Progress in Energy and Combustion Science 73 (2019) 1–25

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Progress in Energy and Combustion Science

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

The effect of ozone addition on combustion: Kinetics and dynamics

Wenting Sun a,∗, Xiang Gao a, Bin Wu a, Timothy Ombrello b
a
School of Aerospace Engineering, Georgia Institute of Technology, Atlanta, GA 30332, United States
b
U.S. Air Force Research Laboratory, Aerospace Systems Directorate, Wright-Patterson AFB, OH 45433, United States

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

Article history: Ozone addition is a promising method to enhance and control combustion and ignition processes. It can
Received 29 May 2018 be produced efficiently at atmospheric or elevated pressure conditions and its lifetime is sufficiently long
Accepted 19 February 2019
to allow for remote production and transport to reaction zones. Over the past decades, the effect of ozone
addition on ignition and combustion processes has been extensively studied from bench top fundamental
Keywords: burners to practical internal combustion engines. Ozone has shown the capability to accelerate ignition
ozone assisted combustion and control ignition timing, enhance flame propagation, improve flame stabilization, pre-process fuel to
ozonolysis reaction modify emission and reactivity characteristics, and reduce certain pollutant formation. Such enhancement
ozone decomposition is closely related to ozone chemistry, especially the decomposition of ozone to produce atomic oxygen
and the rapid exothermic ozonolysis reactions with unsaturated hydrocarbons. The former requires el-
evated temperature to release atomic oxygen and initiate fuel/atomic oxygen reactions typically in the
preheat zone, while the latter initiates low temperature (even room temperature) direct fuel/ozone reac-
tions. These findings provide new opportunities in the development of strategies to enhance and control
combustion/ignition processes. This article provides a comprehensive review of the basic principles of
ozone enhanced reactive processes, including fundamental ozone chemistry, ozone generation and quan-
tification, and the progress in the study of ozone addition in combustion systems.
© 2019 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 2
1.1. Background and motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 2
1.2. Combustion enhancement: challenges and opportunities . . . . . . ................................................. 2
1.2.1. Conventional passive and active control . . . . . . . . . . . . . ................................................. 2
1.2.2. Reactive species addition and other additives . . . . . . . . ................................................. 2
1.2.3. Plasma assisted combustion. . . . . . . . . . . . . . . . . . . . . . . ................................................. 3
1.3. Ozone assisted combustion and history of ozone . . . . . . . . . . . . ................................................. 3
2. Review of ozone chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 3
2.1. Ozone decomposition reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 3
2.2. Reactions with radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 4
2.3. Reactions of ozone with hydrocarbons. . . . . . . . . . . . . . . . . . . . . ................................................. 4
2.4. Reactions with pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 6
3. Generation and measurement of ozone . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 6
3.1. Ozone generation techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 6
3.2. Ozone measurement techniques . . . . . . . . . . . . . . . . . . . . . . . . . . ................................................. 7
4. The effect of ozone addition on combustion . . . . . . . . . . . . . . . . . . . . . ................................................. 7
4.1. The effect of ozone on ignition: from benchtop to real engines ................................................. 7
4.2. The effect of ozone on laminar flames. . . . . . . . . . . . . . . . . . . . . ................................................. 8
4.2.1. Ozone decomposition flame . . . . . . . . . . . . . . . . . . . . . . . ................................................. 8

∗
Corresponding author.
E-mail address: wenting.sun@ae.gatech.edu (W. Sun).

https://doi.org/10.1016/j.pecs.2019.02.002
0360-1285/© 2019 Elsevier Ltd. All rights reserved.
2 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25

4.2.2. The effect of ozone addition on flame propagation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.2.3. The effect of ozone on flame stabilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3. The effect of ozone on turbulent flames . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.4. Ozone induced cool flames . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.5. The effect of ozone on combustion through ozonolysis reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5. Fuel processing using ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.1. Treatment of solid fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2. Treatment of liquid fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
6. Emission control using ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
7. Challenge and future research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
8. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Supplementary materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

1. Introduction damper used to suppress acoustic fluctuations that feed in to com-

1.1. Background and motivation
Combustion plays a vital role in civilian life, such as transporta-
tion and power generation. However, concerns of efficiency, emis-
sion, and operation at extreme conditions highlight the need to
enhance and control combustion processes. For example, to in-
crease efficiency and reduce emissions for ground transportation
application, various new engine technologies have been developed,
such as Homogeneous Charge Compression Ignition (HCCI) engines
[1] and Partially Premixed Compression Ignition (PRCI) engines [2].
However, the control of ignition timing is extremely difficult, and
it becomes necessary to develop an alternative method to con-
trol the ignition process. For air transportation, in order to meet
stringent emission standards, new lean burn aircraft engines have
been developed, such as lean direct injection (LDI) [3] and trapped
vortex lean combustors [4]. Therefore, flame stabilization strate-
gies are necessary to achieve stable combustion at such ultra-lean
conditions. Another example is high-speed air-breathing propul-
sion systems, such as supersonic combustion ramjet (scramjet) en-
gines. The short flow residence times in the engine requires en-
hancement and control of ignition and flame stabilization. If the
reaction rates of limiting reaction steps can be enhanced, igni-
tion and combustion processes could be dramatically accelerated.
For ground power generation and industrial burners, driven by the
needs of NOx emission reduction and CO2 capture, new techniques
such as flameless combustion [5,6] and oxy-fuel [7] combustion
have been developed. In these systems, combustion instability and
flame flashback are challenging issues, which also highlights the
need for novel combustion control techniques.
All of the needs with regard to combustion control and en-
hancement elicit both challenges and opportunities. To provide
some context, recent developments on combustion control will be
briefly reviewed in the next section.
1.2. Combustion enhancement: challenges and opportunities
Facing the challenges discussed above, techniques for combus-
tion enhancement and control, either passive or active, have be-
come necessary. A survey of different methods is briefly reviewed
in this section.
1.2.1. Conventional passive and active control
Passive control methods are typically based on geometrical
modification of combustors. Such concepts have been extensively
used to mitigate the combustion instabilities encountered in gas
turbine combustors [8]. One typical approach is to decouple the
periodic heat release and acoustic pressure oscillations so that they
are not in phase with each other. An example is the Helmholtz
bustion instabilities [9]. Another approach is to maintain uniform
combustion processes by promoting small-scale turbulence and
hampering large-scale structures [8].
Active control involves an actuator which can affect the sys-
tem dynamically through a control unit. It can be categorized as
open-loop or closed-loop. While open-loop control can provide
enhanced level of operability, closed-loop control utilizes infor-
mation feedback, and generally allows a finer tuning of operat-
ing conditions. This concept has been used in automotive engines
[10] for decades. Modern gas turbines operate near the lean sta-
bility limit to reduce emission. However, under such conditions,
a small change in operating condition (a few tens of Kelvin (K)
of temperature change) might be responsible for a dramatic in-
crease in pollutant formation [11]. Active control techniques have
been developed to mitigate these types of variations by precisely
controlling/adjusting the equivalence ratio in gas turbines. How-
ever, the estimation of the air inflow to the combustor rate is diffi-
cult [12] necessitating more robust active control methods. Besides
emission control, combustion instability is another issue where ac-
tive control techniques have been applied. For example, one tech-
nique summarized in Ref. [13] uses a microphone to monitor the
pressure fluctuations, which informs a controller to activate an
acoustic driver to mitigate instabilities in the combustor. Regard-
ing the control and enhancement of combustion process, various
approaches have been proposed. Acoustic forcing was proposed
to control [14] and stabilize [15] lifted non-premixed jet flames.
Vorticity production was used to enhance the fuel/oxidizer mix-
ing, thus promoting more complete combustion [16]. Additives and
plasma assisted combustion are two other promising means of en-
hancing combustion [17].
1.2.2. Reactive species addition and other additives
Due to its low autoignition temperature (∼291 K) and sponta-
neous combustion when coming into contact with air (pyrophoric),
silane has been used to promote ignition in scramjet engines. Mor-
ris et al. [18] experimentally studied silane as a fuel additive to
promote ignition in hydrogen-fueled scramjets. The results indi-
cated that blending as low as 2.5% silane in hydrogen was effective
for scramjets to operate at conditions where hydrogen alone could
not combust. However, storage and handling of such pyrophoric
fluids are extremely difficult and raise significant safety concerns.
Correspondingly, Gerstein and Choudhury [19] proposed a “pro-
grammed ignition” strategy where an ignition promoter (silane)
and volatile diluent (liquid methane) were mixed first, and the liq-
uid mixture was sprayed into the combustion chamber upstream
of the main fuel (e.g. hydrogen). The mixture was initially non-
flammable and then underwent rapid methane vaporization, after
which the mixture became flammable.
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Ignition promoters have also been applied in research using re-
newable fuels. Ethanol is a possible substitute for diesel fuels, how-
ever, it has a lower cetane number and high heat of vaporization.
The addition of an ignition promoter has been proposed as a po-
tential solution. Cipolat and Bhana [20–22] performed a series of
studies using dimethyl ether (DME) as the ignition promoter and
concluded that an ethanol/DME mixture can allow for engines to
achieve similar power as diesel fuel, but with considerably reduced
emissions. Besides diesel engines, DME has also been applied in
spark-ignited engines. Liang et al. [23] blended DME (1–2% volume
fractions) with ethanol and supplied the fuel mixture to a gaso-
line engine. It was found that DME addition increased the thermal
efficiency and the unburned hydrocarbon emissions were reduced.
However, one potential issue of the duel fuel strategy is the com-
plicated fueling system.
In recent years, the addition of reactive metallic nanoparticles
(NPs) to hydrocarbon fuels has drawn great interest for propulsion
systems. Liquid fuels with a stable suspension of NPs are some-
times referred to as nanofluid fuels [24]. Such NPs significantly in-
crease reactive interfacial area, as well as thermal and mass trans-
port properties. The energy stored in these metallic fuels can be
released rapidly by chemical reactions [24]. It has been shown that
the addition of such NPs can increase the volumetric energy den-
sity [25] and decrease ignition delay [26,27], increase the burning
rate [28], and catalyze fuel decomposition [29]. One drawback of
this method is the formation of metal particles after combustion.
For more detailed review of related studies, the readers are re-
ferred to Ref. [30].
1.2.3. Plasma assisted combustion
Non-equilibrium plasma assisted combustion (PAC) has shown
promising potential for enhancing and controlling combustion pro-
cesses [17,31–33]. Plasma discharges may enhance the combustion
process via thermal, kinetic, and/or transport effects. Investigations
have shown its ability to enhance flame stabilization [34,35] and
ignition [31,32], as well as reduce soot [36] and NOx emissions
[37,38]. Potential applications of plasma assisted combustion in-
clude supersonic propulsion and scramjet engines [39–42], gaso-
line and diesel engines [43,44], pulse detonation engines [45], and
gas turbine engines [46,47]. One basic principle of plasma assisted
combustion is that reactive species produced from plasma, such as
atomic oxygen [48], excited O2 [49] and ozone (O3 ) [50], can en-
hance combustion processes. Besides the kinetic enhancement ef-
fect, the Joule heating from plasma causes thermal enhancement
of combustion processes, and the change of molecular structure of
fuels owing to fast plasma kinetics and its induced subsequent re-
actions also change the transport properties of the working fluid.
All of these enhancement mechanisms could couple with aerody-
namic effects to influence the entire combustion system [17,31,32].
For more detailed reviews of plasma assisted combustion, the read-
ers are referred to Ref. [17,31,32].
One outstanding challenge of the plasma assisted combus-
tion technique is that the operating conditions of non-equilibrium
plasma and combustion systems are not well aligned. Most com-
bustion systems operate at elevated pressure conditions, while
non-equilibrium plasmas favor reduced pressure conditions, typ-
ically below atmospheric pressure [51]. High pressure conditions
causes plasma thermal instability, non-uniform structure [51], and
collisional thermalization of the discharge [51]. Therefore, it is
very challenging to generate a uniform large volume plasma at
high pressure conditions. At the same time, radicals have much
shorter lifetime at high pressures [52], and thus they are generally
quenched before being transported to the reaction zone (if radi-
cal generation is not in situ). Another issue which has not been
fully addressed in plasma assisted combustion systems is the po-
tential for increased NO concentration which has been observed
3
for plasma assisted flames when compared to the case without
plasma [53,54].
1.3. Ozone assisted combustion and history of ozone
The difficulty of generating stable, uniform, non-equilibrium
plasmas at high pressures can be mitigated by the injection of
long-lived, plasma-produced species. One promising species is
ozone. Ozone, or trioxygen (O3 ), is a pale blue gas with a distinc-
tively pungent smell at room conditions. Properties of ozone have
been long studied [55] since it plays a vital role in our life in many
different ways. Ozone in the stratosphere (ozone layer) protects
earth from biologically-damaging ultraviolet radiation. On earth, it
is used in many industrial processes and as a disinfectant. Because
of its vigorous oxidizing properties, ozone can be toxic and dam-
age lungs and vital organs once inhaled [56], and is considered a
pollutant at ground level because of being involved in the forma-
tion of photochemical smog. Furthermore, the reactions between
O3 and alkenes may form photochemical air pollution [57,58]. Due
to these important issues, the kinetics of gas-phase reactions of O3
has been extensively studied.
Ozone is one of the strongest oxidizers. It can be efficiently and
economically produced at high pressure conditions, which corre-
sponds to the operating condition of most practical combustion
devices. One advantage of O3 is that it is produced from oxygen
molecules which is the oxidizer of almost all combustion systems.
Therefore, no additional storage of fluids or gases is needed. Ozone
has a very long lifetime of approximately 1500 min in quiescent air
at room temperature (298 K) and zero humidity [59]. Compared to
the time scales in most combustors, the lifetime of O3 could be
long enough to be transported from remote production to the de-
sired combustion region to modify fuel oxidization pathways. Pre-
vious studies have shown that O3 has the ability to accelerate ig-
nition [60–62], enhance flame propagation [63–65] and flame sta-
bilization [66], process fuel to modify the emissions [67] and re-
activity characteristics [68], and reduce certain pollutant formation
[62,69].
2. Review of ozone chemistry
An enormous number of reactions involving O3 have been stud-
ied. For example, searching O3 related reactions on the National
Institute of Standards and Technology (NIST) Kinetic Database1 re-
turns 1974 records for 719 different reactions, predominantly con-
tributed by the atmospheric chemistry community. However, O3
related reactions (except O3 decomposition reactions) did not draw
much attention in the combustion community, as O3 rarely exists
in a conventional combustion system.
2.1. Ozone decomposition reactions
In the study of O3 assisted combustion [70–74], one of the most
important roles that O3 plays is through decomposition (reaction
(R1)) to release atomic oxygen in the preheating zone of a flame,
therefore inducing early fuel oxidation. The reaction is
O3 +M =O2 +O + M (R1)
where M stands for a third-body reactant representing all colli-
sion species. The rate constant of this reaction has been exten-
sively studied. A summary of reaction rate constants of reaction
(R1) from different studies is presented in Table S1 in the Sup-
plementary Material, where A is the pre-exponential factor, n is a
dimensionless parameter, T is the temperature measured in K, R is
the universal gas constant, and Ea is the activation energy.
1
http://kinetics.nist.gov/kinetics/index.jsp, webpage visited on August 26, 2017.
4 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 1. Pressure dependence of reaction rate coefficient of O3 decomposition reac-
tion.
It is noteworthy that the O3 decomposition reaction is a bi-
molecular reaction at its low pressure limit (expressed as (R1))
and a unimolecular reaction only at its high pressure limit. So the
reaction rate constant of O3 decomposition reaction depends on
both temperature and pressure (away from its high pressure limit).
Starting from the high pressure limit, the rate coefficient decreases
with decreasing third body concentration [M] and the correspond-
ing representation of the reaction rate constant as a function of
[M] is termed as the “falloff” curve of the reaction. The pressure
dependence of the rate constant of O3 decomposition could be de-
scribed by the Lindemann-Hinshelwood reaction scheme [75] and
calculated using the classical Troe formalism [75]. A Troe formal-
ism obtained from theoretical model (RRKM model) was presented
by Peukert et al. [76], which is valid in a temperature range from
70 0 K to 140 0 K and pressure range from 5 mbar to 3 bar. The
pressure dependence of O3 decomposition reaction rate constant
is calculated at 900 K using this Troe formalism and is presented
in Fig. 1. Experimental measurements of O3 decomposition reac-
tion rate constants (T = 887 K to 907 K; P = 0.097 bar to 0.49 bar)
from Peukert et al. [76] are also shown in Fig. 1 for comparison. It
can be seen that the experiments agree with the RRKM model rea-
sonably well. The results in Fig. 1 at pressures greater than 3 bar
are extrapolation and for demonstration only as the Troe formal-
ism is invalid beyond 3 bar according to Peukert et al. [76]. It can
be seen that the high pressure limit of O3 decomposition occurs at
very high pressure (above 10 0 0 bar). Expression of the reaction rate
at the low pressure limit works well below approximately 5 bar.
However, if the working pressure is greater than 5 bar, Troe for-
malism should be used to calculate the reaction rate constant for
O3 decomposition. The Troe formalism for O3 decomposition reac-
tion adapted from Ref. [76] is included in an O3 sub-mechanism in
the Supplementary Material. As a majority of studies/applications
of ozone occur well below the high pressure limit of O3 decom-
position reaction owing to the short lifetime of O3 at those condi-
tions, the values presented in Table S1 focus on rates well below its
high pressure limit. The O3 decomposition reaction rate constant at
the high pressure limit is provided as the last entry of Table S1.
The reaction rate of (R1) may depend on the third-body col-
liding partner, M. The results listed in Table S1 are visualized in
Fig. S1 as a function of temperature in the Supplementary Mate-
rial. It shows that the overall deviation among different studies is
reasonably small, regardless of the different rate expressions. For
the results reported using N2 (relevant to most combustion sys-
tems since it is the major component of air) as the base gas, the
reaction rate constants at 800 K calculated using different expres-
sions shows a standard deviation of 28% relative to their average
value.
2.2. Reactions with radicals
Besides the decomposition of O3 , there are several O3 reactions
with radicals that are expected to be important in combustion sys-
tems involving O3 .
O3 +H =O2 +OH (R2)
O3 +H = O + HO2 (R3)
O3 +OH =O2 +HO2 (R4)
O3 +HO2 = OH+O2 +O2 (R5)
O3 +O =O2 +O2 (R6)
For reaction (R2), the earliest research may date back to 1962,
which only reported a kinetic rate. More recent works included ac-
tivation energy [77]. Recent works on reaction (R2), and its tem-
perature dependent reaction rate constants are summarized in Ta-
ble S2 and plotted in Fig. S2 in the Supplementary Material.
For reaction (R3), fewer studies have been conducted. The only
measurement reported was in 1980 by Howard and Finlayson-Pitts
[78], with a value of 4.52 × 1011 at 298 K. The temperature de-
pendence was not investigated. Reactions (R4)–(R6) are relatively
well studied, and their reaction rate constants from past studies
are summarized in Table S3, S4, and S5, respectively, in the Sup-
plementary Material. The temperature range at which reaction (R4)
was investigated is relatively narrow, except the work conducted
by Ju et al. [79]. The results are visualized in Fig. S3 for (R4), Fig.
S4 for (R5) and Fig. S5 for (R6) in the Supplementary Material. The
deviations among existing results for (R4)–(R6) are relatively large.
2.3. Reactions of ozone with hydrocarbons
In the reactions between O3 and hydrocarbons, there is a dra-
matic difference in the behavior of saturated hydrocarbons (alka-
nes) and unsaturated hydrocarbons (alkenes) [80]. While the di-
rect reactions between O3 and alkanes is immeasurably slow and
therefore of little importance in many systems, reactions of alkenes
with O3 can be fast. Alkenes undergo a cycloaddition of ozone,
and this exothermic class of reactions is generally referred to as
“ozonolysis reactions” (R7) where Q means heat release. While the
rate constants for these reactions have been extensively studied ei-
ther experimentally or computationally [81,82], significant uncer-
tainties/unknowns still exist in detailed reaction pathways. Such
information could be critical for its application in combustion sys-
tems, especially for the ozonolysis reaction.
O3 +Fuel = Products + Q (R7)
The reaction between O3 and CH4 (an alkane) is very slow (the
reaction rate constant at 300 K is 0.99 cm3 /mol s [83]), so it is
normally ignored by the combustion community. However, the di-
rect reaction between O3 and ethylene (C2 H4 ) (an alkene) is or-
ders of magnitude faster compared to that with CH4 [80,84] (reac-
tion rate constant at 300 K is 1.12 × 106 cm3 /mol s [85]). The reac-
tion rate constants of these reactions between fuel and O3 have
been studied for several different hydrocarbons, as summarized
in Table 1. For these components, the reaction rate constants for
alkenes are approximately a million times larger than those for
alkanes. For these alkenes, the molecular structures significantly
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25 5

