SOLUTIONS

Revised 10-12-2004. filename: newSSolutionstotal-corrected12-2004.doc

Solutions to Exercises in Chapter 2

Exercise 2.1 Reactivity and steady state

Statements (b), (d) and (e) are correct.

(a) At steady state product and reactant are not in equilibrum, however, the deviation from the state of
equilibrium is at the minimum corresponding to the given conditions.
(c) If a reaction is at equilibrium, forward and backward rates are equal, such that the net rate of
reaction is zero.
(f) A reaction system at equilibrium produces no entropy, because the entropy has a maximum value.
(g) This holds only for an elementary reaction.
(h) A catalyst enhances both the forward and the reverse rates of a reaction to the same extent.

Exercise 2.2 Affinity and extent of reaction

First calculate all concentrations:

t=0 t = t1 t=∞
[A] mol L−1 33.3 20 10
[B] mol L−1 66.7 40 20
[C] mol L−1 0 26.7 46.7
[D] mol L−1 0 13.3 23.3
A kJ mol−1 ∞ 9.4 0
ξ mol L−1 0 13.3 23.3
δ mol L−1 23.3 10 0

(a) The rate constant of the reverse reaction follows from that of the forward reaction once the
equilibrium constant is known:

[C ]2 [D] (46.7) 2 23.3

K= 2
= 2
= 12.7 → k − = k + /K = 0.00787 mol3 l −3 s −1
[A] [B ] 10 (20)

(b) The affinity equals:

c i (t )
− A = ∑ ν i RT ln eq
i ci
answers in the Table.

1
 (c) The extent of reaction and the deviation from equilibrium equal:
1 1
ξ = (c i − c t=
i
0
) ; δ = (c ieq − c i )
νi νi

answers in the Table.

Exercise 2.3 N2O5 Decomposition

In the proposed mechanism oxygen, O2, is formed in the second reaction step. Hence:

d [O 2 ]
= k 1 [ NO 2] [ NO 3]
dt

The concentrations of NO2 and NO3 are unknown but can be eliminated by using the equilibrium
between N2O5 and NO2 + NO3:

[ NO 2][ NO 3]
K= or [ NO 2][ NO 3] = K [ N 2O 5]
[ N 2 O 5]

Substitution of [NO2][NO3] in the rate equation yields:

d [O 2 ]
= k 1 K [ N 2O 5] i.e. k = k1K
dt

which represents the experimentally observed behaviour. Note that the order in the N2O5 concentration
equals 1 and not 2, as the overall reaction suggests.

Exercise 2.4 The steady state assumption

(a) The steady state assumption is:

d [ Ii ]
= 0 ; i = 1 , .... , n
dt
The steady state assumption is best applicable in a flow reactor with a constant supply of reactants
and a constant rate of product formation, and also in chain reactions provided the chain length (i.e.
the number of times a propagation step proceeds) is sufficiently large.

(b) A steady state process is not in equilibrium (otherwise there would be no net production of
products), but is as close to the state of equilibrium as the conditions allow; the entropy is smaller
than the maximum value achieved at equilibrium, and the entropy production assumes a constant,
minimum value larger than zero.

(c) The rate of reaction is:

d [C 6 H 5CH 3 ]
r =V = N k3θ T
dt
where θT is the toluene coverage. Adsorbed toluene is the majority species, hence θT+θ*≈1.
Application of the steady state assumption yields:

2
 d θT
= k2θ M - k3θ T = 0
dt

dθM
= k 1[C 6 H11CH 3] θ * − k2 θ M = 0
dt

k 1 [C 6 H11CH 3]
→ k 3 θ T = k 1 [ C 6 H 11CH 3 ] ( 1 - θ T ) → θ T =
k 3 + k 1[C 6 H11CH 3]

Substitution in the rate of reaction leads to the requested expression:

d[C 6 H 5CH 3] N k 1 [C 6 H11CH 3]

r =V =
dt 1 + k 1 [C 6 H11CH 3]
k3

(d) If the right term in the denominator is substantially larger than unity, the order of reaction in
methyl cyclohexane becomes zero. However, is this term much smaller than 1, than the
reaction is first order in methyl cyclohexane. Or in the more formal manner:

∂ ln(r )
nM ≡ [ C6 H11CH 3 ] * = 1 − θT and nT = 0
∂ [ C6 H11CH 3 ]

Exercise 2.5 Steady State Assumption

The reaction rate equations of the intermediates are:

d [CH 3•]
= k 1[CH 3CHO] − k 4[CH 3 • ]2 − k 2[CH 3•][CH 3CHO] + k 3[CH 3CO•] = 0
dt

d [CH 3CO•]
= − k 3[CH 3CO•] + k 2[CH 3•][CH 3CHO] = 0
dt

If we add these two expressions we get:

1/2
2 ⎛ k1 ⎞ 1/2
k1[CH 3CHO] − k 4[CH 3 • ] = 0 → [CH 3•] = ⎜ ⎟ [CH 3CHO]
⎝ k4 ⎠
The reaction rate of CH4 formation is:

1/2
d [CH 4] ⎛k ⎞
= k 2[CH 3•][CH 3CHO] = k 2 ⎜ 1 ⎟ [CH 3CHO]3/2
dt ⎝ k4 ⎠

Note that the order in acetaldehyde is 3/2, whereas the overall reaction (erroneously!) suggests a first
order dependence.

3
Exercise 2.6 The steady state assumption in the kinetics of chain reactions
The rate of HBr formation follows from:

d [ HBr ]
= k 3f [ H • ] [ Br 2 ] + k f2 [ Br • ] [ H 2 ] − k 2b [ HBr ] [ H •]
dt

Equilibrium between molecular and atomic bromine leads to:

f
k1
[ Br •] = f
[ Br 2 ]
k4

Application of the steady state assumption on [ H •] :

d [H • ]
= 0 = k f2 [ Br • ] [ H 2 ] − k b2 [ HBr ] [ H • ] − k 3f [ H • ] [ Br 2 ]
dt

f
k 2 [ Br • ] [ H 2 ]
[ H • ]= f b
k 3 [ Br 2 ] + k 2 [ HBr ]

Substitution of [ Br •] in [ H •] , and of [ H •] and [ Br •] in d[HBr]/dt leads to the requested formula

with

f b
k1 k
k = 2k 2f f
and k’ = 2f
k4 k3

Exercise 2.7 Heterogeneous Catalysis

(a) Three steps occurring in every heterogeneously catalyzed reaction are:
- adsorption of the reactants on the surface of the catalyst; almost always at least one of the
reactants is dissociated
- reaction between adsorbed species on the surface of the catalyst
- desorption of products into the gas phase

(b) see Fig. 1.2.

(c) Sabatier's Principle: For every catalytic reaction an optimum catalyst and optimum reaction
conditions exist for which the interactions between adsorbed species and he surface of the catalyst
is not too strong but not too weak either, such that the rate of reaction is maximum.

(d) In an autocatalytic reaction one of the reactants promotes its own formation, as in the schematic
reaction: X + Y → 2X.

(e) The reaction NOads + COads → CO2↑ + ½ N2↑ proceeds via the following elementary steps:

4
 NO* + * → N* + O*
CO* + O* → CO2 + 2*
N*+ N* → N2 + 2*

If the surface is entirely occupied, reaction (1) is inhibited, because it needs an empty site. As soon
as an empty site becomes available (by desorption of a CO or an NO molecule) the sequence of
three reactions creates four empty sites (three new free sites and the initial one), implying that
several reaction events are enabled, which on their turn create again more free sites. The reaction
thus explodes until the surface is empty. The reaction is autocatalytic with respect to the free sites.

Exercise 2.8 Potential Energy Profiles

(a)

ABC#

500

AB+C

AB*+C AB#*+C* A+BC

-50 -50 -50
AB*+C*

-125 BC#*+A*

A*+BC
-150
A*+BC* -200

-250
-100

A*+B*+C*

5
 (b) A* is the most stable intermediate and the candidate for MARI

(c) The formation of BC has an activation energy of 250 kJ mol−1 and the most likely candiate
for being the rate limiting step if we consider the energy alone. Be aware that there could
also be entropy barriers in the adsorption process, but since they are considered not activated
here this is not likely.

Exercise 2.9 Langmuir adsorption isotherms

(a)
⎯⎯⎯
CO +* ←⎯⎯ → CO * → θ CO = K CO ( 1 − θ CO )[CO ]
⎯
K CO

K CO [ CO ]
θ CO =
1 + K CO [ CO ]

(b)
Kdiss
CO + 2 * ↔ C* + O * → θ Cθ O = K diss [ CO ] (1 − θ C − θ O) 2

θ C = θ O = θ → θ 2 = K diss [ CO ] ( 1 − 2θ )
2

K diss [ CO ]
θ C=θ O =
1 + 2 K diss [ CO ]

(c)
K CO [ CO ] K H2 [ H 2 ]
θ CO = ; θ H=
1+ K H 2 [ H 2 ] + K CO [ CO ] 1+ K H 2 [ H 2 ] + K CO [ CO ]

1
(d) θ* =
1 + K H 2 [ H 2 ] + K CO [ CO ]

(e) Mechanism:

CO +* ↔ CO *
H2 + 2* ↔ 2 H *
RLS
CO * +H * → CHO * +*
CHO * + 3 H * ↔ CH 3OH * + 3 *
CH 3OH * ↔ CH 3OH + *

6
 r = N k 3+ θ CO θ H
N k 3+ K CO K H 2 [ CO ] [ H 2 ]
=
( 1 + K CO [ CO ] + K H 2 [ H 2 ] + K CH 3OH [ CH 3OH ] ) 2

If hydrogen adsorbs weakly:

N k 3+ K CO K H 2 [ CO ] [ H 2 ]
r =
( 1 + K CO [ CO ] + K CH 3OH [ CH 3OH ] ) 2

Order in hydrogen: nH2 = ½

Order in CO: −1 < nCO < 1, i.e. nCO = 1 − 2θ CO

Order in methanol: −2 < nCH3OH < 0, i.e. nCH3OH = −2θ CH3OH

Exercise 2.10 Problems in PEM fuel cells

k1+
(1) H 2 + 2∗ ↔ 2H∗ kH+ = k1+ pH2 , kH− = k1−
k1−

k2+
+
(2) CO + ∗ ↔−
CO∗ kCO = k2+ pCO , kCO
−
= k2−
k2

dθ H k1+
= k1+ pH2θ∗2 − k1− ⋅ θ H2 = 0 ⇒ θ H = pH θ* = K1 pH2 θ*
dt k1− 2

2 pH2 S0H2 ⎛ − EHd ⎞

+
k =
H , k = ν exp ⎜
−
H ⎟ k H+ ≡ k1+ PH 2
N0 2π mH2 kBT ⎝ RT ⎠ − −
notice k H ≡ k1
pCO S0CO ⎛ −Ed ⎞
+
kCO = −
, kCO = ν exp ⎜ CO ⎟ ect.
N 0 2π mCO kBT ⎝ RT ⎠

dθ CO k+
= k2+ ⋅ pCO ⋅ θ∗ − k2− ⋅ θ CO = 0 ⇒ θ CO = 2− ⋅ pCO ⋅ θ∗ = K 2 pCOθ∗
dt k2

θ∗ = 1 − θ H − θ CO = 1 − K1 pH θ∗ − K 2 pCOθ∗
2

7
 1 kH+ +
kCO
θ∗ = K1 = , K 2 =
1 + K1 pH2 + K 2 pCO kH− pH2 −
kCO pCO

K1 pH2 K 2 pCO
θH = , θ CO =
1 + K1 pH2 + K 2 pCO 1 + K1 pH2 + K 2 pCO

(1) PCO θH θCO θ*

1 ppm 0.46 0.54 0
10 ppm 0.08 0.92 0
100 ppm 0.001 0.99 0

(2) Reduce the bonding energy of CO

Exercise 2.11 Methanol synthesis

Make MeOH methanol by hydrogenation of CO2 over the following intermediates: formate, di-oxo-
methylene, methoxy, and methanol. The overall reaction reads:

3H 2 + CO 2 ⎯⎯
→ CH 3OH + H 2 O

(1) Removal of adsorbed oxygen can go as:

⎯⎯
→ HO* + *
(a) O* + H* ←⎯
⎯

⎯⎯
→ H 2O* + * or as (bb) 2HO* ←⎯
(b) HO* + H* ←⎯
⎯ ⎯⎯
→ H 2 O* + H *
⎯

⎯⎯
→ H 2O + *
(c) H 2 O* ←⎯
⎯

The H2O can be disregarded, i.e. θo = 0, and the process proceeds only forward from the rate
limiting step. If the reaction order in hydrogen should be 1.5 must three hydrogenation steps be
involved. Let us try the following:

⎯⎯
→ 2H* in quasiequilibrium ⇒ θ H =
(1) H 2 + 2* ←⎯
⎯ K1 pH2 θ*

⎯⎯
→ CO 2 * in quasiequilibrium ⇒ θ CO = K 2 pCO θ∗
(2) CO 2 + * ←⎯
⎯ 2 2

K 3θ CO2θ H
⎯⎯
→ HCOO* in quasiequilibrium ⇒ θ HCOO =
(3) CO2 * + H* ←⎯
⎯
θ∗
→ H 2 COO* + ∗ in quasiequilibrium ⇒ θ H COO = K 4θ HCOOθ H
⎯⎯
(4) HCOO* + H* « ←⎯
⎯ 2
θ∗

