ACE 43101 Intro.

to Catalysis School of Energy & Chemical Engineering

Fall 2020 UNIST

Problem Set # 7
(Due December 15)

1. The following mechanism has been proposed for the oxidation of ammonia in
the presence of ClO.

NH3 + ClO  NH2 + HOCl : k1

NH2 + O2  NO + H2O : k2
NH2 + O2  HNO + OH : k3
2HNO  H2O + N2O : k4

(1) Derive an expression for the rate of the formation of N2O that contains
only the concentration of O2, NH3, and ClO and the reaction rate
constants.
r=

Applying QSSA for the intermediates HNO and NH2

Combination of these two eqn. gives:

Then overall rate egn. becomes;

(2) What are the limiting cases of this expression if:

(a) k2 >> k3 ?

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 (b) k3 >> k2 ?

(3) Discuss the relative formation of rates H2O and N2O in the two limiting cases
mentioned in part (b). Be as quantitative as possible.
Let us consider relative rates of formation of rates H2O and N2O:

Thus

From d[HNO]/dt = 0

Combination of the above two eqn. gives;

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 2. At high substrate concentrations, the substrate itself may tie up the enzyme-
substrate complex by forming the nonreactive complex S.E.S.

E.S + S S.E.S : KI
Derive the rate law for the reaction
E+S E.S  E + P: K, k
in which substrate inhibition is also taking place.

r = k [E.S]
Pre-equilibrium: K = [E.S] / [E][S]
Inhibition: KI = [S.E.S] / [E.S][S]
Site balance: [Et] = [E] + [E.S] + [S.E.S]
[E.S] = [Et] K[S] / {1 + K[S]+ KI[S]2}

r= k[Et] [S]
1 + K[S]+ KI[S]2

3. The water-gas shift reaction is taking place on a solid catalyst according to the
following mechanism:

H2O + * H2 + O* : k1, k-1

CO + O* CO2 + * :k2, k-2
H2O + CO === H2 + CO2

(a)The following rate equation was obtained experimentally. What are k and k’ in terms
of the rate constants of the above elementary reactions?
r= k [CO][H2O]
[CO2] + k’[H2O]

(b)Draw relative reaction rates of each step with arrows schematically.

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(a)

(b)

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4. Methanol synthesis from CO2 and H2 over copper catalyst shows the first order in
CO2 and 3/2 in H2 when the reaction is carried out under conditions where the surface
is predominantly empty and the oxygen generated by the process is quickly removed as
water.
CO2 + 3H2  CH4 + H2O; r = k [CO2][H2]3/2
The process goes through the following elementary steps.

H2 + 2* 2H* (1)
CO2 + * CO2* (2)
CO2* + H* HCOO* + * (3)
HCOO* + H* H2COO* + * (4)
H2COO* + H* H3CO* + O* (5)
H3CO* + H* H3COH* + * (6)
H3COH* H3COH + * (7)
(1) Give the rest of the mechanism that removes the adsorbed oxygen.
H* + O* OH* + *
OH* + H* H2O + 2H*
(2) Determine which step is most likely to be the rds if this model can explain the
observed reaction orders. [hint: pay attention to the order w.r.t. hydrogen.]
Step 5.
(3) Derive the rate expression, assuming that the rds proceeds in the forward
direction only and that all other steps are in equilibrium.
r = k5 [H2COO*][H*], [*] = [L]
[H*] = K11/2 [H2][*]
[CO2*] = K2 [CO2][*]
[H2COO*] = K3K4[CO2*][H*]2[*] = K1K2 K3 K4[CO2] [H2][*]
r = k5K13/2K2 K3K4[CO2] [H2]3/2

(4) At which mole fraction of H2 does the rate law have a maximum?
r = k’ (1-x)(x3/2) = k (x3/2 – x5/2)
dr/dx = k’ (3/2 x1/2 – 5/2 x3/2) = 0 x1/2 (3/2 -5/2x) = 0
x = 3/2 x 2/5 = 3/5 = 0.6