n-butanol’s hydrobutyl and butoxy radicals. Their
calculations showed that the channel leading to ethenol þ ethyl in
the a-hydroxybutyl radical is dominant at all temperatures, which
84 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
agrees with the calculations of Simmie and Curran [434]. The b-
radical decomposition was studied theoretically using addition of
OH to 1-butene as an entrance channel and subsequent decom-
position, either back to the reactants or on to methyl þ 2-propenol.
The calculated rate coefficient for OH þ 1-butene was in very good
agreement with experimental studies at low temperatures [435].
Zhang et al. [433] found that the b- and g-hydroxybutyl radicals
decompose primarily to 1-butene þ OH and propene þ CH2OH,
respectively. Below 800 K, the d-radical can isomerize to form a
butoxy radical, which then decomposes to propyl þ CH2O. At higher
temperatures, the d-radical decomposes to ethylene þ CH2CH2OH.
The pressure-dependent rate coefficients calculated by Zhang et al.
[433] are recommended for use in chemical kinetic models for n-
butanol. Similar comprehensive theoretical studies are needed for
the other butanol isomers.
At lower temperatures (below 1000 K), reactions between
C4H9O radicals (from n-, 2-, iso-, and tert-butanol) and O2 become
important. Due to the number of carbon atoms, the possible low-
temperature reactions pathways in C4H9O þ O2 are numerous,
including concerted elimination, stabilization of hydroxybutylper-
oxy (RO2) radicals, and subsequent isomerization, cyclization, and
decomposition reactions. Welz et al. combined quantum-chemical
calculations and experimental measurements of product formation
to explore the low-temperature reaction mechanisms of hydroxy-
butyl radicals from n-butanol [346], iso-butanol [436], and tert-
butanol [436]. For example, Fig. 37 presents stationary points on
the PES for reactions of n-butanol’s a-hydroxybutyl and b-
hydroxybutyl radicals plus O2 with the most important low-
temperature products highlighted in red. The a-hydroxybutyl
radical reacts with O2 to form butanal þ HO2, a reaction similar to
that discussed previously for a-hydroxyethyl radicals. This reaction
proceeds through a shallow well, implying that stabilization of the
a-hydroxybutylperoxy radical intermediate is only possible at high
pressures. This concerted elimination reaction leading to an
aldehyde þ HO2 is the primary consumption pathway of a-
hydroxybutyl radicals derived from iso-butanol [436] and 2-
butanol. However, rate coefficients have not been measured
experimentally or calculated.
The b-hydroxybutyl radical from n-, 2-, iso-, and tert-butanol
reacts with O2 to form the stabilized b-hydroxybutylperoxy radical
(b-RO2), which is then subject to a variety of reactions. The most
important of these is the Waddington reaction, which involves a
six-membered ring isomerization to abstract an H atom from the
hydroxyl moiety (i.e., forming an alkylhydroperoxide alkoxy),
Fig. 37. PES for the a-hydroxybutyl þ O2 (left) and b-hydroxybutyl þ O2 (right) reactions. The most favorable pathways are highlighted in red (see main text in Ref. [346] for details).
Reprinted Welz et al. [346] with permission from ACS Publications.
followed by rapid decomposition. In the n-butanol system, the b-
RO2 Waddington pathway leads to propanal, formaldehyde, and
OH. These reactions are chain propagating and compete directly
with low-temperature chain branching pathways, thereby inhibit-
ing low-temperature reactivity. Sun et al. [344] conducted theo-
retical calculations on these Waddington reactions in the tert-
butanol and iso-butanol systems, showing their importance for the
production of important carbonyl products.
The g- and d-hydroxybutyl radicals from n-, 2-, iso-, and tert-
butanol also react with O2 to form stabilized RO2 radicals. These can
undergo concerted eliminations to form butenol þ HO2, cyclization
to form epoxy alcohols, internal H-atom migration to form butyl-
hydroperoxides (QOOH), and subsequent low-temperature chain
branching reactions. These pathways are largely unexplored, but
can be included in models based on analogies with low-
temperature oxidation schemes of alkanes. Welz et al. [346] also
identified a low-lying water elimination pathway for the con-
sumption of g- and d-QOOH radicals with a radical on the a site.
Their importance in the low-temperature oxidation schemes for
alcohols has not been rigorously tested in butanol combustion
models. Detailed kinetic rate coefficient studies using state-of-the-
art experimental and computational methods are needed to
develop accurate chemical kinetic models for low-temperature
oxidation of butanol and higher alcohols.
The butanol model utilized in the present analysis is that
developed by Sarathy et al. [260] for the four isomers of butanol
with minor modifications to unimolecular decomposition rate co-
efficients, as described recently by Vasu and Sarathy [238]. This
model has been comprehensively developed for combustion of
butanol isomers at low and high temperatures. The model pre-
sented in Refs. [232,233] has also been comprehensively tested
against iso-butanol data. In their paper [260], the authors present
comparisons against shock tube ignition delay data, JSR speciation
data, premixed laminar flame speeds, and low-pressure premixed
laminar flame speciation data.
The laminar flame speeds of n-, iso-, 2-, and tert-butanol/air
mixtures have been measured in a number of studies, as noted in
Table 6, and there is reasonably good agreement across the various
measurements obtained at atmospheric pressure. Recently, Wu
and Law [236] performed a thorough experimental study that
measured premixed laminar flame speeds of the four butanol
isomers at 1, 2, and 5 bar. The authors utilized the chemical kinetic
model developed by Sarathy et al. [260] to interpret their results,
as this model showed excellent agreement with the experimental
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
data (Fig. 38). The authors [236] found that n-butanol has the
fastest flame speed, iso-butanol and 2-butanol have similar flame
speeds, and tert-butanol has the slowest. Wu and Law [236]
further investigated the thermal and kinetic contributions to
flame speeds to rationalize the observed differences. Comparable
adiabatic flame temperatures and heat release profiles between
the fuels indicated that thermal effects cannot be responsible for
the variations in flame speeds. The underlying cause for differ-
ences in laminar flame speeds is attributed to formation of less-
Fig. 38. Premixed laminar flame speeds for the four butanol isomers in air at 1, 2, and
5 bar and various of temperatures. Symbols are data taken by Wu and Law [236] and
lines are simulations.
