Lecture#4

‫ قسم الهندسة الميكانيكية‬/ ‫ كلية الهندسة‬/ ‫جامعة الموصل‬
Department of Mechanical
Engineering
Subject: Internal Combustion Engines

The Second Law Analysis of Combustion Process
Class: M. Sc. / Thermal Power
Lecturer First lecturer: Dr. Abdulrahman Habbo Mohammed Instructor: Dr. Ahmed Fouad Al-Neama
THE SECOND LAW ANALYSIS OF COMBUSTION PROCESS
The second law of thermodynamics can be applied to combustion system. It

can be seen that the second law gives us the sense of what direction a particular
reaction proceeds in, and also specifies the equilibrium products of a given
reactions. However, from the definition of entropy, we have
𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝑄𝑛𝑒𝑡
∆𝑆 ≥ = (1 )
𝑇𝑜 𝑇𝑜
For non-reacting system, and single phase steady state, steady flow system,
the second law can be stated on mass basis as follows:
𝑄𝑛𝑒𝑡
0= ̇
+ 𝑚̇(𝑆𝑖𝑛 − 𝑆𝑜𝑢𝑡 ) + 𝑆𝐺𝐸𝑁 (2)
𝑇𝑜
Hence, 𝑆̇𝐺𝐸𝑁 ≥ 0 (must equal or greater than zero)
Now, assume a reacting system (combustion occurs), the entropy at any
pressure can be found using the following formula:
𝑆̅(𝑇, 𝑃 ) = 𝑆̅ 𝑜 (𝑇, 𝑃𝑅𝐸𝐹 ) + [𝑆̅(𝑇, 𝑃 ) − 𝑆̅ 𝑜 (𝑇, 𝑃𝑅𝐸𝐹 )] (3)
where 𝑆̅ 𝑜 (𝑇, 𝑃𝑅𝐸𝐹 ) is the absolute entropy at fixed reference pressure (1 atm.)
is tabulated.
Equation (3) can be written in the following form:-
𝑃
𝑆̅(𝑇, 𝑃 ) − 𝑆̅ 𝑜 (𝑇, 𝑃𝑅𝐸𝐹 ) = −𝑅̅𝑜 𝑙𝑛 (4 )
𝑃𝑅𝐸𝐹
For combustion process, the entropy for each constituent can be obtained as:
abidhabbo20@uomosul.edu.iq :‫عنوان البريد االليكتروني‬ ‫ عبدالرحمن حبو محمد الحبو‬.‫د‬.‫م‬.‫ أ‬:‫اسم التدريسي‬
ahmedfalneama@uomosul.edu.iq ‫ أحمد فؤاد محمود النعمة‬.‫د‬.‫م‬
Page | 36
𝑃
𝑆𝑖̅ (𝑇, 𝑃 ) = 𝑆𝑖̅ 𝑜 (𝑇, 𝑃𝑅𝐸𝐹 ) − 𝑅̅𝑜 𝑙𝑛 (5)
𝑃𝑅𝐸𝐹
The change in entropy for a process with several species can be written as:
∆𝑆 = ∑ 𝑛𝑃 𝑆𝑃̅ − ∑ 𝑛𝑅 𝑆𝑅̅ (6)

𝑃 𝑅
Hence, the entropy generation for steady flow combustion system is given as
follows:
𝑄𝑛𝑒𝑡
̇
𝑆𝐺𝐸𝑁 = ∑ 𝑛𝑃 𝑆𝑃̅ − ∑ 𝑛𝑅 𝑆𝑅̅ − ≥0 (7)
𝑇𝑜
𝑃 𝑅
We may have a special such as an isothermal and constant pressure

combustion system as might occurs in an isothermal steady flow reactor.
𝑄𝑛𝑒𝑡 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡 = ∆𝐻𝑜
𝐴𝑛𝑑 ∆𝐻𝑜 = ∑ 𝑛𝑖 ℎ𝑓𝑜 − ∑ 𝑛𝑖 ℎ𝑓𝑜

𝑃 𝑅
Hence, equation (7) can be written in the following form:
𝑆𝐺𝐸𝑁 𝑇𝑜 = 𝑇𝑜 [∑ 𝑛𝑃 𝑆𝑃̅ − ∑ 𝑛𝑅 𝑆𝑅̅ ] − ∑ 𝑛𝑖 ℎ𝑓𝑜 − ∑ 𝑛𝑖 ℎ𝑓𝑜

