JID: PROCI

ARTICLE IN PRESS [mNS;August 23, 2022;2:48]

Available online at www.sciencedirect.com

Proceedings of the Combustion Institute 000 (2022) 1–9

www.elsevier.com/locate/proci

Consistent thermodynamics for plasma-assisted

combustion
T. Hazenberg a,∗, J.F.J. Janssen b, J. van Dijk c, J.A. van Oijen a
a Eindhoven University of Technology, Department of Mechanical Engineering, Eindhoven, The Netherlands
b Plasma Matters BV, Eindhoven, The Netherlands
c Eindhoven University of Technology, Department of Applied Physics, Eindhoven, The Netherlands

Received 4 January 2022; accepted 10 July 2022

Available online xxx

Abstract

Excited-state species are a vital component of plasma chemistry modeling. Many previous works have studied
the reactions of excited-state species. In almost all of these studies, the thermodynamic properties of the
excited states are obtained via a modification of the formation enthalpy. It is often assumed that the error
introduced by this procedure can be neglected. However, this is not true when vibrational states are included
in the chemical mechanism. Specifically, we find that the error in adiabatic flame temperature can be as high
as 100 K, and the error in NO concentration is as large as 50%. In this work, we will demonstrate how to
consistently compute the thermodynamic data for these species. Key in computing thermodynamic data for
excited-state species is the realization that an excited state is a subset of a full molecule description. The main
challenge then becomes the consistently distributing the internal states over individual species.
© 2022 The Author(s). Published by Elsevier Inc. on behalf of The Combustion Institute.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

Keywords: Non-equilibrium; Heat capacity; Plasma-assisted; Vibrational; Thermodynamic

1. Introduction librium. A combination of the above ensures that

Thermodynamic properties are of great impor-
tance in combustion simulations. The enthalpy of
reactants and products is vital to determine an
accurate heat release per kilogram of fuel. For a
given heat release rate, the mixture heat capacity
determines the rate change of temperature. Fur-
thermore, the change of Gibbs free energy is vi-
tal for the reverse rates of reactions and thus equi-
∗
Corresponding author.
E-mail address: t.hazenberg@tue.nl (T. Hazenberg).
mixture composition and temperature can be ac-
curately determined in combustion processes. Sta-
tistical mechanics can be used to determine the
thermodynamic properties of species [1,2]. How-
ever, such computation is too expensive for use
during a combustion simulation. Since thermody-
namic properties are usually assumed to depend
exclusively on temperature, they are effectively ap-
proximated by polynomials [3]. Combustion reac-
tion mechanisms include these polynomials, and
large databases (e.g., [4]) exist that contain polyno-

https://doi.org/10.1016/j.proci.2022.07.075
1540-7489 © 2022 The Author(s). Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open
access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
JID: PROCI
ARTICLE IN PRESS [mNS;August 23, 2022;2:48]

