Answers to Exercises

Last update: Tuesday 29th September, 2015.

Comments and suggestions can be sent to i.a.w.filot@tue.nl

Exercise 1

d[CH4 ]
= k2 [CH3 *][CH3 CHO] (1.1)
dt

The target is to express short-lived intermediates (such as radicals) in terms of gas-phase concentrations.
Here, the unknown variable is [CH3 *] and can be found by using the steady state approximation. In the steady-
state approximation, the time-derivative of one or more compounds, typically the reaction intermediates, is
set to zero. We apply this approximation to d[CH
dt
3 *]
and d[CH3dtCHO*] .

d[CH3 *]
= k1 [CH3 CHO] − k2 [CH3 *][CH3 CHO] + k3 [CH3 CO*] − 2k4 [CH3 *]2 = 0 (1.2)
dt

and

d[CH3 CO*]
= k2 [CH3 *][CH3 CHO] − k3 [CH3 CO*] = 0 (1.3)
dt

Combining equations 1.2 and 1.3 yields

r
k1
[CH3 *] = [CH3 CHO]1/2 . (1.4)
2k4

Inserting equation 1.4 into equation 1.1 gives

r
d[CH4 ] k1
= k2 [CH3 CHO]3/2 . (1.5)
dt 2k4

and the rate of formation for [C2 H6 ] becomes

d[C2 H6 ] k1
= k4 [CH3 *]2 = [CH3 CHO] (1.6)
dt 2

Exercise 2
The problem in the exercise can be solved by either applying the steady-state approximation or by assuming a
pre-equilibrium. Here, we have applied the former as such an approximation is more general and also better
exemplifies the mathematical procedure. Obviously, a derivation based on the pre-equilibrium assumption is
also valid.

1
2

d[O2 ]
= k2 [NO2 ][NO3 ] (2.1)
dt

Applying the steady-state approximation to NO and NO3 yield

d[NO]
= k2 [NO2 ][NO3 ] − k3 [NO][NO3 ] = 0 (2.2)
dt

and

d[NO3 ]
= k1+ [N2 O5 ] − k1− [NO2 ][NO3 ] − k2 [NO2 ][NO3 ] − k3 [NO][NO3 ] = 0. (2.3)
dt

Combining equations 2.2 and 2.3 by summation, we obtain

k1+
[NO2 ][NO3 ] = [N2 O5 ] (2.4)
k1− + 2k2

which we can readily insert into the rate equation of O2 formation, resulting in

d[O2 ] k + k2
= −1 [N2 O5 ]. (2.5)
dt k1 + 2k2

For NO2 , the rate equation is

d[NO2 ]
= k1+ [N2 O5 ] − k1− [NO2 ][NO3 ] + 2k3 [NO][NO3 ]. (2.6)
dt

Inserting equations 2.2 and 2.4 to 2.6 gives

d[NO2 ] k+ k− 2k + k2
=k1+ [N2 O5 ] − − 1 1 [N2 O5 ] + − 1 [N2 O5 ] (2.7)
dt k1 + 2k2 k1 + 2k2
k1+ k1− 2k1+ k2
 
+
= k1 − − + − [N2 O5 ] (2.8)
k1 + 2k2 k1 + 2k2
k+
= − 1 k1− + 2k2 − k1− + 2k2 [N2 O5 ]


(2.9)
k1 + 2k2
k1+
= 4k2 [N2 O5 ] (2.10)
k1−
+ 2k2
d[O2 ]
=4 . (2.11)
dt

Exercise 3
Applying the steady-state approximation to [N2 O2 ] gives

d[N2 O2 ]
=k1+ [NO]2 − k1− [N2 O2 ] − k2 [N2 O2 ][H2 ] = 0. (3.1)
dt

From this expression, we can equate the [N2 O2 ] to

 3

k1+ [NO2 ]2
[N2 O2 ] = . (3.2)
k1− + k2+ [H2 ]

The rate of formation of [N2 O] is then found to be

d[N2 O] k2 k1+ [NO2 ]2 [H2 ]

=k2 [N2 O2 ][H2 ] = (3.3)
dt k1− + k2+ [H2 ]
k1+ [NO2 ]2
= . (3.4)
1 + k1− /k2 [H2 ]

Exercise 4
In the overall chain reaction, the elementary reaction steps are denoted as

