Chapter 7

Exercise 1:
Equation (7.2.12) can be used to determine the ratio of S to R at any concentration of
dihydrogen. The following plot shows the relationship graphically:

60
50
[S]/[R]

40
30
20
10
0
0

20

40

60

80

100

120

-1

[H2] (mmol L )

Equation (7.2.16) is valid only at very low concentrations of dihydrogen, while equation
(7.2.22) is valid at only very high concentrations of dihydrogen (concentration of
dihydrogen 150 mmol L-1).
Exercise 2:
As in Exercise 1, equation (7.2.12) can be used to determine the ratio of S to R at any
concentration of dihydrogen. For this analysis, the concentration of dihydrogen is held
constant at 20 mmol L-1.

7.1

16
14
[S]/[R]

12
10
8
6
4
270

280

290

300

310

320

T (K)

Exercise 3:
If the dissociative chemisorption of dinitrogen is the RDS, then all other steps are quasiequilibrated. Therefore, the forward rate can be set equal to the reverse rate. Table 7.3.1
shows the rate expressions for each individual elementary step. If the site balance is used
along with the equilibrium expressions of steps 1 and 3-7, an expression for the surface
coverage of each intermediate can be found. The site balance is shown below:
1 = + N + N 2 + H + NH + NH 2 + NH 3

(1)

After solving the seven equations simultaneously at a typical reaction temperature, [N]
is the most abundant reactive intermediate if the ammonia concentration is high.
However, if the ammonia concentration is very low, the most abundant reactive
intermediate is [H].
Exercise 4:
Over ruthenium based catalysts, the rate of ammonia synthesis is strongly inhibited by
dihydrogen and the most abundant reactive intermediate is [H]. However, over iron
based catalysts the most abundant reactive intermediate is [N]. In addition, the rate of
ammonia synthesis over Ru is not influenced strongly by ammonia (almost zero order in
NH3) whereas the rate over iron catalysts is strongly inhibited by ammonia. Please see
Applied Catalysis 222 (2001) 19-29 for a general discussion of NH3 synthesis on various
metals.
Exercise 5:
Assuming that steps 1, 2, and 3 are quasi-equilibrated, step 4 is irreversible, and C2H5 is
the most abundant reaction intermediate covering the entire surface, a rate expression can
be derived in the following way:
7.2

Since equations 1, 2, and 3 are quasi-equilibrated, the rate is that of step 4.

r = r4 = k 4 [C 2 H 5 ][ H ]

(1)

The equilibrium relationship for step 1:

K1 =

[ H ] 2
[ H 2 ][] 2

(2)

and the site balance is:

[]o = [C 2 H 5 ]

(3)

After substitution of the equilibrium relationship for step 1, the rate expression is the
following:
r = k 4 []o K 11 / 2 [][ H 2 ]1 / 2

(4)

In order to come up with a rate expression that accounts for the experimentally observed
half-order dependence in H2 and zero-order dependence in ethylene, [] is assumed to be
small and constant, which contradicts the equilibrium relationship in equation (2).
If [C2H4] is the most abundant reaction intermediate covering almost the entire surface,
the site balance is now
[]o = [C 2 H 4 ]

(5)

Again, this assumes that the surface is nearly covered with ethylene.
The equilibrium relationship for Step 3 is the following:

K3 =

[C 2 H 4 ][ H ]
[C 2 H 5 ][] 2

(6)

After substitution of the equilibrium relationships (equations (6) and (2)) and the site
balance (equation (5)) into the rate expression (equation (1)),
r=

k 4 K1
[]o [ H 2 ]
K3

7.3

Here, the rate is first-order in dihydrogen and zero order in ethylene. Therefore, the
observed reaction orders cannot be explained by the assumptions of this problem. Thus a
more complex microkinetic model is needed.
Exercise 6:
In this paper, the authors study the hydroisomerization of n-hexane over platinumloaded mordenite and ZSM-5. They write material balances on each component down
the reactor bed and model the reactor as a series of CSTRs instead of a PFR in order to
simplify the calculations. The mechanism that they use is based on the Weisz
mechanism. The mechanism explicitly considers the transfer between the micropores and
both the acid and the metal sites. As a first guess the pre-exponential factors and the
activation energies were taken from experimental studies done previously.
The surface coverages and orders of reaction were then calculated and compared
with experimental data. Specifically, the classical orders of reaction at high pressure
were reproduced (0 in hydrocarbon and 1 in dihydrogen) when the zeolite micropore
was nearly filled. Both low-pressure and high-pressure kinetics were modeled
accurately. In addition, the reason why ZSM-5 activity was greater than that on
mordenite is due to the higher adsorption enthalpy for n-hexane in ZSM-5.

7.4