2 T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx

mials for many species and a wide range of temper-

atures.
Only a very limited number of excited-state
species are tabulated in this way. In plasma-assisted
combustion research, this results in a large data
deficit. In some articles, it is left unspecified how
the thermodynamic data of excited states is ob-
tained [5–9], while in others the thermodynamic
data of excited states is obtained via a modifica-
tion of the formation enthalpy [10–14]. Yet other
articles, avoid the detailed description of plasma
chemistry and employ a phenomenological model
(e.g., [15–17]). They introduce an equation for the
energy stored in the vibrational excitation of ni-
trogen. In all these articles, inconsistencies are in-
troduced via the thermodynamic properties of the
mixture. While most only introduce inconsisten-
cies in electronically excited states, some also intro-
duce inconsistencies in the vibrational states [11–
17]. Specifically in these, the adiabatic flame tem-
perature can be inaccurate by as much as 100 K.
In this work, we will highlight how these in- Fig. 1. Adiabatic flame temperature and relative error
consistencies are introduced and how to construct in the rate constant of N2 + O ↔ NO + N. 1) GRI-
a consistent thermodynamic dataset for plasma- mech 3.0 [18] 2) Current, 3) Mao et al. [12], DeFilippo
et al. [11], Deak et al. [14] and Bellemans et al. [13] and 4)
assisted combustion. In Section 2, we give an exam- Castela et al. [15] and derived work [16,17].
ple of inconsistent thermodynamic modeling found
in the literature. In Section 3, the equations to ob-
tain thermodynamic data of a species are intro-
duced. In Section 4, it is explained how the ther-
modynamics of a set of internal states should be in this case, the sum of equilibrium vibrational en-
obtained. These first sections, provide the theoreti- ergy (eeqvib (T ) in the article of Castela et al. [15])
cal framework from which illustrative examples are and enthalpy is conserved, as is done in Castela
explained. In Section 6, it is explained why the ex- et al. [15] and Bechane et al. [16,17] (Vibrational En-
ample of Section 2 resulted in such a largediscrep- ergy Equation).
ancy. Finally, the authors would like to stress the In the top graph of Fig. 1, the adiabatic flame
value of previous work, even though we have iden- temperature is shown for these mixtures. The Con-
tified inconsistencies in them. Each of these articles sistent line indicates the approach which we will
has added valuable knowledge and improved our outline in the next sections, these results are prac-
understanding of plasma-assisted combustion. tically identical (error less than 0.2 K) to GRI-
3.0 [18]. It can immediately be seen that Shifted
Enthalpy method is inaccurate. As this method
2. Adiabatic flame temperature under-predicts the adiabatic flame temperature by
as much as 100 K. This is because the vibrational
Before we explain any theory, let us demonstrate states of N2 (and in some mechanisms O2 ) are effec-
why we have written this article. The thermody- tively included twice. Once explicitly, as a species,
namic properties of excited states species are con- and once implicitly, as part of the heat capacity.
sistently and erroneously obtained via a modifica- The second type of inconsistency is introduced in
tion of the formation enthalpy (e.g., [10–14] and the articles which introduce a phenomenological
likely those that did not specify how they obtained model for the plasma, e.g., [15–17]. These authors
their thermodynamic data). While this method is have introduced a conservation equation for the vi-
acceptable for electronically excited states, it is brational energy, which is coupled to the conven-
flawed for vibrational species. To demonstrate, the tional energy equation via a relaxation rate. This,
adiabatic flame temperature is computed using: 1) effectively, results in the conservation of the com-
GRI-mech 3.0 [18] (Reference). 2) The mechanisms bined energy vibrational and conventional energy
of DeFilippo et al. [11], Mao et al. [12], Belle- equation. However, the thermodynamic data of the
mans [13] and Deak et al. [14], these results are very species still contains the vibrational states. Effec-
similar (less than 10 K difference) and are there- tively, they have introduced the same inconsistency
fore shown as a single line (Shifted Enthalpy). 3) as in the Shifted Enthalpy method, thus the vibra-
The same mechanism is used but then with con- tional energy is included twice: Once in the vibra-
sistent thermodynamics as outlined in the rest of tional energy equation and once in the species def-
the article (consistent). 4) GRI-mech 3.0 [18], but initions.
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
JID: PROCI
ARTICLE IN PRESS [mNS;August 23, 2022;2:48]

T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx 3

In the bottom graph, the temperature-induced
error in the rate constant for the rate-limiting re-
action in the Zeldovich mechanism is shown (N2 +
O ↔ NO + N). Our Consistent approach is practi-
cally identical (error less than 0.2%) to the Refer-
ence. However, both the Shifted Enthalpy and Vi-
brational Energy Equation under-predict the rate
constant by at least 50%, worse in the fuel-lean
regime where it is less than one-third of the ex-
pected rate. Note, as these inconsistencies are part
of the thermodynamic description, they are present
in the entire burned side of the flame. Moreover,
even without plasma present, the predicted flame
temperature will be inaccurate. As such, we believe
that the prediction of NOx emissions in practical
burners is significantly hampered by these inconsis-
tencies.
Finally, an inaccurate flame temperature predic-
tion in plasma-assisted combustion might be con-
sidered a minor source of uncertainty, when this is
compared to the uncertainty in rate constants [19–
21]. Moreover, at low temperatures, those relevant
to plasma-assisted ignition studies, the induced er-
ror in temperature is significantly smaller. As such,
it is unlikely that ignition delay time will be severely
affected. However, accurate thermodynamic data
can also be employed to improve the rate constants
in plasma-assisted. Elementary reactions involv-
ing excited state species are reversible and should,
therefore, adhere to thermodynamic equilibrium,
i.e., reverse rates can be computed from the change
in Gibbs-free energy. The consistent thermody-
namic description outlined in this article can be
used to reliably compute reverse rates from ther-
modynamic equilibrium. This, in turn, can be used
to reduce the number of uncertain parameters in
plasma mechanisms or it might be used to identify
unlikely reactions in the chemistry.
tions of temperature. In this section, we will shortly
explain the established theory to obtain thermody-
namic properties for a species. In this context, a
species is a collection of internal states.
3.1. Partition sum
The internal partition sum provides a statisti-
cal description of the internal states of a molecule.
To obtain the internal partition sum, we employ
what Burcat [4] referred to as a “direct summation”
method. They consider this class of methods as the
most accurate way to obtain thermodynamic prop-
erties. The method requires the energy and degen-
eracy of each internal state, see the Supplementary
Materials for more details on the method that is em-
ployed. Finally, a distinction is made between the
internal and external contributions to the energy
of a molecule. The external contribution is only the
translational energy, and the internal contributions
are all remaining contributions (electronic configu-
ration, rotations and vibrations). The internal par-
tition sum reads [1,22]
  
Eev j
Zint (T ) = gev j exp − , (1)
ev j
Ru T
in which gev j is the degeneracy of the energy level,
Ru is the universal gas constant, and ev j are the in-
dexes of the electronic, vibrational and rotational
state. The sum either includes all energy levels of
a molecule to form a single species, or a predefined
set of energy levels to form multiple species of a sin-
gle molecule. In our implementation, we have taken
Eev j = 0 at the bottom of the lowest electronic con-
figuration (see Fig. 2 as reference).
3.2. Thermodynamic quantities