𝑃 𝑅 𝑃 𝑅
Rearranging the above equation, we get:
𝑆𝐺𝐸𝑁 𝑇𝑜 = ∑ 𝑛𝑃 (𝑇𝑜 𝑆𝑃̅ − ℎ𝑓𝑜 ) − ∑ 𝑛𝑅 (𝑇𝑜 𝑆𝑅̅ − ℎ𝑓𝑜 ) ≥ 0 (8 )

𝑃 𝑅
Now, it is quite convenient to introduce a new function which is GIBBS

FUNCTION (G)
𝐺 = 𝐻 − 𝑇𝑆 (9)
𝑂𝑟 𝑔 = ℎ − 𝑇𝑠
Page | 37
Dissociation
The maximum adiabatic flame temperature can be obtained for adiabatic
combustion, but this limited by a phenomenon of dissociation. For the following
reaction, heat is released and this reaction is called exothermic reaction.
𝐶𝑂 + 0.5𝑂2 → 𝐶𝑂2 (Exothermic reaction)
At high temperature if sufficient energy is supplied to molecules of CO 2, the
process proceed in the opposite direction, i.e some of CO 2 undergo the
following reaction:
𝐶𝑂2 → 𝐶𝑂 + 0.5𝑂2
Or can be written as follows:
𝐶𝑂 + 0.5𝑂2 ⇄ 𝐶𝑂2 (in equilibrium)
The reversed reaction is accompanied by an absorption of energy, hence it is
called endothermic reaction.
It has been found that at any particular temperature and pressure, the species
of CO2, CO and O2 adjust themselves until the reaction proceed at the same
rate. This means until the number of molecules of CO 2 being formed is equal to
the number of molecules of CO2 dissociates.
Normally dissociation take place at high temperature approximately
more than 1500 K. This applies to H2O as well as to CO2 and this explain why
the temperature in adiabatic combustion is less than the maximum temperature
predicted by simple calculation.
Assume we have a gas of CO2 initially at 1 atmosphere and 300 K is
heated up to 500 K, hence CO2 is quite stable and there is very little tendency
toward dissociation into CO and O2 .
𝐶𝑂2 → 𝑎𝐶𝑂2 + 𝑏𝐶𝑂 + 𝑑𝑂2
i.e a >> b and a >>d
at a temperature of 500 K and a pressure of 1 atmosphere, values of b and d
are very small which is less 10-15 mole and should be ignored.
Now if the temperature is raised to 2500 K, CO 2 will dissociate to CO and O2
and in the same time CO recombine with O2 till it reach an equilibrium state.
And values of b and d are relatively have a significant magnitude.
Page | 38
𝐶𝑂2 → 𝐶𝑂 + 0.5𝑂2
𝐶𝑂 + 0.5𝑂2 → 𝐶𝑂2
Or usually written as:
𝐶𝑂2 ⇄ 𝐶𝑂 + 0.5𝑂2
At equilibrium, the rate of formation of CO2 is the same as the rate of
dissociation of CO2, i.e. the number of moles of (a, b and d) of CO2, CO and O2
remains constant.
However, as the temperature of product mixture is increased, the equilibrium
value of (a) will decrease while (b and d) increase. In order to be able to
determine products composition with dissociation, it is necessary to have a
criterion for chemical equilibrium. Such a criterion for equilibrium at a given
pressure and temperature is provided by thermodynamic property is called
GIBBS FUNCTION (G)
𝐺 = 𝐻 − 𝑇𝑆 (10)
Or in differential form as:
𝑑𝐺 = 𝑑𝐻– 𝑇𝑑𝑆– 𝑆𝑑𝑇 (11)
from the definition of enthalpy 𝐻
𝐻 = 𝑈 + 𝑃𝑉
𝑂𝑟 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 (12)
First law of thermodynamics can be presented as
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 (13)
from Equation (12), we get
𝑑𝑈 = 𝑑𝐻 – 𝑃𝑑𝑉 – 𝑉𝑑𝑃 (14)
substitute Equation (14) in (13), we get
𝑑𝑄 = 𝑑𝐻 – 𝑉𝑑𝑃 (15)
from the definition of entropy we have
𝑑𝑄 = 𝑇𝑑𝑆
hence Equation (15) can be written as
𝑇𝑑𝑆 = 𝑑𝐻 – 𝑉𝑑𝑃 (16)
Page | 39
Substitute Equation (16) in Equation (11), we get
𝑑𝐺 = 𝑉𝑑𝑃– 𝑆𝑑𝑇 (17)
For a reacting system that has reached pressure and temperature equilibrium,
this means (𝑑𝑃 = 𝑑𝑇 = 0), hence Equation (17) gives us (𝑑𝐺 = 0).
dS > 0
Impossible
dS < 0 dG <0 dG>0
impossible
dS = 0
Pure
Pure dG=0
reactants Equilibrium Products
composition 100% 100%
Equilibrium composition based on the reactant Equilibrium Product
entropy criterion composition
Equilibrium composition based