Fig. 2. Criegee mechanism of the ozonolysis reaction.

Table 1 [91] for alkenes. The first step is a 1,3-dipolar cycloaddition of O3

Reaction rate constants between O3 and hydrocarbons, k, at
300 K for different hydrocarbons.
k (cm3 /mol s) Reference
Alkanes CH4 0.99 [83]
C2 H 6 8.95 [86]
C3 H 8 4.19 [86]
C4 H10 6.05 [83]
Alkenes C2 H4 1.12 × 106 [85]
C3 H 6 6.29 × 106 [84]
iso-C4 H8 6.68 × 106 [87]
trans-2-C4 H8 1.43 × 108 [87]
cis-2-C4 H8 7.77 × 107 [87]
1-C4 H8 5.82 × 106 [87]
affect the rate constants. For example, at 298 K, the reaction rates
for trans-2-butene (trans-2-C4 H8 ) and cis-2-butene (cis-2-C4 H8 )
are much higher than that for iso-C4 H8 and 1-butene (1-C4 H8 ). It
is also interesting to see the noticeable difference between the re-
action rate constants of trans-2-butene and cis-2-butene ozonolysis
reactions.
The parameters showing the temperature dependence of the re-
actions for alkanes are listed in Table S6 and the corresponding
reaction rate constants are plotted in Fig. S6 in the Supplemen-
tary Material. The measurements were typically conducted within
a very narrow temperature range. For CH4 , the results reported by
Stedman and Niki [88] is approximately 10 0 0 times faster than the
results by Dillemuth et al. [89] or Schubert et al. [83]. In a recent
experiment conducted [64], the smaller reaction rate constant was
indirectly supported.
The reactions rate parameters for alkenes are listed in Tables
S7–S9 and the corresponding reaction rate constants are plotted in
Figs. S7–S9, respectively, in the Supplementary Material. For C2 H4 ,
the averaged value of reaction rate constant at 298 K using the re-
ported results/expressions is 1.1 × 106 cm3 /mol s, and the stan-
dard deviation among different studies at this temperature is 28%.
If only results from studies after 1980 are considered, the deviation
decreases to 11% and the average value is 1.0 × 106 cm3 /mol s. For
C3 H6 , the averaged value is 7.1 × 106 cm3 /mol s at 298 K, and the
standard deviation is 15.6%. The result from Adeniji et al. [90] de-
viated from the average value the most. If this result is not consid-
ered, the deviation decreases to 9.5% of the average value, which is
6.7 × 106 cm3 /mol s at 298 K. As the number of carbon atoms fur-
ther increases, the ozonolysis reactions become very complex and
the reaction rate constants from different studies also deviate more
significantly. For butene, the molecular structure becomes an im-
portant factor. The ozonolysis reaction rate constants of iso-C4 H8
and 1-C4 H8 are similar while those for trans-2-C4 H8 and cis-2-
C4 H8 ozonolysis reactions are approximately 10 times faster (refer
to Table S9 in the Supplementary Material).
As the direct reactions between O3 and alkanes are generally
very slow at room temperature and can be neglected, only the
ozonolysis reactions of alkenes will be discussed here. A well-
known ozonolysis mechanism was proposed in 1975 by Criegee
to the alkene. In this step, combining with O3 , the double carbon-
carbon bond is broken and a 5-member cyclic structure is formed.
This product is called primary ozonide (POZ), which is typically
not collisionally stabilized under atmospheric conditions [92] and
subject to decomposition. The decomposition of POZ produces a
Criegee intermediate (a carbonyl oxide) and a carbonyl compound.
The Criegee intermediate is in an excited state. In gas phase, ap-
proximately 50% of Criegee intermediates can be stabilized through
collisions and approximately 50% of Criegee intermediates are sub-
ject to decomposition and reaction with other hydrocarbon species,
for example in the ozonolysis process of C2 H4 [93]. The process
mentioned above is summarized in Fig. 2.
In the case of C2 H4 , the carbonyl compound is CH2 O, and the
excited Criegee intermediate is CH2 OO∗ [94], which is the sim-
plest Criegee intermediate and can be collisionally stabilized. Di-
rect detection of Criegee intermediate is very challenging, espe-
cially at elevated pressure conditions. Recently, there has been
significant progress in the measurement of Criegee intermediates
at reduced pressure conditions. In 2008, Taatjes et al. [95] re-
ported direct observation of Criegee intermediates in the oxidation
process of dimethyl sulfoxide (CH2 S(O)CH3 ) using photoionization
time-of-flight mass spectrometry. The oxidation process was pho-
tolytically initiated by a pulsed laser to produce Chlorine atoms.
In a later work, Welz et al. [96] used photolysis of CH2 I2 in O2
to generate CH2 OO and measured CH2 OO directly using photoion-
ization time-of-flight mass spectrometry. Su et al. [97] presented
the infrared absorption spectrum of CH2 OO produced from photol-
ysis of CH2 I2 in O2 at 12.5 kPa. Recently, a method has been ex-
perimentally demonstrated by Berndt et al. [98] to detect Criegee
intermediates directly from ozonolysis reactions at near atmo-
spheric conditions using chemical ionization mass spectrometry.
Elsamra et al. [99] experimentally measured reaction rate constants
of CH2 OO+CH3 COCH3 reaction and CH2 OO+CH3 CHO reaction from
298–500 K and 0.5–6.7 kPa in a photolysis reactor. In the same set
up, Buras et al. [100] measured self-reaction of CH2 OO in a follow
up work. The readers are referred to a recent review [101] on the
kinetics of Criegee intermediates.
The subsequent reactions after the decomposition of POZ are
still not very clear because of their complexity even though various
pathways have been proposed. Criegee suggests that the Criegee
intermediate and the carbonyl compound could recombine and
yield a secondary ozonide (SOZ), with a different molecular struc-
ture than POZ. More recent investigations suggest that the excited
state Criegee intermediate formed in the POZ cleavage may de-
compose unimolecularly [92,94,102] in addition to collisional sta-
bilization. Several pathways for this unimolecular decomposition
reaction of the Criegee intermediate have been proposed as sum-
marized in Ref. [94]: (1) the ester channel, which forms dioxirane
and subsequently decomposes into simpler species, (2) the forma-
tion of an OH radical via H migration, and (3) the split-off of O(3 P)
atoms. The relative branching fractions of decomposition of Criegee
intermediates are predicted to be pressure dependent [92]. As the
products of these channels are highly reactive, secondary reactions
6 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
can be initiated and large uncertainties can be introduced, which
complicates the investigation of ozonolysis. Horie and Moortgat
[103] conducted experiments at 101.1 kPa (∼1 bar) and 297 K using
a continuously-stirred tank-reactor and determined the branching
ratios of the decomposition channels for some types of Criegee in-
termediates. For Criegee intermediates produced from ozonolysis
of C2 H4 , which is CH2 OO, the branching ratio of CH2 OO decom-
position is: (CO+H2 O):(CO2 +H2 ):(CO2 +2H) = 58%:24%:18%. Later
work showed and considered reaction pathways of the yield of OH
radicals [104,105]. In a work conducted by Neeb et al. [93], the
ozonolysis reaction pathways of C2 H4 is summarized as
O3 +C2 H4 = CH2 O + CH2 OO∗
CH2 OO∗ =H2 +CO2
CH2 OO∗ = 2H + CO2
CH2 OO∗ =H2 O + CO
CH2 OO∗ = OH + HCO
CH2 OO∗ = HCOOH
CH2 OO ∗ +M = CH2 OO + M
The branching ratio of (R8a + R8b):(R8c + R8d):(R8e):(R8f)
=0.23:0.23:0.04:0.5 [93], however, the reaction rate constants were
not reported. A recent work by Rousso et al. [106] revealed the
complexity of products from the simplest ozonolysis reaction be-
tween C2 H4 and O3 . They identified the products from C2 H4 /O3
reaction in a jet-stirred reactor including C2 H4 O3 , H2 O2 , CH3 OOH
and C2 H5 OOH using photoionization time-of-flight mass spec-
trometry. They also showed experimental evidence for additional
oxygenated species such as methanol, ketene, acetaldehyde, and
hydroxy-acetaldehyde suggesting multiple active oxidation routes.
Much more work is required in the future to fully understand
ozonolysis reactions.
2.4. Reactions with pollutants
Ozone has been investigated as a reagent to remove NOx [107–
109]. In most practical flue gas, NO is the major NOx species. A
general method is to convert NO, which has low solubility, to a
species that is highly soluble in water, such as NO2 , NO3 , or N2 O5 .
The water soluble species can then be captured later downstream.
The related reactions are listed as followed:
NO+O3 = NO2 +O2
NO2 +O3 = NO3 +O2
The reaction rate constants of (R9) and (R10) have been ex-
tensively studied over the past several decades. The reaction be-
tween O3 and other common pollutants are relatively less studied.
The only study on the reaction CO + O3 = CO2 + O2 was con-
ducted in 1972 by Arin and Warneck [110]. A very low reaction
rate, 0.24 cm3 /mol s, is reported at 296 K. As for the reaction with
SO2 , SO2 + O3 = SO3 + O2 , the reaction rate is higher, of the order
of 100 cm3 /mol s at 300 K [111]. These reactions are summarized
in Table S10 in the Supplementary Material with their measured
reaction rate parameters. The temperature dependence is visual-
ized in Fig. S10 in the Supplementary Material, and relatively small
variability is observed.
3. Generation and measurement of ozone
3.1. Ozone generation techniques
One technique for O3 production is through the interaction of
O2 with light in the ultraviolet (UV) wavelength range. The mech-
anism is responsible for the formation of the O3 layer in the at-
mosphere. Conventionally, a UV lamp (∼100 nm to 260 nm) can be
used in such O3 generators.
O3 can also be produced by electrical discharge, for example
from lightning during a thunderstorm. Most commercial O3 gen-
erators are based on electrical discharges. An electrical discharge
(R8)
(typically corona discharge or dielectric barrier discharge to main-
tain low gas temperatures and minimize O3 decomposition) is used
(R8a) to break the molecular bond of O2 , therefore, producing atomic
oxygen, which then recombines with O2 to form O3 via the reac-
tion O + O2 + M = O3 + M. A relatively high pressure is preferred
(R8b)
for O3 formation as it is a three-body reaction. Modern high-
power O3 generators take advantage of semiconductors to generate
(R8c) square-wave currents or specially formed wave trains with a rep-
etition rate of 0.5–5 kHz. Ozone concentrations up to 5 wt% from
air and up to 18 wt% from oxygen can be reached [112]. Large scale
(R8d) O3 generators with production up to 100 kg/h have been built for
industrial applications. With modern technology, ozone can be pro-
(R8e) duced for less than $2/kg [112].
Simek and Clupek [113] experimentally studied the efficiency of
O3 production by a pulsed discharge in air. The energy needed to
(R8f) produce a given quantity of O3 (O3 yield, g/kWh) was measured
at different air flow rates and O3 concentrations. Ozone yield var-
ied in a range of 15–55 g/kWh. Samaranayake et al. [114] reported
O3 yield of 10–110 g/kWh, with a non-monotonic trend depend-
ing on O3 concentration. Based on the authors’ estimation from
the specification data available [115], the O3 yield for some com-
mercial O3 generators based on pulsed discharges is approximately
67–125 g/kWh, on a similar order of the values reported in Refs.
[113,114]. These measurements of O3 yield (mass per energy input)
suggest that approximately 3 × 107 –3 × 108 J of energy is needed
for the production of 1 kg of O3 . For comparison, the difference be-
tween the enthalpy of 1 kg of O2 and 1 kg of O3 is 3.0 × 106 J at
300 K and 101 kPa, which means only 1–10% of the total consumed
energy is actually used to produce O3 . To improve the efficiency
of O3 production, experimental studies have been conducted con-
cerning the electrode arrangements [116–118], dielectric materials
[119], structure of discharge tube, feed-gas type (dried air or O2 )
[119], feed-gas flow rate [120], operating pressure [120,121], power
supply frequency [121], and humidity [121].
The recombination reaction O + O2 + M = O3 + M, is the dom-
inant channel to consume atomic oxygen and produce O3 . If air is
used as the gas through the discharge, NOx can also be produced
and its collision with O3 will consume and significantly decrease
(R9) the O3 yield through the reactions of NO + O3 = NO2 + O2 and
NO2 + O3 = NO3 + O2 . The production of NOx simultaneously with
O3 arises because the recombination reaction takes approximately
(R10)
10 μs in O2 and 100 μs in air, allowing for a competition of differ-
ent pathways for O consumption [122]. The production of N atoms
from the discharge is potentially more critical for NOx production
as the N + O2 = NO + O reaction is orders of magnitude faster
than the O + N2 = N + NO reaction if N2 is in the ground state.
Therefore, the rate controlling step of NOx production in electrical
discharges is the production of N atoms. If N2 is in the discharge
gas, the production of NOx cannot be avoided [123]. The trace com-