To obtain the thermodynamic properties, two

3. Statistical mechanics moments of the partition sum are introduced [22]:
    
 Eev j Eev j
A molecule has several discrete internal energy Zint (T ) = gev j exp − (2)
levels each can be degenerate. When developing ev j
Ru T Ru T
non-equilibrium chemistry models, an extremely
detailed model could consider each of these energy and
levels as an individual species. Given that even a   2  
 Eev j Eev j
simple molecule like O2 contains 30000 energy lev- Zint (T ) = gev j exp − . (3)
els, it is clear that such a model is computation- ev j
Ru T Ru T
ally unfeasible; even the combustion of methane
Using these moments, the enthalpy H of a species
would easily involve over a million species. Gener-
can be computed as [22–24]
ally, it is silently assumed that the relaxation rates

between some or all internal energy levels are much H (T ) 5 Z (T )
faster than the reaction rates between species. This = + int . (4)
Ru T 2 Zint (T )
means that these internal energy levels are in equi-
librium. The assumption of equilibrium between The heat capacity is the temperature derivative of
energy levels allows us to reduce 30000 energy levels the enthalpy and is expressed through moments of
to a single O2 species. As a result, the heat capac- the partition sum [22–24],
ity of such a single species, a collection of internal 
  2
states, is a function of temperature. Furthermore, Cp (T ) 5 Z (T ) Zint (T )
= + int − . (5)
the enthalpy and entropy become non-trivial func- Ru 2 Zint (T ) Zint (T )
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
JID: PROCI
ARTICLE IN PRESS [mNS;August 23, 2022;2:48]

4 T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx

Fig. 2. An illustrative example of the hierarchy of internal states in a typical diatomic molecule. On the left, the potential
of three electronic states are drawn, designated by X, A and B. In the bottom of the ground state potential, X, a few
vibrational states are shown. In the center, a small region of the potential is shown, which shows that these vibrational
states contain rotational states. On the right, a small region of a single vibrational band is shown.

Finally, the entropy reads [22–24]:
  