on Gibbs free energy criterion
To apply this criterion, let us consider a general case in which species

A, B, C and D are in equilibrium at temperature T and pressure P. the chemical
equation can be formed as:
𝑛𝐴 𝐴 + 𝑛𝐵 𝐵 ⇄ 𝑛𝐶 𝐶 + 𝑛𝐷 𝐷 (18)
since 𝑑𝐺 = 0
𝑖. 𝑒. (𝑛𝐶 𝑔̅𝐶 + 𝑛𝐷 𝑔̅𝐷 − 𝑛𝐴 𝑔̅𝐴 − 𝑛𝐵 𝑔̅𝐵 ) × 𝑑𝜀 = 0 (19)
where 𝑑𝜀: is a measure of the extent of the reaction
𝑔̅ : Gibbs free function per mole of constituent
Depending on the direction of reaction 𝑑𝜀 can have positive or negative value
but cannot be zero, hence
(𝑛𝐶 𝑔̅𝐶 + 𝑛𝐷 𝑔̅𝐷 − 𝑛𝐴 𝑔̅𝐴 − 𝑛𝐵 𝑔̅𝐵 ) = 0 (20)
And at constant temperature ( i.e. 𝑑𝑇 = 0) Equation (17) become
𝑑𝐺 = 𝑉𝑑𝑃– 𝑆𝑑𝑇 = 𝑉𝑑𝑃
Page | 40
which can be written as
𝑑𝑃 𝑑𝑃
𝑑𝑔̅ = 𝑉 = 𝑅𝑜 𝑇 (using PV = NR 𝑜 T)
𝑁 𝑃
𝑃
𝑑𝑃
𝐻𝑒𝑛𝑐𝑒 ∫ 𝑑𝑔̅ = 𝑅𝑜 𝑇 ∫
𝑃
1 𝑎𝑡𝑚
𝑂𝑟 𝑔̅ − 𝑔̅𝑟𝑒𝑓 = 𝑅𝑜 𝑇 𝑙𝑛𝑃
Applying this to Equation (20), we get
𝑛𝐴 𝑔̅𝐴 = 𝑛𝐴 𝑔̅𝑟𝑒𝑓 + 𝑛𝐴 𝑅𝑜 𝑇 𝑙𝑛𝑃𝐴
𝑛𝐵 𝑔̅𝐵 = 𝑛𝐵 𝑔̅𝑟𝑒𝑓 + 𝑛𝐵 𝑅𝑜 𝑇 𝑙𝑛𝑃𝐵
𝑛𝐶 𝑔̅𝐶 = 𝑛𝐶 𝑔̅𝑟𝑒𝑓 + 𝑛𝐶 𝑅𝑜 𝑇 𝑙𝑛𝑃𝐶
𝑛𝐷 𝑔̅𝐷 = 𝑛𝐷 𝑔̅𝑟𝑒𝑓 + 𝑛𝐷 𝑅𝑜 𝑇 𝑙𝑛𝑃𝐷
Combining the above equation, we get
𝑛 𝑛
𝑃𝐴 𝐴 𝑃𝐵 𝐵
𝑛𝐶 𝑔̅𝐶𝑟𝑒𝑓 + 𝑛𝐷 𝑔̅𝐷𝑟𝑒𝑓 − 𝑛𝐴 𝑔̅𝐴𝑟𝑒𝑓 − 𝑛𝐵 𝑔̅𝐵𝑟𝑒𝑓 = 𝑅𝑜 𝑇 𝑙𝑛 𝑛 𝑛
𝑃𝐶 𝐶 𝑃𝐷 𝐷
Or can be written as follows:
𝑛 𝑛
𝑃𝐴 𝐴 𝑃𝐵 𝐵 ∆𝐺𝑟𝑒𝑓
𝑙𝑛 𝑛 𝑛 = (21)
𝑃𝐶 𝐶 𝑃𝐷 𝐷 𝑅𝑜 𝑇
𝑛 𝑛
𝑃𝐴 𝐴 𝑃𝐵 𝐵
The term 𝑙𝑛 𝑛 𝑛 = 𝐾𝑃 (22)
𝑃𝐶 𝐶 𝑃𝐷 𝐷
Where 𝐾𝑃 : is called the equilibrium constant