8
If we assume 5 to be rate limiting with no reverse rate we get:

→ H 3COO * RLS ⇒ r = r+ = k5+θ H2COOθ H

(5) H 2 COO * +H * ⎯⎯

k5+ K 4θ HCOOθ H2
by replacing θ H2COO ⇒ r =
θ*

k5+ K 4 K 3θ CO2θ H3
by replacing θ HCOO ⇒ r =
θ*2

By replacing θ CO2 and θ H we get

3 3
r = k5+ K 4 K 3 K 2 K12 pCO2 pH2 2θ*2

since θ * ≅ 1

3 3
r = k5+ K 4 K 3 K 2 K12 pCO2 pH2 2

Check reaction order

∂ ln r+ 3
nx ≡ p x ⇒ nH2 = , nCO2 = 1
∂px 2

Rate maximum:

pH2
χ= , ⇒ pH2 = χ ptot , pCO2 = (1 − χ ) ptot
ptot

3
r = const ⋅ χ 2 (1 − χ )

Maximum:

∂r 3
= 0 ⇒ χ = = 0.6
∂χ 5

Exercise 2.12 CO oxidation

⎯⎯
K1
(1) CO + ∗ ←⎯ ⎯→ CO ∗

⎯⎯
K2
(2) O 2 + 2∗ ←⎯ ⎯→ 2O ∗

+
⎯⎯
k3
(3) CO* + O* ←⎯ → CO 2 * + * (RDS)
⎯
k− 3

9
 K 4−1
(4) CO 2 ∗ ↔ CO 2 + ∗

θ CO = K1 pCOθ*

θ O = K 2 pO θ* 2

θ CO = K 4−1 pCO θ*
2 2

It is now straightforward to find an expression for the fraction of free sites from the site balance:

1
θ CO + θ O + θ CO + θ* = 1 ⇒ θ* =
2
1 + K1 pCO + K 2 pO2 + K 4−1 pCO2

The rate is that of the rate-determining step:

r = k3+θ COθ O − k3−θ CO2θ*

⎛ pCO2 ⎞
= k3+ K1 K 2 pCO pO2 ⎜1 − ⎟ θ*2
⎜ pCO pO2 K G ⎟
⎝ ⎠

where

K G = K1 K 2 K 3 K 4

ln(r+ ) = ln(k3+ ) + 12 ln( pO2 ) + ln( pCO ) + ln( K1 ) + 12 ln( K 2 )

⎛ pCO2 ⎞
−2 ln ⎜1 + K 2 pO2 + pCO K1 + ⎟
⎝ K4 ⎠

∂ ln r+
nCO = pCO = 1 − 2θ CO
∂pCO
∂ ln r+ 2θ
nO2 = pO2 = 1/ 2 − O = 1/ 2 − θO
∂pO2 2

∂ ln r+
nCO2 = pCO2 ⋅ = −2θ CO2
∂pCO2

Find the overall activation energy Eapp

∂ ln r+ ⎛ ∂ ln k3+ ∂ ln K1 1 ∂ ln K 2 2∂ ln θ∗ ⎞
E app = RT 2 ⋅ = RT 2 ⎜ + + + ⎟
∂T ⎝ ∂T ∂T 2 ∂T ∂T ⎠

10
 E3
−
∂ ln k +
∂ ln k 0 e
3 RT
E3
=3
=+
∂T ∂T RT 2

⎛ − RT
∆G1
⎞ ⎛ − ∆RTH1 + ∆RS1 ⎞
∂ ln ⎜ e ⎟⎟ ∂ ln ⎜⎜ e ⎟⎟
∂ ln K1 ⎜
= ⎝ ⎠= ⎝ ⎠ = ∆H1
∂T ∂T ∂T RT 2

1 ∂ ln K 2 ∆H 2
=
2 ∂T 2kT 2

The difficult part is

⎛ pCO2 ⎞
−2∂ ln ⎜ 1 + K1 pCO + K 2 pO2 + ⎟
∂ 2 ln θ∗ ⎝ K4 ⎠
= =
∂T ∂T

∂ ⎛ pCO2 ⎞
−2 ⋅1 ⎜1 + K1 pCO + K 2 pO2 + ⎟
∂T ⎝ K4 ⎠ ⎛ ∆H1 ∆H 2 ∆H 4 pCO2 ⎞
= −2θ∗ ⎜ + K1 pCO + K 2 pO2 − ⋅ ⎟=
⎛ pCO2 ⎞ ⎝ RT 2
2 RT 2 RT 2 K 4 ⎠
⎜ 1 + K1 pCO + K 2 pO2 + ⎟
⎝ K4 ⎠

2 ⋅ ∆H1θ CO 2∆H 2θ O2 2∆H 4θ CO2

=− − +
RT 2 2 RT 2 RT 2

leading to
E app = E 3 + ∆H1 + 12 ∆H 2 − 2∆H1θ CO − ∆H 2θ O + 2∆H 4 ⋅ θ CO2
⎛1 ⎞
E app = E 3 + (1 − 2θ CO )∆H1 + ⎜ − θ O ⎟ ∆H 2 + 2∆H 4 ⋅ θ CO2
⎝2 ⎠

Exercise 2.13 Steam Reforming Reaction

⎯⎯
→ 3H 2 + CO
(1) CH 4 + H 2 O ←⎯
⎯

High pressure will press the eq. to the left, so use moderate pressure. The process is endothermic
∆H >0 so use high temperature.

(2)
K1 PCH4θ∗
2
⎯⎯
→ CH 3 * + H* pseudoligevægt θ CH ∗ =
(1) CH 4 + 2* ←⎯
⎯ 3
θH

K 2θ CH3θ∗
⎯⎯
→ CH 2 * +H* pseudoligevægt θ CH ∗ =
(2) CH 3 * + * ←⎯
⎯ 2
θH

11
 K 3θ CH2θ∗
⎯⎯
→ CH * +H* pseudoligevægt θ CH∗ =
(3) CH 2 * + * ←⎯
⎯
θH

⎯⎯
→ C* +H* pseudoligevægt θC∗ = K 4θ CHθ∗
(4) CH * + * ←⎯
⎯
θH

⎯⎯
→ H 2 O* pseudoligevægt θ H O ∗ = K 5θ∗ PH O
(5) H 2 O + * ←⎯
⎯ 2 2

K 6θ H2Oθ∗
⎯⎯
→ HO * +H* pseudoligevægt θ OH∗ =
(6) H 2 O* + * ←⎯
⎯
θH

→ O * +H* pseudoligevægt θ O∗ = K 7θ OHθ∗

⎯⎯
(7) HO * + * ←⎯
⎯
θH

PH2
⎯⎯
→ H 2 + 2* pseudoligevægt θ H =
(8) 2H * ←⎯
⎯ θ∗
K8

⎯⎯
→ k9+
⎯ CO * +* RLS r = k9 θ0θ c − ⋅ θ COθ∗
+
(9) C* +O * ←⎯
K9

→ CO + * pseudoligevægt θ CO = PCOθ∗
⎯⎯
(10) CO * ←⎯
⎯
K10

Eliminate θ O ,θ c and θ CO utilizing θ∗ = 1 − ∑ θi

i

PCOθ∗ PH2
θ CO = = iθ∗ , θ H = ⋅ θ∗ = hθ∗ , θ H2O = PH2O K 5θ∗ = gθ∗
K10 K8

K5 K6 P
θ OH = θ∗ PH2O = f θ∗ , θ 0 = K 5 K 6 K 7 K8 H2O θ∗ = eθ∗
PH2 PH2
K8

K1 ⋅ PCH4 ⋅θ∗ K1 K 2 PCH4θ∗ K1 K 2 K 3 ⋅ PCH4 ⋅θ∗

θ CH = = dθ∗ , θ CH2 = = cθ∗ , θ CH = = bθ∗
3
PH2 PH2 ⎛ PH2 ⎞
32

K8 K8 ⎜ ⎟
⎝ K8 ⎠

K 4θCHθ∗ K1 K 2 K 3 K 4 PCH4θ∗
θc = = = aθ*
θH ⎛ PH2 ⎞
2

⎜ ⎟
⎝ K8 ⎠

12
θ* = 1 − θ C − θ CH − θ CH − θ CH − θ O − θ OH − θ H O − θ H − θ CO
2 3 2

θ * = 1 − aθ * − bθ * − cθ * − dθ * − eθ * − fθ * − gθ * − hθ * − iθ CO

1
θ∗ =
(1 + a + b + c + d + f + g + h )

k9+
r = r + − r − = k9+θ Oθ C − θ COθ*
K9

if equilibum
3
θ θ PCO PH
r = 0 ⇒ K 9 = CO ∗ = 2

θ Oθ C PH O PCH K1 K 2 K 3 K 4 K 5 K 6 K 7 K83 K10

2 4

PCO PH32
KG = at equilibrium
PH2O PCH4

K G = K1 K 2 K 3 K 4 K 5 K 6 K 7 K83 K 9 K10

⎛ + 2 PH 2 O ⋅ PCH 4 k9 PCO ⎞ 2
+
r = ⎜ k9 K 5 K 6 K 7 K8 K1 K 2 K 3 K 4 K8 ⋅
⎜
− ⋅ ⎟ θ∗
⎝ PH32 K 9 K10 ⎟⎠

K PH O PCH
−
⎛ PH32 PCO ⎞ 2
r = k9 ⋅ G ⋅ 2 3 4 ⋅ ⎜1 −
⎜ K G PCH PH O ⎟⎟ θ∗
K10 PH2 ⎝ 4 2 ⎠

PH2O PCH4 K G
⋅ θ∗
2
r+ = k9− ⋅ 3
⋅
PH2 K10

if only oxygen on the surface (this is reasonable because O bonds strongly)

1
θ∗ ≈
PH2O
1 + K 5 K 6 K 7 K8
PH2

K G PH2O PCH4 1
r+ ≈ k9− ⋅ 3
⋅ 2
K10 PH2 ⎛ PH O ⎞
⎜⎜ 1 + K 5 K 6 K 7 K8 2 ⎟⎟
⎝ PH2 ⎠

13
(3) Find reaction order

δ ln r+
nx ≡ Px
δ Px

nCH4 = 1 , nCO = 0, nH2O = 1 − 2θ o , nH2 = −3 + 2θ o

So
nCH4 > 0 ,
nH2O can be < 0 if θ 0 > 0.5
nH2 < 0
This does not fit with observations.

(4) All over again. Now let the first step be rate limiting.

CH 4 + 2 ∗ ⎯⎯⎯
RLS
→ CH 3 * +H *

→ CH 3 * + H* RLS r = r+ − r− = k1+ PCH4θ* − k1−θ CH3θ H

2
(1) CH 4 + 2 ∗ ⎯⎯⎯
RLS

⎯⎯ ⇔
→ CO * +* pseudoeq. θ c = 1 θ COθ∗
(9) C* + O ∗ ←⎯⎯ ⋅
K9 θO

Write up expressions for all the various intermediates in terms of free sites:

PCOθ∗ PH2
θ CO = = iθ∗ , θ H = ⋅ θ∗ = hθ∗ , θ H2O = PH 2O ⋅ K 5 ⋅θ∗ = gθ∗
K10 K8

K5 K 6 P
θ OH = θ∗ PH2O = f θ∗ , θ O = K 5 K 6 K 7 K8 ⋅ H2O ⋅ θ∗ = eθ∗
PH2 PH2
K8

PCO PH2
θC = θ*
K 9 K10 K 5 K 6 K 7 K8 PH2O

3
PCO PH22
θCH = 3 θ*
K 9 K10 K 4 K 5 K 6 K 7 K82 PH2O

PCO PH22
θ CH = θ*
2
K 9 K10 K 3 K 4 K 5 K 6 K 7 K82 PH2O

5
PCO PH22
θ CH =
3 5 θ*
K 9 K10 K 2 K 3 K 4 K 5 K 6 K 7 K82 PH2O

14
 ⎛ + PCO PH32 ⎞ 2
r = r+ − r− = k P θ − k θ θ = ⎜ k1 PCH4 − k1 ⎟⎟ θ*
+ 2 − −
1 CH 4 * 1 CH3 H
⎜ K 9 K10 K 2 K 3 K 4 K 5 K 6 K 7 K 38 PH2O
⎝ ⎠

⎛ PCO PH32 ⎞ 2
r = r+ − r− = k P θ − k θ θ =k P ⎟⎟ θ*
+ 2 − +
1 CH 4 * 1 CH3 H 1 CH 4 ⎜⎜1 − 3
⎝ K 9 K10 K1 K 2 K 3 K 4 K 5 K 6 K 7 K 8 PH2O PCH4 ⎠

⎛ PCO PH32 ⎞ 2
r = k1+ PCH4 ⎜1 −
⎜ K G PH O PCH ⎟⎟ θ*
⎝ 2 4 ⎠

Let us again assume that adsorbed oxygen atoms are MARI:

1
θ∗ ≈
PH2O
1 + K 5 K 6 K 7 K8
PH2

we get

2
⎛ ⎞
⎜ ⎟
1
r = k1 PCH4 ⎜
+ + ⎟
⎜ PH2O ⎟
⎜⎜ 1 + K 5 K 6 K 7 K8 ⎟⎟
⎝ PH2 ⎠

δ ln r+
n x = Px
δPx

nCH4 = 1
nH2O = −2θ O
nH2 = +2θ O

All in agreement with observations.

Exercise 2.14 HDS Reaction

We are missing the reverse rate. Probably because the re-adsorption of butadiene is very weak.