S (T ) 5 2π MRu T 3/2 Ru T
= + ln
Ru 2 Na h2 Na P
 using the above equations for the temperature
Zint (T )
+ ln (Zint (T ) ) + , (6)
Zint (T )
where M is the molar mass of the molecule, Na is
Avogadro’s number, h is Planck’s constant and P is
the reference pressure (P = 1atm). Note, in all ther-
modynamic properties an explicit contribution due
to the translational degrees of freedom is present.
This is because we did not include the translational
energy levels in the partition sum and thus assume
they are statistically independent of the (internal)
energy levels.
As we have not yet considered the standard en-
thalpy of formation in the definition of Eev j , an off-
set is computed. The offset enthalpy is computed by
comparing our results for a molecule including all
internal states to that in Burcat’s database [4]:
hi (T ) = Hi (T ) − Hfull (Tref ) + hburcat,full (T ) (7)
where, Hi (T ) is the enthalpy for the newly defined
species computed from Eq. 4, Hfull (Tref ) is the en-
thalpy of the full molecule at the reference tem-
perature (Tref = 298K) as computed from Eq. 4,
hburcat,full (T ) is the enthalpy of the full molecule as
computed from Burcat’s database, and finally hi (T )
is the new species enthalpy. If all internal states
of a molecule are included Hi (Tref ) is identical to
Hfull (Tref ), meaning the enthalpy of the molecule at
298 K is adjusted such that it is identical to that
of Burcat’s database. If not all internal states of
a molecule are included in a single species, then
Hi (Tref ) − Hfull (Tref ) is equal to the excitation en-
ergy of the excited state. The newly defined en-
thalpy at 298 K is then at an offset to Burcat’s
database, with the offset equal to the excitation en-
ergy of the excited state. Using this method, both
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
the chemical contribution and the fact that species
whose elements are in the standard state should
have zero enthalpy at 298 K are taken into account.
The thermodynamic properties are evaluated
range of 200 K-6000 K. After, a modified version
of the simultaneous fitting procedure developed by
Zaleznik and Gordon [3] is used to produce NASA-
format polynomials.
4. Splitting of internal states
In this work, the energy levels of a molecule are
consistently distributed over several species. It is
surprisingly simple to do this; every internal state
must be included exactly once. A concise notation
of species names is introduced to aid with this. We
provide the chemical formula per usual, succeeded
by the states which are included in the species. As an
example, the “classical” oxygen species, for which
all internal energy levels are included, is designated
as O2 (a,a,a). Where, (a,a,a) designates: any elec-
tronic level, any vibrational level, and any rota-
tional level. Note, when a species contains all in-
ternal levels this does imply that the enthalpy is
the highest. On contrary, as the ground state is in-
cluded the enthalpy will, at room temperature, at
least be lower than that of any electronically or
vibrationally excited state. It does imply that this
species has many degrees of freedom to excite and
the heat capacity is thus a function of temperature.
The singlet oxygen species from Konnov’s hy-
drogen mechanism [25], by him, referred to as
O2 (a1 g ), we designate as O2 (1,a,a), the first elec-
tronically excited state and any vibrational or ro-
tational level. Alternatively, a species including the
first two electronically excited states will be desig-
nated as O2 (1–2,a,a). More generally, when x1 − x2
is used and x1 is not provided, we include all until
JID: PROCI
ARTICLE IN PRESS
T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx
Fig. 3. Comparison of computed heat capacity for O2 ,
CO with data from Burcat [4] and O2 (1 ) with data from
Togai et al. [26].
x2 , and if x2 is not provided we include all larger
than x1 . A final rule is necessary if we want to in-
clude all internal states but a designated few. For
this, we will use a forward slash as a negate sym-
bol. As an example, an oxygen species with all elec-
tronic states but the singlet states from before is
designated as O2 (/1–2,a,a). Using this notation, the
species name is also a direct indication of the states
included in the summation of Eqs. 1, 2, and 3.
5. Validation
Given the spectroscopic constants of a
molecule, thermodynamic data can be obtained
with the theory from the previous section. The
dimensionless heat capacity (Cp /Ru ) of O2 (a,a,a)
and CO(a,a,a) is presented in Fig. 3. These are
the classical combustion species as you would find
them in most reaction mechanisms, meaning that
these results should match known species results
tabulated in thermodynamic databases. For both
species, the heat capacity is equal to 3.5Ru around
room temperature. This matches with predictions
of a diatomic that only rotates and translates but
does not vibrate. This is because the separation of
energy levels due to rotations is smaller than the
mean kinetic energy of the gas; Ēkin ≡ 1.5Ru T .
As such, the distribution over rotational energy
levels is not limited to the rotational ground state
(J = 0), and any additional energy is spread both
over the translational and rotational degrees of
freedom. In contrast, the energy separation of the
vibrational levels is much larger than the mean
kinetic energy of the gas, which means that the
distribution over vibrational states is limited to
the vibrational ground state (v = 0). When the
temperature increases, the mean kinetic energy
becomes comparable/larger than the separation
of the vibrational energy levels. As a result, vi-
brational states above v = 0 obtain a (significant)
population, and the heat capacity increases to-
