CN4246E: CHEMICAL AND

BIOCATALYSIS
Term Paper: Water-Gas Shift Reaction
(Carboxyl Mechanism)
TEAM 1

1
2

Wai Ming Hui

Chong Xue Li Cherie

A0066050R
A0066081J

1 DERIVATION FOR WATER-GAS SHIFT REACTION CARBOXYL MECHANISM

The water-gas shift reaction (CO+H2O CO2 + H2) is a slightly exothermic equilibriumcontrolled reaction. The elementary steps for the carboxyl mechanism is proposed by
Mhadeshwar and Vlachos (2005). The original 46 reactions has been narrowed to these few
elementary steps through principal component analysis. Although there appears to be 18
elementary steps, reaction pairings between R1-R2, R7-R8, R13-R14, R19-R20, R21-R22, R25-R26, R29R30, R31-R32, R33-R34 actually produces 9 reversible elementary steps. The reduced elementary
steps are mentioned by the authors to be thermodynamically consistent by keeping the
equilibrium constant fixed with changing the pre-exponential factors.

Here steady-state approximation assumption is applicable for species coverage which

provides the complete steady state balance for species coverage.

= 21 22 + 7 8 25 + 26 + 31 32 + 33 34 = 0 (1)

= 7 8 + 25 26 + 29 30 = 0 (2)

2
= 7 + 8 + 13 14 33 + 34 = 0 (3)

= 19 20 + 25 26 + 29 30 33 + 34 = 0 (4)

2
= 21 22 25 + 26 + 31 32 = 0 (5)

= 29 + 30 31 + 32 + 33 34 = 0 (6)

Overall site coverage equation:

+ + 2 + + 2 + + = 1 (7)
To simplify the expressions above, CO* and H* are found to be the most abundant reactive
intermediate (MARI). Furthermore, reversibility of reaction pairs are analyzed which results in
simplified steady state balance for species coverage.

= 21 22 + 31 32 + 33 = 0 (8)

= 7 8 26 30 = 0 (9)

2
= 13 14 = 0

13 = 14 (10)

= 19 20 = 0

19 = 20 (11)

2
= 21 22 = 0

21 = 22 (12)

= 31 + 32 + 33 = 0

31 = 32 + 33 (13)

MARI assumption is applicable for and .

+ + = 1 (14)
The following site coverage terms can be obtained:
13
2 = ( ) 2 = 13 2 (15)
14
= (

2 = (

19
) = 19 (16)
20

21
) = 21 2 (17)
22 2

33 = 31 32
33 2 = 31 32 2
=

33 2 + 32 2
(18)
31

Substitute (13) into (8) to obtain the following expression for .

21 22 + 233 = 0
21 2 2 22 2 + 233 2 = 0
21 2 2 22 2 + 233 19 13 2 2 = 0
2 2 = 1 2 2 + 33 19 13 2 2
1 2 + 33 19 13 2
=

2
Since

33
1

0.03 as 33 is rate-determining step. can be further simplified.

1 2
=
= 1 2 (19)
2

Substitute the (15), (16) and (19) into (9) and obtain following expression for .
7 8 26 30 = 0
7 2 8 26 30 = 0
7 13 2 2 8 1 2 26 19 30 19 = 0
7 13 2 2 = (8 1 2 + (26 +30 )19 )

7 13 2
8 1 2 + (26 +30 )19

(20)

Substitute (15), (17) and (19) into (18) and obtain following expression for .
= (
33
1

33 13 2 19 + 32 21 2 1 2
31

0.03 as 33 is rate-determining step to simplify the expression into:

32 21 2 1 2
21 2 12
= (
) =
(21)
31
31

Substitute (16) and (19) into simplified site coverage equation (14)
1 2 + 19 + = 1
=

1
1 + 1 2 + 19

(22)