Reprinted from Wu and Law [236] with permission from Elsevier.
85
reactive, unsaturated branched intermediates in the case of iso-,
2-, and tert-butanol compared to the less-reactive straight-chain
intermediates formed from n-butanol. The latter decomposes
primarily to vinyl and methyl radicals, which accelerate flame
propagation. tert-Butanol and iso-butanol flames produce iso-
butene and branched oxygenates (e.g., branched enols and
acetone). iso-Butene is less reactive due to the formation of the
resonantly stabilized 2-methyl-allyl radical following H-atom
abstraction, which results in lower flame speeds [109,417,437].
Similar branched unsaturated oxygenates formed in iso- and 2-
butanol flames results in lower concentrations of reactive vinyl
and methyl radicals and higher concentrations of less reactive allyl
radicals [109], thus lowering flame speeds.
The homogenous ignition delay of the butanol isomers at high
temperatures has been studied by a number of experimentalists, as
shown in Table 6. Recently, Stranic et al. [108] studied the ignition
of n-, iso-, 2-, and tert-butanol at high temperatures (i.e., above
1000 K) and pressures ranging from approximately 1e50 bar (4%
fuel in Ar/O2 mixtures). Both experimental data and simulation
results using the model of Sarathy et al. [260] showed that n-
butanol is the most reactive, followed by 2-butanol, with iso-
butanol exhibiting similar reactivity, while tert-butanol is much
less reactive. Molecular dehydration reactions are important in
controlling the relative reactivity of the butanol isomers under
these high-temperature, high-dilution conditions. tert-Butanol is
the least reactive because molecular dehydration reactions form
the stable iso-butene intermediate. The ignition of butanol isomers
at low to intermediate temperatures and high pressures has not
been studied extensively. Shock tube measurements of butanol/air
mixtures at temperatures below 1000 K and elevated pressures
have not been performed on the four isomers of butanol. n-Butanol
has been studied under such conditions by Heufer et al. [219],
Stranic et al. [223], and Zhu et al. [240].
Fig. 39 displays the measured and simulated n-butanol ignition
delay times using conventional filling methods [219,223] and the
constrained reaction volume (CRV) strategy developed by Hanson
et al. [101] and applied by Zhu et al. [240]. The data obtained
using conventional filling methods are simulated using variable
volumes profiles that account for experimental pre-ignition
pressure rise, while simulations of the CRV data are conducted
under constant pressure conditions. In both cases, the model is
able to simulate the temperature, pressure, and equivalence ratio
dependences. It is interesting to note that significant low-
temperature reactivity of n-butanol is observed at pressures
above 20 bar, a phenomenon not observed in the smaller alcohols.
Therefore, low-temperature peroxy chemistry is needed in n-
butanol chemical kinetic models to simulate engine-relevant
ignition behavior. The ignition of all four isomers of butanol at
low and intermediate temperatures and elevated pressures has
been studied in an RCM by Weber et al. [105], as shown in Fig. 40.
Under such conditions, n-butanol is notably more reactive than
iso-, 2-, and tert-butanol. Variable volume simulations using the
model by Sarathy et al. [260] are in good qualitative agreement
with the experimental data, but improvements in quantitative
agreement are needed. The study by Weber et al. [105] concluded
that low-temperature peroxy chemistry is important to all
butanol isomers, and accurate rate coefficients in this network are
needed. More details on low-temperature reaction pathways are
discussed later.
Species evolving from the oxidation and pyrolysis of the butanol
isomers have been studied in flow reactors, stirred reactors, non-
premixed flames, and premixed flames using various diagnostic
techniques, as shown in Table 3. Most studies have focused on high-
temperature oxidation in flames and pyrolysis reactors. Recent
experimental and modeling studies by Cai et al. on n-butanol [225],
86 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Fig. 39. Measured ignition delay times in a ST (symbols) and simulations (lines). The left panel contains data from Refs. [219,223] at stoichiometric conditions using conventional
filling methods. The right panel contains data from Ref. [240] using the CRV method. The left panel is reprinted from Sarathy et al. [260] and the right panel is reprinted from Zhu
et al. [240] with permission from Elsevier.

2-butanol [235], and tert-butanol [224] have demonstrated the
ability to reproduce high-temperature combustion and pyrolysis
species. The authors combined quantum chemistry calculations to
obtain rate coefficients for important unimolecular decomposition
and b-scission reactions, and then compared their models with
species profiles measured with vacuum ultraviolet photoionization
mass spectrometry (VUV-PI-MS). Sarathy et al. [260] and Frassol-
dati et al. [318] have also developed combustion models of the four
butanol isomers against VUV-PI-MS species profiles in low-
pressure premixed flames studied by Oßwald [221]. Low-pressure
premixed flames of n-butanol and iso-butanol have also been
probed by Hansen et al. [218,232] by VUV-PI-MS. The important
oxygenated hydrocarbon species arising from the combustion of
the four butanol isomers are shown in Table 7. All the butanol
isomers produce formaldehyde, ketene, ethenol, and acetaldehyde.
The C3 and C4 species differ among the isomers due to the different
molecular structures. The pathways leading to the different species
are discussed next.
The high-temperature combustion of the butanol isomers differs
notably from the low-temperature consumption pathways; we
therefore present them separately. Fig. 41 presents the general high-
temperature reaction schemes for n-, iso, 2-, and tert-butanol. The
major product species arising from the direct decomposition of the
fuels are in agreement with those measured in experiments, as
shown in Table 7. At high temperatures, the principal consumption
pathways are unimolecular decompositions (including de-
hydrations) and hydrogen abstractions followed by b-scission of fuel
radicals. The primary stable decomposition products from n-butanol
combustion are ethenol, 1-butene, 2-propenal, propene, ethylene,
along with the radicals ethyl, hydroxyl, methyl, hydroxymethyl, and
a-hydroxyethyl. iso-Butanol yields the stable intermediates n-pro-
penol, n-propanal, iso-butene, and propene, plus the radicals
methyl, hydroxyl, and hydroxymethyl. 2-Butanol combustion is
notably more complex with stable products including iso-propenol,
acetone, ethenol, 1-butene, 2-butene, 1-propenol, n-propanal, and
ethylene, and the radicals methyl, ethyl, hydroxyl, and a-

Fig. 40. Measured ignition delay times in an RCM (symbols) [105] and simulations for the four isomers of butanol at 15 bar and 30 bar.