pounds can interfere with O3 formation and when they reach a
certain concentration, O3 generation completely breaks down. This
“ozoneless” mode of discharge is referred to as the state of dis-
charge poisoning [124]. The reaction between O3 and NOx is sensi-
tive to temperature, and therefore such effects can be reduced by
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 3. Schlieren images of ignition process, 300 K and 0.1 MPa. Case 1: stoichiometric H2 /O2 /O3 /Ar mixture; Case 2: stoichiometric H2 /O2 /Ar mixture. (Reprinted from Liu
et al. [137] with permission of J-STAGE.)
optimizing the dielectric material, which affects the gas temper-
ature of the discharge [119]. The plasma chemistry of O3 forma-
tion can be optimized in electrical discharge by providing electrons
in a suitable energy range of a few electronvolts to reduce energy
losses to ionic species and minimize recombination reaction of O
to form O2 [112]. It was reported that the optimal reduced electric
field is approximately 140 Td in O2 and 200 Td in air [123,125] for
O3 production. Comprehensive kinetic models in ozone generation
can be found in Refs. [121,126,127].
3.2. Ozone measurement techniques
Ozone has strong absorption bands from UV to the IR region
[128–130]. Therefore, a typical technique for ozone quantification
is the absorption method. In Ref. [63], a mercury lamp was used
to provide UV at the wavelength of 253.7 nm where O3 has a
peak absorption cross section of 1.137 × 1017 cm2 at 300 K [131],
then the O3 concentration was determined using the Beer–Lambert
law [132]. A continuous wave deuterium lamp together with a
monochromator can be used to perform O3 measurement at dif-
ferent wavelengths (195–345 nm across the Hartley and Huggins
bands) [128]. Absorption cross-sections at different wavelengths
have been well characterized at different temperature conditions
[128,129,131,133]. Reuter et al. [130] conducted O3 measurement
using absorption spectroscopy in both the UV and IR wavelengths.
In the first method, a deuterium lamp which emits a broadband
spectrum of UV light in the range from 200 to 300 nm was used
as background source. An interference filter with a central trans-
mission wavelength of 254 nm with full width at half maximum
(FWHM) of 10 nm was used to produce light around 254 nm. An
ICCD camera connected to a spectrometer served as the detec-
tor. Ozone concentration around a plasma jet was then calcu-
lated based on the absorption spectrum. In the second method,
a quantum cascade laser in the mid-IR region (center frequency
1027 cm−1 = 9737.1 nm) was used as the light source. Ozone mea-
surement was demonstrated in a 60 cm multipass white cell. Since
the quantum cascade laser has fine spectral resolution, a more ac-
curate measurement of O3 concentration was obtained using mid-
IR absorption spectroscopy. Teranishi et al. [134] investigated mea-
surement of O3 concentration using absorption spectroscopy in the
visible light region. Ozone has photon absorption band in the vis-
ible wavelength region around 450–850 nm, which is referred to
as the Chappuis band, the peak cross-section of which is approxi-
mately 20 0 0 times smaller than that of the Hartley band. In their
work, an LED having an emission peak at 609 nm and a photodiode
sensitive at visible light frequencies was used as the light source
and the photodetector, respectively. The measurement was con-
ducted in a stainless-steel absorption optical cell. Good agreement
between measurement based on the visible absorption method and
UV ozone monitor was reported.
It is noteworthy that most absorption spectroscopy measure-
ments of ozone concentration using broadband UV light sources
has the potential to simultaneously photolytically produce ozone
because of several strong UV absorption bands. When using ab-
sorption spectroscopy, care has to be taken to minimize wave-
lengths other than the wavelength range where the absorption
7
measurement is being performed in order to provide the most pre-
cise concentration measurement. An uncertainty of approximately
2% and a minimum detectable threshold of approximately 15 ppm
were reported in Ref. [63]. Commercial O3 monitors applying the
same principle to measure O3 concentration are available on the
market, as employed in the works [64,65,135].
4. The effect of ozone addition on combustion
4.1. The effect of ozone on ignition: from benchtop to real engines
Initial studies on O3 assisted combustion focused on ignition.
Photolysis of O3 could yield atomic oxygen and therefore was pro-
posed to enhance ignition. In 1987, Lucas et al. [136] conducted
experiments in closed aluminum cells with Plexiglas side windows
using a mixture of H2 /O2 /O3 with KrF excimer laser (248 nm) to
photo dissociate O3 . The photolysis of one O3 molecule could pro-
duce one oxygen atom and one O2 molecule with 90% of atomic
oxygen in the electronic excited (1 D) state and O2 molecules in
the electronic (1 ) state. O(1 D) is extremely reactive, especially
with species like H2 with zero activation energy. The effects of
equivalence ratio, pressure, and initial gas temperature on the min-
imum ozone concentration needed to produce ignition were in-
vestigated. All the experiments were conducted at reduced pres-
sure conditions below 13.3 kPa and it was found that only the
initial temperature had a significant effect on the required mini-
mum ozone concentration for ignition. With the increase of initial
temperature, the required minimum ozone concentration for igni-
tion decreased. Numerical modeling also showed that ignition was
not due solely to thermal effects, but was strongly dependent on
the number and type of radicals present initially after photolysis
[136]. Similar photolysis experiment was conducted by Liu et al.
[137] in 1998 under atmospheric pressure using a pipe burner
with 6 mm inner diameter. The minimum incident laser energy in-
tensity (MILEI) from a KrF excimer laser (248 nm) was measured
for the ignition of H2 /O2 /O3 /Ar mixtures. An ozone generation de-
vice was placed downstream of the O2 flow controller and it was
found that the MILEI decreased with the increase of O3 concen-
tration. The authors further conducted photolysis ignition experi-
ments using ArF laser (193 nm) to dissociate O2 for H2 /O2 /Ar mix-
tures and compared schlieren photographs of ignition processes
with those from H2 /O2 /O3 /Ar mixtures (illustrated in Fig. 3). A
large difference was observed between their flame kernel growth
processes. For H2 /O2 /O3 /Ar mixtures (case 1 in Fig. 3), the flame
propagated along the laser path uniformly compared to the non-
uniform growth pattern for H2 /O2 /Ar mixtures (case 2 in Fig. 3).
Correspondingly, the growth speed of the flame kernel for case
1 was much faster than that in case 2. The growth speed of the
flame kernel was estimated to be 700 m/s, which was two order
of magnitude faster than the 15 m/s in case 2. Moreover, the ig-
nition of H2 /O2 /O3 /Ar mixtures was accompanied by the forma-
tion of shock waves which did not occur in case 2. The authors
explained this observation by the different products from photol-
ysis reactions in the two cases. For H2 /O2 /O3 /Ar mixtures, photol-
ysis of O3 (O3 +hv = O(1 D) + O2 (1 )) yields electronic excited
atomic oxygen (O(1 D)) which reacts with H2 on the order of 0.5 ns.
8 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 4. Calculated ignition process in HCCI for different O3 concentrations.
(Reprinted from Nishida and Tachibana [140] with permission of American Institute
of Aeronautics and Astronautics, Inc.)
Correspondingly, photolysis of O2 (O2 + hv = 2O(3 P)) yields ground
state O atoms (O(3 P)), that reacts with H2 much slower with a
characteristic time of 7.5 ms [137].
In 1988, Nomaguchi and Koda [138] investigated spark ignition
using electric pulses in a closed vessel at reduced pressure for pre-
mixed fuel (CH4 or CH3 OH) and ozonized air. It was found that
the minimum spark pulse duration for successful ignition could be
shortened considerably by adding 0.2% O3 in O2 . Simulations con-
ducted at an initial temperature of 1100 K, and a constant pres-
sure of 20.0 kPa corresponding to their experiments showed that
the acceleration of ignition was due to the atomic oxygen (from
O3 decomposition) attacking fuel molecules. Later, Tachibana et al.
[62] used a diesel CFR engine to examine the effect of O3 addi-
tion on compression ignition. O3 addition accelerated ignition, in-
creased cetane number, and lowered the compression ratio of the
ignition limit. These observations were consistent with the work
by Nomaguchi and Koda [138]. The findings on ignition inspired
researchers to develop O3 addition as an ignition control tech-
nique. Such an attempt was proposed in a patent [139] filed in
1997. Several ways of using O3 were proposed in this patent: (i)
by adjusting the amount of O3 added, O3 can be used to control
the start of combustion; (ii) O3 can be used as a cold starting aid;
and (iii) O3 can be used to reduce cold start emissions. The use
of O3 addition as a way to control ignition was later investigated
by Nishida and Tachibana [140] in 2006 on an HCCI system us-
ing natural gas as the fuel. Ignition timing and combustion du-
ration in HCCI engines are governed by chemical kinetics, not by
spark or injection, and thus techniques to control ignition timing
are essential. Nishida and Tachibana [140] carried out a numeri-
cal analysis, showing the feasibility of controlling ignition timing
by varying the amount of O3 added, as illustrated in Fig. 4. They
also experimentally showed that addition of ∼1200 ppm O3 could
advance the main heat release by 18 crank angle degrees (CAD).
They also found that adding O3 was more effective than the addi-
tion of OH radicals, and was as effective as injection of atomic oxy-
gen radicals. Later Mohammadi et al. [141] investigated O3 addition
as a way to enhance ignition in a Premixed Charge Compression
Ignition (PCCI) natural-gas engine. Besides natural gas, other fuels
were also investigated using ozone as a potential ignition timing
control agent. Yamada et al. [142] explored the effect of different
additives on the ignition timing of an HCCI engine with dimethyl
ether (DME) as the fuel. While methanol was confirmed to retard
ignition, attributed to CH3 OH + OH → CH2 OH/CH3 O + H2 O reac-
tion in which methanol is a radical scavenger and terminates DME
chain reaction system (more than one OH can be produced in the
DME + OH reaction chain) in low temperature oxidation, O3 ad-
vanced the ignition timing up to 20 CAD at an estimated addition
of only 0.015% (15 ppm). Yamada et al. [142] inferred that the early
radical supply from O3 reduced the cool flame onset temperature.
Since n-heptane is a fuel that has a cetane number similar to that
of a commercial diesel fuel, Foucher et al. [143] investigated the
effects of O3 addition on HCCI combustion of n-heptane. It was
observed that 50 ppm of O3 addition is able to advance the igni-
tion by approximately 15 CAD. Based on simplified simulation of
constant volume combustion, they concluded that the O3 addition
(which releases atomic oxygen) promoted the combustion via n-
C7 H16 + O = C7 H15 + OH, and the early production of OH acceler-
ated both cool and hot flames. Masurier et al. [144] further inves-
tigated O3 addition as a way to control the ignition timing of an
HCCI engine fueled with primary reference fuels (PRF). Similar to
previous studies, injection of low concentration O3 showed signifi-
cant impact on the flame phasing. Similar results were found when
the fuel was replaced by alcohol [61]. Masurier et al. [145] later
compared the effects of O3 addition with the addition of NO and
NO2 , respectively, on the enhancement of ignition in an HCCI en-
gine fueled by iso-octane. It was found that the highest effect is
achieved by O3 , and the lowest was for NO2 .
4.2. The effect of ozone on laminar flames
4.2.1. Ozone decomposition flame
The ozone decomposition laminar flame was intensively in-
vestigated and has made a great contribution to the develop-
ment of combustion theory. Owing to the overall exothermic
process of ozone decomposition and subsequent O2 formation
(O3 = 1.5O2 + 34 kcal/mol), O3 is a monopropellant. Ozone de-
composition flames can be created using O2 /O3 mixtures or even
pure O3 with only three species (O, O2 and O3 ) involved in the
reaction. Since the reaction mechanism of an ozone decomposi-
tion flame is the simplest real one having all requisite features of
a truly detailed mechanism, it is suitable for a systematic varia-
tion of the transport models and kinetic models used to investi-
gate/validate flame theoretical models [74,146]. The calculated lam-
inar flame speeds can also be compared with experimental mea-
surements.
Early work on ozone decomposition flames include those from
