Estimation of Combustion

Products under Equilibrium

Conditions in Reciprocating

Under Supervision Of Submitted by

Prof. H.N. Gupta Ashish Kumar Agrawal
Roll No. 08306EN017
 Chemical equilibrium

In a chemical process, chemical equilibrium is the state in

which the chemical activities or concentrations of the reactants
and products have no net change over time.

Usually, this would be the state that results when the forward
 To understand the concept of
Chemical equilibrium one general
chemical equation can be expressed as,

aA + bB ↔ cC + dD

Where, A and B are the reactants and,

C and D are the products.
a, b, c, d are stoichiometric coefficent
 Equilibrium Constant
Equilibrium constant expresses the
ratio of the product of the
concentrations of the reaction
products (right side) to the product of
the concentration of the reactants
(left side).

The equilibrium constant can be

expressed as:
 Thermodynamics of
combustion
The reaction of the hydrocarbon fuel
and air is represented by the general
equation:

a(CnHmOr) + a/Ф(n+m/4 – r/2)[O2 + 78/21 N2 +

1/21 Ar]

Σ xi (i=1 to12)

Where, CnHmOr = General formula fuel

a = Mole fraction of fuel
 The following 12 species (q=12) , are considered to be
present in the products in the cylinder and in the exhaust
gases. They will be refer by the number shown against
their names.
 
3.   H2O 7.
N
4. H2 8.
CO2
5. OH 9.
CO
6. H 10.
O2
7. N2 11.
In the from of Equilibrium constant
 
Kp1 = (x4/√x2) √P
Kp2 = (x11/√x10) √P
Kp3 = (x7/√x5) √P
Kp4 = (x10/b^2)P
Kp5 = (x3/(b√x2)) √P
Kp6 = (bx9/x8)
Kp7 = (x6/(b√x5)) √P
 
Where b = x1/x2
 
The equilibrium constants for this reactions are calculated using
 
ln Kp = [ Σ (υ*g(T)/R*T )R - Σ (υ*g(T)/R*T )P] – ∆Ho/RT
• There are 13 unknowns ; the 12 species fractions (xi) and the
total number of moles of fuel (a) ; we have only 7 equation..

• DOF = 13 – 7 = 6

• Hence, 6 more equations are needed for the solution, One of

these is

Σxi = 1
 
• The remainder are the atomic mass balance for Argon , Carbon
, Hydrogen , Oxygen and Nitrogen.
After that we get 13 non –liner equations and this can be solve by
some approximations
 
 

Expression for a:- When ф>1,

 
a = 1.3 / [{n + 0.5m + 1.863(2n + 0.5m – r)/
ф}*exp(0.13T/1000) ]
 
and when ф<1,
 
a = 1.3 / [{0.25m + 2.363(2n + 0.5m – r)/ ф +
0.5r}*exp(0.13T/1000) ]
 
 
Expression for b :- when T< 3000 K,
 
b = exp[-9.0 + 0.5*logP +
30000/T];
 All the values of xi are calculated and
below shown equations are checked for
balance.

Σxi= 1 (i= 1 to 12)

Mass balance for oxygen,

x1 + x3 + x6 + 2x8 + x9 + 2x10 + x11 =

a*y

Where, y = 1/ ф (n+m/4 – r/2)*2 +r

If they do not balance within a stipulated

accuracy, an adjustment is made to a and b
using the Newton - Raphson technique and
 Computer program
in
Turbo-c and MATLAB
Results and Discussion
 Main curve
0
Composition variation with Temperature at P = 50 atm
10  
H20
N2
H2
CO2 OH
H
­1 N2
10
NO
N
CO2
 CO
­2 O2
10
O
Ar
NO
CO
Mole Fraction

­3
10

­4
10

­5
10
N

­6
10  
1800 2000 2200 2400 2600 2800 3000
Temperature in Kelvin
 Composition variation with Pressure and Temperature for NO
0.018  
first line for lowest pressure of 1 atm with others for +10 atm increments as we move down

0.016

0.014

0.012

0.01
Composition for different Pressures

0.008

0.006

0.004

0.002

0 
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
Temperature in Kelvin
 Composition variation with Pressure and Temperature for CO
0.08  
first line for lowest pressure of 1 atm with others for +10 atm increments as we move down

0.07

0.06

0.05
Composition for different Pressures

0.04

0.03

0.02

0.01

0 
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
Temperature in Kelvin
 Composition variation with Pressure and Temperature for CO2
0.13  

0.12

0.11

0.1

0.09
Composition for different Pressures

0.08

0.07

0.06

0.05

0.04

first line for lowest pressure of 1 atm with others for +10 atm increments as we move down
0.03  
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
Temperature in Kelvin
 Conclusion
Spark-ignition and diesel engines are a major source
of urban air pollution. The spark-ignition engine
exhaust gases contain oxides of nitrogen (nitric oxide
and nitrogen dioxide), carbon monoxide (CO) and
organic compounds which are unburned or partially
burned hydrocarbons.

NOxemission is controlled from exhaust gas

recirculation (EGR). Spark timing significantly affects
NOx emission levels. NOx level is significantly reduce
at the maximum brake torque (MBT). Carbon
monoxide is reduce when the engine is working under
lean condition.
 
A 3-way catalyst removes all the three pollutants
Thank you…