Br2 → 2Br* initiation

CH4 + Br* → CH3 * + HBr propagation
CH3 * + Br2 → CH3 Br + Br* propagation
2Br* → Br2 termination

The steady-state approximation can be readily applied to the reaction rates of the intermediates.

d[Br*]
= 2k1 [Br2 ] − k2 [CH4 ][Br*] + k3 [CH3 *][Br2 ] − 2k4 [Br*]2 = 0 (4.1)
dt

d[CH3 *]
= k2 [CH4 ][Br*] − k3 [CH3 *][Br2 ] = 0 (4.2)
dt

Inserting equation 4.1 in 4.2 results in

 1/2
k1
[Br*] = [Br2 ] . (4.3)
k4

Applying equation 4.3 to 4.2 yields

 1/2
k1
k2 [CH4 ] k4 [Br2 ]
[CH3 *] =
k3 [Br2 ]
1/2
k2 k1 [CH4 ]
= 1/2
. (4.4)
k3 k4 [Br2 ]1/2

Finally substituting the result of equation 4.4 for the concentration of [CH3 *] in the formation rate of
[CH3 Br] results in

1/2
d[CH3 Br] k2 k1
= k3 [CH3 *][Br2 ] = 1/2 [CH4 ][Br2 ]1/2 . (4.5)
dt k4


4

Exercise 5
5a
The elementary reaction step for CO adsorption is

CO + *  CO* (5.1)

Assuming an equilibrium of the above reaction and only one type of surface site yields

θCO
KCO = . (5.2)
pCO θ*

Furthermore, we can apply the site-balance defined as

θ* + θCO = 1. (5.3)

Hence,

θCO =KCO pCO θ* = KCO pCO (1 − θCO ) (5.4)

θCO (1 + KCO pCO ) =KCO pCO (5.5)
KCO pCO
θCO = . (5.6)
1 + KCO pCO

5b
The elementary reaction step for dissociative CO adsorption is

CO + 2*  C* + O*. (5.7)

Assuming equilibrium of the above reaction and only one type of surface site gives us

θC θO
KCO = . (5.8)
pCO θ*2

For the mass balance (or site balance), we get

θ* + θC + θO = 1. (5.9)

Because the surface fraction of C and O are equal

θC2
KCO = . (5.10)
pCO θ*2

Thus,
p p
θC = KCO pCO θ* = KCO pCO (1 − 2θC ) (5.11)
p p
θC (1 + 2 KCO pCO ) = KCO pCO (5.12)
√
KCO pCO
θC = √ . (5.13)
1 + 2 KCO pCO
 5

5c
The two elementary reaction steps for co-adsorption are

CO + *  CO* (5.14)
H2 + 2*  2H*. (5.15)

Assuming pre-equilibrium of these two elementary reaction steps gives

θCO
KCO = (5.16)
pCO θ*

and

2
θH
KH2 = (5.17)
pH2 θ*2

and thus for the fractional coverages in terms of the fraction of free sites

p
θH = KH2 pH2 θ* (5.18)
θCO =KCO pCO θ* (5.19)

Using the site balance,

θCO + θH + θ* = 1 (5.20)

and inserting the equation for the surface fraction into the equation

p
(1 + KCO pCO + KH2 pH2 )θ* = 1 (5.21)

and rearranging for θ* finally yields

1
θ* = p . (5.22)
1 + KCO pCO + KH2 pH2

This equation can be reinserted into the equations for the surface fractions to obtain

p
KH2 pH2
θH = p (5.23)
1 + KCO pCO + KH2 pH2
KCO pCO
θCO = p (5.24)
1 + KCO pCO + KH2 pH2
(5.25)

5d
6

1. CO + *  CO*
2. H2 + 2*  2H*
3. CO* + H*  HCO* + *
4. HCO* + H*  H2 CO* + *
5. H2 CO* + H*  H3 CO* + *
6. H3 CO* + H*  H3 COH* + *
7. H3 COH + *  H3 COH*

The third step is considerd to be the rate-determining step. This gives the following expression for the
overall rate

r = k3+ θCO θH . (5.26)

We here use the result of question 5c and note that besides CO and H2 , methanol is also equilibrated with
the surface. Hence the Langmuir isotherms of CO and H2 are
p
KH2 pH2
θH = p (5.27)
1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH
K p
θCO = p CO CO . (5.28)
1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH

And the overall rate is

k3+
p
KH2 pH2 KCO pCO
r= p
2 . (5.29)
1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH

To obtain the reaction order for CO, H2 and methanol, one needs to solve the following differential:

∂ ln(r+ )
nH2 =pH2 (5.30)
∂pH2
=D1 − 2D2 (5.31)

Here, we are going to split up the complex differential into two smaller (and hopefully simpler) differen-
tials:

∂ ln k3+ + 1 1
 
2 ln KCO + ln pH2 + ln KH2 + ln pCO
2
D1 = pH2 (5.32)
∂pH2

p

∂ ln 1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH
D2 = pH2 (5.33)
∂pH2

D1 can be readily solved as all the terms except the ln pH2 cancel out giving

∂ ln pH2
D1 = pH2 (5.34)
∂pH2
1
= pH2 (5.35)
pH2
1
= (5.36)
2

D2 is a bit more complex and requires applying the chain-rule

 7

∂ ln(a) a
D2 = pH2 (5.37)
∂a ∂pH2

where
p
a = 1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH (5.38)

Thus
p

1 ∂ 1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH
D2 =pH2 (5.39)
a ∂pH2
 
1 1p −1/2
=pH2 KH2 pH2 (5.40)
a 2
p !
1 KH2 pH2
= p (5.41)
2 1 + KCO pCO + KH2 pH2 + KCH3 OH pCH3 OH
1
= θH (5.42)
2

and the final result is

∂ ln(r+ )
nH2 =pH2 (5.43)
∂pH2
1
= − θH (5.44)
2

We can now easily establish the lower and upper limit of the reaction order in H2 :

1 1
θH ∈ [0, 1] → nH2 ∈ [− , ]. (5.45)
2 2

The derivations for the reaction order in CO and methanol are quite similar to the one for H2 and results
in:

∂ ln(r+ )
nCO =pCO (5.46)
∂pCO
=1 − 2θCO (5.47)

and

∂ ln(r+ )
nCH3 OH =pCH3 OH (5.48)
∂pCH3 OH
= − 2θCH3 OH (5.49)

This gives for the lower and upper limits for CO and methanol:

θCO ∈ [0, 1] → nCO ∈ [−1, 1] (5.50)

and

θCH3 OH ∈ [0, 1] → nCH3 OH ∈ [−2, 0] (5.51)


8

Exercise 6
6a
The three steps leading to oxygen removal are:

8. H2 O + *  H2 O*
9. H2 O* + *  OH* + H*
10. OH* + *  O* + H*
(6.1)

6b
The reaction order is determined by the rate-limiting step and all the steps that are in equilibrium before it.
This is most likely step (5) as it involves a hydrogenation step subsequent to two other hydrogenation steps.

6c
The overall rate equation, based on the rate-determining step, is given by

r = k5 θH2 COO θH (6.2)

We need to substitute the surface coverages by expressions that only contain gas-phase pressures and re-
action rate constants. To start, we assume quasi-equilibrium of all elementary reaction steps before the rate-
determining step.

p
θH = K1 pH2 θ* (6.3)
θCO2 =K2 pCO2 θ* (6.4)
K3 θCO2 θH
θHCOO = (6.5)
θ*
K4 θHCOO θH
θH2 COO = (6.6)
θ*
(6.7)

By substituting the expressions for θH and θCO2 in equation 6.5, we get

p
θHCOO = K3 K1 pH2 K2 pCO2 θ* (6.8)

This result can be readily inserted into equation 6.7 to obtain

θH2 COO = K4 K3 K2 pCO2 K1 pH2 θ* (6.9)

Now, we need to use the above expressions in combination with the site-balance to construct the expression
for the free sites

θH + θCO2 + θHCOO + θH2 COO + θ* = 1 (6.10)

 p p 
θ* 1 + K1 pH2 + K2 pCO2 + K3 K1 pH2 K2 pCO2 + K4 K3 K2 pCO2 K1 pH2 = 1 (6.11)

This leads to

1
θ* = p p (6.12)
1+ K1 pH2 + K2 pCO2 + K3 K1 pH2 K2 pCO2 + K4 K3 K2 pCO2 K1 pH2
 9

