Department of Energy

Politecnico di Milano
Via Lambruschini 4 – 20156 MILANO 
 

Exercises of Fundamentals of Chemical Processes

Exercise 3

Outlet temperature of a WGS reactor (Stage I) for the conversion of CO, applied for the abatement of CO to a
fixed value.

The gas stream exiting the second stage of a Reformer supplied with air is sent to a two-stage reactor for the
conversion of CO, where the following reaction occurs (Water Gas Shift, WGS):

CO + H2O ↔ CO2 + H2

With reference to the first stage of the conversion of CO, it can be assumed that the outlet gases reach the
thermodynamic equilibrium composition at the exit temperature TOUT. Determine the exit temperature TOUT that
allows for the amount of CO in the outlet gas stream to be equal to 0.39% (volume %) with respect to the dry
current.

DATA:
Stream 1: T = 360°C P = 30 atm
Stream 2: TOUT = ? P = 30 atm CO/Σdry = 0.39%
Hypothesis: Ideal gas, WGS is at the chemical equilibrium

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 Species Flow Rate (Nm3/h) % Vol. Dry Basis
H2 56.36
N2 22.24
CO 12.56
CO2 8.27
Ar 0.27
CH4 0.3
H 2O 73411
dry 120264 100.00
Total 193675

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Solution
The approach with the extent of reaction is chosen to write the material balances. The basis for the material
balances can be set to 100 mol/h of incoming dry gas. The extent of the reaction λ is defined and the composition
of the outcoming species can be written, in terms of molar flow rates.

Species Flow Rate (Nm3/h) nin (mol/h) nout (mol/h)

H2 56.36 56.36 + 
N2 22.24 22.24
CO 12.56 12.56 - 
CO2 8.27 8.27 + 
Ar 0.27 0.27
CH4 0.3 0.3
H2O 73411 61.04 61.04 - 
dry 120264 100.00 100.00 + 
Total 193675 161.04 161.04

Given the 100 mol/h inlet dry gas basis, the amount of H2O is calculated as follows:

73411
nH 2O  100  61.04 mol/h
120264

The specific on the amount of CO in the outlet dry stream is used to calculate the extent of the reaction λ:

out
nCO 12.56   0.39
 
 dry 100   100

The equation leads to λ = 12.1227 mol/h. Once λ is calculated, the exit composition is readily derived:

Species nout (mol/h) % vol. nout dry basis % vol. nout

H2 68.48 61.07 42.52
N2 22.24 19.84 13.81
CO 0.44 0.39 0.27
CO2 20.39 18.19 12.66
Ar 0.27 0.24 0.17
CH4 0.30 0.27 0.19
dry 112.12 100 -
H2O 48.92 - 30.38

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The exit composition is related to the outlet temperature via the hypothesis of thermodynamic equilibrium
on the WGS reaction. In this case:

 G 
GR (T )     GR0 (T )  RT  ln k eq  0
  T , P

It follows that:

GR0 (T )   RT  ln k eq

In the case of the WGS reaction, assuming the ideal gas approximation, it is obtained:

PCO2  PH 2 yCO2  yH 2 out

nCO  nHout2
keq    2
 65.29
PCO  PH 2O yCO  yH 2O out
nCO  nHout2O
ln keq  4.1788

The ∆G0R(298K) is calculated starting from the ∆G0F(298K) of the reactants and the products:

NC
G R0 ( 298 K )    i  G F0 ,i ( 298 K )
i 1

In the equation, i is the stoichiometric coefficient of the i-th species in the reaction. In the same way, the
∆H0R(298K) is calculated as follows:

NC
H R0 ( 298 K )    i  H F0 ,i ( 298 K )
i 1

∆G0F(298K) and ∆H0F(298K) are found in the thermodynamic property database. The ∆G0R(T) at a T different from
298K is determined with the Van’t Hoff and Kirchoff laws, which express the dependence of the ∆G0 and the ∆H0
from temperature.

 (ΔGR0 (T)/RT) ΔH 0R (T )
 Van’t Hoff
T P
RT 2

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 ΔH 0R (T) NC

T
   C
1
i Pi (T)
Kirchoff
P
 (T)  a  b  T  c  T  d  T
C 2 3
Pi i i i i

To derive the explicit expression of the ∆G0R(T) as a function of temperature T, the Kirchoff law is to be
integrated first, starting from the reference temperature (T0 = 298K), as follows:

T T NC T

T
 ΔH 0R (T)  ΔH 0R (298K)  
TREF 1
i  C Pi (T)  dT  ΔH 0R (298K)  
TREF
(a tot  b tot  T  c tot  T 2  d tot  T3 )  dT

NC
a tot  
1
i  ai
NC
b tot  
1
i  bi
NC
c tot  
1
i  ci
NC
d tot  
1
i  di

b tot c d
ΔH 0R (T)  ΔH 0R (TREF )+a tot  (T  TREF )   (T 2  TREF
2
)  tot  (T 3  TREF
3
)  tot  (T 4  TREF
4
)
2 3 4

T
GR0 (T ) G(298) H R0 (T )
    dT
RT R  T0 TREF
RT 2

For each species, the parameters of the specific heat are also found in the thermodynamic property database:

H0F(298K) G0F(298K)
Species a b x 103 c x 105 d x 109 i
[J/mol] [J/mol]
H2 0.0 0.0 27.140 9.274 -1.381 7.645 +1
H 2O -242000.0 -228800.0 32.240 1.924 1.055 -3.596 -1
CO -110600.0 -137400.0 30.870 -12.850 2.789 -12.720 -1
CO2 -393800.0 -394600.0 19.800 73.440 -5.602 17.150 +1

CP is J/mol/K. Given the data in the table above, the following equations are derived:

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 NC

  C
i
i Pi  16.17  9.364 10 2  T  1.083 104  T 2  4.111 108  T 4

H R0  39665.606  16.17  T  4.682 10 2  T 2  3.609 105  T 3  1.028 10 8  T 4

GR0 T  1
  5.040  4770.94   1.945ln T  5.631 103  T  2.170 106  T 2  4.121 10 10  T 3
RT T
The solving equation is:

G R0 T 
ln k eq  
RT
1
4.1788  5.040  4770.94   1.945 ln T  5.631  10 3  T  2.170  10 6  T 2  4.121  10 10  T
T

The equation is algebraic and implicit in the only unknown T (f(T) = 0), which can be solved with several either
numeric (for instance, the bisection method or the Newton-Raphson method) or graphic methods. Solving the
equation, one obtains:

T = 535.9 K = 262.75°C

A similar solution could have been obtained also by using linearized expressions of the ∆G0R(298K) and the
∆H0R(298K) given in some reference texts (for specific temperature ranges). For the WGS reaction:

G R0 (T )  9418  9.07  T ∆G0R(T) is cal/mol, 300 K < T < 600 K

G R0 (T )  8514  7.71  T ∆G0R(T) is cal/mol, 600 K < T < 1500 K

Using the first linearized equation, the following solving equation is obtained:

9418  9.07  T
4.1788  
1.987  T

In this case, T = 542.2 K = 269.05°C, given R = 1.986 cal/mol/K.

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