Water gas shift equilibria using Shomate Equation

Introduction:-
The water-gas shift reaction (WGSR) describes the reaction of carbon
monoxide and water vapor to form carbon dioxide and hydrogen (the mixture of
carbon monoxide and hydrogen is known as water gas) :
CO + H
2
O CO
2
+ H
2

The water gas shift reaction was discovered by Italian physicist Felice
Fontana in 1780.Before the early 20th century, hydrogen was obtained by
reacting steam under high pressure with iron to produce iron, iron oxide and
hydrogen. With the development of industrial processes that required hydrogen,
such as the Haber-Bosch ammonia synthesis, the demand for a cheaper and more
efficient method of hydrogen production was needed. As a solution to this
problem, the WGSR was combined with the gassification of coal to produce a
pure hydrogen product. As the ideal of Hydrogen economy gains popularity, the
focus on hydrogen as a replacement fuel source for hydrocarbons is increasing.

Importance of WGSR reaction :-
The WGSR is an important industrial reaction that is used in the
manufacture of ammonia, hydrocarbons, methanol, and hydrogen. It is also often
used in conjunction with steam reformation of methane and other hydrocarbons.
In the Fischer-Tropsch process, the WGSR is one of the most important reactions
used to balance the H
2
/CO ratio. It provides a source of hydrogen at the expense
of carbon monoxide, which is important for the production of high purity
hydrogen for use in ammonia synthesis.


Modeling Parameters involving in the Calculation of Equilibrium
Constant :-
The water gas shift reaction is a moderately exothermic reversible reaction.
Therefore with increasing temperature the reaction rate increases but the
conversion of reactants to products becomes less favorable. Here, we will
compute the equilibrium constant for the water gas shift reaction in the
temperature range of 500K to 1000K.

Modeling Steps :-
Setup equations for each species
i. Hydrogen
ii. H
2
O
iii. CO
iv. CO
2

Standard state heat of reaction
Correcting H and G
Plot how the G varies with temperature
Equilibrium constant calculation
Equilibrium yield of WGS
Compute gas phase pressures of each species
Compare the equilibrium constants




From Shomate Equation :-
Cp = heat capacity (J/mol*K)
H = standard enthalpy (kJ/mol)
S = standard entropy (J/mol*K)
with models in the form: C
p
0
=A + B*t + C*t
2
+ D*t
3
+ E/t
2

H
0
- H
0
298.15

= A*t + B*t
2
/2 + C*t
3
/3 + D*t
4
/4 E/t + F - H
S
0
= A* ln(t) + B*t + C*t
2
/2 + D*t
3
/3 E/(2*t) + G

where t=T/1000 , and is the temperature in Kelvin. We can use this data
to calculate equilibrium constants in the following manner. First, we have heats of
formation at standard state for each compound; for elements, these are zero by
definition, and for non-elements, they have values available from the NIST
webbook. There are also values for the absolute entropy at standard state. Then,
we have an expression for the change in enthalpy from standard state as defined
above, as well as the absolute entropy. From these we can derive the reaction
enthalpy, free energy and entropy at standard state, as well as at other
temperatures.
We will examine the water gas shift enthalpy, free energy and equilibrium
constant from 500K to 1000K, and finally compute the equilibrium composition of
a gas feed containing 5 atm of CO and H2 at 1000K.









Setup equations for each species :-
First we enter in the parameters and compute the enthalpy and entropy for
each species.
Hydrogen H
2
O CO CO
2

Temp. Range
in K
298-1000 500-1700 298.15 1300 298.15 1200
A 33.066178 30.09200 25.56759 24.99735
B -11.363417 6.832514 6.096130 55.18696
C 11.432816 6.793435 4.054656 -33.69137
D -2.772874 -2.534480 -2.671301 7.948387
E -0.158558 0.082139 0.131021 -0.136638
F -9.980797 -250.8810 -118.0089 -403.6075
G 172.707974 223.3967 227.3665 228.2431
H 0.0 -241.8264 -110.5271 -393.5224
H
f
in kJ/mol 0.0 -241.83 -110.53 -393.51
S @ 298.15 in
J/mol/K
130.68 188.84 197.66 213.79


Standard state heat of reaction :-
We compute the enthalpy and free energy of reaction at 298.15 K for the
following reaction .
H
rxn
@298.15 = H
f
@298.15_CO
2
+ H
f
@298.15_H
2
-H
f
@298.15_CO- H
f
@298.15_H
2
O;
S
rxn
@298.15 = [email protected]_CO
2
+ [email protected]_H
2
[email protected]_CO [email protected]_H
2
O;
G
rxn
@298.15 = H
rxn
@298.15 - 298.15*(S
rxn
@298.15)/1000;