Reprinted from Weber and Sung [105] with permission from ACS Publications.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 87

Table 7
Important oxygenated hydrocarbon species measured [211,215,221,224,225,235,241] and predicted [121,218,224,225,232,233,235,260,318] from the high-temperature com-
bustion of the four butanol isomers.

n-Butanol 2-Butanol iso-Butanol tert-Butanol

C1 Formaldehyde Formaldehyde Formaldehyde Formaldehyde

C2 Ketene, ethanol, acetaldehyde Ketene, ethanol, acetaldehyde Ketene, ethanol, acetaldehyde Ketene, ethanol, acetaldehyde
C3 2-Propenol 1- Propenol, n-propanal, acetone, iso-propenol n-Propenol, propanal, 2-propenol iso-Propenol, acetone
C4 n-Butanal, butenol isomers 2-Butanone, butenol isomers 2-Methylpropanal, butenol isomers e

hydroxyethyl. tert-Butanol consumption is relatively simple due to
the high degree of symmetry. iso-Propenol, acetone, and iso-butene
are the important stable products, plus methyl radicals.
The low-temperature oxidation of the butanol isomers is shown
in Fig. 42 to help explain the differences in low-temperature
reactivity discussed previously. Following initial H-atom abstrac-
tion by OH, the subsequent possible low-temperature reaction
pathways for the butanol isomers distinguish their reactivity. n-
Butanol radicals react with molecular oxygen and then can either
lead to OH branching (via QOOH), OH propagation (via the Wad-
dington mechanism), or OH termination (aldehyde/enol þ HO2). It
should be noted that some of the QOOH is used to form one OH
radical and one HO2 radical that is also used to form low-
temperature radical branching. The g- and d-hydroxybutyl radi-
cals contribute most to OH branching in n-butanol. The a-hydroxy-
butyl radical leads primarily to OH termination, and the b-
hydroxybutyl radical leads to either OH branching, OH termination,
or OH propagation. iso-Butanol is less reactive than n-butanol
because chain branching evolves from g-hydroxybutyl radicals;
initial H-atom abstractions are slower from g primary sites due to
their high BDEs. In addition, the b-hydroxybutyl radical favors the
OH propagation (Waddington mechanism) route because internal
H-atom migration reaction leading to QOOH (and subsequent chain
branching) can only proceed via high-energy barrier 5-membered
ring transition states. The low-temperature pathways for 2-
butanol show the same chain termination pathways for reactions
involving its a-hydroxybutyl radical. The two b sites (i.e., one of the
ethyl branch and one on the methyl branch) contribute little to OH
branching because of competing OH termination and OH propa-
gation routes. OH branching comes mainly from the g-hydroxy-
butyl radical. tert-Butanol is unique because there are no a-CeH
bonds. The three primary b-radicals can react with O2 and lead to
OH branching and/or OH propagation. OH propagation via the
Waddington mechanism is favored because the high BDEs of the
primary CeH bonds slow internal H-atom migration reactions.
4.9. The combustion chemistry of higher alcohols
The combustion chemistry of higher alcohols (i.e., C5 and larger)
has not been studied extensively. Several recent works in the past

Fig. 41. Reaction path diagrams for high-temperature combustion of (a) n-butanol, (b) iso-butanol, (c) tert-butanol, and (d) 2-butanol. R denotes a radical, such as OH, HO2, and H.
88 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 42. Simplified schematics of important low-temperature reaction pathways for the four isomers of butanol: (a) n-butanol, (b) iso-butanol, (c) 2-butanol, and (d) tert-butanol.
Reprinted from Sarathy et al. [260] with permission from Elsevier.
3e4 years have focused on the isomers of pentanol and n-hexanol.
Togbé et al. conducted experiments on n-pentanol [246] and n-
hexanol [244] in JSRs and premixed laminar flames, and then
developed chemical kinetic models to simulate their experimental
data. n-Pentanol oxidation in the JSR did not exhibit any cool flame
behavior; low-temperature kinetic pathways were therefore not
included in their model. On the other hand, n-hexanol has cool
flame reactivity and a low-temperature oxidation scheme was
assembled to reproduce this behavior in the JSR. Neither of the
models by Togbé et al. [244,246] have been compared against to
low-temperature ignition data. Recently, Heufer et al. [248] and
Sarathy et al. [252] developed comprehensive models for n-pen-
tanol and iso-pentanol (3-methyl-1-butanol), respectively, which
were compared against ignition delay measurements in RCMs and
shock tubes, speciation profiles in JSRs, and premixed laminar
flame speeds. These pentanol isomer models form the basis for the
present discussion on the combustion chemistry of higher alcohols.
An extensive discussion on fundamental kinetic studies of high-
temperature reactions (e.g., hydrogen abstraction, b-scission,
radical isomerization) and low-temperature reaction pathways is
not possible for the pentanol isomers because such studies are
absent from the literature. Zhao et al. [438] employed quantum
chemical calculations with master equation simulations to derive
pressure-dependent rate coefficients for the unimolecular decom-
position of three pentanol isomers (n-pentanol, 3-methyl-1-
butanol, and 2-methyl-1-butanol). As shown previously for the
other alcohols, dehydration reactions leading the formation
of water and an alkene are important from 900 K and above, whilst
CeC and CeO bond scissions are competitive at higher tempera-
tures (above 1200 K). Given the rather limited fundamental kinetic
data available, Heufer et al. [248] and Sarathy et al. [252] developed
comprehensive chemical kinetic models based on analogies to al-
kanes and alcohols of similar structures. The development of re-
action classes follows the methods described in Section 4.3 and
Box 1. This approach was first verified by quantum chemical cal-
culations for CeH, CeC, and CeO bond dissociation energies that
showed higher alcohols can be sub-divided into an alcohol-specific
and alkane-like portion, as shown in Fig. 43 for n-pentanol. All
reaction rate coefficients were assigned based on analogous pri-
mary and secondary alkane (e.g., n-butane and iso-butane) sites and
a, b, and g alcohol sites (e.g., n-butanol and iso-butanol).