Lewis and von Elbe [147], Hirschfelder et al. [148], von Karman and
Penner [149] in the 1930s–50s by employing steady state approx-
imations of atomic oxygen to solve the governing equations. More
detailed studies were performed in the 1970s. Wilde [150] con-
ducted laminar flame speed calculations using three different O3
decomposition kinetic models and compared with experimental
measurements. He showed that the flame speeds calculated us-
ing different kinetic models varied significantly from 60 cm/s to
152 cm/s for an O3 /O2 (mole ratio 28/72) mixture while the exper-
imental measurement was 52 cm/s at atmospheric pressure. Cra-
marossa and Dixon-Lewis [72] solved time-dependent heat con-
duction and diffusion equations for a number of ozone decom-
position flames with different initial ozone mole fractions. Signif-
icant deviation between computations and experiments was ob-
served. The authors suspected both deficiencies in the reaction ki-
netic model and the quenching effects in the ozone flame experi-
ments because of the small diameter of the experimental appara-
tus. In a later work by Warnatz [146], time-dependent conservation
equations of a laminar flat ozone decomposition flame was solved
including complete multicomponent formulations of diffusion and
heat conduction. In the kinetic model, an updated rate constant
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 5. Enhancement of CH4 /air flame speeds as a function of O3 concentration, where φ is the equivalence ratio. (Reprinted from Wang et al. [65] with permission of
Elsevier.)
of the O3 decomposition reaction (O3 + M = O2 + O + M), which
was approximately 10 times smaller at temperatures above 20 0 0 K,
was employed. The calculated flame speeds agreed well with ex-
perimentally measured values.
As already mentioned, during the same period of time as the
calculations of ozone decomposition flame speeds, multiple ex-
periments were performed. Lewis and von Elbe [151] conducted
the first measurement of ozone decomposition flame speed us-
ing a spherical bomb. No experimental details were presented
as the focus of that work was the development of the method-
ology of a spherical bomb for flame speed measurement. In a
later work by Streng and Grosse [152], flame speeds of O3 /O2
mixtures were measured with different O3 concentrations rang-
ing from 17% to 100% O3 mole fraction in the mixture. In their
experiment, ozone was generated by a standard ozone generator
using an electrical discharge. The O3 /O2 stream was then passed
through a dry-ice trap to condense O3 . Small quantities of liquid
oxygen were removed by using standard vacuum techniques owing
to the different boiling points of O3 (−112 °C) and O2 (−183 °C).
Pure ozone was then used to prepare test mixtures with different
ozone concentrations. Two methods were used to determine the
flame speeds of O3 /O2 mixture. One was the open tube method
where a glass tube of approximately 1 m length was filled with
a test mixture. The mixture was burned in the tube in a hori-
zontal position in a dark room and the propagation of the flame
front was recorded to obtain the flame propagation speed. The ob-
served flame speed was then converted into normal flame speed
by assuming a hemispheric flame front. Another technique used
the burner tip method similar to the Bunsen flame method. It
was found that the measured flame speed was a linear function
of O3 mole fraction in the mixture. In the same work, the au-
thors also tested the stability of O3 /O2 mixtures. It was reported
that the decomposition rate of pure O3 at 296 K and 1 bar was
0.9% per day.
4.2.2. The effect of ozone addition on flame propagation
The effects of O3 addition on laminar flames have also drawn
significant attention. It is not surprising that O3 addition could
enhance flame propagation speeds as the addition causes an in-
crease in enthalpy of the combustible mixture. Ehn et al. [50] cal-
culated CH4 /air flame speeds with and without O3 addition at
constant adiabatic flame temperature conditions by adjusting the
9
equivalence ratios slightly and O3 concentrations for different
calculations. They found that O3 addition could still enhance
flame speeds significantly at constant adiabatic flame temperature
conditions.
Besides their work on ignition in 1989, Nomaguchi and Koda
[138] also measured the burning velocity of CH4 /air at room
temperature and atmospheric pressure. Their data showed that
50 0 0 ppm O3 addition increased the burning velocity by 5% at sto-
ichiometric conditions and that the enhancement of flame speed
was greater at fuel-lean and fuel-rich conditions than that at sto-
ichiometric conditions. Ombrello et al. [52,63] studied O3 addition
on propane (C3 H8 ) flame propagation speed (SL ) using lifted lami-
nar flames, in which liftoff height is very sensitive to SL . O3 addi-
tion was observed to decrease the liftoff height, indicating an in-
crease in SL . When accounting for the kinetic and hydrodynamic
effects, an approximately 4% enhancement of SL at a stoichiomet-
ric condition was reported with 1260 ppm O3 addition. These ob-
servations were later supported by Halter et al. [153] with simula-
tions and a similar experiment. A more recent study by Wang et al.
[65] using a heat-flux burner showed a 3.5% increase of CH4 /air
laminar flame speed with 3730 ppm O3 addition at stoichiomet-
ric conditions, and 9% increase for 70 0 0 ppm O3 . Generally, the
enhancement increases with the increase of O3 concentration, as
shown in Fig. 5. Sensitivity analysis was performed for cases with
and without O3 addition and showed very similar results. For a
CH4 /air/O3 system, O3 addition did not significantly change the
combustion kinetics in the flame, with the primary mechanism be-
ing the release of atomic oxygen in the preheat zone of the flame
to promote early fuel oxidation. The addition of atomic oxygen in
the preheat zone did not alter the reaction pathways of CH4 . An
O3 reaction mechanism was also provided in this work [65], con-
sidering the duplicated and missed reactions in previous works. An
approximately 9% enhancement of SL was reported with 8500 ppm
O3 addition at stoichiometric conditions for an H2 /CO/N2 /air mix-
ture by Liang et al. [135], which was also accomplished using a
heat-flux burner.
Gao et al. [64,154] further studied the effects of pressure and
fuel kinetics on CH4 /air/O3 flames and C2 H4 /air/O3 flames using a
Bunsen burner. A significant increase of SL enhancement was ob-
served at elevated pressures: the enhancement on the measured
SL for a stoichiometric CH4 /air mixture with 6334 ppm O3 addi-
tion increased from 7.7% at atmospheric pressure to 11% at 2.5 atm.
10 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 6. Contribution of major O3 consumption pathways in stoichiometric CH4 /air/O3 flames at atmospheric pressure. T0 = 300 K. (Reprinted from Gao et al. [64] with per-
mission of Elsevier.)
Numerical simulations and kinetics pathway analysis showed that
O3 is consumed in the flame preheat zone by primarily two reac-
tions: O3 decomposition and the reaction O3 + H = O2 + OH. The
first reaction provides atomic oxygen, which attacks fuel molecules
and promotes radical production. In contrast, sensitivity analysis
showed that SL has a negative dependence [66] on the reaction
O3 + H = O2 + OH. Elevated pressure suppresses the dissocia-
tion of H-containing species and diffusion of H atoms from the
flame zone, thus lowering the H atom concentration at elevated
pressure conditions in the preheat zone. As a result, the reaction
O3 + H = O2 + OH is suppressed and the competing pathway,
O3 decomposition, became a more dominant pathway at elevated
pressure conditions. As demonstrated in Fig. 6 at 1 atm O3 decom-
position only accounts for 37.5% of total O3 consumption; while
at 2 atm, 57.6% of O3 is consumed by the decomposition reaction.
This trend of increasing contribution of this pathway continues if
the pressure is increased further. A crossover pressure, at which
O3 decomposition starts to dominate, was observed with a value
of approximately 1.5 atm.
As SL positively depends on O3 decomposition, which provides
atomic oxygen, the enhancement of SL due to O3 addition be-
comes more significant at elevated pressure, as observed in the
experiment.
In contrast to the results for saturated hydrocarbons, inconsis-
tencies (both detrimental and beneficial effects due to O3 addi-
tion) exist in previous studies on the measurement of C2 H4 flame
speeds with O3 addition. Gluckstein et al. [155] observed decreased
C2 H4 laminar flame speeds after O3 addition at room temperature
and atmospheric pressure in a Bunsen burner. They suspected that
this was due to production of CH2 O from low temperature reaction
between O3 and C2 H4 . This explanation is not adequate because
CH2 O actually has greater laminar flame speed than that of C2 H4 .
While another work at sub-atmospheric pressure by Pinchak et al.
[156] showed enhanced C2 H4 SL by O3 addition, and explained this
with the early heat release and radical production due to O3 de-
composition which produces atomic oxygen.
Gao et al. [64,154] systematically investigated the effect of O3
addition on C2 H4 laminar flame speeds and showed that the in-
consistencies previously observed were due to the rapid ozonoly-
sis reactions of C2 H4 at 1 atm and 298 K. At atmospheric pressure
and 298 K, the ozonolysis reaction of C2 H4 is very fast compared
to the reactions between CH4 and O3 , therefore, significant quanti-
ties of C2 H4 reacted with O3 while mixing inside the burner. Heat
release from ozonolysis reactions was then lost to the ambient,
which caused decreased SL to be observed in the experiments con-
ducted by Gluckstein et al. [155]. While at sub-atmospheric pres-
sure conditions, as in the work conducted by Pinchak et al. [156],
the progress of ozonolysis reaction was not significant so only an
insignificant quantity of C2 H4 reacted with O3 inside the burner to
release a small amount of heat release. Therefore, O3 decomposi-
tion remained the dominant effect to enhance C2 H4 flame speeds
at reduced pressure conditions. The pressure effect was confirmed
experimentally by conducting experiments at different pressure
conditions by Gao et al. [154]. They performed further experiments
at cryogenic conditions to suppress the ozonolysis reactions at at-
mospheric pressure. In the experiment, the entire burner system
was cooled to approximately 200 K using liquid N2 to avoid con-
densation of reactants but assure insignificant ozonolysis reactions
inside the burner. At such temperature conditions, less than 10%
of O3 was consumed by ozonolysis reactions prior to arriving at
the burner exit. The measured flame speeds with reactant temper-
atures at 200 K with and without O3 addition are shown in Fig. 7
compared with measurements from existing reference [157] and
simulation. It can be seen that experiments from both Gao et al.
[64] and Dugger [157] deviated from simulations by approximately
10%–15%. However, the trend from the experiments by Gao et al.
[64] is consistent in that O3 addition enhanced flame propagation
speeds of C2 H4 at cryogenic conditions in which the ozonolysis re-
action was suppressed at atmospheric pressure.
4.2.3. The effect of ozone on flame stabilization
O3 addition can also improve flame stability of laminar flames.
Vu et al. [66] demonstrated increased blowoff velocity and ex-
tended flammability limits in a Bunsen burner at atmospheric
pressure using CH4 and C3 H8 as the fuels. They observed that an
initially unstable flame can be stabilized by O3 addition. As illus-
trated in Fig. 8, a C3 H8 /air premixed flame was unstable at fuel
rich extinction limit conditions (φ = 1.5) and the flame fluctuated.
If a portion of the O2 in air was converted to O3 , the initially un-
stable flame could then be stabilized without changing the equiva-
lence ratio. The improved flame stability was attributed to the en-
hancement of laminar flame speeds from O3 addition. Regarding
flame speed, they reported a positive sensitivity coefficient of re-
action O3 + N2 = O2 + O + N2 on flame speed, consistent with
the fact that this reaction produces reactive atomic oxygen to en-
hance flame propagation, and a negative sensitivity coefficient of
the reaction O3 + H = OH + O2 . Such sensitivity analysis supports
their hypothesis that O3 + N2 = O2 + O + N2 , a chain initiation
reaction, is more beneficial to enhance combustion. The increase
in flame speed is used to explain the increase in blowoff veloc-
ity and improved flame stability. With 3810 ppm O3 addition, the
extension of blowoff velocity at stoichiometric conditions was ap-
proximately 9% for a CH4 flame and 11% for a C3 H8 flame [66].
Consistently, Zhang et al. [158] found that the flammability limits
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25 11

