CALCULATION OF EQUILIBRIUM FLAME TEMPERATURE AND

COMPOSITION FOR GASEOUS FUELS COMBUSTION USING THE

MINIMISATION OF GIBB`S FREE ENERGY METHOD

F. Farshchi1, A.Zolfaghari1,A.Zolfaghari2
1
University of Sistan and Baluchestan, Dept. of Chemical Engineering
2
University of Wyoming, Dept. of Chemical and Petroleum Engineering

Abstract:
Mathematical formulation and modeling of combustion processes is an important tool
in the understanding of such phenomena. Determination of equilibrium temperature
and composition is often the first stage in calculating combustion characteristics.
There are a number of techniques to carry out this calculation and in this paper
minimization of Gibb’s free energy is used to generate a computer code to perform
this calculation and the set of equations were soled using MathCAD software. The
effect of various effective parameters i.e. initial temperature, pressure, equivalence
ration, and type of fuel on the equilibrium temperature and composition has been
investigated and results are presented in this work.

Key words:
Gibb’s free energy, pollutant, combustion processes

Introduction:
Combustion is the first source of energy known to mankind and today over 95% of all
energy consumed in the world is produced from combustion processes. Therefore a
detailed knowledge of the combustion process phenomena is essential in efficient use
of fuels and prevention or at least minimization of the pollutant formation. Based on
the principle of chemical equilibrium in any reversible process, the system's free
energy must be minimized at constant temperature and pressure. In such conditions, it
is possible to calculate equilibrium temperature and composition of the flame, using
thermodynamic equations and mass balance. One of the methods used to carry out this
calculation is the equilibrium constant method whereby the equations of mass and
energy balances together with the equations for equilibrium reactions is used to fulfill
the calculations. This procedure is a traditional technique and needs a vast amount of
data for various equilibrium equations [1-5] and [11]. This technique has a relatively
simple mathematical and thermodynamic basis but sometimes the thermodynamic
basis of this method can be ill-defined especially if the number of species in the flame
is large and the flame temperature is unknown.
A second method which has a better defined mathematical and thermodynamic basis
is the method of minimization of Gibb’s free energy. This method is used in the
present study. The main results presented ahead are calculated based on the
implementation of this method.

Mathematical formulation of minimization of Gibb’s free energy:

The free energy for a system containing just one phase at constant temperature and
pressure depends only on the number of species moles.
(G ) = G(n , n , n ,..., n ) (1)
T ,P 1 2 3 N

1
E-mail: farshchi@hamoon.usb.ac.ir

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 In order to calculate the molar flow of each species one must consider the energy and
mass balance equations as well as the minimization of the Gibbs free energy. This
may arise solving of the non-linear equations system, which is solved here based on
the modified Newton-Raphson method. Minimization of the Gibbs free energy
function based on its variables is not respect problem constraints for the mass and
energy balance of each species. Therefore an unknown coefficient called the Lagrange
coefficient is used. By multiplying this parameter on the constraints of the problem
and adding to the G function, a new function F could be obtained. By the
minimization of this new function with respect to its parameter, we can find the
solution of free energy function which respects the relevant constraints as well. So if
this function is implemented for the minimization with respect to its variables, the
results minimize the free energy function and will honor the appropriate assigned
limitations. Mass balance constraint could be written based on the input and output
stream of the system as well as production of species during the combustion. Hence a
balance equation is required for every species presented in the study. k and a stand for
each atomic species and number of components which have that atomic species,
respectively. a is a known parameter. a ik Is the number of atoms of element k in the

molecular species i, hence mass balance for the element k could be written as:
k = 1,2,3,... (2)
∑i
n .a − A = 0
i ik k

Now for each species, the Lagrange multiplier λk is introduced and the final form for
function F could be derived as:
⎛ ⎞ (3)
F = G + ∑ λ k ⎜ ∑ ni .a ik − Ak ⎟
k ⎝ i ⎠
The unknown parameters for this problem are ni , λ k and T. In order to solve the
problem we need the same number of independent equations. ni Independent
equations can be written based on the derivation of the F fuction with respect to the ni,
as:
⎛ ∂F ⎞ ⎛ ∂G ⎞ (4)
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + ∑ λk .aik = 0
⎝ ∂ni ⎠T ,P ,n ,λ ⎝ ∂ni ⎠T ,P ,n
j k j
k