wards Cp = 4.5Ru . At even higher temperatures,
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
[mNS;August 23, 2022;2:48]
5
electronically excited states also contribute to the
heat capacity, such that it increases beyond 4.5Ru .
To validate our implementation, we computed
the heat capacity for several diatomics and com-
pared these to Burcat’s database [4]. For all species
presented in this article, we found that the error
of the heat capacity over the entire temperature
range is less than 0.5%. This is comparable to the
maximum error reported for the polynomial fits by
Burcat. Similarly, the entropy and enthalpy have a
typical relative error of less than 0.5% compared
to Burcat’s data. Moreover, we have also com-
pared the singlet oxygen states, of which O2 (0,1,a)
(O2 (1 )) is shown in Fig. 3, with the data presented
in Togai et al. [26] and found an excellent compari-
son.
6. Consistent examples
Non-equilibrium effects in combustion are, gen-
erally, modeled as follows: Several species of the
same molecule are introduced in a reaction mecha-
nism. Each of these species is then associated with
different internal states of the molecule. The num-
ber of species used to describe a single molecule
depends on the degree of non-equilibrium effects
present in the problem of interest and the relative
reactivity of the internal states under considera-
tion. At this stage, it is important to realize that
the temperature dependence of Cp (and the non-
trivial functions for enthalpy and entropy) is a di-
rect consequence of “the equilibrium of internal
states” assumption. Therefore, the thermodynamic
data must reflect the species definition. In this sec-
tion, we provide two examples and highlight when
inconsistencies are introduced by a modification
of the formation enthalpy. These examples are ap-
proached from a plasma-assisted combustion point
of view. However, the theory, analysis or conclu-
sions are not limited to this application.
6.1. Singlet oxygen
In our first example, we consider the two low-
est singlet states of oxygen. These singlet states are
known to have a different reactivity than the triplet
ground state. Due to the relatively long lifetime of
O2 (a1 g ), or following our notation O2 (1,a,a), it
can interact with combustion chemistry; in air, at
298 K the lifetime is τ ≈ 86ms [27]. In contrast,
the second excited state, O2 (2,a,a), relaxes very
fast due to physical quenching to O2 (1,a,a), while
O2 (2,a,a) to O2 (0,a,a) relaxation is slow; typically
the lifetime is in the range of nano to microsec-
onds [21,25,27]. To improve mechanism validity in
non-equilibrium conditions, one might wish to in-
clude O2 (1,a,a) or both of these excited states of
oxygen as an individual species in a reaction mech-
anism (e.g., [25,28,29]).
JID: PROCI
ARTICLE IN PRESS
6 T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx
Fig. 4. Heat capacity of O2 (a,a,a), O2 (1–2,a,a) and
O2 (/1–2,a,a).
The fast relaxation of O2 (2,a,a) to O2 (1,a,a),
combined with the slow relaxation of O2 (1,a,a) and
O2 (2,a,a) to O2 (0,a,a), allows us to assume thermal
equilibrium between O2 (1,a,a) and O2 (2,a,a). Note,
the reverse rate is proportional to the forward rate
and the equilibrium constant, i.e., O2 (2,a,a) and
O2 (1,a,a) relax towards the equilibrium ratio, not
to XO2 (2,a,a) = 0. We, therefore, consider the case
for the thermodynamic properties of O2 (1–2,a,a).
In Fig. 4, a comparison is made between the heat
capacity of O2 (a,a,a) (solid line) and O2 (1–2,a,a)
(dotted line). At low temperatures, the heat ca-
pacity of O2 (1–2,a,a) is only marginally different
from that of O2 (a,a,a). As temperature increases
(T > 1500K) the difference in heat capacity in-
creases. This is because the energy difference be-
tween O2 (0,a,a) and O2 (1,a,a) (E = 94kJ/mol) is
larger than that between O2 (1,a,a) and O2 (2,a,a)
(E = 63kJ/mol). As a result, the O2 (2,a,a) states
contribute to the heat capacity of O2 (1–2,a,a) at a
lower temperature than the O2 (1,a,a) states do to
the O2 (a,a,a) heat capacity.
To obtain a consistent thermodynamic data set
a second step must be taken. After including O2 (1–
2,a,a) as an explicit species, which is part of the
complete O2 (a,a,a) species, we should remove these
states from the summation of O2 (a,a,a). If these
states are not removed and the thermodynamic
data not corrected, the singlet states O2 (1–2,a,a)
are effectively included twice: Once implicitly, as
part of the heat capacity function of O2 (a,a,a)
and a second time, explicitly, as the newly de-
fined O2 (1–2,a,a) species. The third line (dashed) in
Fig. 4 shows the heat capacity of the new corrected
O2 (/1–2,a,a) species, meaning O2 (a,a,a) minus the
O2 (1–2,a,a) states. This new O2 (/1–2,a,a) species re-
places the O2 (a,a,a) species in the mechanism, such
that all states are included once. If O2 (a,a,a) is com-
pared to O2 (/1–2,a,a), it is clear that the heat ca-
pacity is different above 1500 K. This difference
is present because the O2 (1–2,a,a) electronic states
obtain a significant population at equilibrium.
It might seem erroneous that the heat capac-
ity of O2 (a,a,a) is not a weighted average of the
heat capacity of O2 (/1–2,a,a) and O2 (1–2,a,a). Es-
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
[mNS;August 23, 2022;2:48]
Fig. 5. In the top graph the mole fraction of O2 (1–2,a,a)
and O2 (/1–2,a,a) at equilibrium as a function of temper-
ature is shown. In the bottom graph the heat release due
to reactions is shown.
pecially if we consider that below 3000 K and at
equilibrium, the fraction of O2 (1–2,a,a) is less than
0.02 (see the top frame of Fig. 5). From this, it is
clear that the mixture averaged heat capacity,