The low-temperature reaction mechanism for pentanol isomers
is also assembled based on direct analogy with butanol isomers.
Recent experimental and theoretical studies by Welz et al.
[345,439] enabled the addition of several new low-temperature
reaction pathways to the models. Welz et al. [345] described
Waddington-type pathways involving hydrogen transfer from the
OH group as important for the g-ROO and d-ROO radicals via 7- and
8-membered transition state rings. These reaction pathways were
therefore added to the models using estimated rate coefficients
[252]. Welz et al. [439] also presented a water elimination pathway
from hydroxypentylhydroperoxide (QOOH) radicals where the
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102 89

Fig. 43. Premixed laminar flame speeds for n-pentanol/air (left) and iso-pentanol/air (right) at 1 bar. (Left) n-Pentanol symbols are 423 K data presented in Togbé et al. [246].
Reprinted from Heufer et al. [248] with permission from ACS Publications. (Right) iso-Pentanol symbols are 353 K data presented in Sarathy et al. [252] and iso-butanol symbols are
353 K data presented in Liu et al. [228]. Reprinted from Sarathy et al. [252] with permission from Elsevier.

hydroperoxide is on the g-site and the radical is on the a-site. This
reaction pathway is also adopted in the iso-pentanol model
developed by Sarathy et al. using estimated rate coefficients [252].
The laminar flame speeds of n- and iso-pentanol/air mixtures
have been measured in few studies, as noted in Table 3. n-Pentanol
premixed laminar flames speeds were measured by Togbé et al.
[246] at 423 K, and simulations using the present chemical kinetic
model are shown in Fig. 44. The model indicates that the laminar
flame speed is very similar for n-pentanol and n-butanol over the
whole range of equivalence ratios, a phenomenon which has also
been observed for C5eC12 n-alkanes [440]. The concentrations of
reactive H, OH, and CH3 radicals generated during the combustion
of n-butanol and n-pentanol are similar, and thus their global high
temperature reactivities, manifested as premixed flame speed or
ignition delay, are similar. iso-Pentanol measurements and simu-
lations at a temperature of 353 K are also presented in Fig. 44.
Similar to the case of normal alcohols, the data and model indicate
that iso-pentanol and iso-butanol have similar flame speeds. Again
this is due to the fact that the intermediate pools of radical species
are similar in iso-pentanol and iso-butanol flames.
The homogenous ignition delay of the pentanol isomers has
been studied in STs and RCMs, as shown in Table 3. Recently, Heufer
et al. [103,108] studied the ignition of n-pentanol at temperature
from 640 to 1200 K and pressures from 9 to 30 bar. The 30 bar ST
ignition delay data were directly comparable to data obtained for n-
butanol under similar conditions [219], as shown in Fig. 45. Both the
experiments and present chemical kinetic model indicate that n-
pentanol has greater reactivity in the NTC region, which is

Fig. 44. Ignition delay times in an ST and RCM for n-pentanol (left) and iso-pentanol (right). (Left) ST data for n-butanol from Ref. [219] and n-pentanol [103] at 30 bar, stoi-
chiometric conditions. Reprinted from Heufer et al. [248] with permission from ACS Publications. (Right) Data for iso-pentanol from Sarathy et al. [252] at 20 bar and range of
equivalence ratios. Reprinted from Sarathy et al. [252] with permission from Elsevier.
90 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 45. Shock tube reaction path analysis for n-butanol and n-pentanol at 700 K, 30 bar, and 4 ¼ 1.0. The reaction fluxes are given for 20% fuel consumption.
Reprinted from Heufer et al. [248] with permission from ACS Publications.
attributed to its longer chain length promoting low-temperature
chain branching reactions. Above 1000 K, n-pentanol and n-
butanol exhibit similar high temperature reactivity, which is
consistent with the flame speed comparison presented above. iso-
Pentanol ignition delay measurements are available at pressures
ranging from 7 to 60 bar [249,252], and model simulations near
20 bar are presented in Fig. 45. The data spanning lean to rich
conditions show a strong equivalence ratio dependence at low
temperatures that is less prominent at higher temperatures. The
present chemical kinetic model simulations are able to capture the
low-, NTC-, and high-temperature reactivity of iso-pentanol in the
ST and RCM.
Speciation measurements resulting from the oxidation of n- and
iso-pentanol are available in JSRs. Researchers at CNRS Orleans have
presented data at a range from lean to rich equivalence ratios for n-
pentanol near 10 bar [246] and iso-pentanol near 10 bar [245] and
5 bar [252]. The chemical kinetic models for each fuel are able to
qualitatively reproduce the transient fuel reactivity, formation of
major product species, and profiles of oxygenated intermediates. In
general, the important oxygenated products are identical to those
presented previously for n-butanol and iso-butanol (Table 7), albeit
C5 aldehydes are also produced from the reaction of a-hydroxy-
pentyl radicals with molecular oxygen. The chemical kinetic model
for iso-pentanol [252] indicates that the acetone present at low and
intermediate temperatures arises from the water elimination
pathway proposed by Welz et al. [439]. Both experiments and
models indicate that the pentanol isomers do not display low- and
NTC-temperature reactivity in the JSR under the conditions studied
(1000 ppm fuel in air), which is a behavior consistent with smaller
alcohols; however, Togbé et al. [244] showed that low- and NTC-
temperature reactivity is observed for n-hexanol.