Fig. 7. Effect of O3 addition on C2 H4 SL at atmospheric pressure and T0 = 200 K. (Reprinted from Gao et al. [64] with permission of Elsevier.)

Fig. 8. Enhancement of the stability of a C3 H8 /air flame at atmospheric pressure

and room temperature by O3 addition. (Reprinted from Vu et al. [66] with permis-
sion of Elsevier.)

of syngas were substantially extended by O3 addition. Furthermore,

O3 could sustain syngas flames at higher dilution ratios.
The kinetic effect of O3 addition on flames was further inves-
tigated by Weng et al. [159]. A significant increase of CH2 O con-
centration due to O3 addition was detected in a laminar CH4 /air
Bunsen flame using CH2 O-PLIF (planar laser-induced fluorescence),
with effect greater at rich conditions compared to the stoichio-
metric case. With 4500 ppm O3 addition, the CH2 O concentration
was enhanced by 58.5% at a fuel rich condition (φ = 1.4) and
15.5% at a stoichiometric condition. The experimental measure-
ments agreed well with simulation results. To isolate the effects
of the flame, they measured the CH2 O production in heated reac-
tants (no flame), and found that the temperature needed to pro-
duce CH2 O was significantly lowered by O3 addition. Their sim-
ulation showed that the methoxy radical (CH3 O) was the key
species for the production of CH2 O at lower temperature condi-
tions. In laminar flames, CH2 O was formed via decomposition of
CH3 O (CH3 O + M = CH2 O + H + M) and CH3 O was produced via
reactions CH3 + HO2 = CH3 O + OH and CH3 + O3 = O2 + CH3 O.
However, in the pre-heated gas case, CH2 O was formed owing to
the reaction CH3 O + O2 = CH2 O + HO2 and CH3 O comes from
reaction CH3 + O3 = O2 + CH3 O only as the production of HO2
is very low without the presence of a flame. Based on the results
presented by Weng et al. [159], it is very interesting to see how the
Fig. 9. CH2 O-PLIF for a turbulent CH4 /air flame (a) without O3 and (b) with
4500 ppm O3 where φ is the equivalence ratio. (Reprinted from Weng et al.
[159] with permission of Elsevier.)
kinetic process changes in turbulent flames with O3 addition owing
to the expansion of the preheating zone and turbulent transport.
4.3. The effect of ozone on turbulent flames
Only a few works have been devoted to the effect of O3 addi-
tion on turbulent flames. Weng et al. [159] measured the concen-
tration of CH2 O in turbulent CH4 /air flames with or without O3 ad-
dition, using a water-cooled McKenna burner with a jet tube along
the central axis. The Reynolds number of the turbulent flame was
maintained at 6110 with the jet exit flow velocity of 4 m/s. Consis-
tent with observations for laminar flames conducted in the same
work, they observed increased CH2 O concentration in turbulent
flames. Typical CH2 O PLIF images of turbulent CH4 /air premixed
flames are presented in Fig. 9. It was found that such enhance-
ment on CH2 O production was greater than in laminar cases with
12 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
the same quantity of O3 addition (4500 ppm). It was also observed
that there was increased CH2 O concentration in the downstream
region of the flame. The authors explained this phenomenon by
the turbulence-enhanced mixing of unburned and hot gases. No
detailed kinetic analysis was conducted for the turbulent flow case.
Ehn et al. [50] investigated CH4 /air flames in a model gas
turbine swirl stabilized combustor with O3 addition. PLIF mea-
surement showed increased CH2 O concentration as small quanti-
ties of O3 were added owing to the acceleration of the reaction
CH3 + O = CH2 O + H. Their simulation revealed that O3 enrich-
ment could increase laminar flame speed (∼10%) and extend the
extinction strain rate (∼20%) with 0.57% (by volume) O3 addition.
Sensitivity analysis showed that the extension of extinction strain
rate was primarily due to the acceleration of chain branching reac-
tions related with atomic oxygen produced from O3 . The increased
extinction strain rate enabled the flame with O3 addition to burn
under more turbulent conditions than would be possible without
O3 addition. It is worthy to note that the changes of kinetic pro-
cesses presented by Weng et al. [159] and Ehn et al. [50] were not
identical for laminar flames and turbulent flames. More work is re-
quired to understand the interaction between O3 kinetics and flow
field effects to understand the turbulence/chemistry coupling ef-
fect.
A very important phenomenon which has not been studied un-
der turbulent conditions is the effect of O3 addition on hydrody-
namics. In turbulent flames, the flame is stretched and has cur-
vature and equivalence ratio fluctuations. Since flame speed en-
hancement by O3 addition can be very sensitive to small differ-
ences in the flow field interaction with the flame, the coupling be-
tween kinetics and hydrodynamics changes. In the work by Om-
brello et al. [63], the change of kinetic and hydrodynamics owing
to O3 addition was discussed using a laminar lifted jet diffusion
flame. The laminar lifted jet diffusion flame featured a premixed
curved flame head at the base to anchor the jet flame, followed by
a diffusion flame tail. With O3 addition, the non-uniform enhance-
ment of laminar flame speed with the equivalence ratio induced
an increase in the radius of the triple flame front since the lean
and rich premixed flames were enhanced more. The larger radius
of the flame led to more significant flow redirection upstream of
the flame. Therefore, the local flow velocity at the premixed flame
head decreased and allowed for enhanced lifted flame propagation
speeds. In the work by Pinchak et al. [156], it was shown that ax-
ial stretch rate affected flame speed enhancement in a nearly one-
dimensional laminar flame from a Hencken burner. This is owing
to the increased flux of H + O3 reaction at higher flame stretch
rate to provide increased enhancement. These works set the stage
to help explain the more profound effect of O3 addition under tur-
bulent flow conditions.
4.4. Ozone induced cool flames
Ozone was used to induce the formation of cool flames [160–
164]. Cool flames were observed accidentally more than 100 years
ago [165]. Unlike high-temperature flames, the temperature of cool
flames is generally around or below 10 0 0 K. These types of flames
receive attention since low temperature chemistry, which plays a
key role in cool flames, is relevant to practical problems such as
engine knock and fire safety. However, it is challenging to obtain
stable self-sustained cool flames since the low temperature oxida-
tion reactions have long induction times preventing radical chain
branching [163]. After initiation, the cool flame either quenches or
transits to a hot flame. Therefore, addition of O3 , which could as-
sist the initiation and branching of radicals, has been proposed as a
method to induce cool flames. Won et al. [163] demonstrated sta-
ble cool flames experimentally using a counterflow burner with O3
added to the oxidizer side initially. The upper and lower burners
Fig. 10. Direct photos of n-heptane (a) O3 -activated cool diffusion flame and (b)
normal high temperature diffusion flame. (Reprinted from Won et al. [163] with
permission of Elsevier.)
both had a 13 mm inner diameter at the exit. The fuel (n-heptane)
was diluted by N2 and heated to 550 K. The mildly heated fuel
promoted O3 decomposition to release atomic oxygen, which in-
duced the initial fuel oxidation. The early oxidation allowed for
subsequent low temperature chain-branching reactions and cool
flames were observed as shown in Fig. 10(a). Numerical simula-
tions showed that the cool flame extinction limit was substantially
extended by a factor of 3 with 3% (by volume) O3 addition, sug-
gesting that the low temperature chemistry timescale was signifi-
cantly shortened by adding O3 [163]. Ozone addition promotes low
temperature oxidation processes by producing atomic oxygen prior
to the reaction zone. Atomic oxygen then reacts with fuel to gen-
erate OH radicals, which are critical to activate low temperature
chemistry through the pathways of C7 H16 + OH = C7 H15 + H2 O
and C7 H15 + O2 = C7 H15 O2 reactions. Further sensitivity analysis
showed that the cool flame was governed predominantly by low
temperature reactions (relevant to formation of RO2 and QOOH)
and O3 decomposition as shown in Fig. 11(a) rather than those
well-known chain branching/propagation reactions for hot flames,
such as H + O2 = O + OH and CO + OH = CO2 + H. Sensitivity
analysis on the cool flame extinction strain rates on diffusive trans-
port was also conducted and the results are shown in Fig. 11(b). It
is clear that the diffusion of O3 and intermediate species relevant
to low temperature chemistry, such as acetaldehyde (CH3 CHO) and
CH2 O, are critical to cool flames. Cool flames become unstable at
high strain rate (defined as the gradient of axial flow velocities ac-
counting for the density difference between the fuel and oxidizer
streams [163]) or high fuel dilution levels. At low strain rate or
low fuel dilution levels, normal high-temperature flames were ob-
served instead of cool flames as shown in Fig. 10(b).
In a work that followed, Ju et al. conducted numerical simula-
tions on premixed dimethyl ether (DME) flames [160]. Three dif-
ferent branches were observed: normal high-temperature flames,
double flames, and cool flames, as shown in Fig. 12. It was ob-
served that cool flames can exist at the conditions beyond the
flammability of conventional high temperature flames, thus signif-
icantly extending the flammability of the DME mixture. However,
for freely propagating flames at an initial temperature 300 K, only
a normal high temperature flame branch was observed. To observe
cool flames, the temperature of the reactants needed to be raised
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25 13

