Tutorial 2:

- Reactions on Metals
Jimmy Faria
Catalytic Processes and Materials
MESA+ Institute of Nanotechnology

14/09/2018 Master Course

Meeting 1
 Learning targets
- Derive and apply LH and Eley-Rideal mechanisms of
reaction on metal surfaces
- Analyze the effects of heat of adsorption on the
reaction rates

2
 Deriving rate expressions

Agas + X A-X Equilibrium, kads and k-ads

A-X B-X RLS and kr=k-r

B-X Bgas + X Equilibrium, kdes and k-des

a) What is the reaction order with respect to A and B if there is strong

adsorption of B on the catalyst site

Hint: KB*PB >>1, Coverage q ~ 1

b) What is the overall activation energy in this scenario? Show the results in
a the form of an energy diagram.

3
 Deriving rate expressions
A-X B-X If there is strong adsorption
! = #$ ∗ &' − #)$ ∗ &* Eq. 1 #$ ∗ +' ∗ ,'
!= Eq. 6
+* ∗ ,*
Coverage for A and B
+' ∗ ,' #$ ∗ +' ,'
!= ∗ Eq. 7
&' = Eq. 2 +* ,*
1 + +' ∗ ,' + +* ∗ ,*

+* ∗ ,* −3 − ∆8' − 6∆9
&* = Eq. 3 #$/ ∗ 012 564 ∗ 012 56 ,'
1 + +' ∗ ,' + +* ∗ ,* != ∗ Eq. 8
− ∆8* − 6∆9 ,*
012
56
Combining 1,2, and 3 we obtain
#$ ∗ +' ∗ ,' − #)$ ∗ +* ∗ ,* − 34 + ∆8' − ∆8* ,'
!= Eq. 4 ! = #$/ ∗ 012 ∗ Eq. 9
1 + +' ∗ ,' + +* ∗ ,* 56 ,*

If the reaction is irreversible, then

3/:; = 34 + ∆8' − ∆8* Eq. 10
#$ ∗ +' ∗ ,'
!= Eq. 5
1 + +' ∗ ,' + +* ∗ ,*

4
 Deriving rate expressions
For example:
!"#$ = ! + ∆()*$+ − ∆()*$- !"#$ = ! + [∆()*$+ − ∆()*$- ]
!"#$ = 1 + −0.25 − −0.5 =>
Note that: !"#$ = 1.25 ev
−∆.?/1 = ∆./01 A#-M

A(g) + B(g) + M
B(g)

E ~ 2 ev
∆.5 ~-1ev
Energy

Eobs
∆.34
∆./012 ~1.5 ev A-M

A(g) + B-M

B-M

Reaction coordinate 5
 Decomposition of N2O on metals
2N2O
2N2

N2O N2O N2 N2 O O O O

Metal Metal Metal

O2
Metal

Questions:
1) Derive the rate expression
2) Determine the reaction order for PN2O and PO2 when KN2O*PN2O<<KO2*PO2
3) How does it change when a catalyst with stronger interaction with N2O is
employed?
6
 Decomposition of N2O on metals
Derived the rate expression for N2O decomposition:

2 [N2O + S <------> N2O-S] Quasi-equilibrated

2 [N2O-S ------> N2 + O-S] Rate Determine Step

2 O-S ------> O2 + 2 S Quasi-equilibrated

2 N2O ------> 2 N2 + O2

$%&'( )&'(
!" = ,/' ,/' Rate expression
1 + %&'( )&'( + %(' )('
7
 Decomposition of N2O on metals
$%&'( )&'(
1) If KN2O*PN2O << KO2*PO2 !" = ,/' ,/'
1 + %&'( )&'( + %(' )('
Very small
Negative order –
$%&'( )&'( Competitive product
!" = ,/' ,/' adsorption
%(' )('

$%&'( )&'(
2) If KN2O*PN2O >> KO2*PO2 !" = ,/' ,/'
1 + %&'( )&'( + %(' )('

Very small

!" = $ Zeroth order -

Surface is saturated
with the reactant 8
 Rate vs. Temperature
Using the previous equation determine the reaction rate profile as a function of
temperature (between 200 and 725 ºC) and comment the following points:
1) Discuss the trends observed
2) At what temperature does the rate reach its maximum?
Kinetic Parameter Values
P of N2O 200
P of O2 300
Ao 1.00E+10
Ao of N2O 1.00E-12
Ao of O2 1.00E-12
△H of N2O -23000
△H of O2 -27000
Ea 15000

9
 Solution:
T (C) k KA KB rate
200
215
1.2E+03
1.9E+03
4.2E-02
2.0E-02
3.0E+00
1.2E+00
2.2E+01
4.0E+01 Maximum at around
1.E+03
230
245
3.0E+03
4.7E+03
9.9E-03
5.1E-03
5.4E-01
2.5E-01
7.1E+01
1.2E+02
350 C.
260 7.1E+03 2.7E-03 1.2E-01 2.0E+02
275 1.0E+04 1.5E-03 5.9E-02 3.1E+02
290 1.5E+04 8.5E-04 3.0E-02 4.5E+02 8.E+02
305 2.1E+04 5.0E-04 1.6E-02 6.0E+02
320 3.0E+04 3.0E-04 8.9E-03 7.4E+02
335 4.1E+04 1.9E-04 5.1E-03 8.4E+02
350 5.5E+04 1.2E-04 3.0E-03 8.7E+02 6.E+02