K1 PT K 2 PH2
(b) θ T = θH =
1 + K1 PT 1 + K 2 PH2

15
It is assumed that the thiophene adsorbs on ⊗ sites and the hydrogen on * sites. Those sites are
complementary.

(1) TS + ⊗ ⇔ TS⊗ θ TS = K1 PTθ ⊗

(2) H 2 + 2∗ ⇔ 2H∗ θ H = K 2 PH2 ⋅ θ ∗

k3
(3) TS⊗ + H∗ ⇔ HTS ⊗ +∗ RLS r = k3+θ TS⊗ θ H* − θ HTS ⊗ θ∗
K3

PH2 TθS⊗θ*
(4) HTS⊗ + H∗ ⇔ H 2 Tgas + S⊗ +∗ θ HTS⊗ =
K 4θ H*

θ HS⊗ θ∗
(5) S⊗ + H∗ ⇔ HS⊗ +∗ θS⊗ =
K 5θ H∗

θ H S⊗θ∗
(6) HS⊗ + H∗ ⇔ H 2S⊗ +∗ θ HS⊗ = 2

K 6θ H*

PH2Sθ ⊗
(7) H 2S⊗ ⇔ H 2Sgas + ⊗ θ H2S⊗ =
K7

k3
r = k3+ ⋅θ TS⊗ ⋅θ H* − θ HTS⊗ θ∗
K3
k3+ ⋅ PH2T ⋅ PH2S ⋅ θ ⊗ ⋅θ*
r = k ⋅ K1 ⋅ PT ⋅ θ ⊗ ⋅ K 2 ⋅ PH2 ⋅θ ∗ −
+
3 3
K 3 ⋅ K 4 ⋅ K 5 ⋅ K 6 ⋅ K 7 ⋅ ( K 2 PH2 ) 2

⎛ ⋅PH2T PH2S ⎞
r = k3 K1 PT K 2 PH2 ⎜ 1 − ⎟ θ ⊗θ*
⎜ PT PH ⋅ K 2 ⋅ K 3 K 4 ⋅ K 5 ⋅ K 6 ⋅ K 7 ⋅ K 22 ⋅ PH22 ⎟⎠
3 3

⎝ 2
K1

⎛ PH T PH S ⎞
r = k3 K1 PT K 2 PH2 ⎜1 − 2 2 2
⎜ PT PH K G ⎟⎟ θ ⊗ ⋅ θ*
⎝ 2 ⎠
2
K G = K1 K 2 K 3 K 4 K 5 K 6 K 7

r = r+ − r− r+ = k3 PT K1 K 2 PH2 ⋅ θ∗θ ⊗

This fulfills the kinetic when

k3+ PT K1 K 2 PH2 kPT K 2 PH2

r+ = ⋅ = ⋅
1 + PT K1 1 + K 2 PH2 1 + PT K1 1 + K 2 PH2

16
 k3+ PT K1 K 2 PH2 kPT K 2 PH2
r+ = ⋅ = ⋅
1 + PT K1 1 + K 2 PH2 1 + PT K1 1 + K 2 PH2

θ T and θ H are MARI for the two types of sites

(3) r = r+ In an excess of H2 since there is a low tendency for forming hydrogen.

F (5) r + = k3+ K1 PT K 2 PH2 θ ⊗ ⋅θ∗ . the rate increases with PT and PH2.
Notice that the rate will not vanich even if we let PT or PH2 become very large since they each use
their sites. The are no competion between the two sites.

Exercise 2.15 Hydrogenation of Ethane

dθ C2 H5 ∗
⎯⎯
(1) C2 H 6 + 2 ∗ ←⎯
⎯→ C2 H 5 * + H* ,
Q
= k1+ PC2 H6 ⋅ θ∗2 − k1−θ C2 H5θ H = 0 ⇒
dt
K1 PC2 H6θ∗
2

θC H =
2 5
θH

(2) C2 H 5 * +H ∗ ⎯⎯⎯
RLS
→ 2CH 3 ∗ ⇒ r = k2+θ C2 H5θ H − k2−θ CH
2
3

dθ CH3
⎯⎯
Q
(3) CH 3 * + H ∗ ←⎯⎯→ CH 4 + 2∗ = −k3+θ CH3 ⋅ θ H + k3− PCH4θ∗ = 0 ⇒
2

dt
PCH4θ∗
2

θ CH =3
K 3θ H

⎯⎯
(4) H 2 + 2 ∗ ←⎯
Q
⎯→ 2H* ⇒ dθ H = k4+ PH θ∗2 − k4−θ H2 = 0 ⇒
dt 2

θ H = K 4 PH2 ⋅θ∗

(a) By adding D2 will D be incorborated through step one:

. ⇒ C2 H 6 + ⇔ C2 H 5 + H∗ but C2 H 5 * +D * ⎯⎯→ C2 H 5 D

Repeat n times C2 H 6− n Pn .
(c) and (d)

RLS r = k2+θ C2 H5 ∗ θ H − k2−θ CH

2
3

K1 PC2 H6 ⋅θ∗ K1 PC2 H6θ∗ PCH4θ∗ PCH4 ⋅θ∗

2 2

θC H = = , θ CH3 = = ⇒
2 5*
θH K 4 PH2 K 3θ H K 3 K 4 PH2

17
 2
PCH θ
4 ∗
2
⎛ 2
PCH ⎞ 2
r = k ⋅ K1 PC2 H6θ∗ − k ⋅ 2 ⎟⎟ θ∗
+ 2 − +
= k K1 PC2 H6 ⎜1 − 4
2 2
K 3 K 4 PH2
2
⎜ 2
⎝ K1 K 2 K 3 K 4 PC2 H6 PH2 ⎠

⎛ 2
PCH ⎞ 2
r = k2+ K1 PC2 H6 ⎜1 − 4

⎜ K G PC H PH ⎟⎟ θ∗ θ∗ = 1 − θ C2 H5 − θ CH3 − θ H ⇒
⎝ 2 6 2 ⎠

1 1
θ∗ = ≈ when θ C2 H5 = θ CH3 ≈ 0
K1 PC2 H6 PCH4 1 + K 4 PH2
1+ + + K 4 PH2
K 4 PH2 K 3 K 4 PH2

⎛ dθ ⎞
(c) We can not study transients ⎜ x ⎟ = 0 in quasequilibrium.
⎝ dt ⎠

⎛ 2
PCH ⎞ 2 1
⎟⎟ θ∗ θ∗ =
+
(d) Has been derived r = k K1 PC2 H6 ⎜ 1 − 4

⎜ PH PC H K G
2
1 + K 4 PH2
⎝ 2 2 6 ⎠

18
Solutions to Exercises in Chapter 3

Exercise 3.1 Average molecular velocities

(a) The expression for the average velocity of a molecule is:
1

v = ⎛⎜ 8 R T ⎞⎟
2

⎝ πm ⎠

R = 8.314 J K−1 mol−1

T = 298 K
m = 28⋅10-3 kg mol−1
1 J = 1 kg m2 s−2

Substitution gives: v = 475 m s−1

1 1

⎛ 8 R 298 ⎞ 2 ⎛ 8 R T ⎞ 2 mN2
(b) v He = ⎜ ⎟ =⎜ ⎟ = v N2 (T ) → T = 298* = 2090 K
⎝ π 4 ⎠ ⎝ π 28 ⎠ mHe

(c) The average translational energy of every ideal gas is 1.5 RT, equalling 1.247 kJ mol−1 at
100 K, 3.71 kJ mol−1 at 298 K and 12.47 kJ mol−1at 1000 K.

Exercise 3.2 Collisions in the gas phase

1000 liter
(a) ρ N 2 = -1
6.022×10 23 x 0.25 = 6.1×10 24 / m 3 ρ H 2 = 1.82×10 25 / m 3
24.7894 liter mol

(b) The number of collisions between molecules in a mixture is:

1

π d2 ⎛8k T ⎞ 2

Z (A , B ) = ⎜ ⎟ ρ Aρ B
g AB ⎝ πµ ⎠

substituting the values for H2 (note that µ = m/2):

(1.82×10 25 m -3) 2 π (2.71×10-10 ) 2

Z (H 2 , H 2 ) = x
2
1

⎛ 8 (8.31J/K mol)(298 K) ⎞ 2
⎜ ⎟
⎝ π (2×10 kg/mol) ⎠
-3

= 9.55×1034 / m 3 ×s

(c) Z(N2,N2) = 5.5⋅1033 /m3⋅s

(d) The effective collision diameter d is ½(dA + dB) = 0.322 nm, yielding Z(N2,H2) = 6.62×1034 /m3⋅s

19
(e) The total number of collisions is:

Ztotal = Z(H2,H2) + Z(N2,N2) + Z(N2,H2) = 1.672×1035 /m3⋅s

Exercise 3.3 Collision Theory of Reaction Rates

The rate of reaction of a bimolecular collision between unequal molecules is

1

−dC i 2⎛ 8 RT ⎞
2

r= =πd ⎜ ⎟ e
- E a /R T
C 1C 2 b
dt ⎝ πµ ⎠

(with Ci in mol⋅l-1, µi in gram per mol and d in meters).

To bring this expression in its Arrhenius form, we first calculate the activation energy:

2 ∂ ln(r ) 1
E act = RT = Ea + RT
∂T 2

If we rewrite the collision rate expression as follows (i.e. with the activation energy in the
exponential):
1

−d C i ⎛ 8 R T ⎞ 2 -( E a +R T/ 2 )/R T 12
r= = π d2⎜ ⎟ e e C 1C 2
dt ⎝ πµ ⎠

we immediately recognize the preexponential factor:

1

⎛ 8 R T ⎞2
ν eff = e π d 2 ⎜
1
2
⎟
⎝ πµ ⎠

Substitution of values (pay attention to the units): veff =1.4×1011 T½ L mol−1 s−1

The observed value is 108 T1/2 L mol−1 s−1. Within the collision theory, such differences are
attributed to steric factors, which in this case would have to be on the order of 10-3. In reality, the
difference is due to the internal degrees of freedom of the reacting molecules. Transition theory
provides the framework to account for these effects.
bb

Exercise 3.4 General Aspects of Partition Functions

a)
(q )
Ng
V ( 2π mkT ) 2
3

g PV
Qgas = Ng = Na = q = qg =
Ng ! kT h3

use Stirlings approximation ln( N !) ≈ N ln( N ) − N

20
 ∂ ln Qg ⎛ q ⎞ ⎛ qkT ⎞
µ = −kT ⋅ = − kT ⋅ ln ⎜ ⎟ = − kT ⋅ ln ⎜ ⎟
∂N g ⎝ Na ⎠ ⎝ PV ⎠
⎛ qkT ⎞ ⎛ P⎞ ⎛ P⎞
µ = −kT ⋅ ln ⎜ ⎟ + kT ⋅ ln ⎜ ⎟ = µO + kT ⋅ ln ⎜ ⎟
⎝ VPO ⎠ ⎝ PO ⎠ ⎝ PO ⎠

⎡ ( 2π mkT ) 2 kT ⎤
3

where µO = − kT ⋅ ln ⎢ ⎥
⎢⎣ h3 PO ⎥⎦

(b)

kT ⋅ ∂ ln Q kT ⋅ N a ⋅ ∂ ln q kTN a
P= = = i.e. P ⋅ V = N a kT ideal gas
∂V ∂V V

(c)

∂ ln Q ∂ ln q 1 ∂q 3 1
E = KT 2 ⋅ = kT 2 ⋅ N a ⋅ = kT 2 ⋅ N a = kT 2 N a ⋅ ⋅
∂T ∂T q ∂T 2 T

3 3
E= N a kT Na ⋅ k = R ⇒ E = RT
2 2

(d)

∂ ∂ ln Q
S= ⋅ ( kT ln Q ) = k ln Q + kBT
∂T ∂T

3
S = kN a ln q − kN a ⋅ ln N a + kN a + kN a
2

S = R ⋅ ln q − R ⋅ ln N a + R
5
2
( 5
= R ln q − ln N a + ln e 2 )
⎛ V ⋅ e 52 ( 2π mkT ) 2 ⎞
3
⎛ q ⋅ e2 ⎞
5

S = R ⋅ ln ⎜
⎜ Na ⎟⎟ = R ⋅ ln ⎜ ⎟
⎝ ⎠ ⎜ N a h3 ⎟
⎝ ⎠

ideal gas PV = NakT

The Sackur-Tetrode equation helpful for calculating for example the standard entropy of a simple
monoatomic gas like He at standard conditions.

⎡ e 52 ( 2π m ) 2 (kT ) 52 ⎤
3

S = R ⋅ ln ⎢ ⎥
⎢⎣ h3 ⋅ P ⎥⎦

21
Exercise 3.5 Partition Functions
(a) For an ideal gas:
3/2 3/2
(2πm k T ) (2πm k T ) nR T
q trans = 3
V= 3
h h P

Substitution gives q trans = 3.555×1030

(b) q trans is proportional to T5/2, inversely proportional to P and proportional to V. The translational
partition function in three dimensions is proportional to m3/2, and thus q trans (N) = 1.258×1030 and
q trans (N3) = 6.533×1030.

(c) The vibrational partition function of vibrations with frequencies above ±200 cm−1 is in practice
equal to 1, if the temperature is not too high.

(d) The rotational partition function of a diatomic molecule is:

8π 2IkT
q rot = 2
h g AB
in which gAB represents the symmetry number. Substitution yields qrot = 51.4.
8π 2 I
Hint use for example that the energy levels are separated by 2
= 1.9987 cm −1 and 1 meV =
h
8.08 cm-1. As the formula indicates, qrot is proportional to T and independent on either V or P.

(e) The total partition function is the product of the partition functions for translation, vibration, and
rotation, and equals 1.83×1032 at room temperature.