Extensive studies on the reaction pathways for combustion of
pentanol isomers are lacking, so presenting general high- and low-
temperature mechanistic pathways is not warranted. The high
temperature decomposition pathways are analogous to those
already presented for the butanol isomers. For simplicity, we pre-
sent actual pathway analyses performed for the combustion of
pentanol isomers under specific low-temperature conditions. A
reaction path analysis for n-butanol and n-pentanol under similar
shock tube ignition delay conditions is presented in Fig. 46 to
highlight the differences in their reactivity. It was previously shown
that the n-pentanol exhibits greater low-temperature reactivity
than n-butanol in shock tube ignition delay experiments. Both fuels
undergo typical H-atom abstraction reactions followed by O2
addition to form RO2 radicals. The primary driver for greater reac-
tivity in n-pentanol is its longer carbon chain length, which permits
hydrogen atom abstraction on a secondary “alkane-like” carbon.
The subsequent d-ROO undergoes a six-membered ring internal
isomerization to form QOOH, which later reacts with O2 and leads
to significant chain branching. Other minor pathways contributing
to the differences in low-temperature reactivity between n-butanol
and n-pentanol are discussed by Heufer et al. [248]. For iso-pen-
tanol, an NTC region reaction path analysis under JSR and ST con-
ditions is presented. In general, the reaction pathways are similar to
those presented and discussed previously for n- and iso-butanol.
Similar to the other alcohols, a-hydroxypentyl radicals react with
O2 to generate an aldehyde (i.e., iso-pentanal) and HO2. The other
hydroxypentyl radicals react with O2 to form hydroxyalkyl peroxy
(ROO) radicals. These radicals are mainly isomerized to hydrox-
yalkyl hydroperoxide (QOOH) or undergo a 5-centered concerted
reaction to form HO2 and an enol species. Waddington type re-
actions are shown to be important for b-ROO radicals. The con-
sumption of a-hydroxypentyl hydroperoxide radicals results in the
formation of a cyclic ether plus OH (minor route in STs) or a
concerted elimination to carbonyl hydroperoxide plus HO2 (major
route in STs). The water elimination pathway is shown to play an
important role during JSR oxidation, but it is not important during
ignition delay under ST conditions.
5. Insights into engine-relevant phenomena
A primary goal of this article is to use the knowledge gained on
fundamental combustion chemistry of alcohols toward under-
standing their performance in internal combustion engines. In this
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Fig. 46. Reaction path analysis for iso-pentanol oxidation in a JSR and ST. Black JSR 5 atm/850 K/italic (4 ¼ 0.35) bold(4 ¼ 1.0) plain (4 ¼ 4.0). Gray ST 20 atm/800 K/4 ¼ 1 at 20% fuel
consumed.
Reprinted from Sarathy et al. [252] with permission from Elsevier.
section, the comprehensive C1eC5 alcohol kinetic model is utilized
to predict the effects of alcohol fuel structure on laminar flame
speed, homogenous ignition delay time, and combustion products.
These are then related to engine-relevant phenomena, specifically
pre-ignition and super-knock, fuel autoignition, and pollutant
emissions.
Kalghatgi [88,441] explains that pre-ignition is an abnormal
combustion phenomenon that occurs in turbocharged DI SI en-
gines, wherein a propagating flame front is established prior to the
spark plug firing. Pre-ignition is different than traditional knock,
which is an autoignition phenomenon caused by temperature and
pressure increasing in the end-gas ahead of the spark-initiated
flame front. Pre-ignition may cause the temperature and pressure
of the end-gas to increase faster than it would under conventional
spark timing, and thus may lead to a heavy knock or “super-knock”
event. The criteria for pre-ignition to occur are a local hot spot that
initiates thermal runaway followed by a propagating flame front.
The probability of pre-ignition increases as as the fuel/air mixture’s
laminar flame speed increases [88,441].
Fig. 47 displays simulated laminar flame speeds for alcohol/air
mixtures using the C1eC5 alcohol kinetic model presented herein.
The figure also presents simulated laminar flame speeds for stoi-
chiometric fuel/air mixtures of C1eC5 alkanes, n-heptane, and iso-
octane using the kinetic model of Mehl et al. [86,442]. Amongst the
alcohols, methanol has the highest laminar flame speed, followed
by ethanol. The remaining C3eC5 normal alcohols (i.e., n-propanol,
n-butanol, and n-pentanol) display similar laminar flame speeds,
91
which are comparable to those of n-alkanes (ethane, propane, n-
butane, n-pentane, and n-heptane). All the alcohols and alkanes
have similar stoichiometric fuel/air adiabiatic flame temperature,
so differences in laminar flame speed are attributed to fuel com-
bustion chemistry. Chemical kinetic modeling reveals that meth-
anol is the most reactive in premixed flames because high-
temperature decomposition reactions (i.e., hydrogen abstraction
and b-scission) primarily produce formaldehyde, which de-
composes quickly to reactive H radicals. Normal C2eC5 alcohols
decompose to intermediates that populate the H-radical pool at
approximately the same rate, so these fuels display similar laminar
flame speeds. It can be concluded with a high degree of confidence
that larger normal alcohols (i.e., >C6) will display similar laminar
flame speeds. Substitution of methyl or OH in C3eC5 alcohols (i.e.,
branching) leads to a reduction in flame speed when compared to
normal alcohols, as is also shown for iso-alkanes. For example, tert-
butanol/air and iso-octane/air mixtures display dramatically sup-
pressed laminar flame speed due to multiple substitutions.
Substituted molecules are not as effective at populating the H
radical pool because their decomposition leads to the formation of
resonantly stabilized radical intermediates. A complete under-
standing on the effects of substitution (i.e., location and degree) on
combustion of alcohols is not yet available due to the lack of
experimental data and chemical kinetic models for the many iso-
mers of C5 and greater alcohol fuels.
The aforementioned analysis suggests that methanol and
ethanol will increase pre-ignition propensity due to their higher
92 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102

Fig. 47. Simulated laminar flame speeds for C1eC5 alcohols in air at 1 atm, 353 K (left) and laminar flame speeds for various alcohols and hydrocarbons in air at 1 atm, 353 K, 4 ¼ 1.1.