Fig. 11. Sensitivity analysis of extinction strain rate to (a) reaction rate constants; (b) the species diffusivity, for n-heptane cool diffusion flame. X refers the mole fraction, Tf
refers the initial fuel stream temperature and T0 refers the initial oxidizer temperature. (Reprinted from Won et al. [163] with permission of Elsevier.)

creased the flame reactivity more significantly compared to merely

Fig. 12. Dependence of DME/O2 flame temperature on equivalence ratio for
DME/O2 freely propagating premixed flames. (Reprinted from Ju et al. [160] with
permission of Elsevier.)
to 530 K, or O3 needed to be added in the reactants. It is true
that the enthalpy was increased as part of O2 was replaced by O3 ,
but the authors [160] explained that the formation of cool flames
at 300 K with O3 addition was not solely a thermal effect. They
showed that even at a lower mixture enthalpy, O3 addition in-
heating the reactants. Therefore, O3 kinetically promoted the for-
mation of cool flames as O3 decomposition releases atomic oxygen
in the preheating zone of the cool flame, thus accelerating chain-
branching and stabilizing cool flames at low temperature. Similarly,
for stretched counterflow flames, it was reported that O3 addition
could extend the range of stretch rates at which cool flames can
exist [160]. Sensitivity analysis of the flame speed to reaction rates
and mass diffusivity was performed, as illustrated in Fig. 13, which
shows the cool flame is sensitive to typical low temperature re-
actions and diffusivities of intermediate species. However, for high
temperature flames, it is more sensitive to the reactants and prod-
ucts.
The numerical prediction of the DME premixed cool flame
activated by O3 addition was later experimentally demonstrated
by Reuter et al. [161]. The experiment was performed at atmo-
spheric pressure in a counterflow burner with 13 mm diameter,
with very lean premixed reactants at 300 K, and the counterflow
being heated N2 (600 K). Cool flames were observed when O3 was
added and different flame dynamics compared to normal high-
temperature flames was exhibited. For example, the location of the
cool flame showed little dependence on equivalence ratio, indicat-
ing the weak dependence of its flame speed on equivalence ratio.

Fig. 13. The normalized DME/O2 flame speed sensitivities to (a) the reaction rates for cool flames, and (b) the mixture averaged mass diffusivity for both high temperature
flames (HTF) and cool flames. (Reprinted from Ju et al. [160] with permission of Elsevier.)
14 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 14. Raw CH2 O PLIF images of (a) a O3 -activated DME/O2 cool flame and (b) a DME/O2 normal high-temperature flame at the same flow conditions, (c) the measurement
along the centerline for (a) and (b), and (d) the calculated CH2 O mole fraction and heat release rate (HRR). (Reprinted from Reuter et al. [161] with permission of Elsevier.)
The result is in contrast to normal high-temperature flames where
there is a well-known strong correlation between the flame speed
and equivalence ratio. Difference in flame structure was also ob-
served. CH2 O PLIF measurements showed that the CH2 O profile for
the cool flame was much broader than that of its normal high-
temperature flame counterpart, as compared in Fig. 14.
Hajilou et al. [162] further investigated O3 activated DME pre-
mixed cool flames using a Hencken burner at sub-atmospheric
pressures. Such a platform has been used to study freely prop-
agating flames [166], and was used to measure the propagation
speeds of cool flames [162]. Consistent with previous work [161],
the flame speed was found to be insensitive to equivalence ratio at
very lean conditions. However, it was also reported that the propa-
gation speed decreases as the equivalence ratio increases from 0.6
to 1.4, shown in Fig. 15. The peak flame temperatures decreased as
equivalence ratio increased in the reported range, which is in stark
contrast to normal high-temperature flames.
As a continuation of the previous work [161], Reuter et al.
[164] investigated cool diffusion flames for large n-alkanes. As the
presence of O3 slightly complicates the chemical kinetics, they gen-
erated “ozone-less” cool flames by turning off the O3 generator
after cool flames were established. Without O3 , the cool flames
were much dimmer in terms of the chemiluminescence intensity,
as shown in Fig. 16, but remained self-sustained. “Ozone-less” cool
flames were generated using this method for large n-alkanes rang-
ing from n-heptane to n-tetradecane. Similar to previous work,
the cool flames showed different behavior compared to normal
high-temperature flames. It was found that the chain length of
n-alkanes significantly affected the ozone-less cool flame reactiv-
ity. Given the same fuel mole fraction, the extinction strain rate of
ozone-less cool flames increases significantly with the chain length
of n-alkane. In contrast, the extinction strain rates of normal high-
temperature flames were not very sensitive to the chain length of
n-alkane molecules. However, for the case with O3 , as the low-
temperature reactivity was significantly promoted, the reactivity of
the cool flames could be essentially independent of the size of n-
alkane molecules.
4.5. The effect of ozone on combustion through ozonolysis reactions
While the majority of fuel oxidation reactions require high-
temperature conditions, those involving O3 and alkenes (ozonol-
ysis), occur very rapidly at low temperature conditions, e.g., 300 K,
as indicated by the reaction rate constants in Table 1. The sub-
sequent radical production and heat release could induce in situ
fuel reforming, or even autoignition in a fuel/air mixture. It is
anticipated that ozonolysis could significantly enhance combus-
tion processes. For mixtures containing O3 and alkenes, ozonoly-
sis is dominant at low temperature conditions (approximately be-
low 700 K) and O3 decomposition is only important at higher tem-
perature. A simulation of autoignition in a closed constant pres-
sure homogeneous reactor at 1 atm was performed by the au-
thors of this paper and is shown in Fig. 17 for a mixture of
C2 H4 /O2 /N2 /O3 = 6.3:76.2:13.1:4.4. The simulation was conducted
using USC Mech II [167] combined with a sub O3 mechanism
[65] including simplified ozonolysis reactions [64], which assume
four branches equally for the decomposition of Criegee intermedi-
ate produced from C2 H4 ozonolysis: (1) CH2 O + OH + HCO, (2)
CH2 O + 2H + CO2 , (3) CH2 O + H2 + CO2 , (4) CH2 O + H2 O + CO.
The sub-O3 kinetic model including simplified ozonolysis reactions
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 15. O3 -activated Cool DME flame propagation speeds derived from lift-off height analyses at sub-atmospheric pressures. (Reprinted from Hajilou et al. [162] with
permission of Elsevier.)
Fig. 16. Direct photographs of n-dodecane cool flames with (a) and without (b)
ozone addition. (Reprinted from Reuter et al. [164] with permission of Elsevier.)
Fig. 17. Simulation of autoignition delay for C2 H4 /O2 /N2 /O3 = 6.3:76.2:13.1:4.4
(φ = 1) at 1 atm as a function of initial temperature. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version
of this article.)
of C2 H4 is provided as Supplementary Material for the readers’ ref-
erence. In this simulation, reactions between Criegee intermedi-
ates and other hydrocarbons are omitted because they are largely
unknown. The simplification artificially increases the reactivity of
the mixture because the decomposition of the Criegee intermedi-
ates generates radicals and H2 and is faster than reactions between
Criegee intermediates and hydrocarbons. Therefore, this simulation
is for demonstration only. Without O3 addition, such a mixture
does not autoignite at low temperature conditions, but with O3
addition, it only takes 10 ms to autoignite at 300 K, as shown in
Fig. 17. The result is primarily due to ozonolysis, without which it
takes more than 10 0 0 ms to autoignite as O3 decomposition is rela-
15
tively slow. The effects of ozonolysis become less significant as ini-
tial temperature increases. As shown in Fig. 17, the simulation re-
sults using the models with and without ozonolysis (red and blue,
respectively) gradually converge as initial temperature increases.
These simulation results imply that, at low temperature, ozonol-
ysis of alkenes becomes the dominant O3 consumption pathway
and can significantly promote the combustion to the extent that
O3 decomposition cannot achieve. At temperatures above approxi-
mately 800 K, the effect of ozonolysis reactions becomes negligible
as O3 decomposition becomes very fast. Regardless, the simulation
results show that O3 can dramatically change the autoignition de-
lays at any temperatures. As shown in the simulation, autoignition
can be easily activated by ozonolysis reactions even at room tem-
perature conditions. Following this idea, ozonolysis reactions have
been proposed as a new way to enhance combustion processes
[168–172].
By adding O3 into a C2 H4 /O2 /N2 system, different phenomena
were observed [168–172]. In those studies, non-premixed burners
were used to avoid the heat released from ozonolysis being lost to
the ambient as the time scale of ozonolysis reactions is in the or-
der of milliseconds. An experimental setup used in these studies
is shown in Fig. 18. To minimize the fluctuation of O3 concentra-
tion, a mixing buffer was added between the O3 generators and
the O3 monitor. During the experiment, initially the oxidizer and
O3 generators were turned on, but the fuel stream was turned off.
When the generation of O3 reached steady state, fuel was suddenly
turned on, and autoignition may occur, which was recorded by a
high-frame-rate camera.
It was observed that ozonolysis reactions initiated autoigni-
tion events, as illustrated in Fig. 19. Before the autoignition ker-
nel was formed, a region with weak filtered chemiluminescence
centered at 430 nm with ±10 nm bandwidth was observed, as in-
dicated for t = 1.6–2 ms in Fig. 19. While further investigations
are necessary to identify the emitters of the chemiluminescence
observed around 430 nm before autoignition, one possible emit-
ter is CH2 O∗ (electronically excited CH2 O) whose emission cov-
ers a wide band (centered at 420–430 nm [174]). The chemilu-
minescence could not arise from soot, as there is no combustion
at this moment and therefore no soot. Typically, CH2 O∗ chemilu-
minescence is not used to study conventional high temperature
(>10 0 0 K) flames because at such condition CH∗ chemilumines-
cence (which is centered at 431.5 nm [175,176]) from combustion
is significantly stronger than CH2 O∗ chemiluminescence. However,
it is possible that at low temperatures CH2 O∗ becomes the ma-
jor chemiluminescence emitter. In an early work, Sheinson and
16 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 18. Experimental setup of non-premixed jet flame for the study of ozonolysis
activated autoignition. (Reprinted from Gao [173].)
Williams [174] obtained resolved chemiluminescence spectra from
cool flames (473–673 K) and concluded that the primary emission
source was CH2 O∗ . Other possible emission sources such as CO∗ ,
CH∗ , C2 ∗ , OH∗ , and HCO∗ were shown to be insignificant at such
conditions. Particularly, CH∗ emission only becomes comparable
with the CH2 O∗ signal at higher temperature (∼1073 K). Therefore,
CH2 O∗ can be used to identify cool flames owing to low temper-
ature chemistry, such as demonstrated in Ref. [177]. Chemilumi-
nescence from CH2 O∗ was also reported in ozonolysis reactions
of C3 H4 (propadiene) at room temperature conditions (no flame)
[178]. A simulation conducted using a PLUG flow reactor [179] with
a sub-mechanism of OH∗ , CH∗ , and CO2 ∗ [180,181] shows that at
the experimentally interrogated condition the mole fraction of CH∗
is less than 10−18 so its effect is negligible before hot ignition.
Thus, the authors of Ref. [172] presume the filtered chemilumines-
cence before hot ignition (t ≤ 1.6 ms) was from CH2 O∗ and the fil-
tered chemiluminescence after hot ignition (t = 2.4–4.0 ms) was
Fig. 19. Filtered chemiluminescence images centered at 430 nm of ozonolysis activated autoignition, Re = 1317. (Reprinted from Gao et al. [172] with permission of IOP
Publishing.)
Fig. 20. Simulation results of plug flow reactor model at 101 kPa. Inlet conditions:
U0 = 2.37 m/s, T0 = 300 K, C2 H4 /O2 /O3 /N2 = 9.6/66.5/3.7/20.2. (Reprinted from Gao
et al. [172] with permission of IOP Publishing.)
from CH∗ . At intermediate times (t = 1.6–2.4 ms) chemilumines-
cence from both CH2 O∗ and CH∗ existed, as is evident in Fig. 19 at
2 ms where relatively weak chemiluminescence from CH2 O∗ (pre-
sumed emitter) and strong emission from the ignition kernel from
CH∗ were observed. At highly diluted conditions without a flame,
gas chromatography (Inficon Fusion μGC) sampling confirmed the
existence of CH2 O, CO, H2 , CO2 , which are products of ozonolysis
reactions. Although OH could be produced directly from ozonolysis
reactions, its chemiluminescence was not observed probably due to
its extreme low concentration at low temperature conditions. The
findings implied that autoignition occurred in such a sequence: ox-
idizer and fuel were mixed in the shear layer; at the same time,
ozonolysis reactions occurred and induced heat release and forma-
tion of chemiluminescence emitters (presumed CH2 O∗ as discussed
above); and finally autoignition was induced by the combined ef-
fect of reactive species and heat production from ozonolysis and
its subsequent reactions.
The role of ozonolysis at low temperature can be further illus-
trated using simulations in a PLUG flow reactor, and the results are
shown in Fig. 20. The kinetic model used in this simulation is the
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25 17

