Beruflich Dokumente
Kultur Dokumente
7. System Equilibria
Leili Tafaghodi
2
Simultaneous Equilibria
1
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3
Simultaneous Equilibria
CH 4 H 2 O(g ) CO 3H 2 (1)
CO H 2O H 2 CO 2 (2)
Stoichiometry
n CH4 n oCH4 1 n H 2O n oH 2O 1 2
n H 2 n oH 2 3 1 2 n n o 2 1
Partial Pressures 4
n oCH 1
p CH4 4 P
n
n oH2O 1 2
p H 2O P
n
no 1 2
p CO CO P
n
n oCO2 2
p CO2 P
n
n oH2 31 2
p H2 P
n
2
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p H 2 p CO2 X H 2 X CO2
K2 fn( P )
p CO p H 2O X CO X H 2O
6
Example
1 mole of CH4, 2 moles of H2O and 0.1 mole of CO at total
pressure of 1 atm, react according to the following
reactions. Calculate the final equilibrium composition for
the above gas mixture. Calculate the overall Gibbs free
energy of the reaction and the Gibbs free energy of mixing.
CH 4 H 2O(g ) CO 3H 2 (1)
CO H 2O H 2 CO 2 (2)
Reaction 1 Reaction 2
∆G° ∆G°
Temp (K) (J/mol) K (J/mol) K
900 -1820 ? -7191 ?
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Example (continued)
Reaction 1 Reaction 2
∆G° ∆G°
Temp (K) (J/mol) K (J/mol) K
900 -1820 1.28 -7191 2.61
Initial Composition
CH4 H2O CO CO2 H2 total
mole 1 2 0.1 0 0 3.1
X 0.32 0.65 0.03 0.00 0.00 1.00
8
Example (continued)
Final Comosition
CH4 H2O CO CO2 H2 total
mole 0.29 0.90 0.42 0.39 2.52 4.52
X 0.06 0.20 0.09 0.09 0.56 1.00
ε error Target
Reaction 1 0.71 0.00 0.00
Reaction 2 0.39 0.00 Target = error1 2+error2 2
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Example (continued)
∆ =∆ −∆
= (1 − ) + 2− − + 0.1 + − +
(3 + ) +
─ -2 -0.1
=− + − − + − + (3 + ) +
= ∆ + ∆ = -4105 J
G M n A RT ln p A n B RT ln p B n C RT ln p C ∆ =−
RT n A ln X A P n B ln X B P n A ln X B P
CH 4 CO 2 2CO 2H 2
CH 4 H 2 O( g ) CO 3H 2
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Combustion
Predict oxidation level for H2 and C
Equilibrium for methane combustion
Simultaneous Equilibria
CH 4 2O 2 CO 2 2H 2O
CO 0.5O 2 CO 2
H 2 0.5O 2 H 2 O
60
H2O
H2
50 CO2
CO
Mole Percent
40 O2
30
20
10
0
1500 1700 1900 2100 2300 2500
Combustion Temperature (C)
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14
7
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2C O 2 2CO (2)
16
Other Reactions
Derived from (1) and (2)
2C O 2 2CO (2)
C O 2 CO 2 (1)
C CO 2 2CO (3)
C O 2 CO 2 (1)
C CO 2 2CO (3)
2CO O 2 2CO 2 (4)
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Simultaneous Equilibria
p CO2
C O 2 CO 2 K1 (1)
a Cp O2
2
p CO
2C O 2 2CO K2 (2)
a C2 p O2
p CO2 p CO p O2 P (3)
3 Equations; 4 Unknowns;
a C ; p CO 2 ; p CO ; p O 2
Specify aC
Algebraic Manipulation
Specified aC
3 Equations; 3 Unknowns; p CO2 ; p CO ; p O2
C O 2 CO 2 p CO2 K 1a C p O2 (1)
2C O 2 2CO p CO a C K 2p O 2 (2)
Simplify p O 1 K 1a C a C K 2p O P
2 2
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Log PO2
50 -25
40 -30
30 -35
20 -40
10 -45
0 -50
200 400 600 800 1000 1200 1400
Temperature (C)
20
Example
950oC; P = 1; aC = 1
C O 2 CO 2 K 1 7.96x1016
2C O 2 2CO K 2 4.75x1018
p CO
Per mole of gas n CO X CO
P
For P 1
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Molar O : C Ratio
950oC; P = 1; aC = 1
O n p CO 2p CO 2 2p O 2
O 1.016
C nC p CO p CO 2
For n oO 1.016n oC 22
1.0
% C Gasified
n oO n oC 1.016
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All C is gasified
Gas composition is function of O/C ratio
24
Apply Extent of Reaction
Stoichiometry
CO + 0.5O2 = CO2
n CO n oCO n O 2 n oO2 0.5
n oCO
X CO ; p CO X CO P
n
n oCO 0.5
XO2 ; pO2 XO2 P
n
n oCO 2
X CO 2 ; p CO 2 X CO 2 P
n
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Thermodynamics
CO + 0.5O2 = CO2
X CO2
K
X CO X O0.52 P 0.5
26
Direct Method
p CO2
CO 0.5O 2 CO 2 K (1)
p CO p O0.52
p CO 2 p CO p O 2 P (2)
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Solution
p CO2
K (1)
p CO p 0O.52
O p CO 2 p CO2 2 p O2
(3)
C p CO p CO2 Substitute into (3)
O
p CO2 ( P p O 2 ) ( P p O2 ) (4)
C
Therefore
O
p CO P ( P p O2 ) ( P p O2 ) p O 2 (5)
C
-2
CO
-4 CO2
-6
-8
Log (p)
-10
-12 O2
-14
-16 O2
CO2
-18 CO
-20
0.0 0.5 1.0 1.5 2.0 2.5
O/C Ratio
14
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Gas Phase aC
Gas of aC in contact with steel [aC]
CO; CO 2 ; a C
[ aC ]
aC
[C] C G RT ln
[a C ]
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CO-CO2 Mixtures 31
Soot Formation
CO-CO2 can form C ‘soot’
2CO C CO 2
G o 169,008 172.19T
2CO=C + CO2 32
The Equilibrium for Soot Formation
4
2 No Soot
Log(PCO2/PCO)
-1
-2 5 atm
-3 1 atm
0.5 atm
-4 0.1 atm
-5
400 600 800 1000 1200 1400
Temperature (C)
16