laminar flame speeds. Higher molecular weight normal and ignition delay time at 825 K and 25 atm. The ignition delay time of
branched alcohols will not increase pre-ignition propensity PRF fuels are simulated using the comprehensively tested gasoline
compared to typical n- and iso-alkanes found in conventional surrogates model by Mehl et al. [86,442]. n-Heptane has a RON of
gasoline fuels. Although higher laminar flame speeds can increase 0 and iso-octane has a RON of 100, and a non-linear relationship is
pre-ignition propensity, other fuel factors need to be considered. observed versus the predicted homogenous ignition delay time.
For example, low-molecular-weight alcohols have higher latent Methanol, ethanol, the propanol isomers, and tert-butanol have
heats of vaporization, which can reduce in-cylinder temperatures RON values greater than 100 and predicted ignition delay times
and decrease pre-ignition propensity. Furthermore, an increase in longer than those of PRF100. However, n-propanol is predicted as
pre-ignition propensity does not necessarily result in a super-knock less reactive than ethanol despite its lower RON (104 versus 109,
event. As will be shown next, higher octane fuels with longer ho- respectively). n-, iso-, and 2-Butanol isomers have octane ratings
mogenous ignition delay times decrease knock propensity. Thus, similar to that of conventional gasoline (90e105) and shorter
although methanol and ethanol exhibit higher laminar flame ignition delay times than PRF100. n-Pentanol has a RON of 82 and
speeds that increase pre-ignition propensity, their high octane the model predicts its decreased reactivity compared to the other
numbers can inhibit the occurrence of super-knock. alcohols. The measured RON of iso-pentanol (3-methyl-1-butanol)
The autoignition of fuel/air mixtures is an important design is 93, but the model predicts an ignition delay time closer to
consideration in SI, CI, and HCCI engines. Premixed fuel/air auto-
ignition in SI engines, referred to as knock, occurs in the end-gas
region due to increasing in-cylinder temperature and pressure
following spark plug firing. A fuel’s resistance to autoignition under
SI engine conditions is quantified by its RON and MON values.
Higher RON and MON values indicate lower autoignition pro-
pensity. In CI and LTC engines fuel/air autoignition is desired for
controlling combustion timing and susbequent heat release. The
cetane number of a fuel quantifies its autoignition propensity under
CI engine conditions; higher cetane numbers indicate higher pro-
pensity for autoignition. There is an inverse correlation between CN
and octane number (RON or MON). Fuels with RON < w60 and
CN > w30 are suitable for CI engines [88,443], those with
RON > w60e80 are suitable for LTC engines [444e447], and fuels
with RON > w80 are appropriate for SI engines. It was previously
stated that premixed fuel/air ignition delay time can be correlated
with its octane rating [86,87].
ST and RCM ignition delay time measurements at high pressures
(e.g., greater than 10 bar) and low to NTC temperatures (e.g., 600e
1000 K) correlate better with fuel octane and cetane ratings than
measurements at lower pressures and/or higher temperatures.
Sarathy et al. [87] have proposed that the RON of normal and
branched octane isomers can be closely correlated with their ST
ignition delay time under specific conditions (e.g., 825 K and
25 atm). Fig. 48 presents the measured RONs of C1 to C5 alcohol Fig. 48. Correlation of research octane number (RON) with ignition delay time for
fuels (from Table 1), as well as the primary reference fuel (PRF) stoichiometric fuel/air mixtures near 835 K and 20 atm. The line represents PRF
mixtures of n-heptane and iso-octane, versus simulated fuel/air mixtures of n-heptane and iso-octane.
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
PRF100. The aforementioned discrepancies for n-propanol and iso-
pentanol suggest that additional RON measurements are needed to
reduce the uncertainties in applying the correlation, and more
fundamental ST or RCM data is required to further refine detailed
chemical kinetic models. The high sensitivity of alcohols fuels
causes the correlation for alcohols to be quantitatively different
than that for PRF fuels, which have zero sensitivity by definition.
Higher molecular weight normal alcohols (C5 and higher) have
lower octane ratings and display significant low- and NTC-
temperature reactivity, thus making them more suitable for CI
engine applications. C1eC4 alcohols have higher octane numbers
and are more applicable to SI engines. The high sensitivity of al-
cohols fuels will improve performance in advanced engines, such as
LTC and turbocharge DI SI engines [88,443]. An alcohol’s ignition
propensity is closely related to its molecular structure. Hydrogen
abstraction from alcohol fuels is favored at the a-site (i.e., the C
bonded to the OH group) due to its proximity to the OH moiety and
lower BDE. The subsequent a-hydroxyalkyl þ O2 reaction in alcohol
fuels suppresses low-temperature reactivity by competing with
conventional low-temperature radical chain propagating and
branching reactions that initiate ignition processes. This inhibition
of low- and NTC-temperature reactivity is the cause of high octane
sensitivity in alcohol fuels. The branching ratio of forming the a-
hydroxyalkyl radical decreases as the carbon chain length in-
creases, so its inhibiting effects on ignition are lesser for larger al-
cohols. It is postulated that the critical chain length at which the OH
moiety no longer affects low- and NTC-temperature ignition delay
is 7e8 carbon atoms. Therefore, n-heptanol or n-octanol are ex-
pected to have ignition delay times and octane numbers similar to
n-heptane and n-octane, respectively, but further research is
needed on higher molecular weight alcohols to confirm this.
Methyl and OH substitution in alcohols tends to increase ignition
delay times (i.e., increase the octane number) because substitutions
increase the number of primary CeH sites, which have higher BDEs
and suppress low-temperature radical chain propagating and
branching reactions.
Fundamental speciation studies presented in this manuscript
confirmed that carbonyl emissions commonly observed in engine
research are due to the hydroxyl moiety in alcohol fuels. The
important oxygenated emissions from C1eC5 alcohols are form-
aldehyde, acetaldehyde (i.e., ethanal), propanal acetone, butanal
isomers, and pentanal isomers. The production of these species is
directly linked with molecular structure and combustion chemis-
try pathways. At high-temperature stoichiometric or fuel-lean
conditions, carbonyl products are formed primarily via hydrogen
abstraction from the a-site and subsequent b-scission reactions.