Cp = XiCp,i , (8)
i
of an O2 (/1–2,a,a) and O2 (1–2,a,a) mixture, can
never equate to that of O2 (a,a,a). Even though
these mixtures are, by definition, identical. How-
ever, this kind of direct comparison fails to take
into account reactions that convert O2 (/1–2,a,a)
into O2 (1–2,a,a) and back; reactions that should
be present to ensure correct thermodynamic equi-
librium. To better explain this a mixture of O2 (/1–
2,a,a) and O2 (1–2,a,a) is heated at a rate slower
than the rate at which the mixture equilibrates.
Meaning, no non-equilibrium effects are present.
To approximate such a hypothetical mixture, equi-
librium calculations are performed in a sweep of
temperature. During heating, the composition of
the mixture will change as the thermodynamic
equilibrium shifts towards O2 (1–2,a,a). In these
conditions, an “enthalpy change due to composi-
tion change per Kelvin temperature rise” can be de-
fined as
 dXi
Cp,reac = hi , (9)
i
dT
where, hi is the species enthalpy from Eq. 7, and
Xi is the mole fraction of species i. This term is
sometimes referred to as the reactive contribution
to the heat capacity. When comparing a mixture of
non-equilibrium species at equilibrium to a single
equilibrium species, this reactive contribution can
JID: PROCI
ARTICLE IN PRESS [mNS;August 23, 2022;2:48]

T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx 7

not be neglected. From now on we will refer to this

contribution as the reactive heat capacity, or reac-
tive contribution to the heat capacity. In the bottom
graph of Fig. 5, the reactive contribution of oxygen
is illustrated. This graph is obtained by comput-
ing the equilibrium composition of an O2 (/1–2,a,a)
and O2 (1–2,a,a) gas at a range of temperatures. The
composition is illustrated in the top graph, in the
bottom graph the enthalpy multiplied by the tem-
perature derivative of the composition is shown.
Because of the conservation of mass i dXi = 0,
meaning that changes in the dotted line (O2 (/1–
2,a,a) + O2 (1–2,a,a)) are due to differences in chem-
ical enthalpy. The “missing” part in the heat ca-
pacity observed in Fig. 4 can be, exactly, recovered
by the heat release of reactions due to the moving
equilibrium as temperature increases.

