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Problem 2

A

= 2 2
+ 2 2 + 2 2


= 2 33.2 10 20 = 66.4 = 66400


= 2 2
+ 2 2 + 2 2


= 2 51.3 10 20 = 102.6 = 102600


(, ) = [ ]


102600
(298.15 , 1 ) = [ ] = 1.057 1018

8.314 298.15

B

Since we are treating this system as an ideal gas mixture, enthalpy does not depend on pressure.
Therefore, the equilibrium constant only has a temperature dependence. From Eq. 13.1-22a:
2
(2 , ) ()
ln ( )=
(1 , ) 1 2

Using 13.1-23a and the constants for Cp from the table:


2 4
() = (298.15 ) + ( 1 ) + ( 12 ) + ( 3 13 ) + ( 14 )
2 3 4

= 2 2 + 2 2 + 2 2 = 2 22.929 1 27.318 2 28.167 = 37.794

Same for b, c, and d.

= 0.09539

= 6.793 105

= 1.5732 108
0.09539 2
() = 66400 37.794( 298.15 ) + ( (298.15 )2 )
2
6.793 105 3 1.5732 108 4
( (298.15 )3 ) + ( (298.15 )4 )
3 4
Substitute into the integral:
0.09539 2 6.793 105 3 1.5732 108 4
2 66400 ( (298.15 )2 ) ( (298.15 )3 ) + ( (298.15 )4 )
ln (
(2 , )
)= 37.794( 298.15 ) + 2 3 4
(1 , ) 1 2

0.09539 2 6.793 105 3 1.5732 108 4


1200 66400 ( (298.15 )2 ) ( (298.15 )3 ) + ( (298.15 )4 )
ln (
(1200 , 150 )
)= 37.794( 298.15 ) + 2 3 4
(298.15 , 150 )
298.15 8.314 2

0.09539 2 6.793 105 3 1.5732 108 4


1200 66400 ( (298.15 )2 ) ( (298.15 )3 ) + ( (298.15 )4 )
ln (
(1200 , 150 )
) = 37.794( 298.15 ) + 2 3 4
1.057 1018 2
298.15 8.314

Evaluate with software or by hand:

(1200 , 150 )
ln ( ) = 19.7071
1.057 1018

(1200 , 150 ) = 1.057 1018 [19.7071] = 3.826 1010


As the temperature increases, the equilibrium constant increases. This makes sense for an endothermic
reaction. We need combustion processes to occur at low temperatures to reduce NOX production. This
isnt very practical, though.

We are defining x as the extent of reaction.

Component Initial Final Change Mole Frac


N2 (1) 2 2-x -x 2
6
O2 (2) 4 4-2x -2x 2(2 )
6
NO2 (3) 0 +2x +2x 2
6
Total 6 6-x -x 1

3 2
2
= =
2 2 2
=1

Since we have an ideal gas mixture:

=
2
2
2 2 6 2 6 2 (6 )
= 2 =( ) ( ) ( )=
2 2 6 2(2 ) 2 (2 )3
2 (6 ) 1
3.826 1010 =
(2 )3 150
Solve for x (There will be three solutions. Choose the one that is physically relevant.)

= 0.000277
Equilibrium Compositions:
2(0.000277)
2 = = 9.23 105
6 0.000277
(This is 92 ppm, which is not an insignificant considering NO2 emissions are reported using ppm.)
2(2 0.000277)
2 = = 0.667
6 0.000277
(2 0.000277)
2 = = 0.333
6 0.000277
D

Since Ka increases with temperature, the extent of reaction will increase, which means more nitrogen
dioxide will be produced at 1500 K. The mole fraction will increase.

Our equilibrium expression is re-written as follows:

2 (6 )
= =
(2 )3
I have defined an effective equilibrium constant which is the product of pressure and the equilibrium
constant. In part C, I said an increase in the equilibrium constant will increase the amount of nitrogen
dioxide produced. A decrease in pressure will reduce this effective equilibrium constant, which means
the nitrogen dioxide mole fraction will decrease.

We can also look at the reaction. Let consider only pressure for a moment. In the limit of high
pressures, the system will try to reduce the number of moles in the system. For this particular reaction,
there are 2 moles on the products side of the reaction and 3 on the reactants side. High pressures will
push the equilibrium towards the products. At low pressures, there is less of a driving force for this to
occur, so we see a shift of the equilibrium back to the reactant side.
F

Argon is inert.

Component Initial Final Change Mole Frac


N2 (1) 2 2-x -x 2
8
O2 (2) 4 4-2x -2x 2(2 )
8
NO2 (3) 0 +2x +2x 2
8
Ar 2 2 0 2
8
Total 8 8-x -x 1

This change results in a new equilibrium expression:

2 (8 )
=
(2 )3
2 (8 )
3.826 1010 =
(2 )3
Solving for the extent of reaction:

= 0.000240
The conversion to nitrogen dioxide is reduced by adding argon.