Correcting H and G :-
We have to correct for temperature change away from standard state. We
only correct the enthalpy for this temperature change. The correction looks like
this:

Where are the stoichiometric coefficients of each species, with appropriate
sign for reactants and products, and is precisely what is
calculated for each species with the equations
H
rxn
= H
rxn
@ 298.15 + dH_CO
2
+ dH_H
2
- dH_CO - dH_H
2
O;
The entropy is on an absolute scale, so we directly calculate entropy at each
temperature. Recall that H is in kJ/mol and S is in J/mol/K, so we divide S by 1000
to make the units match.
G
rxn
= H
rxn
T *(S_CO
2
+ S_H
2
- S_CO - S_H
2
O)/1000;

Plot how the G varies with temperature :-
Over this temperature range the reaction is exothermic, although near
1000 K it is just barely exothermic. At higher temperatures we expect the reaction
to become endothermic.

Equilibrium constant calculation :-
Note the equilibrium constant starts out high, i.e. strongly favoring the
formation of products, but drops very quicky with increasing temperature.
From , we can write
K = exp(-G
rxn
/R*T); Where R (gas constant)= 8.314 kJ/mol/K

Equilibrium yield of WGS :-
Now let's suppose we have a reactor with a feed of H
2
O and CO at 10atm at
1000K. What is the equilibrium yield of H
2
? Let be the extent of reaction, so that
F
i
=F
i,0
+ v
i
. For reactants, v
i
is negative, and for products, v
i
is positive. We have to
solve for the extent of reaction that satisfies the equilibrium condition.
A = CO ; B = H
2
O; C = H
2
; D = CO
2

P
a0
= 5; P
b0
= 5; P
c0
= 0; P
d0
= 0; pressure in atm Temperature = 1000 K;
If we let X be fractional conversion then we have [A] = [A
0
](1-X), [B] = [B
0
](1-X),
[C]=[C
0
]+[A
0
]X, and [D] =[D
0
]+[A
0
]X. We also have K(T) = [C] [D]/[A] [B], which
finally reduces to K(T) - X
eq
2
/(1-X
eq
)
2
=0.
Compute gas phase pressures of each species :-
Since there is no change in moles for this reaction, we can directly
calculation the pressures from the equilibrium conversion and the initial pressure
of gases. we can see there is a slightly higher pressure of H2 and CO2 than the
reactants, consistent with the equilibrium constant of about 1.44 at 1000K. At a
lower temperature there would be a much higher yield of the products. For
example, at 550K the equilibrium constant is about 58, and the pressure of H2 is
4.4 atm due to a much higher equilibrium conversion of 0.88.
P_CO = P
a0
*(1-X
eq
)
P_H
2
O = P
a0
*(1-X
eq
)
P_H
2
= P
a0
*X
eq

P_CO
2
= P
a0
*X
eq

Compare the equilibrium constants :-
We can compare the equilibrium constant from the Gibbs free energy and
the one from the ratio of pressures. They should be the same.

Matlab Code For Water gas shift equilibria using
Shomate Equation :-
close all; clear all; clc;
T = linspace(500,1000); % degrees K
t = T/1000;

%Setup equations for each species
% For hydrogen T = 298-1000K valid temperature range
A = 33.066178;
B = -11.363417;
C = 11.432816;
D = -2.772874;
E = -0.158558;
F = -9.980797;
G = 172.707974;
H = 0.0;
Hf_29815_H2 = 0.0; % kJ/mol
S_29815_H2 = 130.68; % J/mol/K
dH_H2 = A*t + B*t.^2/2 + C*t.^3/3 + D*t.^4/4 - E./t + F - H;
S_H2 = (A*log(t) + B*t + C*t.^2/2 + D*t.^3/3 - E./(2*t.^2) + G);
% For H20 T= 500-1700 K valid temperature range
A = 30.09200;
B = 6.832514;
C = 6.793435;
D = -2.534480;