Using equations , , and , we can construct the overall rate equation

r = k5 θH2 COO θH (6.13)

p
= k5 K4 K3 K2 pCO2 K1 pH2 K1 pH2 θ*2 (6.14)
p
k5 K4 K3 K2 pCO2 K1 pH2 K1 pH2
= p p
2 (6.15)
1+ K1 pH2 + K2 pCO2 + K3 K1 pH2 K2 pCO2 + K4 K3 K2 pCO2 K1 pH2
3/2
k5 K4 K3 K2 pCO2 (K1 pH2 )
= p p
2 (6.16)
1+ K1 pH2 + K2 pCO2 + K3 K1 pH2 K2 pCO2 + K4 K3 K2 pCO2 K1 pH2

Let us now check whether our hypothesis that the order in H2 is 3/2 is correct. To make things a bit easier,
let us assume that the surface is nearly empty and that θ* ≈ 1, the rate equation then is

3/2
r ≈ k5 K4 K3 K2 pCO2 (K1 pH2 ) (6.17)

and

3/2
∂ ln(r+ ) ∂ ln pH2
pH2 = pH2 = 3/2 (6.18)
∂pH2 ∂pH2

Note that in the above expression, I significantly simplified the equation by applying the same trick as I did
in exercise 5d.

6d
In order to find the optimal fraction, we define the constant α which is the ratio between the partial pressure
of H2 and CO2 .

pH2
α= (6.19)
pCO2

From this, the total pressure becomes

pT = pCO2 + pH2 = pCO2 + αpCO2 = (1 + α)pCO2 (6.20)

and I can relate the partial pressure of H2 and CO2 to the total pressure as

αpT
pH2 = (6.21)
1+α
pT
pCO2 = (6.22)
1+α
(6.23)

Filling out these new expressions and assuming that the surface is nearly empty results in

 3/2
pT αpT
r = k5 K4 K3 K2 K1 (6.24)
1+α 1+α

To find out the optimal value in α, we need to take the first derivative towards α and equate this to zero.
Therefore, we can simplify the above equation by collecting all variables that do not depend on α

α3/2
r=c 5/2
(6.25)
(1 + α)

where c is a factor that does not depend on α.

10

3 1/2 5/2 3/2

∂r 2α (1 + α) − 25 α3/2 (1 + α)
= 5 =0 (6.26)
∂α (1 + α)

To find the value for α, only the nominator of the above expression is relevant and we can ignore the
denominator

3 1/2 5/2 5 3/2

α (1 + α) − α3/2 (1 + α) =0 (6.27)
2 2
3 1/2 5/2 5 3/2
α (1 + α) = α3/2 (1 + α) (6.28)
2 2
5
1+α= α (6.29)
3
3
α= (6.30)
2

This result is to be expected, as the best ratio between the partial pressures of the reactants is of course the
ratio between the reaction orders of said reactants. The fraction of CO2 in terms of the total pressure is then 25
and the fraction of H2 is then 35 .

Exercise 7
7a
We assume the steady-state approximation on θO . Furthermore, we assume that θCO  θO and that CO is in
quasi-equilibrium with the surface.

7b
First, we apply the quasi-equilibrium assumption to CO giving

θCO = K1 pCO θ* (7.1)

Next, we apply the steady-state assumption to θO

dθO
= 2k2+ pO2 θ*2 − k3+ θCO θO = 0 (7.2)
dt

Note that the second and third elementary reaction step in our mechanism are irreversible, significantly
reducing the complexity of the equation. The above result gives us an expression for the partial coverage of O
as

2k2+ pO2 2
θO = θ* (7.3)
k3+ θCO

To obtain the expression for the free site coverage we assume that θCO  θO giving

θCO + θ* = 1 (7.4)
θ* (1 + K1 pCO ) = 1 (7.5)
1
θ* = (7.6)
1 + K1 pCO

Plugging this result into the overall rate equation yields

 11

r = k3+ θCO θO (7.7)

K1 pCO 2k2+ pO2 2
= k3+ θ (7.8)
1 + K1 pCO k3+ θCO *
2  −1
K1 pCO 2k2+ pO2

1 K1 pCO
= k3+ (7.9)
1 + K1 pCO k3+ 1 + K1 pCO 1 + K1 pCO
2k2+ pO2
= 2 (7.10)
(1 + K1 pCO )

Note that from the above expression, we can easily see that the order in O2 is +1 and the order in CO is
between -2 and 0.