2 DERIVATION FOR FORWARD REACTION

The net rate of 2 is used to determine overall reaction rate. Through the stoichiometry of
the global reaction (CO+H2O CO2 + H2), the net rate for other species can be determined
in terms of net rate of 2 . 33 is chosen as the rate-determining step for the forward
reaction.
2 = 1 2 = 33 = 33 2 = .
. = 33 19 13 2 2
. =

33 19 13 2
(1 + 1 2 + 19 )

(23)

3 DERIVATION FOR REVERSE REACTION AND SIMPLIFIED NET RATE

EQUATION
34 is chosen as the rate-determining step for the reverse reaction since this reaction is not
found to be in equilibrium for the reverse reaction. The global water-gas shift reaction is
equilibrium-controlled which implies that the terms that were derived for the forward

reaction is equivalent to reverse reaction. Hence, the site coverage expressions for the
intermediates and adsorbed species (15), (16), (17), (19), (20) and (21) can be used.
1 2 = 34 = 34 = .
1
. = 34 = 34 21 2 1 31
2 2

. =

1
34 21 2 1 31
2

(1 + 1 2 + 19 )

(24)

The net rate equation for global water-gas shift reaction is shown below:
. = . .
1
. = 33 19 13 2 2 34 21 1 31
2 2 2 (25)

. =

1
33 19 13 2 34 21 1 31
2 2

(1 + 1 2 + 19 )

(26)

This form of equation (26) will be used for model fitting against Grabow (2009) experimental
data.

4 DERIVATION FOR FULL NET RATE EQUATION

When MARI is not assumed in the site coverage equation (7), the net rate equation (25) will
be very detailed since the behavior of all coverage species is captured in the site coverage
equation (7) as shown below:
+ + 2 + + 2 + + = 1

1 2 +

7 13 2
8 1 2 + (26 +30 )19

1
+ 13 2 + 19 + 21 2 + 21 2 31
1 2 + = 1

1
(27)
7 13 2
1
1 + 1 2 +
+ 13 2 + 19 + 21 2 + 21 2 31

1 2
8 1 2 + (26 +30 )19

Substitute (27) into (25)

1
33 19 13 2 34 21 1 31
2 2

. =

(1 + 1 2 +

7 13 2
1
+ 13 2 + 19 + 21 2 + 21 2 31
1 2 )
8 1 2 + (26 +30 )19

(28)

5 MODEL FITTING USING MATLAB

A universal water gas shift reaction mechanism is still not well-understood and agreed upon.
But kinetic studies on platinum (Pt) is especially limited. Current research on water-gas shift
reaction uses a lot of first-principle analysis and transition state theory ([2], [4], [5] and [6]) to
elucidate the reaction mechanism. However, such analysis is computationally intensive.
Another method to analyze and elucidate reaction mechanism efficiently is to conduct model
fitting and discrimination against available experimental data to determine possible reaction
mechanisms. The simplified carboxyl rate equation (26) will be used in model fitting against
experimental data from Grabow (2008) [2].

. =

1
33 19 13 2 34 21 1 31
2 2

(1 + 1 2 + 19 )

(26)

The experiment on water-gas shift reaction was done on Pt/Al2O3 catalyst by introducing
different components (CO, H2, H2O and CO2) at different temperature. The total pressure was
kept constant at 1 atm with inert He introduced as balance gas. The turnover frequency (TOF)
is expressed as moles of product species produced per moles of active catalytic sites per unit
time (min-1). The experimental data from [2] is selected and compiled in Appendix 8A.
For model fitting and analysis, nlinfit command is first used to determine the equilibrium
constants in (26) at 548K. However in order to determine if the results obtained from nlinfit is
statistically significant, the nlparci function can be used to determine the upper bound and
lower bound of a coefficient at a certain percentage interval. For this analysis, 90%
confidence interval is used.