Exercise 3.6 Rotational Partition Functions

In order to calculate the partition function we need to know the energy levels of the molecule. Note that
the given frequencies correspond to transitions between energy levels, and not the levels themselves.

According to quantum mechanics, the rotational levels of a diatomic molecule are given by the general
relation:
2
h
εj = j ( j + 1) ; I = µ r2
8π I2

where in transitions the rotational quantum number changes by one unit only. Notice that for photons:
The measured spectrum gives us the values of εj–εj−1 expressed in wave numbers (frequencies), and

hc
EPhoton = hν = =ω = =ckPhoton =
λ
1 meV = 8.08 cm−1 .

22
Hence we can construct the energy level scheme as in the following table:

j j(j+1) εj−εj−1 (cm−1) εj (cm−1)

0 0 - 0
1 2 20 20
2 6 40 60
3 12 60 120
4 20 80 200
5 30 100 300

The partition function equals

5 5 10
qrot = ∑e
j=0
-ε j / kT
= ∑ e - 69.5
j=0
j ( j + 1)

qrot = 1 + 0.75 + 0.422 + 0.178 + 0.056 + 0.013 = 2.42

Exercise 3.7 Vibrational Partition Functions

The expressions for the vibrational partition function with respect to the ground state, and the
fraction of molecules in a certain state labeled i are:
− /kT
1 e εi 1
q vib = − hν /kT
; xi = → xo =
1− e q vib q vib

Application of these expressions gives the following results:

molecule v (cm−1) qvib qvib qvib xo xo xo

300 K 600 K 1500 K 300 K 600 K 1500 K
I2 213 1.563 2.500 5.411 0.640 0.400 0.185
Cl2 557 1.074 1.357 2.416 0.931 0.737 0.414
O2 1556 1.006 1.024 1.290 0.999 0.976 0.775
HCl 2886 1.000 1.001 1.067 1.000 0.999 0.937
H2 4160 1.000 1.000 1.019 1.000 1.000 0.982

The table clearly shows the trends that the partition function increases with decreasing frequency
and increasing temperature. For many molecules under typical catalytic reaction conditions,
however, the vibrational partition function deviates only slightly from unity, implying that these
molecules are predominantly in their vibrational ground state. This also have the interesting
implication that the vibrational energy cannot contribute to the heat capacity at low temperatures.
Note that upon adsorption on a surface, the bonds between the substrate and the adsorbed molecule
usually give rise to low frequency modes with partition functions that are significantly larger than 1.

23
Exercise 3.8 Partition Function, Average Energy and Equilibrium Constant
(a) We choose the ground state of the molecule A as the zero of energy:

q = ∑e −ε i /kT = 1+ e −∆E/kT
i

T → 0 : q →1
T →∞: q→2

Thus, at T = 0 K the molecule A is entirely in the ground state, while at T = ∞K both levels are
equally occupied.

(b) Application of the logarithmic derivative yields:

∂
ε = kT 2 ln (q )
∂T
1 ∂ (q )
= kT 2
q ∂T
1 ∆E −∆E/kT
= kT 2 −∆E/kT 2 e
1+ e kT
∆E
= ∆E / kT
e +1

The limiting values are ε = 0 at low and ε = ∆E/2 at high temperature (as expected!)

(c) The energy levels of B are ∆E/2, 3∆E/4 and ∆E with respect to the ground state of A and thus
the partition function of B equals:

q B = e −∆E/ 2 kT + e -3∆E/ 4 kT + e - ∆E/kT

Hence the equilibrium constant becomes:

q B e - ∆E/ 2 kT + e -3∆E/ 4 kT + e −∆E/kT

K = Π qi ν i = =
i qA 1 + e −∆E/kT

which has limiting values of 0 and 3/2 at low and high temperatures, respectively. The value K = 0
indicates that the equilibrium is on the side of A only, due to the ground state of A being the
lowest energy state overall. At higher temperatures, entropy becomes important as well, which
favours the formation of the three-level system B over the two level system A. In the limit of
T→∞, all levels are equally occupied, resulting in a limiting value of K = 3/2.

Exercise 3.9 Equilibrium Constants from Partition Functions

The equilibrium constant for the isomerization reaction is

24
 ∞ ∞
i ∆E

qB ∑e − ε iB/kT
∑e −
2 kT

K= = i=0
∞
=e ⋅−
∆E
kT
i=0
∞
qA ∆E
∑e ε ∑e −i
A
− i /kT
kT
i=0 i=0

i=
A B i=6
4 i=5
i= i=4
3 i=3
i= i=2
2 i=1
i= i=0
1
∆E
i=
0

∞
1
Using the expression for the sum of an infinite series ∑e
i =0
− ix
=
1 − e− x
, this becomes:

1 − e− x ∆E
K = e− x − x /2
; x=
1- e kT

(a) At low temperatures such as T = 0.1 ∆E/k (or x = 10) the equilibrium constant is very small, in this
case K = 4.57 10−5. Hence the equilibrium lies mainly on the left, at A.

(b) T = 2 ∆E/k (or x = ½) yields K = 1.08, A and B are present in almost equal concentrations.

(c) T = 10 ∆E/k (or x = 0.1) yields K = 1.78.

(d) The limiting values of the equilibrium constant are K = 0 at T = 0 and K = 2 for T → ∞. Notice we
must use le hospitals rule for finding this latter limit. The example illustrates that at low
temperature the lower energy of the ground state of A dictates the equilibrium to lie at the left,
while at high temperatures the higher number of levels (twice as many as in A per energy
therefore K = 2) available for isomer B draws the equilibrium to the right. In other words, energy
is dominant at low temperatures while entropy is dominant at high temperatures.

Exercise 3.10 Equilibrium Constants for Reactions on Steps

Number of step sites occupied S
Total Number of step sites M
Number of terrace sites T
Total Number of Terrace sites N

M!
Qstep = Qs = qsS
( M − S )! S !

25
 N!
QTerrace = QT = ⋅ qT
( N − T )!T ! T

µ S = µT ⇒ qs
(M − S ) = q (N −T )
T
S T

S T
θs = θT =
M N

1−θ s 1 −θT
⋅ qs = ⋅ qT
θs θT

We choose the zero point of energy for the step ⇒ the terrace site is ∆E higher.
−∆E
qstep = qvib s , qT = qvib T e kT

The partition function of the atoms adsorbed on the steps could be smaller as they are bonded
stronger to the surface, but here we will assume:

qvib s = qvib T ⇒

θs
−∆E
1 − θ s qs θ
= ≈ e kT g = T ⇒
θT qT 1 − θT
1 − θT

−∆E
θ s = (1 − θ s ) ⋅ g ⋅ e kT
⇒

⎛ θT ⎞ −∆kTE
⎜ ⎟e
g ⋅ e−∆E / hT ⎝ 1 − θT ⎠
θs = =
1 + ge−∆E / hT ⎛ θ ⎞ −∆E
1 + ⎜ T ⎟ e kT
⎝ 1 − θT ⎠

θT → 0 ⇒ θ S → 0
θT → 1 ⇒ θ S → 1

26
 1
Coverage terrace θΤ

0.1

0.01

0.001

0.0001
0 0.2 0.4 0.6 0.8 1
Coverage Steps θS

Exercise 3.11 Transition State Theory

#
kT
(a) ⎯⎯
K
R ←⎯ → R # ⎯⎯
⎯
h
→ P

kT # k T q′# − ∆E
(b) r= K [ R ]= e k T [ R ] in which q' has been taken with respect to the energy
h h q′
of R, and q'# with respect to that of R#.

(c) In collision theory all translational energy (the collision energy) is available for the
overcoming the reaction barrier, whereas in transition state theory internal degrees of freedom
of the reacting molecules may also exchange energy, as accounted for by the partition functions
of vibration and rotation, i.e. entropy is an important quantity in transition state theory.

(d) A sticking coefficient much smaller than unity indicates that the transition state of adsorption
possesses a much smaller partition function than the molecule in the gas phase. This is the case
if the transition state has no rotational freedom and/or freedom of two-dimensional translation
over the surface. If the molecule can rotate and translate freely along the surface, as is the case
in a so-called precursor state, the sticking coefficient will be close to unity.

(e) Dissociation proceeds usually through a rather rigid transition state in which e.g. CO binds via
two atoms to the surface. In this geometry the molecule has only few degrees of freedom left
(although the molecule may possess several additional low frequency vibrational modes which
increase the vibrational partition function qvib#) and the factor q’#/q’ in the expression under b)
becomes small.

Exercise 3.12 Equilibrium Constants for Adsorption

(a)

27
 dθ∗ K A pA k+
A + ∗ ⇔ A∗ ⇒ = pA k + (1 − θ A∗ ) − k −θ A∗ = 0 ⇒ θ A∗ = KA = b
dt 1 + K A pA k

(b) Adsorption.

⎯⎯
→ A ∗#
A + ∗ ←⎯
⎯

#
A * ⎯⎯
→A*

Let M be the number of sites on the surface and M* the number of sites free

N
qA g M *!
QA = QA*# = ⋅ (qA*# ) N#
Ng ! M − N# ! N# !
*
( )

µA = µA* ⇒
qA
= qA∗# ⋅
M * − N# (
since θ * =
M* )
#
Ng N# M

dθ # kTST ν N # pA q′ # (θ* − θ A*# )

A*
= = = ⋅ 2D A*
dt N0 AN 0 N 0 2π mkT qA trans-unitcell qA gas
rot
gas
⋅ qA vib

gas
qArot = qAvib
gas
=1

−∆Eads
′ # = qA*
qA* ′ # e 0 kT

′ #
qA* ′ #
qA*
0 −∆Eads −∆Eads
S0 (T ) = 2D
= 2D
e kT
=S e
A
0
kT
qtms-unitcell qtms-unitcell

dθ A*#
= k + p (θ* − θ A*# ) ⇒ k + =
(θ * − θ A*# )
⋅
q′A*#
≅
(1 − θ A* )
S0 (T )
N 0 2π mkT q N 0 2π mkT
2D
dt tms-unitcell

Since the coverage of the transition state is low and θ* = (1 − θ A* ) .

⎯⎯
→ A *# QA* = M *! # ( M * − N A* )!
A * ←⎯
⎯ Q =
( )
M * − N A* ! N A* !
A*
(
M * − N A' − N A*# ! N A*# ! )
A *# → A + ∗

qA*θ∗ qA*#θ∗
µA* = µA* ⇒ = again assuming that θ A*# → 0
θ A* θ A*
#
#

28
dθ A* − kTST −ν N A* −kT q′#
#
= = = ⋅ ⋅ θ A*
dt N0 N0 A h qA*

−E −E −E
q ′# d
dθ − kT kTd kT d

≈ e kT ⇒ A* = ⋅ e θ A* = ν ⇒ k − = ν ⋅ e kT
qA* dt h h

(c)

dθ A*
Now if we have equilibrium = 0 = pA ⋅ k + (1 − θ A* ) − k − ⋅ θ A* = 0 ⇒
dt

S0 (T )
K A pA k +
N 0 2π mkT
θ A* = KA = − =
1 + K A pA
d
− ECO
k
ν ⋅e kT

Notice that if we had not made approximations on q´# and qA* we would have got a KA

−∆Eads Ed
q′ e #o
e kT kT
KA = vib2DA*

N 0ν 2π mhT ⋅ qtrans-unitcell
2D

′#o
qvib2D 1
S =
0
≅
a ( 2π mkT )
A 2D 2
q trans-unitcell

A 1
S0 =
(
9×10 × 6.3×16×1.6×10 ×1.38×10-23 ×300 × kg J m 2
-20 -27
)
( 6×10 )
2
-34
J 2s 2

A
S0 = 6×10−3

Exercise 3.13 Dissociation in the Gas Phase

kT # kT q‘ #rot q‘ #trans -
∆E
(a) r = K [AB] = e k T [AB]
h h q‘ vib q‘ rot q‘ trans

All partition functions have been taken with respect to the lowest occupied levels of AB and AB#.
Note that the expression does not contain qvib’#, as the A–B stretch mode represents the reaction
coordinate of the dissociation, accounted for by the factor kT/h.

29
(b) A loose transition state lies close to the product (in the exit channel of the reaction), and
corresponds to rc > r0. This considerably increases the moment of inertia of the transition state with
respect to the ground state, causing the ratio qrot’#/q’rot to be substantially larger than 1. A tight or rigid
transition state resembles the state of the reactants, and corresponds to rc ≈ r0. The preexponential
factor of a dissociation reaction in the gas phase which proceeds through a tight transition state is
therefore approximately equal to ekT/h, or 1013 s-1.

(c) The molecule AB reaches the transition state by means of collisions with other molecules.
Transition state theory is valid as long as the number of unreactive collisions is much larger than the
number of reaction events. At low pressures, the number of collisions decreases steeply and according
to Lindemann's theory we write symbolically:
AB + AB ←⎯⎯⎯ ⎯→ AB# + AB ⎯⎯ → A + B + AB
with

kT # 2
r= K [AB]
h

which is indeed second order in [AB].

