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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
kJ/mole 1 atm 10 atm 100 atm 1 atm
T(C) T(K) ∆Gr ln(Kr) Kr Kr Kr Xco2 Xco
25 298 112.8 -45.5590 1.6E-20 1.6E-21 1.6E-22 1.000 0.000
127 400 95.7 -28.7902 3.1E-13 3.1E-14 3.1E-15 1.000 0.000
227 500 78.9 -18.9920 5.6E-09 5.6E-10 5.6E-11 1.000 0.000
327 600 62.1 -12.4598 3.9E-06 3.9E-07 3.9E-08 0.998 0.002
427 700 45.3 -7.7940 4.1E-04 4.1E-05 4.1E-06 0.980 0.020
527 800 28.5 -4.2946 1.4E-02 1.4E-03 1.4E-04 0.890 0.110
627 900 11.8 -1.5729 2.1E-01 2.1E-02 2.1E-03 0.637 0.363
727 1000 -5.0 0.6045 1.8E+00 1.8E-01 1.8E-02 0.282 0.718
827 1100 -21.8 2.3860 1.1E+01 1.1E+00 1.1E-01 0.078 0.922
927 1200 -38.6 3.8706 4.8E+01 4.8E+00 4.8E-01 0.020 0.980
1027 1300 -55.4 5.1268 1.7E+02 1.7E+01 1.7E+00 0.006 0.994
1127 1400 -72.2 6.2035 4.9E+02 4.9E+01 4.9E+00 0.002 0.998
1227 1500 -89.0 7.1367 1.3E+03 1.3E+02 1.3E+01 0.001 0.999

The "Free energy of formation" of various reactions permits calculation of various chemical equilibria
(1) ∆Gr = ∆Hr - T∆Sr = -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 Relationship of pressure to equilibrium constant, Kp is the equilibrium
where P is the sum of Pco + Pco2
(3) Xco = 1-Xco2 Binomial solution of two equations in two unknowns
(4) Xco2 = (K/2+1) - [(K/2 + 1)^2 -1]^1/2

Data from "Free Energy of Binary Compounds", (T. Reed, MIT Press (1971), available from the Biomass Energy Foundatio
∆G = ∆H ∆S REACTIONS
Calories BOUDOUARD EQU
CO(kcal/m) -55.6 0.04 2C + O2 ==> 2CO 1 ATM, K
CO2(kc/mol) -94.5 0 CO2 ==>C + O2 1.00
Adding.. C + CO2 ==>2CO 0.90
Joules 0.80
Fraction CO or CO2

CO(kJ/m) -232.7 0.1679 2C + O2 ==> 2CO 0.70


CO2(kJ/mol) -395.6 0 - C + O2 ==> CO2 0.60
Adding.. C + CO2 ==>2CO 0.50
0.40
0.30
0.20
0.10
0.00
400 500 600 700 800 90
Temperat
0
peratures above 900 C, CO is much more
C CO2 dominates the reaction, so little CO is made.
nded to CO

10 atm 100 atm


Xco2 Xco Xco2 Xco
1.000 0.000 1.000 0.000
1.000 0.000 1.000 0.000
1.000 0.000 1.000 0.000
0.999 0.001 1.000 0.000
0.994 0.006 0.998 0.002
0.964 0.036 0.988 0.012
0.866 0.134 0.955 0.045
0.654 0.346 0.874 0.126
0.368 0.632 0.720 0.280
0.150 0.850 0.507 0.493
0.053 0.947 0.295 0.705
0.019 0.981 0.147 0.853
0.008 0.992 0.069 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

iomass Energy Foundation Press)

BOUDOUARD EQUILIBRIUM
1 ATM, K

600 700 800 900 1000 1100 1200 1300 1400


Temperature - K
The Boudouard Equilibrium (K)
C + CO2 <==> 2 CO
1.00

0.90

0.80

0.70
Fraction of CO and CO2

0.60

0.50

0.40

0.30

0.20

0.10

0.00
0 200 400 600 800 1000 1200 1400
Temperature (K)
The Boudouard Reaction
C + CO2 <==> 2 CO
100%

90%

80%

70%

60%
% CO and CO2

50%

40%

30%

20%

10%

0%
0 200 400 600 800 1000 1200 1400

Temperature - C