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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
= 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
(1200 , 150 )
ln ( ) = 19.7071
1.057 1018
3 2
2
= =
2 2 2
=1
=
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.
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.
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:
() = ( )
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 )
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
( 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.