Exercise 8
8a
Synthesis gas is a mixture of CO and H2 . It is used in Fischer-Tropsch catalysis and in methanol formation.
The former reaction is typically performed over a Fe or Co catalyst. The latter reaction is typically performed
over a Cu catalyst.

8b
In order to further increase the production of H2 , CO can be mixed with H2 O to give CO2 and H2 . This reaction
is called water-gas shift.

8c
From the reaction equation (CH4 + H2 O  CO + 3H2 ) we can see that the reaction produces more moles of
gas than are consumed. Hence, in principle the reaction should be performed at low pressure to drive the
equilibrium to the right hand side of the equation. However, in a typical reactor a moderate pressure is used
as to reduce the reactor volume.
Furthermore, the reaction needs to be performed at high temperature, because this reaction is strongly
endothermic. Again, the high temperature pushes the equilibrium to the right hand side of the equation.

8d
To start, we need to propose a reaction mechanism in terms of a set of elementary reaction steps. To convert
methane and water into synthesis gas, a set of 10 elementary reaction steps is necessary.

1. CH4 + 2*  CH3 * + H*
2. CH3 * + *  CH2 * + H*
3. CH2 * + *  CH* + H*
4. CH* + *  C* + H*
5. H2 O + *  H2 O*
6. H2 O* + *  OH* + H*
7. OH* + *  O* + H*
8. H2 + 2*  2H*
9. C* + O*  CO* + *
10. CO + *  CO*

We assume that all the above steps, except the rate-limiting step (9) are in quasi-equilibrium. As such, we
can express all surface coverages by one or more equilibrium constants as follows
12

θCO = K10 pCO θ* (8.1)

p
θH = K8 pH2 θ* (8.2)
θH2 O = K5 pH2 O θ* (8.3)
K6 pH2 O θ* K5 K6 pH2 O
θOH = = p θ* (8.4)
θH K8 pH2
K K p
K7 √5 6 H2 O θ*2
K7 θOH θ* K8 pH2 K5 K6 K7 pH2 O
θO = = p = θ* (8.5)
θH K8 pH2 θ* K8 pH2

In the above expressions for O and OH, we have applied subsequent substitution of the surface coverages
in such a way that we can express every surface coverage in terms of the partial pressures of the reactants or
products and the equilibrium constants. These equilibrium constants correspond to the elementary reaction
steps that connect the partial pressures with the surface coverages. Below, the same is done for the surface
coverages of the CHx intermediates

K1 pCH4
θCH3 = p (8.6)
K8 pH2 θ*
K1 K2 pCH4
θCH2 = (8.7)
K8 pH2 θ*
K1 K2 K3 pCH4
θCH = 3/2
θ* (8.8)
(K8 pH2 )
K1 K2 K3 K4 pCH4
θC = 2 θ* (8.9)
(K8 pH2 )

Now we can construct the site-balance

θCO + θH + θH2 O + θOH + θO + θCH3 + θCH2 + θCH + θC + θ* = 1 (8.10)

and plug the above equations for the surface coverages into it

p K5 K6 pH2 O K5 K6 K7 pH2 O K1 pCH4

θ* = 1 + K10 pCO + K8 pH2 + K5 pH2 O + p + +p ···
K8 pH2 K8 pH2 K8 pH2
!−1
K1 K2 pCH4 K1 K2 K3 pCH4 K1 K2 K3 K4 pCH4
··· + + 3/2
+ 2 (8.11)
K8 pH2 (K8 pH2 ) (K8 pH2 )

Since the overall rate is determined by the rate of step 9 we can construct the following expression

r = k9+ θC θO − k9− θCO θ* (8.12)

k9+
= k9+ θC θO − θCO θ* (8.13)
K9

If we assume that there is an equilibrium r = 0, we can express K9 as

3/2 3/2
θCO θ* pCO pH2 K83 K10 pCO pH2 1
K9 = = = (8.14)
θC θO pH2 pCH4 K1 K2 K3 K4 K5 K6 K7 pH2 pCH4 Keq

and using this result for K9 for our overall rate expression results in
 13

r = k9+ θC θO − k9− θCO θ* (8.15)

 
+ 1 θCO θ*
= k9 θC θO 1 − (8.16)
K9 θC θO
3/2
!
K1 K2 K3 K4 K5 K6 K7 pCH4 pH2 O 1 pCO pH2 1
= k9+ 3 1− θ* (8.17)
(K8 pH2 ) K9 pH2 pCH4 Keq

