Chapter Three Chemical kinetics Fuel & Energy Department

(3.1)Equilibrium Constant
In this section, can be show the condition of equilibrium for given by the
equation:

va A  vb B  vcC  vd D (3.1)

The equilibrium constant K P for the chemical equilibrium of ideal gas

mixture defined as:

PCvC . PDvD
K P  v A vB (3.2)
PA . PB

The values of equilibrium constant can be funded from table 3.1, where
the values in table 3.1 is the logarithm to the base e value of K P . Or
(ln( K P ))

From definition in chapter two, the partial pressure, can be written :

( vC  vB v A vB )
 
vC vD  
nC . nD  P 
K P  v A vB
n A . nB   (3.3)
  n
 i1 

Or, in mole fraction terms:

xCvC . xDvD ( vC vB vA vB )

K P  v A vB  P  (3.4)
x A . xB

(3.2)Equilibrium Constant and dissociation

The equilibrium composition of a chemical system at high
temperature can be quite different from that at low temperature owing to
possible dissociation and subsequent interaction of the constituents.
Although the degree of dissociation increasing with temperature,
dissociation, in many cases, can be neglected at room temperature and
atmospheric pressure.

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Chapter Three Chemical kinetics Fuel & Energy Department

Example 1: Nitrogen gas, N2, is heated to 4000 K, 10 kPa. What

fraction of the N2 is dissociated to N at this state?

Solution:

From table 3.1, ln(k)= -12.671 at 4000 K,

N2 <=> 2 N

Initial 1 0 K = 3.14x10-6
Change -x 2x
Equil. 1-x 2x ntot = 1 - x + 2x = 1 + x

1 x 2x
xN2  , xN 
1 x 1 x
21
x N2 P 4 x2
KP  2    3.14 *10  6
1  x  0.000886
xN2  Po  1  x2

nN2 = 0.99911 , nN = 0.00177

xN2 = 0.9982 , xN = 0.0018

Example 2:
1 kmol of CO2, ½ kmol of O2 and ½ kmol of N2 reacts to
form mixture consisting of CO2, CO, O2, N2 and NO at
3000K and 1 atm. Determine the equilibrium composition of
the product mixture.
Solution:

By atoms balance, we have:

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Chapter Three Chemical kinetics Fuel & Energy Department

Have two unknown a, b so need two equilibrium equations:

Equilibrium constants take from table 3.3

From the equilibrium constant expression:

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

Substituting yields:

Similarly for the second equilibrium reaction

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

Substituting and dividing through by the total number of moles gives:

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Chapter Three Chemical kinetics Fuel & Energy Department

(3.3) Chemical Rate (Global Chemical Reactions)

The overall reaction of a one mole of fuel with (a) moles of an

oxidizer to form (b) moles of combustion products can be expressed by
the global reaction mechanism [ ].

F  aO2  b Pr (3.5)

The rate at which the fuel is consumed , can be expressed as :

d [Y f ]
  KG (T )[Y f ]n [Yox ]m (3.6)
dt

Where the notation [x] is used to denote the molar concentration

(Kmol/m3) is in SI units. And m , n are constants.

For Arrhenius form, the bimolecular rate coefficient KG(T ) can be

expressed as :

KG(T )  A exp( EA / RuT ) (3.7)

Then,

d [Y f ]
  A exp(  EA / RuT ) [Y f ]n [Yox ]m (3.8)
dt

Where :

A is a constant termed the pre-exponential factor or the frequency factor,

gmol 1mn 1
its unit [ ] and can be convert as
cm 3 s
gmol 1000000 1mn 1 kmol 1mn 1
[ . ] [ 3 ]
cm 3 1000 s m s

o d [Y f ] kmol kg
f   3
 MW f  3
dt m .s m s

(EA/Ru) activation temperature (K)

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Chapter Three Chemical kinetics Fuel & Energy Department

The parameter pre-exponential, activation energy and m , n constants are

shown in the table (3.2).

Example 3: A steel vessel has content 0.1 Methane & 0.3 Oxygen as
concentration at 2000K, find the time to consumption all fuel after
ignition it.

Solution:

From table 3.2

A=1.3*108 , EA/Ru=24358 , m=-0.3, n=1.3

t  d [Y f ] 
0

 dt
  A exp(  EA / RuT ) [Y f ]n [Yox ]m  dt


[Y f ]2  [Y f ]1   A exp(  EA / RuT ) [Y f ]n [Yox ]m  . t

After combustion finishing, [Y f ]2 =0, then

0-0.1=-1.3*108 exp(-24358/2000) [0.1] 1.3 [0.3]-0.3 * t

t=2.08*10-3sec or t=2.08 msec

Note: to convert concentration value [x] to mass fraction, you can be used
the relation
 Yi
[ xi ]  (3.9)
MWi
d [ x] d (Yi  / MWi )  dYi
  (3.10)
dt dt MWi dt

dY f
  A . ( MW f /  ) . exp(  EA / RuT ) .[Y f ]n .[Yox ]m (3.11)
dt

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Chapter Three Chemical kinetics Fuel & Energy Department

dY f
Note: Assuming the chemical rate of consumption of fuel is  f  ,
dt
then the chemical rate for any species (i) is i   i . f where  i
stoichiometric ratio and can be calculated from stoichiometric equation as
v f F  vo O2  va A  vb B  vcC

 O  vo / v f
2
,  A  va / v f ,  B  vb / v f ,  C  vc / v f (3.12)

Can be shown the chemical rate for 6-species for burnt Methane in
figure below:

(mm)

Figure 3.1 the one - dimension flame propagation of Methane

Note: Employ all gases as ideal gas and applied the equation of state for
ideal gases in all equations if that necessary .

Q1: Repeat solution example 3 at T=1500K.

Q2: A steel vessel, it's volume 0.1m3, has 1kmole of Methane and air at
atmospheric pressure and 1200K, the equivalence ratio is 1.3, then
the mixture is ignited, determine the total time to consumption
fuel?

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