Table 2 nation for the flame stabilization and propagation mechanism cor-
Summary of PLUG products and corresponding burning velocity.
respondingly. Fuel was “preprocessed” in situ owing to ozonolysis
Reactor length (cm) 0 2 3.5 3.8 4 reactions upstream of the flame front, which released heat and
Amount of fuel reacted 0% 3% 11% 13% 15% produced reactive species. For large hydrocarbon molecules, the
Exit temperature (K) 300 372 538 594 641
transport properties were also modified. Therefore, the reactivity
Flame speed (m/s) 2.2 2.8 4.3 5.7 10.5
Burning rate (g/s cm2 ) 0.28 0.29 0.30 0.36 0.62 of the fuel-oxidizer mixture increased, and the flame propagation
Increase of burning rate 0% 1% 6% 27% 115% speed was significantly increased. During the interval of t = 2.0–
Mole fraction∗ O2 67% 66.4% 66.0% 65.8% 65.6% 3.6 ms in Fig. 19, the front of the reaction zone propagated approx-
N2 20% 20.1% 20.0% 19.9% 19.9% imately 1.8 cm, corresponding to a very high propagation speed
C2 H 4 10% 9.3% 8.6% 8.3% 8.1%
(∼11 m/s) relative to the burner. For comparison, the laminar flame
O3 4% 3.3% 2.3% 2.0% 1.8%
CO 0 0.2% 0.9% 1.1% 1.3% speed calculated by PREMIX [182] is 2.0 m/s at T0 = 300 K without
H2 O 0 0.2% 0.8% 1.0% 1.2% including ozonolysis reactions in the kinetic model. An extreme
CH2 O 0 0.2% 0.5% 0.6% 0.7% event of fuel preprocessing is an autoignition kernel formed up-
CO2 0 0.1% 0.4% 0.5% 0.6%
stream of an existing combustion zone. One example is given in
H (ppm) 0 0.0 0.0 0.1 0.1
O (ppm) 0 0.0 0.0 0.1 0.2 Fig. 22. At t = 0, the first detectable autoignition kernel (Kernel-1)
OH (ppm) 0 0.8 1.3 1.4 1.5 was generated at approximately 11.5 cm downstream of the burner
∗
exit. For a time 0.25 ms later, a second autoignition event (Kernel-
Only O, H, OH and species with mole fraction greater than 0.1% are listed.
2) was generated upstream of Kernel-1. Both kernels started to
grow and finally merged. The authors also noticed that once the
flame propagated to the lower boundary of the CH2 O zone (below
same as the one used to produce the results in Fig. 17. Simula- which CH2 O concentration was negligible), the propagation speed
tion results show that autoignition is a two-stage process. Start- of the flame was significantly reduced. The result indicated that
ing from the inlet of the reactor, temperature starts to increase the abnormally high flame propagation speed was a result of high
gradually owing to ozonolysis reactions and induced subsequent CH2 O concentration and elevated temperature.
reactions. At approximately 5.5 cm downstream, the temperature The autoignitive environment also allows for the interaction be-
reaches a plateau at approximately 800 K. In the meantime, both tween autoignition kernels and the flame front. Gao et al. [184] ob-
O3 and C2 H4 concentrations continue to decrease (from the inlet served the oscillation of the flame front due to the formation and
of the reactor) due to the production of CH2 O and other ozonolysis blow-out of the autoignition kernel upstream of the flame front.
products. Once O3 is consumed, ozonolysis reactions cease and the Fig. 23 (broadband line-of-sight chemiluminescence) showed an
temperature reaches a plateau. Because the dominant product from example of this process. As shown in Fig. 23(a)–(d), autoignition
ozonolysis reactions, CH2 O, is relatively stable at this temperature, kernels formed upstream of the main flame front. This effectively
reactions slow and the temperature does not change substantially. decreased the lift off height from 2.55 cm in Fig. 23(a) to 1.21 cm in
Following the temperature plateau, complete combustion occurs. It Fig. 23(f). However, the new flame front formed by the autoignition
was observed that ozone decomposition only starts to dominate kernels failed to propagate downstream further owing to the large
when the temperature is above 800 K. It is worth noting that the jet velocity and decreased radical concentrations and temperature
reaction O3 + H = OH + O2 also plays an important role for O3 owing to the decreased level of ozonolysis closer to the nozzle exit:
consumption. If ozonolysis reactions are turned off in the simula- once the kernels extinguished, as shown in Fig. 23(f)–(j), and the
tion, no intermediate temperatures or CH2 O can be observed; O3 liftoff height of the flame returned to a similar level as Fig. 23(a).
decomposition only occurred in the preheat zone very close to the The results discussed above illustrate that it is possible to modify
reaction zone. The results of the simulation also indicate that be- the flame propagation and stabilization mechanism using the au-
fore hot ignition occurred and in a region away from the reaction toignitive environment created using rapid exothermic ozonolysis
zone, ozonolysis is the dominant O3 consumption pathway and is reactions.
responsible for the induced autoignition phenomenon. The inter-
mediate products and temperature are listed in Table 2, together 5. Fuel processing using ozone
with the corresponding simulated burning velocities. Besides heat
released from ozonolysis reactions, reactive species and radicals 5.1. Treatment of solid fuels
are produced, supporting the claim that ozonolysis reactions en-
hance the combustion via kinetic effects. Ozone treatment for coal desulfurization was attempted by
To better understand the experiment, a 3D FLUENT transient Steinberg et al. [67]. In their work, enrichment of the sulfur (SO2 )
simulation was also conducted. The kinetic model employed in this in the effluent gas was detected after O3 treatment of solid coal
simulation was USC Mech II [167] combined with a sub-O3 mech- in a glass tube, indicating the possibility of desulfurization. It was
anism [65] including simplified ozonolysis reactions [64], as pre- reported that the organic sulfur was harder to remove than the
sented in the Supplementary Material. The simulation was able to pyritic sulfur. A sulfur balance for the reaction system indicated
predict similar transient phenomena observed in the experiment. that the sulfur content of the coal sample was reduced by approx-
As illustrated in Fig. 21, at t = 0, the maximum temperature was imately 0.1–1.3%. The authors concluded that such sulfur enrich-
only 831 K with incoming reactants at 300 K and a CH2 O region ment could not indicate a practical desulfurization process unless
downstream was formed with peak mole fraction of ∼3%. Approxi- the enrichment can be significantly increased. No further discus-
mately 2 ms later, a small elevated temperature region was formed sion on the kinetic process was presented.
inside the CH2 O region and the maximum temperature increased Because O3 can react with almost all functional groups of lignite
to 2068 K, indicating the formation of a hot ignition kernel. The ac- organic matter, even with polyaromatic fragments at room tem-
cumulation of CH2 O before autoignition upstream of the localized perature [185], O3 has been used as one reagent to treat lignite.
elevated temperature region was consistent with the experimen- Sharypov et al. [186] investigated the influence of ozonization of
tally observed process shown in Fig. 19. Kansk-Achinsk lignite on the chemical composition, structure, and
With such an autoignitive environment, flame propagation modified lignite reactivity. Lignite particles of size less than 0.1 mm
showed different characteristics. Based on simulation results and were treated by a flowing mixture containing O2 and O3 (2% mole
experimental observations, the authors [172] proposed an expla- fraction) at room temperature in a quartz reactor. The ozonized
18 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25

Fig. 21. Cross-sectional plane of 3D FLUENT simulation of the generation of autoignition kernels in a coflow burner at atmospheric pressure and T0 = 300 K. Center flow is
C2 H4 and coflow is O2 /N2 /O3 , (a, b) heat release rate; (c, d) CH2 O mole fraction; (e, f) temperature profile. (Reprinted from Gao et al. [172] with permission of IOP Publishing.)

Fig. 22. Chemiluminescence of observed autoignition kernels in a coflow burner at atmospheric pressure and T0 = 300 K. Center flow is C2 H4 and coflow is O2 /N2 /O3 .
(Reprinted from Gao et al. [183].)

lignite was compared with those treated by air or helium at 100 °C.
Chemical analysis indicated the incorporation of oxygen into the
organic matter of lignite during ozonization. The authors suspected
that the oxygen might be attributed to simple and complex ethers
and oxygen heterocycles. It was also found that the oxygen in car-
bonyl groups (>C=O, –COOH) increased while the concentration
of hydroxyl groups was reduced after ozone treatment. Ozoniza-
tion also resulted in loosening of the overall molecular structure
of lignite based on results from X-ray diffraction measurement.
Ozonized lignite was also reported to have higher reactivity in hy-
drogenation processes in the presence of hydrogen–donor solvents
and pyrite catalysts. Gao et al. [187] demonstrated that O3 was
able to reduce the surfactant absorptivity of fly ash carbon. A re-
cent work by Patrakov et al. [188] studied the treatment of coal
organic matter (COM) by O3 . Redistribution of atomic oxygen in
the functional groups was detected after ozonization because of
changes in the macromolecular organization. Covalent bonds in-
side large macromolecular fragments are destroyed by ozonolysis
reactions, which in turn decreased the asphaltenes under thermal
liquefaction and increased the low weight compound yields. One
important kinetic effect is the decreased effective activation energy
of thermal liquefaction after O3 treatment, as shown in Fig. 24. It
was shown that C–O bonds were formed in the COM structure of
ozonized coals. These bonds have a lower dissociation energy value
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25 19

Fig. 23. The instantaneous images of the C2 H4 jet with O2 /O3 /N2 coflow at atmospheric pressure and T0 = 300 K showing oscillatory flame liftoff heights. The time differences
between frame (a) and the remaining frames are (b) 0.6 ms, (c) 1.0 ms, (d) 2.0 ms, (e) 2.8 ms, (f) 3.0 ms, (g) 4.2 ms, (h) 7.4 ms, (i) 9.4 ms, (j) 10.4 ms, (k) 11.4 ms, (l) 11.8 ms,
(m) 12.2 ms, (n) 13.0 ms, (o) 14.0 ms, (p) 15.0 ms, (q) 16.0 ms, (r) 17.0 ms, (s) 18.0 ms, and (t) 19.0 ms. (Reprinted from Gao et al. [184].)