For nlinfit command to work, initial estimates are required and such estimates are obtained
through trial and error method to obtain positive coefficient. Several attempts to make initial
estimates has to be used. This is because negative equilibrium constant or rate constant does
not have physical meaning. Hence, the initial estimates that gives positive coefficient are
given in Table 1. The results for the 7 coefficients are tabulated in Table 3a, 3b and 3c.

Table 2: Initial estimates for constants for nlinfit function in MATLAB

Initial estimates
for equilibrium constants

k33 K19
10 100

K13
0.1

k34
500

K21
0.9

K1
20

K31
1

Table 3a: Results of non-linear model fitting at 90% confidence interval

T (K)
548

MSE
1.1315

k33
mean
U.L
L.L
118.7447 118.7459 118.747

L.L
1.1315

K19
mean
4.887

U.L
9.7301

K13
L.L
mean
14.5715 1.0744

U.L
1.1875

Table 3b: Results of non-linear model fitting at 90% confidence interval

T (K)
548

MSE
1.1315

L.L
59.691

k34
mean
59.7024

U.L
59.7138

L.L
-6.2041

K21
K1
mean
U.L
L.L
mean
U.L
0.1075 6.4191 1.2532 17.2362 33.2193

Table 3c: Results of non-linear model fitting at 90% confidence interval

Temperature(K) MSE
548
1.1315

L.L
4.7189

K31
mean
4.8588

U.L
4.9986

6 DISCUSSION
A) Equilibrium constants and statistical significance
The rate constants and equilibrium obtained from non-linear fitting display positive values
However if statistical significance is to be properly accounted for, the model may not
describe the reaction mechanism accurately because K21 which is the equilibrium constant
for CO2 adsorption and desorption from active sites is -6.2041 at the lower limit and 6.4191

at the upper limit. However, more attempts on initial estimates need to be done to confirm
that K21 is truly statistically insignificant.
B) Uncertainty in determining rate-determining step (RDS)
One possible reason for the statistical insignificance of [26] is the uncertainty in predicting
the rate-determining step in the carboxyl mechanism. R7-R8, R25-R26, R29-R30 are also potential
RDS identified because these reactions are found to be far from equilibrium at various
temperature [1]. L.C Grabow et al [2] conducted Campbells rate control analysis and found
that water activation (R7-R8) is the next possible rate-determining step after (COOH*+* <->
CO2*+H*). Possible attempts to better elucidate the reaction mechanism could include
deriving the rate equation based on possible rate-determining steps (R7-R8, R25-R26 and R29R30) and conduct non-linear fitting to determining the most likely reaction mechanism.

7 CONCLUSION
The net rate equation for water gas shift reaction catalyzed on Pt/Al2O3 has been derived
based on CO* and H* as the most abundant reactive intermediate (MARI) and R33-R34 as the
rate-determining step. Non-linear model fitting nearly yielded positive values for the rate
constants and equilibrium constants in the model at 90% confidence interval. However, only
K21 is found to be statistically insignificant which affects the validity of the model. There is
also uncertainty in determining the rate-determining step as R7-R8, R25-R26 and R29-R30 are
also potential RDS [2]. Future work involves deriving rate equation based on possible ratedetermining steps and fitting against experimental data to determine the most likely reaction
mechanism.

8 REFERENCE
[1] A.B Mhadeshwar, D.G Vlachos. Is the water-gas shift reaction on Pt simple? Computeraided microkinetic model reduction, lumped rate expression, and rate-determining step.
Catalysis Today (2005), 105, 162-172.
[2] L.C Grabow, A.A Gokhale, S.T Evans, J.A Dumesic, M Mavrikakis. Mechanism of the Water
Gas Shift Reaction on Pt: First Principles, Experiments and Microkinetic Modeling. Journal of
Physical Chemistry C (2008), 112, 4608-4617.
[3] W.F Podolski, Y.G Kim. Modeling the Water-Gas Shift Reaction. Ind. Eng. Chem. Process
Des. Dev (1974), 13 (4), 415-421.
[4] A.A Gokhale, J.A Dumesic, M Mavirikakis. On the mechanism of low temperature water
gas shift reaction on copper. J. Am. Chem. Soc (2008), 130(4), 1402-1414.
[5] H.N Chiang, J.C Jiang. Density Functional Theory Study of Water-Gas-Shift Reaction on
3Cu/-Al2O3(0001) Surface. J. Phys. Chem. C(2013), 117 (23), 1204512053.
[6] A.B Vidal, P Liu. Density functional study of water-gas shift reaction on M3O3x/Cu(111).
Phys. Chem. Chem. Phys (2012),14, 16626-16632.