Exercise 3.14 Transition states and preexponential factors

Reactant Transistion state Product
a
)
q#>q 1016-1017s-1

b )

q# ~ q 1013s-1
c
)
q# ~ q 1013s-1

d )

q# ~ q 1013s-1

e
)
q# ~ q 1013s-1

30
Exercise 3.15 Dissociation of Molecular Oxygen
(a) We choose the vibration between the O atoms as the reaction coordinate. The expression for
the reaction rate constant becomes:

kT # kT q / # −∆E/k t
k diss = K = e
h h q/
/# /# 2
kT q trans q rot −∆ E/k T kT ⎛ r # ⎞ −∆E /k T
= / / e = ⎜ ⎟ e
h q trans q rot
h ⎝ r0 ⎠

(b) The definition of activation energy is:

∂
E act = k T
2
ln k diss → E act = ∆E + kT
∂T

If we write the preexponential factor as:

2
kT ⎛ r# ⎞
ν eff = e ⎜ ⎟
h ⎝ r0 ⎠

than the expression under (a) equals:

2
kT ⎛ r # ⎞ − ( ∆ E + k T )/k T
k diss = e ⎜ ⎟ e =ν eff e − E act/kT
h ⎝ r0 ⎠

Exercise 3.16 Desorption of Molecular Hydrogen

2π m kT 2π ⋅1.66×10−27 ×1.39 ⋅10−23 ×500

a) q trans (H * ) = l 2 = 10−19 ⋅ = 16.4
( )
2 2
h 6.62×10−34

d[H 2 ]
b) r des = V = N k des θ H 2
dt

#
kT
c) ⎯⎯
K
Transition state theory : 2H * ←⎯⎯→ H #2 ** ⎯⎯
h
→ H 2 + 2*

/# /#
kT # k T q # kT q trans q rot −∆E/kT
k des = K = 2
= e
h h (q H ) h ( q H)2

∂
Rewrite k des as ν eff ⋅ e − E act /RT with E act = R T 2 ln k diss = ∆E + R T and
∂T
31
 kT q / # 3
ν eff = e 2
= 2.71× 2× 1010 × 500× 2
= 3.2×1011 s -1
h (q )
/
(16.4)

Exercise 3.17 Thermal Desorption of Silver from Ruthenium

(a) The rate expression for the desorption process is:

kT
K#
⎯⎯→ Ag # * ⎯⎯
Ag * ←⎯⎯ h
→ Ag +*

−∆E
′#
kT # kT q‘# - − ∆ E kT qtrans
k des = K = e R T = e RT
h h q‘ ′ qvib
h qtrans ′

Partition functions which may play a role are qtrans, qvib and qtrans# (qvib# corresponds to the reaction
coordinate); qvib is unknown and since hν < kT we can expect that is is somewhat larger than unity.
The translational partition functions cancel, except for the factor l2 and l#2, which represents the
effective area of an adsorption site and the transition site respectively:

2
kT ⎛ l # ⎞ - ∆ E
k des = e RT
′ ⎜⎝ l ⎟⎠
hqvib

Thus:
∂
E act = RT
2
ln k des = ∆E + R T = 290 kJ / mol ( → ∆E = 282 kJ / mol)
∂T
and
2
kT ⎛ l# ⎞ 1 kT 86.7meV
ν eff = e ′ =
⎜ l ⎟ qvib − hν
≅ = ≈ 20
′
hqvib ⎝ ⎠ hν 5? meV
1− e kT

Because ekT/h approximately equals 5×1013, and q’vib > 1 it follows that the factor l# > l meaning that
the transition state is getting somewhat lose at this high temperature.

(b) The order n = 0 in silver in the rate expression indicates that Ag desorbs from the edges of
relatively large islands (the existence of silver islands on ruthenium has indeed been confirmed
experimentally). The situation is the two-dimensional analogue of evaporation, the rate of which often
also shows zero-order kinetics. This together with the above information indicates that the Ag atoms
diffuses freely along the edges of the silver islands.

Exercise 3.18 Cyclopropane Isomerization

32
a)

Eact=274kJ/mol-RT
Energ

propylene
y

cyclopropane

Reaction coordinate

(b) The prefactor is considerably higher than ekT/h ≈ 1013, indicating that the transition state has a
loose configuration.

(c) In general qtrans and qrot provide the largest contributions to the overall partition functions.
Substantial differences between qtrans# and qtrans, and between qrot# and qrot are usually the main
reason that prefactors deviate from the 'standard' value, ekT/h = 1013 s-1. As for gas phase
isomerizations qtrans# ≡ qtrans and qvib~qvib#, the high prefactor implies that qrot# >> qrot. It appears
that the compact cyclic form of cyclopropane is unfolded in the transition state, resulting in a
substantial increase in the moment of inertia of the molecule.

kT q′rot - ∆E
#
kT I A# I B# I C# − ∆E
(d) r ≅ e kT = e k T where IB = IC for cyclopropane
h q′rot h IA IB IC

∂ kT I A# I B# I C#
E act = R T
2
ln r = ∆E + R T ; ν eff = e where we assume that the molecule
∂T h IA IB IC
has three independent axis of rotation in the transition state.

Note that in the drawing the actual barrier height should be 274 − RT kJ mol−1!

(e) The rate constant of this unimolecular reaction falls off at low pressures because the number of
collisions between cyclopropane molecules decreases strongly. As a consequence only few molecules
make it to the transition state.

33
Exercise 3.19 Molecular desorption
By definition:

∂ ln(kdes )
E act ≡ R T
2

∂T

As for taking the logarithmic derivative only the T-dependence matters, we write:

k des = α T e
3 − E des /R T

which yields:

∂ ⎡ E des ⎤
⎢⎣ln( α T ) − R T
2 3
E act = R T ⎥⎦ = 3RT + Edes
∂T

Rewrite kdes as an Arrhenius equation:

kT 2 ⎛ 2π m cmkT ⎞ 8π 2µ r 2kT 3 − E des + 3 RT

k des = l e e RT
h ⎜⎝ h
2 ⎟
⎠ h
2

and thus:

kT 2 ⎛ 2π m cmkT ⎞ 8π 2µ r 2kT
ν eff = e3 l
h ⎜⎝ h
2 ⎟
⎠ h
2

and E act = E des + 3kT

Exercise 3.20 Medium effects

a)
CH3 NC → CH 3CN

d [CH 3 NC ]
high pressure : − = k 1 [CH 3 NC ]
dt
d [CH 3 NC ]
low pressure : − = k 2 [CH 3 NC ]2
dt

(b) Transition state theory: CH3NC ↔ (CH3NC)# → CH3CN

The molecule reaches the transition state by collisions with other molecules:
+
⎯⎯
k3
CH 3 NC + CH 3 NC ←⎯ → CH 3 NC# + CH 3 NC
-⎯
k3
k4+
CH 3 NC ⎯⎯→ CH 3CN
#

34
d [CH 3NC]#
= k3+ [CH 3 NC]2 − k3− [CH 3 NC# ] [ CH 3 NC] − k4+ ⎡⎣CH 3 NC# ⎤⎦ = 0
dt
(steady state assumption)

k3+ [CH 3NC]2

Thus : [CH 3CN]# =
k4+ + k3− [CH 3NC]

d [CH 3 NC] k + k + [CH NC]2

Rate of reaction : − = k4+ ⎡⎣ CH 3 NC# ⎤⎦ = +4 3 − 3
dt k4 + k3 [CH 3 NC]

At high pressures k3− [CH 3NC] >> k4+

d [CH 3 NC] kT # +
and − = K [CH 3 NC] = k4 K 3 [CH 3NC]
dt h

Low pressure:
k3− [CH 3NC] << k 5

d [CH 3NC]
and − = k3+ [CH 3]2
dt
kT
* Note that k4+ =
h

Exercise 3.21 Collision Theory

The Table indicates that reaction sets in if the collision energy equals almost 40 kJ mol−1, we estimate
the barrier at Eb ≈ 39 kJ mol−1.

At higher energies the reaction cross section decreases, because the colliding molecules have excess
energy after the collision. As a result they separate rapidly and the time available for reaction is too
short.

The activation follows by definition from:

2 ∂ ln(k ) 1
E act = RT = E b + RT
∂T 2

or Eact = Eb + ½RT = 39 + 2 = 41 kJ mol−1 at 500 K.

35
 Solutions for Exercises in Chapter 5

Exercise 5.1 Ammonia Catalyst

(a) −∆H Fe3O4 << −∆H Al2O3 Meaning that Al2 O3 is basically impossible to reduce out as
metallic Al. This means that the alumina stabilizes the structure and that the magnetite keeps
its volume, but is becoming porous when the oxygen from the iron is removed.

(b) Consider a piece of 1 g:

0.97g 0.03g
Vi = + = 0.187 cm3 + 0.0076 cm3 = 0.195 cm3
ρ Fe O
3 4
ρ Al O
2 3

mFe 0.03 g 0.97g mFe

Vf = Vpore + + ⇒ Vpore = −
ρ Fe ρ Al O
2 3
ρ Fe O
3 4
ρ Fe

Reducing nFe4O4 mole of Fe3O4 to iron result in 3 times a many moles of iron i.e.
mFe mFe3O4 3 ⋅ 0.97gM WFe 0.97×3×55.85
nFe = 3nFe3O4 ⇒ =3 ⇒ mFe = = = 0.702 g
M W Fe M W Fe3O4 M WFe O ( 3×55.85 + 4×16 )
3 4

0.97 g 0.702
Vi = Vf ⇒ Vpore = − = 0.187 − 0.089 = 0.098cm3
ρ Fe O
3 4
ρ Fe
Vpore100%
Thus the pore volume constitutes = 50% . The pore volume per gram can also
Vi
be given as 0.098 cm3 g−1 non-reduced catalyst or 0.133 cm3 g−1 active catalyst.

(c) Usually the close packed surface, i.e. the Fe(110) since Fe is BCC (at least at temperature
relevant for catalysis, T> ~925°C is it FCC ), is the most stable surface since it has the
lowest surface energy. This is however not the case for Fe where Fe(100) is slightly lower.
The distribution of surface plane will be given by the Wulff construction.

(d) The BET area measures the total area(metal + oxide) Al2O3 +Fe=29m2
PV 1× 105 × 2, 2 × 10−6
1g catalyst chemisorbs 2.2 ml N 2 = 2* = 2* −23
= 1.1×1020 N atoms
k BT 1,38 × 10 × 298

If we assume a c(2×2) overlayer on a BCC(100) surface we have that the atomic distances a
is equal to the lattice distance d see figure 5.3 in C&N. Since the new unit cell in a c(2x2) is
the same as a 2 × 2 we get that the area is for each N atom is 2 d × 2d = 2d 2 .
The total area covered with N atoms is then the number af atoms adsormed times the area
each occupy = 1.1×1020 x 2 ⋅ ( 0.286 nm ) = 18 m 2 g −1
2

(e) Since the Iron now occupy 18m2g-1 and the total area is 29m2g-1 must the area of the support
be 11m2g-1.

36
Exercise 5.2 BET Method
(a) First we normalize the amount adsorbed to per gram catalyst. Then we plot
p
vs P / P0 from this plot we find the slope α and intersection η . It is then
Va ( P0 − P)
possible to estimate the volume that exactly covers the whole surface with one monolayer
1
V0 = = 21.84 ml . Having the volume at standard condition we can from the ideal
η +α
gas low fin the number and since we know how much area each molecule takes up at the
surface we can estimate the total area as

P ⋅ V0
N= = 5.79×1020 N 2 molecules ⇒ A = NA0 = 5.79×1020 ⋅ 0.164 nm 2 = 95.05 = 95 m 2 g −1
kT

30
P0=773.81 torr
Adsorbed volume Va (ml stp)

25

0.010
20
data
0.008 Linear Regression
P/(Va(P0-P)) (ml-1)

15 0.006

0.004
10 α=0.04537 ml
-1
0.002 -1
η=0.0004247 ml
5 0.000
0.00 0.05 0.10 0.15 0.20
Pressure in mmHg vs adsorption ml std
Extrapolation P/P0
0
0 20 40 60 80 100 120 140 160 180

Pressure P (torr)

k2 1
(b) =χ= = 108 >> 1. Meaning that the bonding of the first layer is much stronger
k1 η ⋅ V0
than the following layers. In other words the first layer interacts stronger with the substrate
than the gas layer interacts with each other.

37
 (c) Since the BET method just measures the total area should the impregnation with Cu not
change the area to much. Usually a lower area is measured.

(d) We measure 6.7 ml of water (standard gas phase conditions T=298,15 K) meaning that N0
=1.63 1020 Oxygen atoms have been released from the surface. Since each oxygen atom
takes up two unit cells (coverage 0.5) we just need to figure out the area of the Cu unit cells.
Cu is a FCC metal where the Cu(111) is expected to be the most stable surface.
2
3alattice
The area of a Cu(111) unit cell is Aunit(111) = where alattice is the lattice distance in
4
3 2
Cu. This means the area per oxygen atom is: = ⋅ alattice = 11.3×10−20 m 2 .
2

The total Cu(111) area is then = N 0 A0 = 1.63×1020 x11.3×10−20 m 2 = 18, 4m 2

(e) The number of Cu sites is N Cu = 2 N 0

The number of water molecules formed per second is:
VH O/S P
N H2O/S = 2 = 2.43×1018 H 2 O s −1
kT
The Turn Over Frequency TOF is then the total number formed per second divided by the
number of Cu sites which in this case is assumed to be the number of surface atoms i.e.
N H 2O 2.43×1018
TOF = = 20
= 7.5×10−3 s −1
N Cu 2×1.63×10

Eapp
(f) Plot TOF vs 1/T that is an Arrhenius plot and extract the slope α = −
R

(g) The fact that the apparent activation energy is halved should make the researcher suspicious
that he/she may have made an experiment where there are transport limitations.