Further assuming that O is the MARI, we can use the following equation for the free sites

 −1
K5 K6 K7 pH2 O
θ* = 1+ (8.18)
K8 pH2

giving
 3/2

K1 K2 K3 K4 K5 K6 K7 pCH4 pH2 O 1 pCO pH2 1
3 1− K9 pH2 pCH4 Keq
(K8 pH2 )
r = k9+  2 (8.19)
K5 K6 K7 pH2 O
1+ K8 pH 2

For low conversions, the second term between parenthesis in the nominator can be neglected, further sim-
plifying the equation to

 −2
K1 K2 K3 K4 K5 K6 K7 pCH4 pH2 O K5 K6 K7 pH2 O
r= k9+ 3 1+ (8.20)
(K8 pH2 ) K8 pH2

8e
Note that for CH4 and CO, there are no dependencies in the term between parentheses, so we only need to
evaluate the derivative for the part in front of the parentheses. Again, we apply the same trick as in Exercise 5,
so that we obtain:

∂ ln(r+ )
pCH4 =1 (8.21)
∂pCH4

∂ ln(r+ )
pCO =0 (8.22)
∂pCO

The reaction order in H2 O and H2 is a bit more complicated but with some rewriting the derivatives equate
to

∂ ln(r+ ) K5 K6 K7 ∂pH2 O /∂pH2 O

pH2 O = 1 − 2pH2 O p (8.23)
∂pH2 O K8 1 + KK5 K 6 K7 H2 O
8 pH2 pH 2
 −1
K5 K6 K7 pH2 O K5 K6 K7 pH2 O
=1−2 1+ (8.24)
K8 pH2 K8 pH2 pH2
= 1 − 2θO (8.25)

and similarly for H2

∂ ln(r+ )
pH2 = −3 + 2θO (8.26)
∂pH2
14

From the above expressions for the order, we note that the experimental results are not within the limits of
the reaction orders. Consequently, the proposed reaction mechanism is not in agreement with the experiment
and needs to be revised.

8f
Applying the same procedure as previously, the reaction rate now equates to

pCH4
r = k1+  2 (8.27)
K5 K6 K7 pH2 O
1+ K8 pH2 pH2

Note that steps 2-4 do not appear in the rate equation, because only the first diossciative methane adsorp-
tion step is kinetically relevant. The equilibrium constants for steps 5-8 appear in the denominator because
they control the amount of O on the surface.
From the above rate equation, we can establish the reaction orders to be

∂ ln(r+ )
pCH4 =1 (8.28)
∂pCH4

∂ ln(r+ )
pCO =0 (8.29)
∂pCO

∂ ln(r+ )
pH2 O = −2θO (8.30)
∂pH2 O

∂ ln(r+ )
pH2 = 2θO (8.31)
∂pH2

These results are consistent with the experimental observation.

Exercise 9
9a
C2 H6 adsorption coincides with D2 adsorption. Upon adsorption, the hydrogen in the C2 H6 complex can be
exchanged for a deuterium by successive dehydrogenation, deuteration and a desorption step.

9b

r = k2+ θC2 H5 * θH* − k2− θCH

2
3
(9.1)

9c
Considering competitive adsorption, the Langmuir isotherms for ethyl, methyl and hydrogen become.
The steady state equation applied to elementary reaction steps 1,3 and 4 yields

K1 pC2 H6 2
θC2 H5 = θ* (9.2)
θH
 15

pCH4 2
θCH3 = θ (9.3)
K3 θH *

p
θH = K4 pH2 θ* (9.4)

Plugging equation 9.4 into and into , gives

K1 pC H
θC2 H5 = p 2 6 θ* (9.5)
K4 pH2

and
p
θCH3 = pCH4 θ* (9.6)
K3 K4 pH2

Using the site balance, we obtain the following equations

1
θ* = K1 pC2 H6 pCH4 p (9.7)
1+ √ + √ + K4 pH2
K4 pH2 K3 K4 pH2

K1 pC2 H6
√
K4 pH2
θC2 H5 = K1 pC2 H6 pCH4 p (9.8)
1+ √ + √ + K4 pH2
K4 pH2 K3 K4 pH2

pCH4
√
K3 K4 pH2
θCH3 = K p pCH4 p (9.9)
1 + √1 C2 H6 + √ + K4 pH2
K4 pH2 K3 K4 pH2

p
K4 pH2
θH = K1 pC2 H6 pCH4 p (9.10)
1+ √ + √ + K4 pH2
K4 pH2 K3 K4 pH2

9d
Plugging the above equations into the overall rate equation yields
 
p2CH
k2+ K1 pC2 H6 1− 4
K1 K2 K32 K4 pC2 H6 pH2
r=  2 (9.11)
K1 pC2 H6 pCH4 p
1+ √ + √ + K4 pH2
K4 pH2 K3 K4 pH2