6.2. The significant presence of vibrational states

Species definitions do not have to be limited

to either electronic states or complete molecules,
stronger non-equilibrium effects can be captured if
vibrational states are included as individual species
in a mechanism. These vibrationally excited states
are included as species because they can have signif-
icantly altered reaction rates and can act as a tem-
porary energy buffer. Several authors have included
vibrational levels of several species in a methane-
air mechanism to study this [11–14], while others
introduced a conservation equation for the vibra-
tional energy [15–17]. In the work of DeFilippo
et al. [11] and Mao et al. [12], vibrational relaxation
is included as an irreversible process. Therefore,
the adiabatic flame temperature should be accurate
even though the thermodynamics is inconsistent.
Note, during the relaxation process itself the tem-
perature is underpredicted as the heat capacity is
still too high. But, in the works of Bellemans and
Deak [13,14], Castela [15], and Bechane [16,17], vi-
brational relaxation is reversible and the thermody-
namics is inconsistent, i.e., the flame temperature is
incorrect as illustrated in Fig. 1.
The consequences of inconsistent thermody-
namic modeling accumulate as more states are sep-
arated. When introducing vibrational states with-
out correcting the thermodynamic data, the ac-
cumulated inconsistencies will produce significant
errors in equilibrium properties. The reason for
this is the smaller energy difference between vibra-
tional energy levels compared to electronic levels,
see Fig. 2. As a consequence, the distribution of vi-
brational states, even at modest temperatures (T ≥
500K), can not be neglected. This can be concluded
from Fig. 4, where Cp > 3.5Ru indicates that the
vibrational states contribute to the heat capacity.
Note, this is not limited to equilibrium conditions,
the heat (release) of reactions between vibrational
states must be accurate to capture the slow heating
effects of VT-relaxation accurately.
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
Fig. 6. In the bottom graph the concentration at equilib-
rium for the lowest three vibrational states of oxygen is
shown, in the second graph the individual contribution
of these states to the reactive part of the heat capacity is
provided and in the top graph the cumulative effect of all
states is shown.
These concerns are depicted in Fig. 6, where re-
sults of equilibrium calculations for a gas mixture
containing ground state oxygen with separated vi-
brational states are shown. In these computations,
all the vibrational states of the electronic ground
state of oxygen are included. This means that they
should have properties identical to O2 (0,a,a) if the
system is in equilibrium. For a single species in this
mixture (e.g., O2 (0,0,a)), the heat capacity is almost
constant and equal to Cp = 3.5Ru . From the bot-
tom graph, it is visible that significant changes in
the population of the vibrational energy levels oc-
cur as temperature increases. Vibrationally excited
molecules can not be considered an exotic occur-
rence: Above 1000 K more than one in ten oxy-
gen molecules is vibrationally excited. In the mid-
dle graph, the reactive contribution to the heat ca-
pacity of the three lowest vibrational states is de-
picted, while in the top graph the cumulative effect
is depicted. The middle graph clearly shows that
the vibrational states of an oxygen mixture are con-
tinuously reacting as the temperature is increased.
Only because of these reactions, does the heat ca-
pacity of an O2 (0,a,a) gas mixture (each vibrational
JID: PROCI
ARTICLE IN PRESS
8 T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx
Fig. 7. The reactive heat capacity for three different mix-
tures. 1) oxygen with all vibrational states, 2) oxygen with
the lowest six vibrational states and 3) oxygen with the
lowest three vibrational states.
state as an individual species) evolving along equi-
librium is increasing to 4.5Ru as temperature in-
creases. These vibrational states are exactly the rea-
son why the flame temperature is underpredicted in
Fig. 1.
As including all vibrational states of a molecule
increases the species count significantly, many au-
thors only include a limited set [11–14]. In itself,
there is nothing inconsistent with this simplifica-
tion. However, if the thermodynamic data are cor-
rected care must be taken for the highest vibrational
species that is included, in Fig. 7 this concern is il-
lustrated. Again, equilibrium calculations are per-
formed with three mixtures; a mixture of the three
lowest, the six lowest and all vibrational states of
oxygen. For each of these mixtures, the reactive
heat capacity is computed and illustrated. The solid
line, with all vibrational species included, is the ex-
pected result for an oxygen mixture with individ-
ual vibrational states. The dotted and dashed lines
are the result when no care is taken for the highest
vibrational state included. As a limited number of
vibrational states is included, the concentration of
the lower states is slightly overpredicted at equilib-
rium. This is because it is impossible in these mix-
tures to keep on populating higher and higher vi-
brational states, which results in an underpredic-
tion of the reactive contribution to the heat capac-
ity. Luckily, this can be easily resolved by defin-
ing the highest vibrational state as a “remainder”
species, in these instances O2 (0,2-,a) and O2 (0,5-
,a), respectively. Doing this ensures that every single
vibrational state is included and the collective be-
havior of the vibrational species is, at equilibrium,
identical to O2 (0,a,a).
7. Conclusion
In this work, we provide a methodology to com-
pute the thermodynamic properties of any set of in-
ternal states, called a species. Excited-state species
are crucial in the modeling of plasma-assisted com-
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
[mNS;August 23, 2022;2:48]
bustion. Several examples are given in which the
thermodynamics of these excited states are in-
cluded consistently. While these examples were only
for relatively simple molecules, extension to more
complex molecules or an entire reaction mecha-
nism is, in principle, straightforward.
Several authors have, due to the lack of data,
used the shifted enthalpy method to obtain thermo-
dynamic data for excited-state species. For vibra-
tionally (or rotationally) excited states this method
certainly introduces significant errors. These errors
are easily identified when the system is at equilib-
rium. In addition, each of these errors accumulates
when more and more internal states of a molecule
are included as separate species. When a vibrational
energy equation is introduced care should also be
taken that the vibrational energy is not counted
twice. As such, the community should be aware of
this pitfall and develop consistent reaction mecha-