Exercise 5.3 Effectiveness Factor

(1) Since S is just the ratio of the pore area to the catalyst volume and since we assume
that all the area of the catalyst is sitting in the pores, we get:
A 29 m 2 g −1
S = cat = ≅ 1.5×108 m −1
Vcat 0.2 cm3 g −1

(2) The average pore radius can be estimated assuming that all the pores have the same
diameter. The pore volume is known from Exercise 5.1 to be 0.1 cm3 g−1 thus
Acat ≈ Apore = 2π Rp Lp = 29 m 2 and Vpore = π Rp2 Lp = 0.1cm3 ⇒
Vp 0.1cm3
Rp = 2 =2 = 6.9 nm
Ap 29 m 2

(3) The overall rate of the process is estimated from the fact that we know the TOF per
iron atom and we know the active area per gram catalyst. N N was estimated in
exercise 5.1.d. and N Fe = 2* N N . Thus is we look at 1g catalyst then

38
 TOF× N Fe 0.05× 2×1.1×1020
rate = = 23
= 1.8×10−5 mol s −1 but the rate is also given by
NA 6×10
rate = Vcat SkC0 . If we continue considering 1 g of cat we know the volume. S is
known and C0 can be estimated from the ideal gas law as
n P 1×105 rate
C0 = = = = 20 mol m -3 thus k = = 3 ⋅10−8 m3 m surfcat
−2
s −1
V RT 8.31× 600 Vcat SC0

(4) The Thiele diffusion modulus can now be calculated

Sk 1.5×108 ×3×10-8
Φ s = Rsphere = 2×10−4 = 0.67
Deff 4×10-7

(5) This Thiele modulus can easily be converted to an effectiveness factor since
3 ⎡ 1 1 ⎤ 3 ⎡ eΦs + e −Φs 1 ⎤
ε= ⎢ − ⎥= ⎢ Φs − ⎥ = 0.97 thus the chosen particle
Φ s ⎣ tanh Φ s Φ s ⎦ Φ s ⎣ e − e −Φs Φ s ⎦
radius is way on the safe side.

(6) If we use a reactor with a radius of 2 mm and 1 g of catalyst we can estimate that
there can be roughly 10 particles across the reactor, but what about the height. If we
just consider the catalyst before it is crushed the 1 g correspond to 0.2 cm3. But if it
is spherical particles will there naturally be voids in between the particles allowing
for the gas transport. Ideally packing of those particles would be the FCC structure
mentioned in chapter 5. That means that the volume increases roughly by a factor
2 . Thus our 1g will have a volume of 0.28 cm3 and the plug will then have a
0.28
height of h = cm ≅ 2.2 cm which is just the needed factor 5 of the reactor
π ⋅ 0.22
diameter. Taking more catalyst or using smaller particles in combination with
smaller reactor diameter can obtain higher ratios. The latter is god for the
effectiveness factor but there are limits to how fine powders that can be kept in place
and how large a pressure drop is accepted over the plug. The first is naturally easy,
but as we shall see can we easily run into problems of not being in the zero
conversion limit.

(7) We are only accepting a 5% conversion over the catalyst plug. We have just
estimated the rate per gram catalyst to be rate = 1.8 ⋅10−5 mol/g sec . That means that
rate
the flow of nitrogen must be FN2 = = 3.6×10−4 mol s −1 . Since 1mol equals 50 L
0.05
under the described conditions (T=600K) and since the total amount of gas is 4 time
that of Nitrogen we have that this corresponds to a total flow of
F = 4 ⋅ FN2 ⋅ 0.05 m3 s −1 = 7.2×10−5 m3 s −1 = 72 mls −1 thus the space velocity is
F 72 cm3 ×3600 −1
Space velocity = = 3
h = 9.2×105 h −1 This illustrates that
Vcatpowder 0.28cm
space velocities should in general be large numbers if we want to test our catalyst in
the zero conversion limit. Alternatively we would have to integrate the rate equation,
since the partial pressure of N2 is no longer constant down through the reactor.

39
Solutions for Exercises in Chapter 7
Exercise 7.1 Sticking of N2 Fe(100) Continuation of Exercise 5.1

a)
Since it is saturated θ = 1 and we can assume since it is symmetric that θ = ½ at maximum.

⎛ kTm ν
2 ⎞
ν = 1 ⋅ 1013 s −1 β = 2K / s Tm = 740 K ⇒ Edes = kTm ⋅ ln ⎜ ⎟ for second-order
⎜ Edes ⋅ β ⋅ 2 ⋅ 1 ⎟
⎝ 2⎠
desorption

0
guess Edes = 100 kJ mol−1 ⇒

1
Edes = 203.289 J mol−1 1 iteration
2
Edes = 198.926 J mol−1 2 iteration
3
Edes = 199.059 J mol−1 3 iteration
4
Edes = 199.055 J mol−1 4 iteration
5
Edes = 199.055 J mol−1 5 iteration

Edes = 199 kJ mol−1

3 iterations is sufficient.

(b)
∆Eact
− Eact = 3kJ / mol
S0 (T ) = S00 ⋅ e kT
Eact = 0.03eV ≈ 3 kJ mol−1

( ⎡⎣ S (500) = 2.5×10
0
−5
⇒ S00 = 5×10−5 ⎤⎦ )
Edes = 199kJ / mol
∆H = Eact − Edes = −196 kJ mol−1

c) ∆H = −196kJ / mol
+ ∆S
−5 q #0
S = 5×10
0
0 S ≈
0
0 = e R ⇒ ∆S < 0
qgas

Adsorption results in a massive loss of entropy. The entropy of gas molecules is huge primarily due
to the translational degrees of freedom. Those are lost upon adsorption where the molecule is not
free to move any longer.

d)
− Edes
dθ N 2 ⋅ F ⋅ S0 (T )
⋅ (1 − θ N ) 2 −ν ⋅ l RT ⋅ θ N = 0 for equilibrium.
2
=
dt N0

− Eact + Edes
K ⋅ pN 2 2 ⋅ pN2 ⋅ S00 ⋅ e RT
θN = where KpN =
1 + K ⋅ pN 2 N 0ν 2π mkT

40
 The number of sites per m2 N0 comes in here because we must normalise to per site. The numbers
of sites can be estimated by utilizing the information given in exercise 5.4. If we assume that the
saturation coverage is a c(2x2) structure will each Nitrogen take up two Fe(100) unit cells. As Fe is
bcc will the lattice distance d be equal the inter atomic distance in the Fe(100) a, meaning each N
takes up an area of 2a2. (we could also have performed this exercise assuming that each Fe atom
was an reactive center).

for PN2 = 1bar = 10000 Pa T = 800 K and ν = 1×1013

1
N0 = = 6.11×1018 m 2 you get KpN2 = 1.89 × 104
2a 2
1.89 × 104
θN = = 0.993 (If pN2 = 1mbar ⇒ θ N = 0.81)
1 + 1.89 × 104

see Figure 7.11 where we have made a similar calculation for Edes=190 kJ mol−1 and N0 = 1/a2

(e)
Since H2 desorbs at T= 350 K must EdesH2 << EdesN2 so the surface is dominated by N or NH species

Exercise 7.2 Sticking of Methane on Ni(100)

(a) Ni is a fcc metal so the unit cell has volume d3 contains 4 Ni atoms. We shall first find the lattice
constant for Ni.

8,9×106 g 8,9×106 8.9×106 × 6×1023

1 m3 = mol = × 6×1023 atoms. = unitcells
58, 71g 58, 71 58.71× 4

4⋅MW 58.71× 4
1 unitcell = = = 4.40×10−29 m3
N a ⋅ ρ Ni 8.9×10 × 6×10
6 23

1 unitcell = d 3 ⇒ d = 3 4× 4×10−29 m = 3.52×10−10 m. The lattice constant.

d
The unit cell for a Ni(100) surface has length a = = 2.5×10−10 m. each containing one Ni atom.
2
1
The area for each atom is therefore a2 so the number of sites is N 0 = 2 = 1.60×1019 m −2 .
a

(b)

dθ c PCH4 ⋅ S0 (T )
= ⋅ (1 − θ c ) 2 solve for θ c
dt N 0 ⋅ 2π mkT

41
 PCH4 ⋅ S0 (T ) ⋅ t
N 0 ⋅ 2π mkT
θ c (t ) =
PCH4 ⋅ S0 (T ) ⋅ t
+1
N 0 2π mkT

PCH4 ⋅ S0 (T ) ⋅ t
If we only consider small doses so t → 0 ⇒ θ c (t ) ≈ = α ⋅ pCH4 ⋅ t = α × Dosis
N 0 2π mhT

Draw a tangent to the uptake curves at zero dosis and determine, for example, at which dosis this
crosses the horizontical line that corresponds to 0.8 Ml carbon. This would be the line the uptake
would follow if there were no blocking as in the zero dosis limit. By repeating this procedure for
each temperature we can read of the dosis that corresponds to 0.8 Ml if there was no blocking.

PCH4 ⋅ S0 (T ) ⋅ t x
θ (t x ⋅ PCH ) = 0.8 = α ⋅ dosis = ⇓
4
N 0 ⋅ 2π mhT

0.8 ⋅ N 0 2π mkT T (K )
S0 (T ) = = 1.9×10−10 ⋅ all in correct units.
PCH4 ⋅ t x PCH4 t x (bar × sec)

we can now construct the following table:

T (K) PCH4 ⋅ tx of 0.8 ML S0(T)
550 2.4 × 10−2 1.8 × 10−7
500 6.6 × 10−2 6.4 × 10−8
475 13.4 × 10−2 3.1 × 10−8
450 20.0 × 10−2 2.0 × 10−8

c)
− Ea
Make an Arrhenius plot Ln ( S0 (T ) ) vs 1/ T slope α = ⇒ Ea ≈ 46 kJ mol−1
kT

d)

0.2 bar s took 152 s.

200 mbar s
pCH4 = = 1.31mbar = 1.0 torr
152 s

Exercise 7.3 Hydrogen Adsorption/Desorption and Equilibrium Coverage

(a)

⎯⎯
→ 2H *
H 2 + 2* ←⎯
⎯

42
dθ H 2 FH2 S (T ) 2 pH 2
= θ* − k −θ H2 where FH2 = and θ H = 1 − θ *
dt N0 2π mkT

since k − ≅ 0 this differential eq is easily solved:

θh
θH t
2 FH S (T ) 2 FH S (T )t
∫0 θ θ
1 − θ H ∫0
−2
(1 − H ) d H = = 2
d t = 2
leading to:
N0 N0

2 pH2 S (T )t
N 0 2π mkT
θH =
2 pH2 S (T )t
+1
N 0 2π mkT

b)

By extending the tangent at θ = 0 to θ = 1 and read of the dosis in bar*sec can the following table
N0
be made since S0 (T ) = and D = PH2 t
2D
2π mkT

T(K) D(bar*s) S0(T)

200 6250 9.1×10−14
210 1870 3.1×10−13
220 591 1.0×10−12
230 212 2.9×10−12
240 83 7.5×10−12

c) Make an Arrhenius plot and find slope =-5299 resulting in Ea=44kJ/mol and pre-factor
S 00 = 0.029 .

(d) Second-order desorption.

⎛ ν RTm 2 ⎞ ⎛ ν RTm 2 ⎞ −1
Ed = RT ln ⎜ ⎟ ≅ RT ln ⎜ ⎟ solved iteratively at Tm =408 K resulting in 110 kJ mol
⎝ β Ed 2θ m ⎠ ⎝ β Ed ⎠
(e) Total area is measured by BET using N2 = area of oxide + area of metal. Only the metal area is
measured by H2

43
 General Exercises

Block 1

Task 1. Catalytic NO Reduction (30%, weighted as 5% for each of the questions)

(a) Surfaces with highest density has lowest surface energy therefore the low index surfaces are
abundant in the order Rh(111) > Rh(100) > Rh(110). Reactivity has the reverse order
Rh(111) < Rh(100) < Rh(110).

(b) In a BET experiment the phenomena physisorption is utilized and the total area (metal +
oxide) is measured.

(c) Simple estimate for TM = 460 K and ν = 1013 s −1 β = 2 K min −1 :

⎛ RTM2ν ⎞ −1 −1 −1
Edes = RTM ln ⎜ ⎟ ⇒ Edes = 100 kJ mol ⇒ Edes = 138 kJ mol ⇒ Edes = 137 kJ mol
⎝ Edes β ⎠

2
PV ⎛ a ⎞ PVa 2 1×105 × 1.85 × 10−5 × (3.81× 10−10 ) m 2
(d) Atot = N NO × ANO = × 2⎜ ⎟ = = −23
= 65 m 2
kBT ⎝ 2⎠ kBT 1.38 × 10 × 300

e)
− Edes
dθ NO S (T ) PNO (1 − θ NO )
= −ν e RT
θ NO = 0
dt N 0 2π mNO kBT
Edes
KPNO S (T )e RT 1
θ NO = where K = and N 0 = 2
1 + KPNO N 0ν 2π mNO kBT a
140000
−10 2
100 × (3.81× 10 ) e 8.31×900
KPNO = = 3.2
1×10 6.28 × 30 × 1.6 × 10 × 1.38 × 10−23 × 900
13 −27

3.2
θ NO = = 0.76 with respect to sites. (0.38 with respect to Rh atoms)
1 + 3.2

(f) Use Le Sabatiers Principle: Since the reactivity decreases as we go to the right in
the transition metals the metals Pd and Ag are not reactive enough to dissociate the
NO while Mo and Ru are to reactive so the products O and N will not leave the
surface. Thus we get an optimum in between at Rh.