Methanol’s a-hydroxymethyl radical produces formaldehyde,
whereas ethanol’s a-hydroxymethyl produces acetaldehyde. The
a-hydroxyalkyl radicals in C3eC5 normal alcohols form ethenol,
which quickly isomerizes/tautomerizes to form acetaldehyde. The
high temperature formation of carbonyl compounds may be
averted at fuel-rich conditions, wherein hydrogen abstraction re-
actions are less favorable and unimolecular water elimination re-
actions favor the formation of alkenes. The C1eC5 alcohols also
produce carbonyls directly via a-hydroxyalkyl þ O2 % aldehyde/
ketone þ HO2 reaction. At low and intermediate temperatures, this
is the primary pathway to production of aldehydes and ketones,
especially the higher molecular weight carbonyls found during
combustion of C3 and larger alcohols.
As noted in Section 1, fueling engines with alcohols decreases
soot and particulate matter compared to petroleum hydrocarbon
fuels. The chemical kinetic modeling work presented in this
article does not enable the direct simulation of soot emissions
during alcohol fuel combustion. Nevertheless, the present
model’s insights into fuel decomposition pathways, together with
93
related works in the literature, enable a lucid understanding of
how alcohol fuels reduce soot and particulate matter during en-
gine combustion. Fig. 49 from McEnally and Pfefferle [448] pre-
sents the measured yield sooting idex (YSI) for various alcohols,
n-alkanes, and ethers as a function of their carbon number. The
alcohol data is presented for linear alcohols with various OH
substitutions (e.g., n-butanol is a 1-alcohol, 2-butanol is a 2-
alcohol and 3-pentanol is a 3-alcohol). The YSI is determined
by doping an atmospheric pressure non-premixed methane/air
coflow diffusion flame with 1000 ppm of the test compound and
measuring the maximum soot mass concentration with laser-
induced incandescence. The measured soot mass concentrations
are normalized to a YSI using n-hexane as YSI ¼ 0 and benzene as
YSI ¼ 100 (i.e., analogous to an octane rating) [448]. The domi-
nant fuel consumption pathways in the YSI flames are high-
temperature thermal decomposition reactions. Westbrook
et al.’s chemical kinetic modeling study of soot formation in
diesel engines has shown that soot is formed in rich combustion
regions [83], wherein fuel consumption is dominated by high-
temperature thermal decomposition reactions. Thus, the YSI
measurements are useful for understanding fuel structure effects
on soot emissions from engines.
The results in Fig. 49 [448] indicate that the YSI of linear alcohols
increases as the carbon number increases, which is also true for n-
alkanes. Higher carbon number fuels increase soot formation
because they inevitably form larger alkenes via unimolecular
decomposition (i.e., Reaction class 1) and radical b-scission re-
actions (i.e., Reaction class 4). These large alkenes subsequently
participate in PAH growth and soot formation processes [448,449].
The present chemical kinetic model has demonstrated that alcohol
combustion at high temperatures directly results in the formation
of large alkenes via four-center unimolecular decomposition re-
actions [206] (i.e., Reaction class 1 and Fig. 15). These reactions also
sequester the fuel bound oxygen atom into a water molecule,
thereby preventing the oxidation of carbon atoms and allowing
them to participate in soot growth processes. Therefore, C4 and
larger alcohol fuels have higher sooting tendencies compared to n-
alkanes of the same carbon number. OH substitution in alcohols
increases sooting tendency because the faster rates of four-center
unimolecular decomposition reactions yield more large alkenes.
McEnally and Pfefferle [448] explain that alcohol fuels exhibit
lower soot emissions in engines studies because they are used to
Fig. 49. Yield sooting index (YSI) of alcohols, n-alkanes, and ether as a function of
carbon number. Symbols are measured data points and the line is a quadratic least-
squares fit data for n-alkanes.
Reprinted from McEnally and Pfefferle [448] with permission from ACS Publications.
94 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
Box 2
Future directions for alcohol combustion chemistry research
- Detailed insights into alcohol combustion chemistry are
primarily driven by experimental observations, which
enable the development of comprehensive chemical ki-
netic models. Additional fundamental experimental
measurements are needed to better understand alcohol
combustion under conditions of relevance to internal
combustion engines. These include laminar flame speed
measurements at higher pressures (5e30 bar) and un-
burnt gas temperatures (400e600 K) and ignition delay
time measurements at higher pressures (10e100 bar) and
lower temperatures (550e950 K). Speciation measure-
ments in flames and flow reactors have been largely
restricted to high temperatures and low pressures. Ef-
forts are needed to better capture alcohol combustion
intermediates at elevated pressures (>1 bar) and low- to
intermediate-temperatures (550e950 K).
- Advances are needed in chemical kinetic model devel-
opment to reduce uncertainties in the large number of
reactions and rate constant parameters. For example,
chemical kinetic models for iso-butanol combustion
[233,260] with widely discrepant reaction rate constants
are able to accurately simulate historically measured
data. This indicates a need to advance experimental and
theoretical methods to further constrain kinetic model
parameters.
- Theoretical studies exploring the potential energy sur-
face of low-temperature alcohol oxidation can reveal new
reaction classes (e.g. [345,346,436,439]). As shown in this
paper, theoretical estimates of reaction rate constants
can be readily adopted to improve chemical kinetic
models, but improvements in even the highest level
theoretical calculations presently available are needed
[410,451]. Theoretical tools should be applied to calculate
rates for low-temperature reaction pathways and site-
specific hydrogen atom abstraction reactions.
- Undoubtedly, there is a need for elementary kinetic rate
measurments for alcohol specific reactions. These
experimental studies have seen a decline in the recent
years, but resources must be allocated to continue such
efforts and advance them [369,384]. Measurements at
combustion relevant temperatures (600e1400 K) are
needed to ensure the accuracy of reaction rate constants
used in chemical kinetic models.
- In addition to the aforementioned experimental and
theoretical studies, alcohol combustion modeling can be
improved using uncertainty quantification/optimization
tools [452e459]. These approaches can develop predic-
tive models needed to advance the design of energy
systems.