9 APPENDIX
A) Selected experimental kinetics data on Pt/Al2O3 catalyst taken from [2]
No of runs

T (K)

PCO(atm) PH2O(atm)

PCO2(atm)

PH2(atm) measured TOF(min^-1)

523

0.154

0.208

3.68

548

0.055

0.208

8.56

548

0.105

0.208

8.06

548

0.137

0.062

3.63

548

0.144

0.104

4.81

548

0.148

0.145

5.56

548

0.145

0.208

7.27

548

0.106

0.208

0.068

6.05

548

0.104

0.208

0.109

5.59

10

548

0.14

0.208

0.151

6.12

11

548

0.102

0.208

0.192

6.03

12

548

0.134

0.208

0.037

4.13

13

548

0.156

0.208

0.097

2.77

14

548

0.13

0.208

0.123

2.67

15

548

0.134

0.208

0.177

0.123

2.67

16

548

0.132

0.208

0.173

2.55

17

548

0.146

0.208

0.191

2.28

18

548

0.159

0.208

0.208

2.29

19

548

0.198

0.208

7.29

20

548

0.223

0.208

7.09

21

573

0.15

0.208

15.44

B) MATLAB Code for nlinfit and nlparci function

Function file
function yhat=wgs_carboxylmechanismvlachos(beta,x)
yhat=(x(:,1).*x(:,2).*beta(1)*beta(2)*beta(3)x(:,3).*x(:,4).*beta(4)*beta(5)*beta(6)*(beta(7)^1))./(1+((x(:,4).*beta(6)).^0.5)+x(:,1).*beta(2)).^2;

Domain file
% Mhadeshwar&Vlachos 2005 model is fitted with Grabow 2008 experimental
% data.p=partial pressure of components (atm),v=measured TOF(min^-1)
% x(:,1) is the partial pressures of CO,x(:,2) is the partial pressures of
H2O,x(:,3) is the partial pressures of CO2,x(:,4) is the partial pressures
of H2,
% previous intial values are [1000 1 1 1500 1 1 2] and eventually [375.8356
9.7301 0.3752 105.4530 0.0703 17.2363 5.6143],[10 100 0.1 500 0.9 20 1]
.The latter one produces the best results thus far.
p=[0.055 0.105 0.137 0.144 0.148 0.145 0.106 0.104 0.14 0.102 0.134 0.156
0.13 0.134 0.132 0.146 0.159 0.198 0.223;0.208 0.208 0.062 0.104 0.145
0.208 0.208 0.208 0.208 0.208 0.208 0.208 0.208 0.208 0.208 0.208 0.208
0.208 0.208;0 0 0 0 0 0 0.068 0.109 0.151 0.192 0 0 0 0.177 0 0 0 0 0;0 0 0
0 0 0 0 0 0 0 0.037 0.097 0.123 0.123 0.173 0.191 0.208 0 0]';
v=[8.56 8.06 3.63 4.81 5.56 7.27 6.05 5.59 6.12 6.03 4.13 2.77 2.67 2.67
2.55 2.28 2.29 7.29 7.09]';
[beta,r,J,sigma,mse]=nlinfit(p,v,@wgs_carboxylmechanismvlachos,[10 100 0.1
500 0.9 20 1])
ci=nlparci(beta,r,'covar',sigma,'alpha',0.1)