Additional λ k independent equations could be obtained based on the derivative of the

F function with respect to the λk :
⎛ ∂F ⎞ (5)
⎜⎜ ⎟⎟ = ∑ ni .aik − Ak = 0
⎝ ∂λk ⎠T , P ,ni ,λ j i

And finally, energy equation:

(6)
ΔH ° = ΔH R° + ΔH 298 °
+ ΔH P°
The first term on the right hand side of the equation (4) is the chemical potential.
Therefore for the gaseous phase reaction it can be written as:
∂G (7)
( ) T , P ,n j = μ i = ΔGi° + RT .Ln ( y i .ϕ i . p )
∂ni

Since the temperature of exhausted gas is high, one can safely assume the fugacity
coefficient of species i in the gaseous mixture to be unity. Assuming the adiabatic

2
condition for the flame, equation (6) is set equal to zero and thus the maximum flame
temperature is calculated. If the calculations are carried out on the basis of mole
fractions, i.e. y i , a further equation for the evaluation of ∑ ni is needed. This equation
is:
(8)
∑ y −1 = 0
i

Now based on the appropriate numerical method for solution of the non-linear
equations system, one can find the final solution based on the various input
parameters.

Results:
After solving the equations using MathCAD software, the results have been compared
with a number references [1-5]. Table 1 and 2 summarize some parts of the achieved
results and the appropriate comparisons with the experimental data. These data show
very good agreement between the model result and published data. After justifying
the accuracy and capability of the algorithm, it is possible to investigate the various
parameters which affect the equilibrium condition in the combustion. The effect of
input air temperature on the adiabatic flame temperature for combustion of methane
with air is presented in Figure (1).

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The observed differences between our results and references can be explained in
several ways:
І) The main reason is the different implemented calculation techniques in the
references. The references have used the equilibrium constant method for their
calculations.
ІІ) the accuracy of thermodynamic data for the ΔG °f , C P can also affect the final
results. In this work JANAF tables [4] have been used. For the equilibrium reactions,
that Kp is not available in the JANAF table, and we used the thermodynamical
relationships in order to estimate the appropriate value for Kp versus temperature.
Ш) The numerical method implemented for obtaining solution can also affect final
results, for example in the reference [5] an iterative procedure is chosen for the
calculations while in the present study Newton-Raphson method is used.

Effective parameters on equilibrium conditions:

After justifying the accuracy and capability of the algorithm, it is now possible to
investigate the various parameters which affected the equilibrium condition in the
combustion process.
One of the main parameters in the combustion process is the fuel/air ratio. This
parameter is usually presented as the equivalence ratio (ϕ ) . For ϕ > 1 , the amount
oxidizer or air is in excess and hence a large amount of the released energy is
absorbed which results in the lowering of the flame temperature with respect to ϕ = 1
conditions. At condition when we have ϕ < 1 , the total available energy will not be
released due to the shortage of oxidizer and hence the flame temperature will again be
lower compared to when ϕ = 1 . The calculations carried out to show that for
hydrocarbons, the maximum flame temperature occur in approximate ϕ = 0.95 . This
is shown in figure 1.

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As illustrated in the Figure (1) any increase in the initial temperature of the fuel
and/or oxidizer cause an increase in the flame temperature. That is a reasonable result
from the conversation of energy principal.
The effect of pressure on the equilibrium temperature and composition can be
justified using the Le-chatellier principle. According to this principle, increasing
pressure cause a shift towards reactions which produce smaller moles of product.
Figure (2) illustrate the effect of pressure on the composition and temperature.