- The determination of premixed fuel/air laminar flame
speeds is continuously evolving with uncertainties being
reduced. Improved experimental methods and the anal-
ysis and/or interpretation of measured data are needed to
provide accurate laminar flame speed values for alcohols
at a range of pressures, temperatures, and equivalence
ratios.
- An important area of practical relevance largely missing
in the scientific literature is experimental and modeling
studies on NOx and soot formation during alcohol com-
bustion. Basic research should attempt to measure the
effects of alcohols on formation of soot precursors and
NOx (i.e., prompt and thermal) under idealized condi-
tions, such that comprehensive chemical kinetic models
can be developed with PAH growth [460,461] and NOx
formation [462] sub-mechanisms. These models can then
be used to simulate soot in more complex reacting flows,
such as laminar non-premixed flames [463e465], turbu-
lent non-premixed flames [466,467], and eventually
practical engine systems.
- Additional fundamental studies are needed to determine
the effects of alcohol blending with conventional petro-
leum hydrocarbon fuels. This paper highlighted several
fundamental studies on alcohol/PRF blends, but further
studies with multicomponent surrogates and real trans-
portation fuels are required to better understand the
synergistic and/or antagonistic effects of alcohol
blending on important combustion properties (e.g., oc-
tane number [468]).
- Chemical kinetic modeling and fundamental experiments
should be utilized to enable a deeper understanding of
alcohol combustion chemistry in engines. Important
phenomena of relevance to future alcohol-fueled engines
(e.g., turbocharged DI SI and lean-burn LTC) and
requiring more fundamental research are the effects of
exhaust gas recirculation and negative valve overlap [469
e472], thermal and mixture stratification [473e475], in-
termediate temperature heat release [90,97,476], the
chemical origins of octane sensitivity [477,478], and the
pressure [443] and equivalence ratio sensitivity [474,475]
of autoignition.
displace higher carbon number n-alkane fuels, which invariably
have higher sooting tendencies. The fuel bound oxygen atom does
not actually have any chemical benefit toward reducing soot; it’s
primary role is the modification of physical properties that enables
smaller hydrocarbon chains and higher H/C ratio structures to be
blended as liquid fuels [448]. Displacing high carbon number n-
alkanes (e.g., n-heptane) and highly sooting aromatics [450] with a
small carbon number alcohols (e.g., ethanol) decreases soot emis-
sions from internal combustion engines.
6. Summary and conclusions
The flammability of alcohols has been known for many cen-
turies, and their combustion for energy dates back more than a
hundred years. Despite this long history, a lucid understanding of
alcohol combustion chemistry has only become available in the
three decades preceding this article’s publication date. Literature
since the early 1930s was surveyed to provide a comprehensive
summary of experimental and theoretical studies. A rapid growth
in alcohol combustion chemistry in recent years can be attributed
to the improvement of experimental facilities, development of
innovative diagnostic techniques, and advances in computational
hardware and software.
This article’s compiled knowledge of alcohol combustion
chemistry enabled a better understanding of combustion in en-
gines. Engine-relevant combustion phenomena considered were
the fuel’s ignition delay time, laminar flame speed, and emissions
characteristics. These combustion features were analyzed by
surveying fundamental combustion experiments in premixed
laminar flames, batch reactors (i.e., STs and RCMs), and flow re-
actors (i.e., JSRs). This manuscript highlighted the progress made
toward understanding detailed chemistry during low- and high-
temperature oxidation; with new experimental targets and new
 S.M. Sarathy et al. / Progress in Energy and Combustion Science 44 (2014) 40e102
theoretical insights, it is now possible to assemble semi-predictive
models for alcohols fuels. Thus, a consistent and comprehensive
chemical kinetic model for C1eC5 alcohols was compared with the
experimental data, and then used to understand chemical con-
tributions toward the aforementioned global combustion
properties.
The detailed understanding of alcohol combustion chemistry
presented in this article provides a fundamental explanation of
why these are fuels suitable for internal combustion engines.
Higher molecular weight alcohols (e.g., C4 and larger) are benefi-
cial for practical applications due to their higher energy densities.
However, ignition delay times and octane numbers are lower for
larger alcohols, making them more suitable for CI engines. Methyl
or OH substituted alcohols of the same carbon number have
higher octane values, so are inherently better SI engine fuels.
Advanced LTC engine concepts may utilize the unique chemical
features of alcohols to control ignition processes, improve com-
bustion performance, and reduce emissions. From a fuel produc-
tion perspective, engineers should strive toward producing
alcohols spanning a range of carbon numbers for use in SI, CI, and
LTC engines. Conventional refining processes (e.g., catalytic
isomerization) can be used to produce the most desirable isomers.
The increased carbonyl emissions that are unavoidable when
burning alcohol fuels may be abated using appropriate catalytic
after treatment technologies. Displacing higher carbon number
hydrocarbons with lower carbon number alcohols having similar
physical properties can reduce soot and particulate matter emis-
sions. Thus, this combustion chemistry review suggests that al-
cohols are suitable alternative fuels for a wide range of
combustion applications. A principal contribution of this review
article is presented in Box 2, wherein directions for future com-
bustion chemistry research are suggested to enable the clean and
efficient utilization of alcohol fuels in future internal combustion
engines.
Acknowledgments
SMS is thankful for support from Clean Combustion Research
Center at KAUST. PO acknowledges financial support within the
DLR Center-of-Excellence "Alternative Fuels". NH is supported by
the U.S. Department of Energy, Office of Basic Energy Sciences in
part under the Energy Frontier Research Center for Combustion
Science (Grant No. DE-SC0001198). Sandia is a multi-program
laboratory operated by Sandia Corporation, a Lockheed Martin
Company, for the National Nuclear Security Administration under
contract DE-AC04-94-AL85000. KKH is grateful for a sabbatical
period, including a research stay with the Clean Combustion
Research Center and SMS at KAUST, which greatly facilitated the
collaboration in the conception phase of this article.
Appendix A. Supplementary material
Supplementary data relates to this article can be found at http://
dx.doi.org/10.1016/j.pecs.2014.04.003.
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