than C–C bonds, which explained the decreased effective activation
energy.
5.2. Treatment of liquid fuels
Ozone has also been applied to treat renewable fuels. The crys-
tallization of saturated fatty acid methyl ester (FAME) during cold
weather seasons can cause fuel starvation and operability prob-
lems. For this reason, the pour point needs to be depressed for
neat biodiesel derived from vegetable oils. Ozone was investi-
gated as a pour point depressant by Soriano et al. [189]. In their
work, ozonized vegetable oil was prepared by bubbling an O3 /O2
mixture into vegetable oil. Ozonized vegetable oils (1%–1.5% by
weight) were reported to be effective in reducing the pour point
of biodiesel prepared from sunflower oil, soybean oil and rape-
seed oil to −24, −12 and −30 °C, respectively. The effect is due
to the ozonolysis reaction of alkenes in vegetable oil with for-
mation of 1,2,4-trioxolane polar rings. The polar groups are the
typical molecular structure of pour point depressants for conven-
tional diesel, which act on the growing sites of the crystals during
cooling. Complete solidification of sunflower oil biodiesel was con-
ducted. Treatment with 1% ozonized vegetable oils minimized the
solidification. Microscopic analysis revealed that neat sunflower oil
biodiesel fused together into large irregular-shaped agglomerates
after subjecting it to temperatures of 3 °C for 20 min as shown in
Fig. 25. However, the ozonized sunflower oil impeded the agglom-
eration, giving smaller crystals with sizes of approximately 10 μm
which maintained the fluid flow properties and improved the pour
point of biodiesel.
Ozone treatment has also been investigated to modify fuel
reactivity adaptively to control ignition timing. Schönborn et al.
[68] demonstrated a method to control ignition timing under HCCI
combustion conditions by modifying the molecular structure of
the fuel using ozone. The result was achieved by bubbling air
that contained O3 (4% by volume) through a variable proportion
of the fuel (1,1-Diethoxyethane) prior to injecting into the engine
20 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 24. The effective activation energy of thermal liquefaction process of (1) initial
and (2) ozonized coal vitrinites. (Reprinted from Patrakov et al. [188] with permis-
sion of Elsevier.)
(single-cylinder direct injection diesel engine). The bubbling pro-
cess lasted approximately 4 h at 293 K and 1 atm. The contact
of fuel with ozone resulted in partial oxidation of the fuel. Even
though the change of fuel composition was not clear, elemental
analysis carried out before and after O3 treatment suggested an
increase in oxygen content occurred during the oxidation of the
fuel with O3 . The authors suspected that the reactions between
fuel and O3 -containing air converted a portion of the fuel to per-
oxide (e.g., 1-ethoxy-1-(ethylperoxy)ethane) based on nuclear mag-
netic resonance (NMR) spectra and standard iodometric titration
analysis. The hydroperoxides in the fuel induced by reactions with
ozone could promote autoignition through decomposition to pro-
duce OH. It was shown that as the proportion of oxidized fuel in-
creased, the ignition timing was advanced more in the engine test.
As a continuation of the work, Schönborn et al. [60] further investi-
gated the possibility of controlling the ignition timing with another
fuel, 1-hexene, by altering its molecular structure using prior reac-
tion with O3 . NMR was used to analyze the fuel before and after its
reaction with O3 . Several oxygenated products were identified in
the fuel treated by O3 , which resulted in the formation of ozonide
molecules with a peroxidic structure. Correspondingly, an engine
system utilizing such “smart fuel” was proposed. A portion of fuel
was pre-processed by O3 and then mixed with the non-processed
fuel. The ignition timing was therefore advanced, likely due to the
early decomposition of peroxidic molecules (1-hydroperoxyhexane)
owing to the O3 /fuel reaction, as suspected by the authors. There-
fore, the ignition timing could be controlled via the fuel mix-
ture composition. Still, no definite composition changes of ozone
Fig. 25. Sunflower oil biodiesel viewed under the microscope (200×) at 3 °C for 20 min ((A) neat sample; (B) with 1% ozonized sunflower oil). (Reprinted from Soriano Jr.
et al. [189] with permission of Elsevier.)
treated fuel were identified, which indicates the complexity of the
underlying chemical reactions.
6. Emission control using ozone
The effect of O3 addition on pollutants from combustion sys-
tems has been investigated as well. In 1980, Slater and Rizzone
[69] conducted experiments to investigate the removal of sulfur
oxide by ozone. Ozonated O2 was mixed with SO2 , NO, and Ar in
a heated stainless-steel reactor. A cold trap maintained at −80 °C
was used downstream to condense SO3 and NO2 formed in the re-
actor. Without NO addition, O3 decomposed to form atomic oxygen
and then reaction SO2 + O + M = SO3 + M converted SO2 to SO3
inside the reactor. The SO2 conversion ratio was found to be non-
monotonic with increased reactor temperature, initially increas-
ing and then decreasing. The SO2 conversion ratio was reduced
in the presence of NO, which consumed O3 quickly through reac-
tions NO + O3 = NO2 + O2 and NO2 + O = NO + O2 . Tachibana
et al. [62] measured the concentration of CO, unburned hydrocar-
bons, and NOx in the exhaust gas of a diesel CFR (Cooperative Fuel
Research) engine with and without O3 addition. Ozone produced
by a commercial ozonizer was introduced through the inlet port.
In the case without combustion, the authors measured the con-
centration of O3 in the intake and exhaust of the engine and no
change in concentration was found. The result indicated that the
lifetime of O3 was quite long and therefore all of the O3 that was
produced would be available for reaction in the engine. In case
of combustion, the advancement of crank angle and improvement
on ignition (decrease ignition delay and increase cetane number)
were observed with ozone addition. With O3 addition, the concen-
trations of CO and unburned hydrocarbons decreased with the in-
crease of O3 concentration. Regarding NOx , the emission slightly
decreased and then slightly increased with the increase of O3 con-
centration. The authors suspected that the increased NOx concen-
tration was caused by the changes of combustion temperature as
the enthalpy increased after adding O3 . Filter paper was placed in
the exhaust to trap particulates, and the contamination level was
estimated using the light intensity passing through the filter pa-
per. The level of particulates decreased as well, though not to the
same extent as CO and unburned hydrocarbons decreased. Simi-
lar results were observed by Wilk and Magdziarz [190], who sup-
plied natural gas and air mixtures to a modified Mecker burner.
The concentrations of CO, unburned hydrocarbons, NO, and NO2
were measured for cases with and without O3 . Consistent with
results from Ref. [62], O3 addition reduced concentrations of CO
and unburned hydrocarbons, and slightly increased NO concentra-
tion. No effects on NO2 were detected. Besides the addition in the
 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
Fig. 26. NO conversion property with O3 added at different temperatures.
(Reprinted from Wang et al. [107] with permission of Elsevier.)
oxidizer, O3 injection has also been used in processing flue gas.
Commercially, Cannon Technology Inc. and BOC Gases developed a
low temperature oxidation (LTO) process for removing NOx emis-
sions using O3 injection in 2003 [191]. O3 was injected into the
cooled exhaust flue gas from a boiler. NOx was then oxidized in the
oxidation chamber to N2 O5 (via reactions: NO + O3 = NO2 + O2 ;
NO2 + O3 = NO3 + O2 ; NO2 + NO3 = N2 O5 ), with a portion of
CO oxidized to CO2 , and SO2 oxidized to SO3 . Later, a two-step
technique was proposed by Mok and Lee [109] to remove NOx and
SO2 simultaneously using O3 . In this technique, NO was first oxi-
dized to NO2 in the ozonizing chamber and an absorber contain-
ing a reducing agent solution (Na2 S) was used downstream to re-
move NO2 and SO2 . It was reported that NOx removal efficiency
was approximately 95% and SO2 removal efficiency was 100%. A
detailed kinetic model of ozone–nitrogen oxides summarized from
the NIST Chemical Reactions Database was also presented in this
work [109]. Wang et al. [107] investigated the possibility of simul-
taneously removing NOx , SO2 , and Hg using O3 . Another process
simultaneously removing NOx and SO2 by O3 was also investigated
by Sun et al. [192]. A general observation from these works is that
NO contained in flue gas can be effectively oxidized by O3 owing
to the fast NO + O3 = O2 + NO2 reaction. However, as O3 decom-
poses at high temperature, the effect of O3 injection on pollutant
oxidization may be reduced. For example, as shown in Fig. 26, at
373 K, adding 200 ppm O3 oxidized more than 80% of NO, but at
673 K, adding O3 essentially did not oxidize NO as O3 decomposed
and recombined to O2 before reacting with NO.
7. Challenge and future research
While many investigations have contributed significantly to an
understanding of ozone related reactions, inconsistency remains,
which is hampering accurate kinetic modeling of O3 assisted com-
bustion. Previous studies suggest that several kinetic pathways
may exist in parallel, including direct reactions with fuel (ozonoly-
sis), as well as with intermediate/radical species. However, it is still
not clear how and to what extent the different O3 reaction path-
ways affect combustion processes. It is possible that such effects
are dependent on local conditions, including temperature, pres-
sure, and chemical composition. Therefore, a systematic study con-
ducted over a wide range of operating conditions relevant to prac-
tical combustion systems is needed. Furthermore, ozonolysis reac-
21
tions for alkenes have shown potential to enhance flame propa-
gation and stabilization, but only a limited number of studies have
been conducted on this topic. Since O3 can potentially be deployed
in situ to promote the reactivity of a system, such research is of
relevance to a number of practical devices.
Regarding the effects of O3 addition on fundamental combus-
tion processes, only several small molecule fuels have been inves-
tigated (syngas, CH4 , C3 H8 , and C2 H4 ). It is not clear how conclu-
sions change if fuels with larger molecules, or fuels with differ-
ent functional groups such as aromatics, are applied. For exam-
ple, large molecules generally break down into smaller molecules
before entering into the rapid reacting/high temperature burning
state of a flame. However, when O3 is added, ozonolysis or ozone
decomposition reactions may fundamentally change reaction path-
ways by changing both kinetic and transport properties of the mix-
tures. Furthermore, the effects of O3 addition on multi-component
fuels are also not clear.
Ozone can be economically produced at a large scale and in sig-
nificant quantities at elevated pressure conditions which is benefi-
cial to combustion systems. In most experiments, ozone was pro-
duced by commercial ozone generators typically based on corona
discharge which used pure oxygen as a working fluid. For most
practical applications, air has to be the working fluid, which poses
challenges on ozone production and lifetime for transport owing
to the existence of nitrogen and water vapor in air. More stud-
ies are needed to optimize ozone generation using different exci-
tation means and under different flow conditions. For example, if
the ozone generator is based on absorption of UV radiation, selec-
tive wavelengths could be used for optimizing production. If the
ozone generator is based on an electrical discharge, optimizing the
reduced electric field of the discharge can potentially maximize the
production of select products like ozone [193].
8. Conclusion
With our increasingly growing appetite for creative energy con-
version means by pushing the limits of traditional combustion
processes, O3 has drawn significant attention as a means to en-
hance and control combustion/ignition processes. Compared to
other combustion enhancement techniques, potential advantages
of O3 addition are that it can be efficiently and economically gen-
erated at elevated pressures and it has a relatively long lifetime to
be transported. Significant advancements in ozone assisted com-
bustion have been made in the past decade, where it has been
shown to process fuels, control emissions, and enhance ignition,
flame propagation, and improve flame stabilization.
Ozone decomposition at relatively low temperature is responsi-
ble for the majority of combustion enhancements achieved with
O3 addition. Such reactions release reactive atomic oxygen and
accelerate the chain branching process. However, in the reaction
zone of flames, where a radical pool has already been established,
O3 decomposition may not affect the combustion process signifi-
cantly. For example, every ∼10 0 0 ppm O3 addition could enhance a
CH4 /air laminar flame propagation rate by approximately 1%, while
the autoignition delay of a CH4 /air mixture could be dramatically
shortened (by several orders of magnitude) with the same quantity
of O3 addition. Another potential mechanism to enhance and con-
trol combustion processes is via low-temperature reactions related
to O3 , such as ozonolysis. Such reactions could initiate fuel oxida-
tion/dissociation far upstream of the flame or combustion zone to
change the molecular structures (compositions) of reactants. It can
potentially change both kinetic and transport properties of the re-
actants, therefore affecting flame/ignition characteristics. However,
large knowledge gaps remain with regard to a fundamental un-
derstanding of O3 assisted combustion, especially when ozonoly-
sis reactions are the dominant pathways. The detailed pathways of
22 W. Sun, X. Gao and B. Wu et al. / Progress in Energy and Combustion Science 73 (2019) 1–25
ozonolysis reactions remain unclear, which brings large uncertainty
in simulation and the interpretation of the kinetic effects. Further-
more, the available studies focus on small molecule fuels and re-
search using real fuels are limited. It is not clear if or how the con-
clusions change when O3 addition is applied to, for example, liquid
fuels. With the potential for many pathways for O3 to couple into
the kinetics of combustion systems, there is a future full of pos-
sibilities, from simple burners to high-speed air-breathing propul-
sion systems.
Acknowledgments
This work is supported by the Air Force Office of Scientific Re-
search (FA9550-16-1-0441), with Dr. Chiping Li as technical mon-
itor. The authors acknowledge thorough reviews and insightful
feedback from both anonymous reviewers and the editor (Prof. Hai
Wang).
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.pecs.2019.02.002.
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Mr. Bin Wu received his B.E. degree from University of

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Science and Technology of China in 2014, and is currently
makov V, et al. Some features of chemical composition, structure and re-
a Ph.D. candidate at Georgia Institute of Technology. He
active ability of Kansk-Achinsk lignite modified by ozone treatment. Fuel
has been working on the ozone-assisted combustion since
1999;78:663–6.
2016, focusing on ozone related chemistry.
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the chemical modification of carbon surfaces in fly ash. Fuel 2001;80:765–8.
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of ozone treatment on change of structural–chemical parameters of coal
vitrinites and their reactivity during the thermal liquefaction process. Fuel
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depressant for neat biodiesel. Fuel 2006;85:25–31.
[190] Wilk M, Magdziarz A. Ozone effects on the emission of pollutants coming
from natural gas combustion. Polish J Environ Stud 2010;19:1331–6. Timothy Ombrello earned his Ph.D. in Mechanical and
[191] Jarvis JB, Day A, Suchak N. LoTOxTM process flexibility and multi-pollutant Aerospace Engineering from Princeton University in 2009
control capability. In: Proc combined power plant air pollution control mega where he worked towards developing an understanding
symposium, Washington, USA; 2003. p. 19–22. of the kinetic effects of long lifetime plasma-produced
[192] Sun W-Y, Ding S-L, Zeng S-S, Su S-J, Jiang W-J. Simultaneous absorption of species. Upon completing his graduate degree, he went
NOx and SO2 from flue gas with pyrolusite slurry combined with gas-phase on to work at the Air Force Research Laboratory, ini-
oxidation of NO using ozone. J Hazard Mater 2011;192:124–30. tially as a National Research Council Research Associate
[193] Li H-P, Ostrikov KK, Sun W. The energy tree: non-equilibrium energy transfer for one year before joining civil service as a Research
in collision-dominated plasmas. Phys Rep 2018;770-772:1–45. Aerospace Engineer in the Aerospace Systems Directorate.
He works predominately on research related to high-
Dr. Wenting Sun is currently an assistant professor in speed air-breathing propulsions systems, specifically su-
the School of Aerospace Engineering, Georgia Institute of personic combustion ramjets, covering a range of fluid dy-
Technology. He received his B.E. and M.E. degrees from namic, combustion, and diagnostic challenges. His inter-
Tsinghua University in 2005 and 2007, respectively and ests lie in performing research and crafting techniques to enhance reactivity for
received his Ph.D. degree from Princeton University in more rapid ignition and more robust flame propagation and stabilization, from fun-
2013. He was selected for the U.S. AFOSR Young Inves- damental bench-top to supersonic wind tunnel experiments. For his contributions
tigator Program in 2016 to study ozone chemistry and thus far, he has been given the Early Career Award from the Air Force Research
the effect of ozone on combustion dynamics. He has been Laboratory, and the Presidential Early Career Award for Scientists and Engineers
working in the field of plasma-assisted combustion since (PECASE) from the White House.
2007. His work on plasma/ozone assisted combustion is
to induce plasma generated species into combustion sys-
tem to enable combustion at extreme conditions.

Dr. Xiang Gao received his B.E. degree from Beijing Uni-
versity of Aeronautics and Astronautics in 2012, and his
Ph.D. degree from Georgia Institute of Technology in 2017.
He has been working on the ozone-assisted combustion
since 2014, covering the kinetic and dynamic parts. He
is currently a Data & Applied Scientist at Microsoft Re-
search.