9e
Applying the MARI approximation and assuming low conversion simplifies the overall rate equation to

k2+ K1 pC2 H6
r= p
2 (9.12)
1 + K4 pH2
16

9f
The apparent activation energy can be readily evaluated to

app ∂ ln(r+ )
∆Eact = RT 2 (9.13)
∂T
p
!
2 ∂ ln k2+ ∂ ln K1 ∂ ln 1 + K4 pH2
= RT + −2 (9.14)
∂T ∂T ∂T
(2) (1) (4)
= Eact + ∆Hads − θH ∆Hads (9.15)

Exercise 10
10a
From the quasi-equilibrated steps (1), (2) and (4), it follows that

θNO = K1 pNO θ* (10.1)

θCO = K2 pCO θ* (10.2)

p
θN = K4 pN2 θ* (10.3)

To derive the surface coverage of O*, we apply the steady-state approximation to this surface intermediate

2k3+ pO2 θ*2 − k6+ θCO θO = 0 (10.4)

Note that we have neglected the term k5+ θCO θO , because we assume that NO dissociation is rate-determining.
Therefore, this term is negligible compared to the other two terms.
It follows then that

2k3+ pO2 2
θO = θ* (10.5)
k6+ θCO

Combining this expression with the expression for θCO , we obtain

2k3+ pO2 2k3+ pO2

θO = + θ*2 = θ* (10.6)
k6 K2 pCO θ* k6+ K2 pCO

Applying the site balance for all surface intermediates yields

1
θ* = (10.7)
2k3+ pO2 p
1 + K1 pNO + K2 pCO + k6+ K2 pCO
+ K4 pN2

Finally, we can evaluate the rate of N2 and CO2 production

k5+ K1 pNO
rN2 = r5 = k5+ θNO θ* =  2 (10.8)
2k3+ pO2 p
1 + K1 pNO + K2 pCO + k6+ K2 pCO
+ K4 pN2
 17

2k3+ pO2
rCO2 = r6 = k6+ θCO θO =  2 (10.9)
2k3+ pO2 p
1 + K1 pNO + K2 pCO + k6+ K2 pCO
+ K4 pN2

10b
This catalytic reaction pertains to three-way catalytic convertors for environmental pollution control.

Exercise 11

1.C2 H4 + ∗  C2 H4 * (11.1)
2.O2 + 2∗  2O* (11.2)
3.C2 H4 * + O* → C2 H4 O* + * (11.3)
4.C2 H4 O + ∗  C2 H4 O* (11.4)

11a
Applying pre-equilibria, we obtain the following expressions for the partial coverages as a function of the
partial pressures and equilibrium constants

θC2 H4 = K1 pC2 H4 θ* (11.5)

and
p
θO = K2 pO2 θ* (11.6)

Using the site-balance we obtain

K1 pC2 H4
θC2 H4 = p (11.7)
1 + K1 pC2 H4 + K2 pO2

and
p
K2 pO2
θO = p (11.8)
1 + K1 pC2 H4 + K2 pO2

11b

rC2 H4 O = k3 θC2 H4 θO (11.9)

p
k3 K1 pC2 H4 K2 pO2
= p
2 (11.10)
1 + K1 pC2 H4 + K2 pO2

Note that because ethylene-oxide desorbs rapidly, the surface coverage of ethylene-oxide is negligible.
18

11c
If oxygen strongly adsorbs, we can assume that oxygen is the MARI and hence the overall rate expression
simplifies to
p
k3 K1 pC2 H4 K2 pO2
rC2 H4 O = p
2 (11.11)
1 + K2 pO2

The reaction orders in oxygen and ethylene are

∂ ln(r+ )
nC2 H4 = pC2 H4 (11.12)
∂pC2 H4
=1 (11.13)

∂ ln(r+ )
nO2 = pO2 (11.14)
∂pO2
1
= − θO (11.15)
2

11d
The surface is predominantly occupied with adsorbed O.

