c14ChemicalandPhaseEquilibrium.

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14.3 Calculating Equilibrium Compositions 857

cccc EXAMPLE 14.1 c

Evaluating the Equilibrium Constant at a Specified Temperature

Evaluate the equilibrium constant, expressed as log10K, for the reaction CO 1 12 O2 d
S CO2 at (a) 298 K and
(b) 2000 K. Compare with the value obtained from Table A-27.

SOLUTION
Known: The reaction is CO 1 12 O2 S
d CO2.
Find: Determine the equilibrium constant for T 5 298 K 1258C2 and T 5 2000 K.

Engineering Model: The ideal gas model applies.

Analysis: The equilibrium constant requires the evaluation of ¢G8 for the reaction. Invoking Eq. 14.29b for this
purpose, we have

¢G8 5 1hCO2 2 hCO 2 12 hO22 2 T1s C8 O2 2 s C8 O 2 12s O8 22

where the enthalpies are evaluated at temperature T and the absolute entropies are evaluated at temperature T
and a pressure of 1 atm. Using Eq. 13.9, the enthalpies are evaluated in terms of the respective enthalpies of
formation, giving
0
¢G8 5 31h8f 2CO2 2 1h8f 2CO 2 12 1h8f 2O24 1 31¢h2CO2 2 1¢h2CO 2 121¢h2O24 2 T1s C8 O2 2 s 8CO 2 12 s O8 22

where the ¢h terms account for the change in specific enthalpy from Tref 5 298 K to the specified temperature
T. The enthalpy of formation of oxygen is zero by definition.
(a) When T 5 298 K, the ¢h terms of the above expression for DG8 vanish. The required enthalpy of formation
and absolute entropy values can be read from Table A-25, giving

¢G8 5 312393,5202 2 12110,5302 2 121024 2 2983213.69 2 197.54 2 12 1205.0324

5 2257,253 kJ/ kmol
With this value for DG8, Eq. 14.31 gives

12257,253 kJ/ kmol2

ln K 5 2 5 103.83
18.314 kJ/ kmol ? K21298 K2

which corresponds to log10K 5 45.093.

Table A-27 gives the logarithm to the base 10 of the equilibrium constant for the inverse reaction:
1
CO2 Sd CO 1 2O2. That is, log10K* 5 245.066. Thus, with Eq. 14.34, log10K 5 45.066, which agrees closely with
the calculated value.
(b) When T 5 2000 K, the ¢h and s 8 terms for O2, CO, and CO2 required by the above expression for DG8 are
evaluated from Tables A-23. The enthalpy of formation values are the same as in part (a). Thus

¢G8 5 312393,5202 2 12110,5302 2 12 1024 1 31100,804 2 93642 2 165408 2 86692

2 12167,881 2 868224 2 20003309.210 2 258.600 2 12 1268.65524
5 2282,990 1 5102 1 167,435 5 2110,453 kJ/ kmol

With this value, Eq. 14.31 gives

12110,4532
ln K 5 2 5 6.643
18.3142120002
which corresponds to log10 K 5 2.885.