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Chemical Equilibrium

In general the combustion products consist of more than just


CO2, H2O, O2, and N2
For rich mixtures CO also exists in the products and at high temperatures
the molecules dissociate to form H, O, OH, NO via the following reactions:
H 2 2H

O2 2O

H 2 O2 2OH

O2 N 2 2 NO

The opposite direction reactions are also possible


2H H 2

2O O2

2OH H 2 O2

2 NO O2 N 2

At equilibrium the rate of the forward reaction equals the rate of the
backward reaction.
H 2 2H

O2 2O

H 2 O2 2OH

O2 N 2 2 NO
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Chemical Equilibrium
At equilibrium the relative proportion of the species mole fraction is fixed
For the general equilibrium reaction
n A A nB B ncC nD D
The equilibrium composition for species CD is given by:
X
K (T )
X

nC
C
nA
A

X
X

nD
D
nB
B

P
ref

nC nD n A nB

where K is the equilibrium constant which is tabulated as a function of


temperature for different equilibrium reactions, Pref is 1 atm and P is in
units of atmospheres.
Note

XA

nA
n A nB nC nD
2

Chemical Equilibrium
Recall that for a rich mixture (<1) the reaction equation could not be
balanced (5 unknowns a, b, d, e, f and only 4 atom balance equations for
C,H,O,N ) even if we neglect dissociation (i.e., low product temperature)

C H ( )(O2 3.76 N 2 ) aCO2 bH 2O dN 2 eCO fH 2


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If the product species CO2, H2O, CO and H2 are at equilibrium and described
by the water-gas reaction:
CO2 H 2 CO H 2O
The equilibrium constant for this reaction provides the fifth equation :
K (T )

X CO X H O
2

X CO X H
2

Note K is tabulated as a function of T

eb
a f

P 1 atm

Chemical Equilibrium (example)


1 kmol of CO2, kmol of O2 and kmol of N2 reacts to form a mixture
consisting of CO2, CO, O2, N2 and NO at 3000K and 1 atm. Determine the
equilibrium composition of the product mixture.
CO2 1 / 2O2 1 / 2 N 2 aCO bNO cCO2 dO2 eN 2
3000K and 1 atm
C
O
N

1 = a+c
3 = a+b+2c+2d
1 = b+2e

c=1-a
d = 1/2(1 + a - b)
e = 1/2(1 - b)

Have 2 unknowns a, b so need 2 equilibrium equations

1.

CO2 CO 1 / 2O2

K1( 3000 K)

2.

1 / 2O2 1 / 2 N 2 NO

K 2( 3000 K)

Chemical Equilibrium (example)


From the equilibrium constant expression
K1 0.3273

X CO X O1 / 2
2

X CO

ntot= a+b+c+d+e = a+b+(1-a)+1/2(1+a-b)+1/2(1-b) = (4+a)/2


X CO

a
(4 a) / 2

X O2

1 / 2(1 a b)
(4 a) / 2

X CO2

1 a
(4 a) / 2

Substituting yields:
K1 0.3273

X CO X O1 / 2
2

X CO

a 1 a b

1 a 4 a

1/ 2

(1 )

Chemical Equilibrium (example)


Similarly for the second equilibrium reaction
K 2 0.1222

X NO
2b

X O1 / 2 X 1N/ 2 (1 a b)(1 b)1 / 2


2

(2)

Solving equations 1 and 2 yields:


a= 0.3745

b= 0.0675

From the atom balance equations get:


c= 0.6255

d= 0.6535

e= 0.4663

Role of Equilibrium Solvers


If the products are at high temperature (>2000K) minor species will be
present due to the dissociation of the major species CO 2, H2O, N2 and O2.

C H ( )(O2 3.76 N 2 ) aCO2 bH 2O cN 2 dO2 eCO fH 2


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gH hO iOH jNO kN
Hand calculations are not practical when many species are considered,
one uses a computer program to calculate product equilibrium composition.

Composition of Octane-air Mixtures at Equilibrium


(stoich)

Mole fraction of each species

(lean)

Temperature (K)

(rich)