Task 2. Oxidation of Hydrogen on Pt (35%, weighted as 5% for each of the questions

44
(a) For example
⎯⎯
→ H2 *
H 2 + * ←⎯
⎯
⎯⎯
→ O2 *
O2 + * ←⎯
⎯
OH * +OH * ⎯⎯
→ H 2 O * +H *

(b) (3) r = r+ − r− = k3+θ OHθ H − k3−θ OHθ*

(c)

dθ H
(1) = k1+θ*2 PH2 − k1−θ H2 = 0 ⇒ θ H = K1 PH2 θ*
dt
dθ O
(2) = k2+θ*2 PO2 − k2−θ O2 = 0 ⇒ θ O = K 2 PO2 θ*
dt
dθ OH θH O PH2O
(4) = − k4+θ OHθ H + k4−θ H2Oθ* = 0 ⇒ θ OH = 2 θ* = θ*
dt K 4θ H K 4 K 5 K1 PH2
dθ H 2 O PH2O
(5) = − k5+θ H2O + k5− PH2Oθ* = 0 ⇒ θ H2O = θ*
dt K5
⇓
k3− PH2Oθ*2 ⎛ PH2O ⎞
(3) r = k +
K1 K 2 PH2 PO2 θ −
2
= k3+ K1 K 2 PH2 PO2 ⎜ 1 − ⎟ θ*2
3 *
K 4 K 5 K1 PH2 ⎜ K G PH PO ⎟
⎝ 2 2 ⎠
⇓
K G = K1 K 2 K 3 K 4 K 5

1
(d) θ* = 1 − θ H − θ O − θ OH − θ H O ≅ 1 − θ O = 1 − K 2 PO θ* ⇒ θ* =
2 2
1 + K 2 PO2

δ ln(r+ ) 1 1
(e) nx = Px ⇒ nH = , nO = − θ O , and nH O = 0
δ Px 2
2
2 2 2

PH2 PO2
r ≅ k3+ K1 K 2 PH2 PO2 and χ H2 = , = (1 − χ H2 ) ⇒
(f) Ptot Ptot
r = k3+ K1 K 2 Ptot χ H2 (1 − χ H2 )
Find maximum for r as a function of χ H2

δr 1
= 0 ⇒ χH = i.e. max rate for PH2 = PO2
δχ H 2 2

45
 (g) (1) Since oxygen is MARI can the apparent activation energy become dependent
on the oxygen coverage i.e. (sufficient)
δ ln(r+ ) ∆H1 ∆H 2
Eapp = RT 2 = + + E3act − ∆H 2θ O (this is not needed)
δT 2 2

(2) If the rate is high there will always be a danger of transport limitations at very
high rates i.e. pore diffusion or normal diffusion limitations.

Task 3 N2O5 Decomposition (35%, weighted as 10% for each of the first three questions and
5% for the last ).

a) Based on the information can the following table be constructed:

T(K) 1/T k (s−1 ) ln(k)

273 0.003663 7.87×10−7 −14.06
298 0.003356 3.46×10−5 −10.27
308 0.003247 13.5×10−5 −8.91
318 0.003145 49.8×10−5 −7.60
328 0.003049 150×10−5 −6.50
338 0.002959 487×10−5 −5.32

By plotting ln(k) versus 1/T an activation energy of Eact = 103 kJ mol−1 and ν = 4.0×1013 s −1 is
found.

(b)We shall now use the steady-state approximation for the intermediates NO3 and NO:

d [ NO3 ]
= k1 [ N 2 O5 ] − k−1 [ NO 2 ][ NO3 ] − k2 [ NO 2 ][ NO3 ] − k3 [ NO ][ NO3 ] = 0
dt

k1 [ N 2 O5 ]
[ NO3 ] =
k−1 [ NO 2 ] + k2 [ NO 2 ] + k3 [ NO ]

d [ NO ]
= k2 [ NO 2 ][ NO3 ] − k3 [ NO ][ NO3 ] = 0
dt

k2 [ NO 2 ][ NO3 ] k2
[ NO] = = [ NO2 ]
k3 [ NO3 ] k3

By inserting this we get

k1 [ N 2 O5 ]
[ NO3 ] =
k−1 [ NO 2 ] + k2 [ NO 2 ] + k2 [ NO 2 ]

The reaction rate is then given by

46
d [ N 2 O5 ] ⎛ k−1k1 ⎞
= k1 [ N 2 O5 ] − k−1 [ NO 2 ][ NO ] = ⎜ k1 − ⎟ [ N 2 O5 ] i.e. a first order reaction.
dt ⎝ k−1 + 2k2 ⎠

c)

The temperature dependence is first determined for each of the partition functions:
3
⎛ 2π mkBT ⎞ 2 3
qtrans =V ⎜ 2 ⎟ contributes with T 2
.
⎝ h ⎠

8π IkBT 1
qrot = for each degree of rotational freedom i.e. T 2 for each degree.
σh

−1−1
⎡ ⎛ − hν ⎞ ⎤ kBT
qvib = ⎢1 − exp ⎜ ⎟⎥ ≅ when hν << kBT i.e. each vibration contributes with T.
⎣ ⎝ kBT ⎠ ⎦ hν

Since NO3 and the activated complex are non-linear we get the following table:

NO NO3 NOONO2
translation 3 3 3
rotation 2 3 3
vibration 1 6 12

The prefactor is given by

3 3
kT q# T 2T 2T 11 5
ν (T ) = κ B ∝T 3 =T 2
h qNO qNO3 3 3
T 2TT T 2T 2T 6 ( )( )
where we remember that one of the vibrational mode in the transition state complex has been
converted into the reaction coordinate resulting in the T in front of the expression.

(d) Reactions that have similar rates in gas phase and in liquid phase are characterized by being
relative slow so that they are not diffusion limited and by nor involving charged particles (ions).

47
 Block 2

Task 1. Automotive Catalyst (35%, weighted as roughly 5% for each of the questions)
(a) The net scheme is:
P P
→ CO 2 + 1 N 2 and K G = CO2 N2
⎯⎯
NO + CO ←⎯
⎯
2 PNO PCO

(b) Other relevant elementary steps could be:

⎯⎯
O * +O * ←⎯ → O2 * + *
⎯
⎯⎯
→ O2 + *
O 2 * ←⎯
⎯
⎯⎯
→ N 2O * + *
NO * +N * ←⎯
⎯
⎯⎯
→ N 2O + *
N 2 O * ←⎯
⎯
etc.

dθ NO
(c) (1) = 0 = k1+ pNOθ* − k1−θ NO ⇒ θ NO = K1 pNOθ*
dt

(2) r = r+ − r− = k2+θ NOθ* − k2−θ Nθ O

dθ CO
(3) = 0 = k3+ pCOθ* − k3−θ CO ⇒ θ CO = K 3 pCOθ*
dt

dθ O θ CO2θ*
(4) = 0 = k4+θ COθ O − k4−θ CO2θ* ⇒ θ O =
dt K 4θ CO

dθ CO2 pCO2θ*
(5) = 0 = k5+θ CO2 − k5− pCO2θ* ⇒ θ CO2 =
dt K5

dθ N θ N 2 θ*
(6) = 0 = k6+θ N2 − k6−θ N2θ* ⇒ θ N =
dt K6

dθ N2 pN 2
(7) = 0 = k7+θ N2 − k7− pN2θ* ⇒ θ N2 = θ*
dt K7

θ N θ* pN 2
By substituting (7) into (6) we get θ N = 2
= θ*
K6 K6 K7
pCO2θ*
θ*
θ CO θ* K5 pCO
And substituting (3) and (5) into (4) we get θ O = = =
2
θ* 2

K 4θ CO K 3 K 4 pCOθ* K 3 K 4 K 5 pCO

whereby all coverages are expressed by equilibrium constants and partial pressures.
Inserting in (2) we get

48
 pN 2 pCO2 ⎛ 1 pN2 pCO2 ⎞
r = k2+ K1 pNOθ*2 − k2− θ*2 = k2+ K1 pNOθ*2 ⎜ 1 − ⎟
K 6 K 7 K 3 K 4 K 5 pCO ⎜ K1 K 2 K 3 K 4 K 5 K 6 K 7 pCO pNO ⎟
⎝ ⎠

⎛ 1 pN2 pCO2 ⎞
r = k2+ K1 pNOθ*2 ⎜1 − ⎟
⎜ KG pNO pCO ⎟
⎝ ⎠

(d) meaning that K G = K1 K 2 K 3 K 4 K 5 K 6 K 7

(e) θ* = 1 − θ O − θ N − θ NO − θ CO − θ CO − θ N insert the expression for each coverage and find

2 2

1 1
θ* = ≅
pCO2 pN 2 pCO2 pN 2 pCO2
1+ + + K1 pNO + K 3 pCO + + 1+
K 3 K 4 K 5 pCO K6 K7 K5 K7 K 3 K 4 K 5 pCO

δ ln(r+ ) 1
(f) Find the reaction order n x ≡ p x gives since θ* ≅
δp x pCO2
1+
K 3 K 4 K 5 pCO
nN2 = 0
nNO = 1
nCO = 2θ O
nCO2 = −2θO

δ ln(r+ )
(g) since θ * ≅ 1 and Eact
app
≡ RT 2 we get app
Eact = E2 + ∆H1
δT
+ ⎛ − E2 ⎞ ⎛ − (∆H 1 − T∆S1 ) ⎞
where we have assumed that k2 = k 2 exp ⎜ ⎟ and K 1 = exp⎜
0
⎟
⎝ RT ⎠ ⎝ RT ⎠

Task 2. Capacity and Methanization Reaction (30%, weighted as roughly 5% for each of
the questions)

(a) The reactivity will go up as the Ni overlayer is strained by being pseudomorfic

with the larger Ru(0001) lattice. When the layer is being strained the overlap
between the d-orbital will decrease and the d-band will become more narrow
leading to an upward shift of the d-band. This means that the distance between the
d-band and the anti-bonding orbital becomes less leading to a stronger chemical
interaction.

49
(b) The desorption energy for a 1. order desorption can be estimated iteratively
from
⎛ RT 2ν ⎞
Edes = RT ln ⎜ ⎟
⎝ Edes β ⎠
Guess Edes(Tm = 500 K) = 150.000 J mol−1 then insert and find
Edes=132.414 kJ mol−1
Edes=132.933 kJ mol−1
Edes=132.916 kJ mol−1
Edes=132.917 kJ mol−1
Edes=132.917 kJ mol−1

Guess Edes(Tm = 550 K) = 150.000 kJ mol−1 then insert and find

Edes=146.527 kJ mol−1
Edes=146.634 kJ mol−1
Edes=146.631 kJ mol−1
Edes=146.631 kJ mol−1

Change in bonding energy =146.6 − 132.9=13.7 kJ mol−1

PVCO
(c) The number of CO molecules adsorbed is N CO = and since each
kT
molecule takes up two unit cells the total metal area is:

A = 2 N CO ANi on Ru = 10.4 m 2

− Edes
dθ CO S0 pCO
(d) Equilibrium =0= θ* − ν e RT
θ CO
dt N 0 2π mCO kBT

KpCO S0
⇒ θ CO = where K = − Edes
=9.64×10−4 (N m−2)−1 where N0
1 + KpCO
N 0 2π mCO kBTν e RT

is the
1
total number of sites per m2 i.e. N 0 =
ANi on Ru
This lead to θ CO = 0.49

pCH4 F
(e) The number of CH4 produced per second N CH4 = = 4.03 ×1018 s −1
kT
2
15 m
The number of sites N NI = = 2.36 × 1020
ANi om Ru
N CH4
TOF = = 1.71×10−2
N Ni

50
 (f) The flat Ni(111) on Ru(0001) surface is the thermodynamically most stable
surface due to the lower surface energy. That, however, according to the Wulff
construction does not exclude the possibility of other more open sites like for
example step sites. There will be fewer of those and if they account for the
reactivity the TOF for those sites must be accordingly larger.

Task 3 Pyrolysis of Ethane (35%, weighted as 5% for the first and 10% for
each of the following questions).

a)
Based on the data the following table can be made:

t(s) [C2H6](mol m−3) Ln([C2H6](mol m−3))

0.06 381 5.94
0.15 318 5.76
0.36 254 5.54
0.62 191 5.25
0.79 159 5.07
0.98 127 4.84

A plot of t vs ln([C2H6])) shows a straight line; i.e. the reaction is first order in [C2H6]). The same
result can be obtained by comparing the half-lives for [C2H6]) which are roughly constant (0.60
±0.04s) independent of starting concentration.

b)
The simplified mechanism for C2H6 pyrolysis at lower pressures, i.e. with reaction (R11) second
order, is:

R9 C2 H 6 ⎯⎯
→ CH 3 + CH 3

R10 CH 3 + C 2 H 6 ⎯⎯
→ CH 4 + C2 H 5

R11a C2 H 5 + M ⎯⎯
→ C2 H 4 + H + M

R12 C2 H 6 + H ⎯⎯
→ H 2 + C2 H5

R13 C 2 H 5 + C2 H 5 ⎯⎯
→ C4 H10

R14 C2 H 5 + C2 H 5 ⎯⎯
→ C2 H 4 + C2 H 6

on this reaction mechanism, the following equations can be derived:

d [C 2 H 6 ]
= −k 9 [C 2 H 6 ] − k10 [CH 3 ][C 2 H 6 ] − k12 [C 2 H 6 ][H ] + k14 [C 2 H 5 ]
2

dt

51
d [ CH 3 ]
= 2k9 [ C2 H 6 ] − k10 [ CH 3 ][ C2 H 6 ]
dt

d [C2 H5 ]
= k10 [ CH 3 ][ C2 H 6 ] + k12 [ C2 H 6 ][ H ] − 2( k13 + k14 ) [ C 2 H 5 ] − k11a [ C 2 H 5 ][ M ]
2

dt

d [H]
= k12 [ C 2 H 6 ][ H ] + k11a [ C2 H 5 ][ M ]
dt

Assuming CH3 in steady state:

d [ CH 3 ]
= 2k9 [ C2 H 6 ] − k10 [ CH 3 ][ C2 H 6 ] = 0 ⇒
dt

2 k9
[CH3 ] =
k10

Also C2H5 and H can be assumed in steady state:

d [C2 H5 ]
= k10 [ CH 3 ][ C2 H 6 ] + k12 [ C2 H 6 ][ H ] − 2( k13 + k14 ) [C2 H 5 ] − k11a [ C 2 H 5 ][ M ] = 0
2

dt

d [H]
= k12 [ C2 H 6 ][ H ] + k11a [ C2 H 5 ][ M ] = 0
dt

Addition of these two equations leads to :

2 k9
k10 [CH 3 ][C 2 H 6 ] − 2(k13 + k14 )[C 2 H 5 ] = 0 and by utilizing [ CH 3 ] =
2
we get:
k10

k9
[ C2 H5 ] = [ C2 H 6 ]
k13 + k14

The steady state concentration of H is then

k11a [ C2 H 5 ][ M ] k11a k9 [M]

[H] = =
k12 [ C2 H 6 ] k12 k13 + k14 [ C2 H 6 ]

Ignoring minor contributions to ethane formation and destruction in initiation

and termination steps, we get

d [C2 H 6 ]
= k12 [ C2 H 6 ][ H ] = k [ C2 H 6 ] [M] ≈ k [M]
0.5 1.5

dt

Consequently, the reaction is of order 1.5 in [C2 H6].