Equation (22) can be written as:
∆𝐺𝑟𝑒𝑓
𝑙𝑛𝐾𝑃 = (23)
𝑅𝑜 𝑇
It can be seen that 𝐾𝑃 is function of temperature only, its values for various
equilibrium reaction are taken from table.
Page | 41
Example 1:
The exhaust analysis from the combustion of a stoichiometric mixture of CO
and O2 at a pressure of 2 atmosphere and a certain temperature shows that
20% of CO2 dissociate. Determine the equilibrium constant at this temperature.
Thereafter, find the percentage of dissociation when the products of combustion
are kept at the same temperature but it’s compressed to 10 atmosphere.
Example 2:
A mixture of 2 mole of CO2, 3 mole of N2 and 1 mole of O2 initially at a
temperature of 300 K and a pressure of 1 atmosphere. The mixture is heated
up to 3000 K. Find the equilibrium composition of the mixture at this temperature
if the final pressure is 12 atmosphere.
Example 3:
A mixture of 3 mole of CO and 2.5 mole of O2 in an engine cylinder arrangement
is ignited and combustion take place at constant pressure of 5.065 bar. Find the
equilibrium composition of the products if the final temperature is 2800 K.
Home Work:
Q1. A stoichiometric mixture of a hydrocarbon fuel C 6H12 and air is burned in
steady flow combustion chamber. Both the fuel and air enters at 25 ºC and
products leaves at 2200 K. Find:-
1- The enthalpy of combustion at 25 ºC.
2- The mass flow rate of fuel required to supply heat at a rate of 1000 kW,
(Assume no dissociation).
The percentage of CO2 that would be dissociate at products temperature.
Page | 42

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‫ قسم الهندسة الميكانيكية‬/ ‫ كلية الهندسة‬/ ‫جامعة الموصل‬

Subject: Internal Combustion Engines

THE SECOND LAW ANALYSIS OF COMBUSTION PROCESS

The second law of thermodynamics can be applied to combustion system. It

∆𝑆 = ∑ 𝑛𝑃 𝑆𝑃̅ − ∑ 𝑛𝑅 𝑆𝑅̅ (6)

We may have a special such as an isothermal and constant pressure

𝐴𝑛𝑑 ∆𝐻𝑜 = ∑ 𝑛𝑖 ℎ𝑓𝑜 − ∑ 𝑛𝑖 ℎ𝑓𝑜

Hence, equation (7) can be written in the following form:

𝑆𝐺𝐸𝑁 𝑇𝑜 = 𝑇𝑜 [∑ 𝑛𝑃 𝑆𝑃̅ − ∑ 𝑛𝑅 𝑆𝑅̅ ] − ∑ 𝑛𝑖 ℎ𝑓𝑜 − ∑ 𝑛𝑖 ℎ𝑓𝑜

Rearranging the above equation, we get:

𝑆𝐺𝐸𝑁 𝑇𝑜 = ∑ 𝑛𝑃 (𝑇𝑜 𝑆𝑃̅ − ℎ𝑓𝑜 ) − ∑ 𝑛𝑅 (𝑇𝑜 𝑆𝑅̅ − ℎ𝑓𝑜 ) ≥ 0 (8 )

Now, it is quite convenient to introduce a new function which is GIBBS

Equilibrium composition based

To apply this criterion, let us consider a general case in which species

Where 𝐾𝑃 : is called the equilibrium constant

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