11e

app ∂ ln(r+ )
∆Eact = RT 2 (11.16)
∂T  
(3) (1) 1 (2)
= Eact + ∆Hads + − θO ∆Hads (11.17)
2

Exercise 12
12a

1.SO2 + ∗  SO2 * (12.1)

2.O2 + 2∗  2O* (12.2)
3.SO2 * + O* → SO3 * + * (12.3)
4.SO3 + ∗  SO3 * (12.4)

12b

rSO3 = k3 θSO2 θO (12.5)

Applying the pre-equilibrium, the irreversible step and the rate-limiting step approximation we can derive
the following expression for the free sites and for the overall reaction rate.
 19

1
θ* = p (12.6)
1 + K1 pSO2 + K2 pO2 + K4 pSO3

p
k3 K1 pSO2 K2 pO2
rSO3 = p
2 (12.7)
1 + K1 pSO2 + K2 pO2 + K4 pSO3

12c
From the form of the overall reaction equation, the limits of the reaction orders can be established as

nSO2 ∈ [−1, 1] (12.8)

nSO3 ∈ [−2, 0] (12.9)
1 1
nO2 ∈ [− , ] (12.10)
2 2

12d
If O2 strongly adsorbs, then we can apply the MARI approximation for O. This gives the following expression
for the rate and the reaction orders
p
k3 K1 pSO2 K2 pO2
rSO3 = p
2 (12.11)
1 + K2 pO2

nSO2 = 1 (12.12)
nSO3 = 0 (12.13)
1
nO2 = − θO (12.14)
2

12e

app ∂ ln(r+ )
∆Eact = RT 2 (12.15)
∂T  
(3) (1) 1 (2)
= Eact + ∆Hads + − θO ∆Hads (12.16)
2

12f
From the form of the equation, it is clear that two different types of Langmuir isotherms are present. This
indicates that there are two different types of surface sites that have particular adsorbates that adsorb on these
sites. The rate-determining step proceeds between two species that are adsorbed on these two different sites.

Exercise 13
20

1.C2 H5 OH + *  C2 H5 OH* (13.1)

2.O2 + 2∗  2O* (13.2)
3.C2 H5 OH* + O* → C2 H4 O + H2 O + 2∗ (13.3)

13a

K1 pC2 H5 OH
θC2 H5 OH = p (13.4)
1 + K1 pC2 H5 OH + K2 pO2

p
K2 pO2
θO = p (13.5)
1 + K1 pC2 H5 OH + K2 pO2

13b

p
k3 K1 pC2 H5 OH
K2 pO2
r = k3 θC2 H5 OH θO = p
2 (13.6)
1 + K1 pC2 H5 OH + K2 pO2

13c

p
k3 K1 pC2 H5 OH K2 pO2
r = k3 θC2 H5 OH θO = 2 (13.7)
(1 + K1 pC2 H5 OH )

nC2 H5 OH ∈ [−1, 1] (13.8)

1
nO2 = (13.9)
2

13d

app ∂ ln(r+ )
∆Eact = RT 2 (13.10)
∂T
(3) (1) 1 (2)
= Eact + (1 − θC2 H5 OH ) ∆Hads + ∆ Hads (13.11)
2

The apparent activation energy depends on the reaction barrier of the rate-determining step and all kineti-
cally relevant steps that proceed before the rate-determining step (which are at equilibrium). In this particular
case, this means that the apparent activation energy is decreased by to the release of energy due to O2 adsorp-
tion and is increased in the case that there is a high surface coverage of ethanol. When the surface coverage of
ethanol is high, one ethanol molecule needs to desorb in order to form a vacant site necessary for this reaction
to occur. If on the other hand the surface coverage of ethanol is very low (and a sufficiently large amount of
free sites are present), the apparent activation energy is decreased even more as the adsorption heat of ethanol
further decreases the apparent activation energy.
 21

13e
In the case of evelated temperatures, both ethanol and oxygen only sporadically adsorb on the surface as these
compounds have a higher entropy in the gas phase than adsorbed on the surface. Consequently, the catalytic
surface is predominantly empty.