52
(d)
The collision frequency factor z is given as:

z = πd 2 u

d is the sum of the reactant radii: d = rC2 H5 + rH =6.0×10−10 m

8kBT
u= =4678m/a is the relative speed.
πµ

mC2 H5 mH
The reduced mass is found as µ = = 0.967 mH =1.606×10−27 kg
mC2 H5 + mH

( )
2
z = π 6.0×10−10 m 4678 m s −1 = 5.29×10 −10 m 3 s −1 = 3.2×109 m3 mol−1s −1

53
Block 3

Task 1. Catalytic Synthesis of Hydrogen Peroxide (35%, weighted as roughly 5% for

each question)

(a) Good candidates are the transition metals to the right in the periodic table as they
interact most weakly with oxygen.

(b) For example

⎯⎯
→ 2H* QE
(1) H 2 + 2* ←⎯
⎯
⎯⎯
→ 2O* QE
(2) O 2 + 2* ←⎯
⎯
⎯⎯
→ HO * +* RLS
(3) O * +H * ←⎯
⎯
(4) 2HO * ←⎯ ⎯⎯→ H 2 O 2 * +* QE
⎯
⎯⎯
→ H 2O 2 + * QE
(5) H 2 O 2 * ←⎯
⎯

(c) Since 2 moles of reactant is reduced to one mole of product is high pressure
favourable. Since the process is exothermic is low temperatures favourable, but
as the process is also activated is there a limit to how low the temperature can be
as a significant rate is required.

(d) From the equations the following set of relations appears

dθ H
(1) = k1+ pH2θ*2 − k1−θ H2 = 0 ⇒ θ H = K1 pH2 θ*
dt
dθ O2
(2) = k2+ pO2θ* − k2−θ O2 = 0 ⇒ θ O2 = K 2 pO2θ*
dt
(3) r = k3+θ O2θ H − k3−θ HO2θ*
dθ HO2 θ H O θ*
(4) = k4+θ HO2θ H − k4−θ H2O2θ* = 0 ⇒ θ HO2 = 2 2

dt K 4θ H
dθ H2O2 pH O θ*
(5) = k5+θ H2O2 − k5− pH2O2θ* = 0 ⇒ θ H2O2 = 2 2

dt K5
θ H O θ*
r = k3+θ O2θ H − k3−θ HO2θ = k3+ K1 pH2 θ* K 2 pO2θ* − k3− θ*
2 2

K 4θ H
pH2O2
= k3+ K1 pH2 K 2 pO2θ*2 − k3− θ*2
K 5 K1 pH2 K 4
⎛ 1 pH2O2 ⎞
= k3+ K1 pH2 K 2 pO2θ*2 ⎜1 −
⎜ K1 K 2 K 3 K 4 K 5 pH pO ⎟⎟
⎝ 2 2 ⎠

⎛ 1 pH2O2 ⎞
= k3+ K1 pH2 K 2 pO2θ*2 ⎜1 − for K G = K1 K 2 K 3 K 4 K 5
⎜ K G pH pO ⎟⎟
⎝ 2 2 ⎠

e)

54
 θ H O θ* pH O θ*
θ* = 1 − θ H − θ O − θ HO − θ H O = 1 − K1 pH θ* − K 2 pO θ* − 2 2
− 2 2
2 2 2 2 2 2
K 4θ H K5
pH2O2θ*
θ
K5
*
pH O θ*
= 1 − K1 pH2 θ* − K 2 pO2θ* − − 2 2
K 4 K1 pH2 θ* K5
⎛ pH2O2 pH O ⎞
= 1 − ⎜ K1 pH2 + K 2 pO2 + + 2 2 ⎟ θ* ⇒
⎜ K 4 K 5 K1 pH2 K5 ⎟
⎝ ⎠
1
θ* =
pH2O2 pH O
1 + K1 pH2 + K 2 pO2 + + 2 2
K 4 K 5 K1 pH2 K5

(f)
Oxygen is MARI 1
θ* ≅ 1 − θ O = ⇒
2
1 + K 2 pO2
2
⎛ 1 ⎞
+
r =k +
K1 pH2 K 2 pO2θ ≅ k 2 +
K1 pH2 K 2 pO2 ⎜ ⎟⎟
3 * 3
⎜ 1 + K 2 pO
⎝ 2 ⎠

nx ≡ p x
( )⇒n
∂ ln r + 1
= , nH2O2 = 0, nO2 = 1 −
2 K 2 pO2
= 1 − 2θO2
∂px 1 + K 2 pO2
H2
2

g)

Now
θ* ≅ 1 ⇒
3 pH2 pH2
r + = k3+ K1 pH2 K 2 pO2 = k3+ K1 K 2 ptot2 χ H2 (1 − χ H2 ) where χ H2 = =
pH2 + pO2 ptot
∂r + 1 1
∂χ H2
=0⇒
2 χ H2
( )
1 − χ H2 − χ H2 = 0 ⇒ χ H2 =
3

1
R is maximal when pH2 = pO
2 2

Task 2. Effectiveness of Pt Catalyst (30%, weighted as roughly 5% for each of the

questions)
PVH2O
(a) How many oxygen atoms were there on the surface? N O = = 5.21×1020 .
kBT
Each oxygen take up on an area of 2 × 2 area unit cell . Pt is fcc meaning
the (100) unit cell has an area of a2/2. Thus
2
N O 2a 2 PVH2O a 105 × 21.4×10−6 (3.92×10−10 ) 2 2
APt = = = m = 80 m 2 / g
2 kBT 1.38×10−23 ⋅ 298

55
 (b) Under vacuum conditions will the Pt(111) the most stable surface and the
amounts of other facets would be given by the Wulff construction.

(c) The number of active sites are NO/2 since each site is consisting of 4 Pt atoms.
The rate of one gram of catalyst is then simply
N PVH2O mol
rate = O TOF = TOF = 4.3×10−7 = 2.58×1017 s −1 .
2 2kBT s
The amount of gas passing over the catalyst per second is
100×10−6 3
flow = m = 1.66×10−6 m3s −1 resulting in a product concentration of
60s
−7
4.3×10 mol mol
−6 3
= 0.26 3 or ca. 1.1%.
1.66×10 m m

(d) The volume of 1 g catalyst is 0.5 cm3. Since S is the amount of Pt area per
80 m 2 g −1
volume catalyst S = = 1.6×108 m −1 . The concentration of the reactant
0.5cm3g −1
n pO 0.21×1×105 mol
oxygen is Co = = 2 = = 5.1 3 . Notice the concentration of
V RT 8.31×500 m
oxygen must be at the catalyst condition. Meaning that
rate 4.3×10−7 m m
k= = −6
= 1.1×10−9
VSCO 0.5×10 ⋅1.6×10 ×5.1 s 8
s

(e) The rate is seen to bend of for temperatures above 660K indicating that the rate is
being transport limited. The apparent activation energy is found from the
Arrhenius plot for temperatures below 660K.

Not transport limited rate

EApp=120kJ/mol
-5
Ln(rate)

-10

-15

Transport limited rate

-20

0,0010 0,0012 0,0014 0,0016 0,0018 0,0020 0,0022 0,0024

-1
1/T (K )

(f) The efficiency of the catalyst is estimated using the Thiele Modulus as:

56
 3 ⎡ 1 1 ⎤ kS
ε= ⎢ − ⎥ where Φ s = R .
Φs ⎣ tanh(Φ s ) Φ s ⎦ Deff

k can be found at 900 K since we know the k at 500 K and the apparent activation
EApp
R (T =500K)
energy i.e.. k0 = k (T = 500K) *e ⇒
− EApp
m
k (T = 900 K) = 3730e R (T = 900K ) = 4.0×10−4
s
1.6×108 × 4.0×10−4
Φ s = 1×10−4 = 46
3×10−7

ε = 6 × 10−2, i.e. most of the Pt inside the particle is not in contact with the reactants.
We should therefore only have Pt catalyst in an outer shell of the particles. Thus a
shell impregnation would do cutting down on the loading of the expensive Pt metal.

Task 3 Uncertainties in Determining Rates and Activation Energies (35%, weighted

as 5% for the first and 10% for each of the following questions).

To bring the TST estimate into accordance with the experimental determination at 1000 K, we need
an increase of a factor of 2.1×10−12/7.8×10−13 = 2.7 in the estimated rate constant.

(a)
A decrease of kJ mol−1 in the activation energy will increase kTST by a factor of:
exp(−( Ea − 8000 J mol-1 )/RT
= exp(8000 / RT ) = exp(8000 / R *1000) = 2.6
exp(− Ea / RT )

The difference between kexp and kTST is roughly consistent with the uncertainty
in Ea.

(b)
The rotational partition function is estimated as,

8π 2 IkBT
q =
2

σ h2
R

Only the moment of inertia depends on the bond length. An increase in the H–H
bond length of 10% causes in increase in the estimated rate constant:

(q ) 2
R X′ I ′ 2(0.93×10−10 m ⋅1.1) 2 ⋅ mH
= = = 1.12 = 1.21
(q ) 2
R X
I −10
2(0.93×10 m) ⋅ mH
2

A 10% increase in the H–H bond length in the activated complex leads to a
minor increase in the rate constant of 21%.

57
(c)
There are 3×3 − 5 = 4 vibrational degrees of freedom in the activated complex: two bending modes,
one stretching mode, and the dissociation mode.

The TST rate constant can be increased if the vibrational frequencies are decreased:

1
( qV ) X = ∏
i ⎛ − hν i ⎞
1 − exp ⎜ ⎟
⎝ kBT ⎠
−2
⎡ ⎛ −6.636×10−34 J s× 2193cm −1 × 2.99×1010 cm/s ⎞ ⎤
= ⎢1 − exp ⎜ ⎟⎥
⎣ ⎝ 1.382×10−23 J K −1 ×1000 K ⎠⎦
−1
⎡ ⎛ −6.626×10−34 J s ⋅ 978cm −1 ⋅ 2.99×1010 cm/s ⎞ ⎤
⋅ ⎢1 − exp ⎜ ⎟ ⎥ = 1.445
⎣ ⎝ 1.381×10−23 J K −1 ⋅1000 K ⎠⎦

1
( qV ) X ′ = ∏
i ⎛ − hν i ⎞
1 − exp ⎜ ⎟
⎝ kBT ⎠
−2
⎡ ⎛ −6.636×10−34 J s× 2093 cm −1 × 2.99×1010 cm/s ⎞ ⎤
= ⎢1 − exp ⎜ ⎟⎥
⎣ ⎝ 1.382×10−23 J K −1 ×1000 K ⎠⎦
−1
⎡ ⎛ −6.626×10−34 J s×878 cm −1 × 2.99×1010 cm/s ⎞ ⎤
⋅ ⎢1 − exp ⎜ ⎟⎥
⎣ ⎝ 1.381×10−23 J K −1 ×1000 K ⎠⎦
= 1.542

k ′ qV′ 1.542
= = = 1.07
k qV 1.442

That is only a 7% increase in the rate constant.

(d)

The collision frequency factor z is given as

z = πd 2 u

d is the sum of the reactant radii:

d = rH2 + rH = 0.27 nm + 0.2 nm = 0.47 nm = 4.7 × 10−10 m
u is the relative speed of the reactants:

8kBT
u=
πµ

mH2 mH 2
The reduced mass is found as µ = = mH = 1.108×10−27 kg
mH2 + mH 3

58
 ⎛ 8× (1.38×10−23 J/K ×300 K ⎞
u =⎜ ⎟ = 3085 m/s
⎜ π ×1.108×10−27 kg ⎟
⎝ ⎠

z = π ( 4.7×10−10 m ) ×3085 m/s = 2.14×10−15 m3 / s = 1.29×1015 cm3 mol−1s −1

2

The probability factor P is calculated as the observed A factor divided by the collision frequency
factor:

2.3×1014 cm3 mol−1s −1

P= = 0.18
1.29×1015 cm3mol−1s −1

59