T REED-12/1/06

THE BOUDOUARD REACTION:

C + CO2 <==> 2 CO
This reaction is possibly the most important reaction in biomass gasification. At temperatures above 900
stable than CO2, so once this has been exceeded, CO quenches in. Below ~ 700 C CO2 dominates the r
During pyrolysis at 300-450 C "prompt CO" also forms from the carbons already bonded to CO
THERMODYNAMIC CALCULATIONS
T(C)
25
127
227
327
427
527
627
727
827
927
1027
1127
1227

T(K)
298
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500

kJ/mole
Gr
112.8
95.7
78.9
62.1
45.3
28.5
11.8
-5.0
-21.8
-38.6
-55.4
-72.2
-89.0

1 atm
ln(Kr)
-45.5590
-28.7902
-18.9920
-12.4598
-7.7940
-4.2946
-1.5729
0.6045
2.3860
3.8706
5.1268
6.2035
7.1367

Kr
1.6E-20
3.1E-13
5.6E-09
3.9E-06
4.1E-04
1.4E-02
2.1E-01
1.8E+00
1.1E+01
4.8E+01
1.7E+02
4.9E+02
1.3E+03

10 atm
Kr
1.6E-21
3.1E-14
5.6E-10
3.9E-07
4.1E-05
1.4E-03
2.1E-02
1.8E-01
1.1E+00
4.8E+00
1.7E+01
4.9E+01
1.3E+02

100 atm

1 atm

Kr
1.6E-22
3.1E-15
5.6E-11
3.9E-08
4.1E-06
1.4E-04
2.1E-03
1.8E-02
1.1E-01
4.8E-01
1.7E+00
4.9E+00
1.3E+01

Xco2
1.000
1.000
1.000
0.998
0.980
0.890
0.637
0.282
0.078
0.020
0.006
0.002
0.001

Xco
0.000
0.000
0.000
0.002
0.020
0.110
0.363
0.718
0.922
0.980
0.994
0.998
0.999

The "Free energy of formation" of various reactions permits calculation of various chemical equilibria
Gr = Hr - TSr = -RTlnKr = -RT ln (pco)2/pco2
Relationship of Gibbs free energy to enthalpy and entropy change; to
(2) Kx = Kp*P = (1-Xco2)^2/Cco2
(3) Xco = 1-Xco2
(4) Xco2 = (K/2+1) - [(K/2 + 1)^2 -1]^1/2

Relationship of pressure to equilibrium constant, Kp is the equilibrium

where P is the sum of Pco + Pco2
Binomial solution of two equations in two unknowns

Fraction CO or CO2

Data from "Free Energy of Binary Compounds", (T. Reed, MIT Press (1971), available from the Biomass Energy Foundatio
G =
H
S
REACTIONS
Calories
1.000
CO(kcal/m)
-55.6
0.0401
2C + O2 ==> 2CO
CO2
CO2(kc/mol)
-94.5
0
CO2 ==>C + O2
0.900
Adding.. C + CO2 ==>2CO
0.800 BOUDOUARD EQUILIBRIUM
Joules
1 ATM , K
0.700
CO(kJ/m)
-232.7
0.1679
2C + O2 ==> 2CO
0.600
CO2(kJ/mol)
-395.6
0
- C + O2 ==> CO2
0.500
Adding.. C + CO2 ==>2CO
0.400
0.300
CO

0.200
0.100
0.000
400

500

600

700

800
Tempera

peratures above 900 C, CO is much more

CO2 dominates the reaction, so little CO is made.
ded to CO
10 atm
Xco2
1.000
1.000
1.000
0.999
0.994
0.964
0.866
0.654
0.368
0.150
0.053
0.019
0.008

100 atm

Xco
0.000
0.000
0.000
0.001
0.006
0.036
0.134
0.346
0.632
0.850
0.947
0.981
0.992

Xco2
1.000
1.000
1.000
1.000
0.998
0.988
0.955
0.874
0.720
0.507
0.295
0.147
0.069

Xco
0.000
0.000
0.000
0.000
0.002
0.012
0.045
0.126
0.280
0.493
0.705
0.853
0.931

py and entropy change; to the equilibrium constant and to concentrations

tant, Kp is the equilibrium constant in atm, Kx in mole fraction.
CO2

CO

omass Energy Foundation Press)

CO2

OUARD EQUILIBRIUM
1 ATM , K

00

CO

600

700

800 900 1000 1100 1200 1300 1400

Temperature - K

1.000
0.900
0.800

CO2

Fraction of CO and CO2

0.700
0.600

The Boudouard Equilibrium (K)

C + CO2 <==> 2 CO

0.500
0.400
0.300

CO

0.200
0.100
0.000
0

200

400

600

800

Temperature (K)

1000

1200

1400

1.000
0.900
0.800

% CO and CO2

0.700

Carbon
Dioxide

0.600

The Boudouard Reaction

C + CO2 <==> 2 CO

0.500

10

100

atm

0.400
Carbon
Monoxide

0.300
0.200
0.100
0.000
0

200

400

600

800

Temperature - C

1000

1200

1400