2 + 2 2
There would be no effect because the number of moles of reactant is equal to the number of moles of
product.

Proof:

Component Initial Final Change Mole Frac


N2 (1) 2 2-x -x 2
6
O2 (2) 4 4-x -x 4
6
NO (3) 0 +2x +2x 2
6
Ar 0 0 0 0
Total 6 6 0 1
2
2 2 6 6 4 2
( ) = =( ) ( )( )=
2 2 6 4 2 (2 )(4 )

Component Initial Final Change Mole Frac


N2 (1) 2 2-x -x 2
8
O2 (2) 4 4-x -x 4
8
NO (3) 0 +2x +2x 2
8
Ar 2 2 0 2
8
Total 8 8 0 1
2 2
2 6 6 4 2
() = =( ) ( )( )=
2 2 6 4 2 (2 )(4 )

() = ( )
Problem 3
Part a,b )
At the first step, we need to calculate equilibrium constant for the two reactions in both temperatures:

rxn G
rxn G RT ln K a K a exp(

)
RT
T Ka1 Ka2
500 K 1.8710-7 4.191102
2000 K 3.63103 9.5910-1

We setup a stoichiometry table in terms of the extent of reaction. A stoichiometry table gives the (molar)
amount of each species entering and exiting the reactions. We have two extents of reactions (X1 for reaction 1
and X2 for reaction 2). We will assume one mol basis of H2O(g) entering.

(1)C ( s ) H 2 O( g ) CO ( g ) H 2 ( g )
(2)CO ( g ) H 2 O( g ) CO 2 ( g ) H 2 ( g )

Component Enter Exit


H 2O 1 mol 1-X1-X2
CO 0 X1-X2
H2 0 X1+X2
CO2 0 X2
C Excess Excess X1
yi P
For the next step, we need to write Kai in terms of activities. For the gas-phase species, ai . Since we
1bar
are at a low pressure, we can assume an ideal gas mixture. Further since the system pressure is just 1 bar , this
equation simplifies to ai=yi. The activity of solid carbon is one because it is in the pure solid phase. In other
words, it is not a component in a mixture, therefore its activity will not appear in the Kai expressions.
Finally we can write Kai expressions

aCO a H 2 y CO y H 2
K a1
a H 2O y H 2O
aCO 2 a H 2 y CO 2 y H 2
K a2
a H 2O aCO y H 2O y CO

For each component, yi is found by dividing its number of mols by the total number of mols in the mixture
where Nt= (1-X1-X2) + (X1-X2)+(X1+X2)+X2= 1+X1
( X 1 X 2 )( X 1 X 2)
(1 X 1)(1 X 1) ( X 1 X 2)( X 1 X 2)
Ka1
(1 X 1 X 2) (1 X 1)(1 X 1 X 2)
(1 X 1)
( X 2 )( X 1 X 2)
(1 X 1)(1 X 1) ( X 2)( X 1 X 2)
Ka 2
(1 X 1 X 2)( X 1 X 2) ( X 1 X 2)(1 X 1 X 2)
(1 X 1)(1 X 1)

By knowing the ka values for each temperature, we have two equations with two unknowns and we can solve
for X1 and X2 to get the equilibrium composition:

( X 1 X 2)( X 1 X 2)
For T=500 K : 1.8710-7= (1)
(1 X 1)(1 X 1 X 2)

( X 2)( X 1 X 2)
4.191102= (2)
( X 1 X 2)(1 X 1 X 2)

( X 2)( X 1 X 2) 2
Multiplying the two equations gives: 7.83710-5=
(1 X 1)(1 X 1 X 2) 2

Solving by iteration :X1=X2=0.026


NH2O= 1-X1-X2=0.948, NCO= 0.0000035 , NH2= X1+X2= 0.052, NCO2= X2= 0.026
For T=2000 K

( X 1 X 2)( X 1 X 2)
3.63103= (1)
(1 X 1)(1 X 1 X 2)

( X 2)( X 1 X 2)
9.5910-1= (2)
( X 1 X 2)(1 X 1 X 2)
Solving by iteration : X1= 0.99973 , X2=1.32110-4
NH2O= 1.37910-4 , NCO= X1-X2 = 0.9996 , NH2= X1+X2=0.9999, NCO2= 1.32110-4
The first reaction goes to completion at higher temperatures since X1 is a stronger function of temperature.
X2 decreases with increasing temperature. The mol fractions are also calculated by dividing calculated mols
by the total number of mols.

Component Exit (500K) Yi (500K) Exit(2000K) Yi(2000K)


H2O 0.948 0.924 1.37910-4 6.910-5
CO 3.510-6 3.4110-6 0.9996 0.4998
H2 0.052 0.0507 0.9999 0.5
CO2 0.026 0.002534 1.32110-4 6.610-5
c) At 2000K , the total number of H2 produced per mol of H2O to the system is higher as it is obvious from
the calculations so it is better for the reaction to be done at 2000 K to produce more H2

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