E = 0.082139;
F = -250.8810;
G = 223.3967;
H = -241.8264;
Hf_29815_H2O = -241.83; %this is Hf.
S_29815_H2O = 188.84;
dH_H2O = A*t + B*t.^2/2 + C*t.^3/3 + D*t.^4/4 - E./t + F - H;
S_H2O = (A*log(t) + B*t + C*t.^2/2 + D*t.^3/3 - E./(2*t.^2) + G);
% For CO T=298.15 1300 K valid temperature range
A = 25.56759;
B = 6.096130;
C = 4.054656;
D = -2.671301;
E = 0.131021;
F = -118.0089;
G = 227.3665;
H = -110.5271;
Hf_29815_CO = -110.53; %this is Hf kJ/mol.
S_29815_CO = 197.66;
dH_CO = A*t + B*t.^2/2 + C*t.^3/3 + D*t.^4/4 - E./t + F - H;
S_CO = (A*log(t) + B*t + C*t.^2/2 + D*t.^3/3 - E./(2*t.^2) + G);
%For CO2 T= 298.15 1200 K valid temperature range
A = 24.99735;
B = 55.18696;
C = -33.69137;
D = 7.948387;
E = -0.136638;
F = -403.6075;
G = 228.2431;
H = -393.5224;
Hf_29815_CO2 = -393.51;
S_29815_CO2 = 213.79;
dH_CO2 = A*t + B*t.^2/2 + C*t.^3/3 + D*t.^4/4 - E./t + F - H;
S_CO2 = (A*log(t) + B*t + C*t.^2/2 + D*t.^3/3 - E./(2*t.^2) + G);

%Standard state heat of reaction
Hrxn_29815 = Hf_29815_CO2 + Hf_29815_H2 - Hf_29815_CO - Hf_29815_H2O;
Srxn_29815 = S_29815_CO2 + S_29815_H2 - S_29815_CO - S_29815_H2O;
Grxn_29815 = Hrxn_29815 - 298.15*(Srxn_29815)/1000;
sprintf('deltaH = %1.2f',Hrxn_29815)
sprintf('deltaG = %1.2f',Grxn_29815)
deltaH = -41.15
deltaG = -28.62

%Correcting H and G
Hrxn = Hrxn_29815 + dH_CO2 + dH_H2 - dH_CO - dH_H2O;
Grxn = Hrxn - T*(S_CO2 + S_H2 - S_CO - S_H2O)/1000;


%Plot how the G varies with temperature
figure; hold all
plot(T,Grxn)
plot(T,Hrxn)
xlabel('Temperature (K)')
ylabel('(kJ/mol)')
legend('\Delta G_{rxn}', '\Delta H_{rxn}', 'location','best')



%Equilibrium constant calculation
R = 8.314e-3; %kJ/mol/K
K = exp(-Grxn/R./T);
figure
plot(T,K)
xlim([500 1000])
xlabel('Temperature (K)')
ylabel('Equilibrium constant')

%Equilibrium yield of WGS
A = CO
B = H2O
C = H2
D = CO2
Pa0 = 5; Pb0 = 5; Pc0 = 0; Pd0 = 0; % pressure in atm
R = 0.082;
Temperature = 1000;
f = @(X) K_Temperature - X^2/(1-X)^2;
Xeq = fzero(f,[1e-3 0.999]);
sprintf('The equilibrium conversion for these feed conditions is:
%1.2f',Xeq)
ans =The equilibrium conversion for these feed conditions is: 0.55

%Compute gas phase pressures of each species
P_CO = Pa0*(1-Xeq)
P_H2O = Pa0*(1-Xeq)
P_H2 = Pa0*Xeq
P_CO2 = Pa0*Xeq

P_CO = 2.2748
P_H2O = 2.2748
P_H2 = 2.7252
P_CO2 = 2.7252

%Compare the equilibrium constants
K_Temperature
(P_CO2*P_H2)/(P_CO*P_H2O)
K_Temperature = 1.4352
ans = 1.4352

Result :-




Conclusion :-
From above graph, we can say that the equilibrium of this reaction
shows a significant temperature dependence and the equilibrium constant
decreases with an increase in temperature, that is, higher carbon monoxide
conversion is observed at lower temperatures. In order to take advantage
of both the thermodynamics and kinetics of the reaction, the industrial
scale water gas shift reaction is conducted in multiple adiabatic stages
consisting of a high temperature shift (HTS) followed by a low temperature
shift (LTS) with intersystem cooling. The initial HTS takes advantage of the
high reaction rates, but is thermodynamically limited, which results in
incomplete conversion of carbon monoxide and a 2-4% carbon monoxide
exit composition. To shift the equilibrium toward hydrogen production, a
subsequent low temperature shift reactor is employed to produce a carbon
monoxide exit composition of less than 1%.