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As it can be seen from table (3) the number of selected species for calculation in the
equilibrium mixture can have an effect on the on the final results. Increasing the
number of species causes a decrease in the flame temperature and of course increases
the accuracy of the calculations. The investigations showed that considering ten
species for calculation is sufficed for the most required engineering accuracy. Any
further increase in the number of species will have a negligible effect on the final
flame temperature calculation. It is obvious that for the environmental studies, where
an small amount of a particular species is vital and even very small concentrations of
that species can be crucial, that species must be included in the species list for
calculations.

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Environmental pollution:
Using the above method for calculation of the equilibrium condition, it is possible to
determine the concentration of the pollutants in any combustion processes. Therefore,
instead of performing very expensive and difficult experiments, it is most desirable to
use computer programs to determine the amount of pollutants exhausted in gaseous
fuel combustion processes.
For example, the oxides of nitrogen have a critical role in the air pollution. The most
important species of these types is nitrio oxide (NO). Experimental studies
demonstrate that emission NO became significant at flame temperature above 1300K.
Since the flame temperature for most gases is above 2200K, NO emission must be
taken into account seriously for them. NO2 is another component of nitrogen oxides
families. The allowable concentration of the NO2 and NO in the air are 0.15 PPM and
5 PPM, respectively [5]. The other four nitrogen oxides components are produced in a
little concentration in the gaseous combustion reactions and maybe neglected. The
Figure (3) effect of percentage of excess input air and input air temperature on the NO and NO2 are shown in the
Figure (3) and (4), respectively.

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Carbon mono oxide is another concerning combustion-generated pollutants. The
effect of percentage of excess input air and input air temperature on the CO and CO2
molar flow for a methane- air mixture are shown in the figure (5) and figure (6),
respectively.

In order to investigate another type of fuel for simulation, we choose the Dimethyl
ether (DME). DME has been proposed as an alternative diesel fuel. Dimethyl ether
has the following desirable properties that make it an attractive diesel fuel. First, it has
a high cetane (i.e., low octane) number. Second, when used in diesel engines, it
reduces combustion noise and emissions of particles. Another privilege is the trade-
off between NOx emissions and soot using conventional diesel fuel is eliminated in
DME-fueled engines because the combustion is soot-free. Hence, a DME-fueled
engine can be tuned to give reduced NOx emissions. Also, DME can be produced
from hydrocarbons via a relatively cheap one-step synthesis. Engine tests have shown
that DME-fueled diesel engines have emission levels that surpass the available ultra
low emissions vehicle (ULEV) regulation for medium duty vehicles. Interestingly,
ethers like MTBE (methyl tert-butyl ether), ETBE (ethyl tert-butyl ether), and TAME
(tert-amyl methyl ether) have high octane (i.e., low cetane) numbers and are used to
boost the octane number of gasoline. It is surprising that DME, which is structurally
similar to MTBE, ETBE, and TAME, has a high cetane number and hence is a good
diesel fuel, while the other ethers have low cetane numbers and would make poor
diesel fuels.

Since we want to have a comparison for two different types of fuel, we would present
similar graph for the DME case as of the CH4 case graphs. Figure (7) demonstrates
the adiabatic flame temperature vs. relative amount of input air. Various graphs
represent different air input temperature as it revealed by the appropriate captions.

8
As it obvious from the above figure, the peak of each graph is relied before the x=1
axis and the location of these peaks is shifted toward the less values as the input
stream temperature increases. Figure (8) shows the effect of the pressure on the flame
temperature for various input air temperature.

NO2 and NO molar flow rate as a function of percentage of excess air and various air
temperatures are demonstrated in the Figures (9) and (10), respectively.

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Figures (11) and (12) show the CO and CO2 flow rates as a function of percentage of
excess input air at various air input temperature, respectively.