Rate
365 7.3E+04 7.6E-05 1.8E-03 8.6E+02
380 9.5E+04 5.0E-05 1.1E-03 8.1E+02
395 1.2E+05 3.4E-05 6.8E-04 7.5E+02
410 1.6E+05 2.3E-05 4.4E-04 6.8E+02 4.E+02
425 2.0E+05 1.6E-05 2.8E-04 6.1E+02
440 2.5E+05 1.1E-05 1.9E-04 5.5E+02
455 3.1E+05 8.0E-06 1.3E-04 4.9E+02
470 3.9E+05 5.8E-06 8.8E-05 4.4E+02
485 4.7E+05 4.3E-06 6.1E-05 4.0E+02
2.E+02
500 5.7E+05 3.2E-06 4.3E-05 3.6E+02
515 6.9E+05 2.4E-06 3.1E-05 3.3E+02
530 8.3E+05 1.8E-06 2.2E-05 3.0E+02
545 9.8E+05 1.4E-06 1.6E-05 2.7E+02 0.E+00
560 1.2E+06 1.1E-06 1.2E-05 2.5E+02 0 200 400 600 800
575 1.4E+06 8.5E-07 9.1E-06 2.3E+02
590
605
1.6E+06
1.8E+06
6.7E-07
5.3E-07
6.9E-06
5.3E-06
2.1E+02
2.0E+02
Temperature (◦C)
620 2.1E+06 4.3E-07 4.1E-06 1.8E+02
635 2.5E+06 3.4E-07 3.2E-06 1.7E+02
650 2.8E+06 2.8E-07 2.5E-06 1.6E+02
665 3.2E+06 2.3E-07 2.0E-06 1.5E+02
680 3.6E+06 1.9E-07 1.6E-06 1.4E+02
695 4.1E+06 1.6E-07 1.2E-06 1.3E+02
710 4.6E+06 1.3E-07 1.0E-06 1.2E+02
725 5.2E+06 1.1E-07 8.2E-07 1.1E+02

10
 Selecting the appropriate catalyst
1) Which catalyst is the most
active and why?

2) Can you explain this in

terms of the Oxophilicity of
the metals (PS)?

Plot of heat of formation per equivalent, -

(AH.) against the catalytic activity (defined as
the temperature, in “C, at which the reaction
first becomes appreciable) of the shown
oxides for the decomposition of N2O.

A. K. Vijh, Sabatier-Balandin Interpretation of the Catalytic Decomposition

of Nitrous Oxide on Metal-Oxide Semiconductors, Journal of Catal. 31, 51-54 (1973)
11
 Dissociation of Hydrogen
1. For the hydrogenation reactions,
Ni supported catalysts are always
pretreated in hydrogen whereas H2
pretreatment is not required for Au
supported catalyst.

The volcano plot for the biding of

oxygen to metal surfaces is given in
the Figure.

Give an explanation based on the

volcano plot why pretreatment is an
important step prior to
hydrogenation reactions for Ni
supported catalysts.

Metals such as Cu and Ni bind oxygen too strongly. For metals that bind oxygen too strongly
the activity is limited by the removal of adsorbed O and OH species; that is, the surface
becomes quickly oxidized and thus unreactive. For metals such as Ag and Au, the opposite is
true and it is difficult to bind oxygen onto the metal surface. For these metals the rate is
limited by dissociation of O2.
12
 Oxidation Reactions
For the epoxidation of ethene (C2H4) to ethylene epoxide (C2H4O) following reaction
mechanism is observed

C2H4O
+1/2O2 a) What conditions (in terms of partial pressure of O2
(PO2) and rate constants of reaction (K1, K2) are
K1 desirable to favor the selective formation of C2H4O?

C2H4 K1 >> K2 and low PO2

K3 +5/2O2

K2 b) What should be the conditions (in terms of PO2

+3O2 and PC2H4O) to suppress the conversion of C2H4O to
CO2?
2CO2 + 2H2O
PO2 and PC2H4O low to suppress formation of CO2
from C2H4O. The concentration of ethylene oxide
in the outlet of the reactor is only 1-2% to
suppress formation of CO2 from C2H4O.

13
 Hydrogenation of Alkanes
Alkene hydrogenation is a thermodynamically favorable reactions, however, it will not proceed
without a catalyst. The mechanism of ethene hydrogenation is shown here.

H2
CH2CH2

H H H H H2C CH2 HH H H H2C CH2

Metal Metal

H3C CH3 H3C

HH HH H CH2

Metal Metal

14
 Hydrogenation of Alkanes
Based on the volcano plot, suggest
the appropriate metal catalyst for
the hydrogenation of an alkene.
Give the motivation for the choice
of catalyst.

The mechanism involves hydrogen

dissociation as one of the steps of
importance in the reaction. There is also
C-M adsorption, but no information is
given regarding the C-M bonding to the
surface. If the rate limiting step is the
hydrogen dissociation, then it will be
possible to achieve maximum activity on
Pt, Rh, and Ir.

If the rate limiting step is the insertion of

the hydrogen (hydrides) in the ethylene,
then other considerations should be
included. For example, geometric effects
of the surface and the surface coverage.
15