nisms by computing the thermodynamic properties
using the method described in this paper. Future re-
search is required to investigate the impact of these
inconsistencies on ignition and simulations of prac-
tical plasma-assisted burners.
Via GitHub, we have provided the code used to
obtain the thermodynamic properties, a code to fit
NASA-format polynomials to that data, the input
data of several species to this code, and several ex-
ample polynomials. The code is released under the
LGPL-v3.0 license and future developments will
be released through GitHub at: https://github.com/
thijsa93400/Therm4NEC.
Declaration of Competing Interest
The authors declare that they have no known
competing financial interests or personal relation-
ships that could have appeared to influence the
work reported in this paper.
Acknowledgments
This work is part of the research program
“Making plasma-assisted combustion efficient”
with project number 16480, which is partly financed
by the Dutch Research Council (NWO).
Supplementary material
Supplementary material associated with this ar-
ticle can be found, in the online version, at doi:10.
1016/j.proci.2022.07.075.
References
[1] R. Jaffe, The calculation of high-temperature equi-
librium and nonequilibrium specific heat data for N2 ,
O2 and NO, in: 22nd Thermophysics Conference,
JID: PROCI
ARTICLE IN PRESS
T. Hazenberg, J.F.J. Janssen, J. van Dijk et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx
American Institute of Aeronautics and Astronautics,
1987.
[2] M.W. Chase, NIST-JANAF Thermochemical Ta-
bles, Physical and Chemical Reference Data, vol-
ume 1, 4th, 1998.
[3] F.J. Zeleznik, S. Gordon, Simultaneous equations
least squares approximation of a function and its first
integrals with application to thermodynamic data,
NASA TN D-767, 1961.
[4] A. Burcat, B. Ruscic, Third millenium ideal gas and
condensed phase thermochemical database for com-
bustion, Tech. rep. (2005).
[5] N.L. Aleksandrov, S.V. Kindysheva, I.N. Kosarev,
S.M. Starikovskaia, A.Y. Starikovskii, Starikovskii,
Mechanism of ignition by non-equilibrium plasma,
Proc. Combust. Inst. 32 (1) (2009) 205–212.
[6] I.V. Adamovich, I. Choi, N. Jiang, J.-H. Kim, S. Ke-
shav, W.R. Lempert, E. Mintusov, M. Nishihara,
M. Samimy, M. Uddi, Plasma assisted ignition and
high-speed flow control: non-thermal and thermal
effects, Plasma Sources Sci. Technol. 18 (3) (2009)
034018.
[7] M. Uddi, N. Jiang, I.V. Adamovich, W.R. Lempert,
Nitric oxide density measurements in air and air/fuel
nanosecond pulse discharges by laser induced fluo-
rescence, J. Phys. D: Appl. Phys. 42 (7) (2009) 075205.
[8] Z. Yin, A. Montello, C.D. Carter, W.R. Lempert,
I.V. Adamovich, Measurements of temperature and
hydroxyl radical generation/decay in lean fuel-air
mixtures excited by a repetitively pulsed nanosec-
ond discharge, Combust. Flame 160 (9) (2013)
1594–1608.
[9] S. Yang, S. Nagaraja, W. Sun, V. Yang, Multiscale
modeling and general theory of non-equilibrium
plasma-assisted ignition and combustion, J. Phys. D:
Appl. Phys. 50 (43) (2017) 433001.
[10] J.K. Lefkowitz, P. Guo, A. Rousso, Y. Ju, Species
and temperature measurements of methane oxida-
tion in a nanosecond repetitively pulsed discharge,
Phil. Trans. R. Soc. A 373 (2048) (2015) 20140333.
[11] A.C. DeFilippo, J.Y. Chen, Modeling plasma-as-
sisted methane-air ignition using pre-calculated elec-
tron impact reaction rates, Combust. Flame 172
(2016) 38–48.
[12] X. Mao, Q. Chen, Effects of Vibrational Excitation
on Nanosecond Discharge Enhanced Methane-Air
Ignition, AIAA Journal 56 (11) (2018) 4312–4320.
[13] A. Bellemans, N. Kincaid, N. Deak, P. Pepiot,
F. Bisetti, P-DRGEP: a novel methodology for the re-
duction of kinetics mechanisms for plasma-assisted
combustion applications, Proc. Combust. Inst. 38 (4)
(2021) 6631–6639.
[14] N. Deak, A. Bellemans, F. Bisetti, Plasma-assisted ig-
nition of methane/air and ethylene/air mixtures: Ef-
ficiency at low and high pressures, Proc. Combust.
Inst. 38 (4) (2021) 6551–6558.
[15] M. Castela, B. Fiorina, A. Coussement, O. Gicquel,
N. Darabiha, C.O. Laux, Modelling the impact of
Please cite this article as: T. Hazenberg, J.F.J. Janssen, J. van Dijk et al., Consistent thermodynamics for plasma-assisted
combustion, Proceedings of the Combustion Institute, https://doi.org/10.1016/j.proci.2022.07.075
[mNS;August 23, 2022;2:48]
9
non-equilibrium discharges on reactive mixtures for
simulations of plasma-assisted ignition in turbulent
flows, Combust. Flame 166 (2016) 133–147.
[16] Y. Bechane, N. Darabiha, V.R. Moureau, C.O. Laux,
B. Fiorina, Large Eddy Simulations of turbulent
flame ignition by Nanosecond Repetitively Pulsed
discharges, AIAA Scitech 2019 Forum, American In-
stitute of Aeronautics and Astronautics, 2019.
[17] Y. Bechane, B. Fiorina, Numerical investigations of
turbulent premixed flame ignition by a series of
Nanosecond Repetitively Pulsed discharges, Proc.
Combust. Inst. 38 (4) (2021) 6575–6582.
[18] G.P. Smith, D.M. Golden, M. Frenklach, N.W. Mo-
riarty, B. Eiteneer, M. Goldenberg, C.T. Bowman,
R.K. Hanson, S. Song, W.C. Gardiner, V.V.L. Jr., Z.
Qin, GRI-Mech 3.0.
[19] I.V. Adamovich, W.R. Lempert, Challenges in un-
derstanding and predictive model development of
plasma-assisted combustion, Plasma Phys. Con-
trolled Fusion 57 (1) (2014) 014001, doi:10.1088/
0741-3335/57/1/014001.
[20] Y. Ju, W. Sun, Plasma assisted combustion: Dynam-
ics and chemistry, Prog. Energy Combust. Sci. 48
(2015) 21–83.
[21] N.A. Popov, Kinetics of plasma-assisted combus-
tion: effect of non-equilibrium excitation on the igni-
tion and oxidation of combustible mixtures, Plasma
Sources Sci. Technol. 25 (4) (2016) 049601.
[22] J.M.L. Martin, J.P. François, R. Gijbels, First princi-
ples computation of thermochemical properties be-
yond the harmonic approximation. i. method and ap-
plication to the water molecule and its isotopomers,
J. Chem. Phys. 96 (10) (1992) 7633–7645.
[23] P.W. Atkins, J. de Paula, Atkins’ Physical chemistry,
Oxford University Press, Oxford New York, 2006.
[24] M. Capitelli, Fundamental aspects of plasma chem-
ical physics: Thermodynamics, Springer, New York,
NY, 2012.
[25] A.A. Konnov, On the role of excited species in hy-
drogen combustion, Combust Flame 162 (10) (2015)
3755–3772.
[26] K. Togai, N. Tsolas, R.A. Yetter, Kinetic modeling
and sensitivity analysis of plasma-assisted oxidation
in a H2 /O2 /Ar mixture, Combust. Flame 164 (2016)
239–249, doi:10.1016/j.combustflame.2015.11.020.
[27] C. Schweitzer, R. Schmidt, Physical Mechanisms
of Generation and Deactivation of Singlet Oxygen,
Chem. Rev. 103 (5) (2003) 1685–1758.
[28] A.M. Starik, N.S. Titova, L.V. Bezgin,
V.I. Kopchenov, V.V. Naumov, Control of combus-
tion by generation of singlet oxygen molecules in
electrical discharge, Czech. J. Phys. 56 (2) (2006)
B1357–B1363.
[29] A.V. Lebedev, M.A. Deminsky, A.V. Zaitzevsky,
B.V. Potapkin, Effect of O2 (a1 g) on the low-tem-
perature mechanism of CH4 oxidation, Combust.
Flame 160 (3) (2013) 530–538.