Conclusion:
In this paper the method of the minimization of Gibb’s free energy for the calculation
of equilibrium temperature and composition of premixed flames has been used and its
capability has been investigated. The effects of parameters such as pressure,
equivalence ratio, initial temperature of reactants and the type of fuel have been
scrutinized. It is also possible to use this program in the determination of the
pollutants concentration in combustion processes of new fuels such as ethanol,
dimethyl ether…

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References:
Journal Articles:
1. “Modeling of the pollutant reduction (CO x , NO x , SO x ) in the industrial
furnaces.”
Atiye Parishan Naddaf, Mohammad Reza Omidkhah Nasrin,Journal of
iranian chemistry and chemical engineering, [No. (1), (2006)].
2. “first international Non-Renewable energy sources”
Books:
2. J.A. Barnard, J.N. Bradley, Flame and Combustion, 2nd ed., Chapman &
Hall, (1985).
3. C.Ferguson, Internal combustion engine, Wiley, (1988).
4. JANAF thermochemical tables, 2nd ed., (1971).
5. A.G.Gaydon, H.G.WolfhardD, Flame, their structure, Radiation
temperature, 4th ed., Chapman & Hall, (1977).
6. A.H.Lefebver, Gas turbine combustion, Mc-Graw Hill, (1983).
7. I.Glassman, Combustion, Academic Press, (1977).
8. J.M. Smith, H.C.Van Ness, Introduction to chemical engineering
thermodynamics, 7th ed., Mc-Graw Hill, (1975).
9. K.Kuan, Y.Kuo, Wiley, Principles of combustion, (1986).
10. R.D. Reed, Furnace operations, 2nd ed., Golf publication, (1976).
Proceedings:
11. A.A. Hmidi, F.Farshchi, proceedings of The 2nd Int. Cong. on Non-
Renewable Energy Sources, Tehran, Iran,Dee.(1993)

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 ‫ﭼﻜﻴﺪه‪:‬‬
‫در اﻳﻦ ﻣﻘﺎﻟﻪ روش ﺑﻪ ﺣﺪاﻗﻞ رﺳﺎﻧﺪن اﻧﺮژي آزاد ﮔﻴﺒﺲ ﺑﺎ ﺗﻮﺟﻪ ﺑﻪ ﻣﺒﺎﻧﻲ ﻣﺤﻜﻢ رﻳﺎﺿﻲ و ﺗﺮﻣﻮدﻳﻨﺎﻣﻴﻜﻲ آن ﺑﺮاي‬
‫ﺗﺤﻠﻴﻞ ﺗﺮﻣﻮدﻳﻨﺎﻣﻴﻜﻲ ﺷﻌﻠﻪ ﻫﺎي ﭘﻴﺶ آﻣﻴﺨﺘﻪ ﻣﻮرد اﺳﺘﻔﺎده ﻗﺮار ﮔﺮﻓﺘﻪ و ﻧﺘﺎﻳﺞ ﺣﺎﺻﻠﻪ ﺑﺎ ﻣﺮاﺟﻊ ﻣﻌﺘﺒﺮ ﻣﻘﺎﻳﺴﻪ ﺷﺪه‬
‫اﺳﺖ‪ .‬ﻋﻮاﻣﻞ ﻣﺆﺛﺮ ﺑﺮ دﻣﺎ و ﺗﺮﻛﻴﺐ ﺗﻌﺎدﻟﻲ ﺷﻌﻠﻪ ﻧﻈﻴﺮ ﻓﺸﺎر‪ ،‬ﻧﺴﺒﺖ ﻫﻢ ارزي و دﻣﺎي اوﻟﻴﻪ در ﺷﻌﻠﻪ ﻫﺎي ﭘﻴﺶ آﻣﻴﺨﺘﻪ‬
‫ﺑﺮرﺳﻲ ﺷﺪه اﺳﺖ‪ .‬ﺑﺎ اﺳﺘﻔﺎده از اﻳﻦ ﻣﺤﺎﺳﺒﺎت ﺗﻌﺎدﻟﻲ‪ ،‬ﻣﻴﺰان ﻧﺸﺮ آﻻﻳﻨﺪه ﻫﺎ و روش ﻫﺎي اﻣﻜﺎن ﻛﺎﻫﺶ آﻟﻮدﮔﻲ ﻗﺎﺑﻞ‬
‫ﺑﺮرﺳﻲ ﻣﻲ ﺑﺎﺷﺪ‪.‬‬

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