Kinetics and Reaction Rate Theory:

Surface Reactions
a tutorial
J W Niemantsverdriet
Schuit Institute of Catalysis
Eindhoven University of Technology

The Catalytic Cycle

desorption

adsorption

reaction

Langmuir - Hinshelwood Kinetics

1915
Langmuir Isotherm
1927
Kinetics of Catalytic
Reactions
Cyril Norman
Hinshelwood
1897 - 1967
Nobel Prize 1956

Irving Langmuir
1881 - 1957
Nobel Prize 1932

The Arrhenius Equation

k

+
A

r =

AB

d [AB]

= k [A] [B]

dt

k = ve

- Eact /RT

E
+

Eact

Svante
Arrhenius
1859 - 1927

Nobel Prize 1903

reaction parameter

Empirical !

Temperature Dependence of the Rate

k

A + B

d [AB]
r =
dt

AB

k [A] [B]

1000

8,2
Arrhenius:

900

ln k

800
700

k= ve

600

- Eact / RT

ln k =
ln v

rate

R=

500
400
300
200
100
0
1

200

400 T (K) 600

800

1000

1000 / T

Eact / RT

Reaction Rate Theory

(Transition State Theory)
to rationalize
preexponential factors of surface reactions
adsorption
desorption
dissociation
sticking coefficients
direct versus precursor-mediated adsorption
catalytic mechanisms
Langmuir-Hinshelwood versus Eley-Rideal

Reaction Rate Theory

Molecules collide, but ..
only a small fraction of the
collisions is reactive

collision theory
transition state theory

Reaction Rate Theory

E

reaction parameter

Collision Theory of Reaction Rates:

Reaction:
H + Br2

[H-Br-Br]#

HBr + Br

Hard Spheres
Redistribution of
Kinetic Energy:
H + Br2

[H-Br-Br]#

H + Br2

Collision Theory of Reaction Rates:

Reaction:

Hard Spheres
H + Br2

[H-Br-Br]#

HBr + Br

Redistribution of
Kinetic Energy:
H + Br2

[H-Br-Br]#

H + Br2

Collision Theory
reaction if collision energy > barrier energy
incidentally successful
usually predicts prefactors that are too high
major problem: disagrees with vant Hoff
equation for the equilibrium constant

Reaction Rate Theory

Collision Theory:
hard spheres scatter or react upon collision

Transition State Theory

molecules possess internal degrees of freedom
translation
vibration
rotation
described by statistical thermodynamics
(partition functions)

Ludwig Boltzmann
(1844-1906)

xi =

i / RT

i / RT

i=0

Boltzmann Statistics:
the basis of statistical thermodynamics

S = k ln (W )

Partition Function:

q=

i =0

i / k BT

thermodynamical function of state,

contains information on energy and entropy

Partition Function: q =

i / k B T

i =0

energy

ln q
= kT
T

chemical
potential

entropy

kT ln q
s =
T

(average)

- kT ln q

Partition Function: q =

i / k B T

i =0

chemical
potential

equilibrium
constant

qproducts
K =
qreactants

- kT ln q

All Molecules
vibrate
rotate
translate

Partition Function: q = e

i / k B T

i =0

translation
( 2 m kBT ) 1/ 2
qtrans = l
h
(per dimension!)

may be large if
length l over which
molecule moves
is large

vibration
qvib =

1
1 e

h / k B T

(per vibration!)

usually equals 1
unless vibrations have
very low frequency

rotation
qrot

8 2 Ik B T
=
h2

(per dimension!)

large:
H2: 2.9 at 500 K
CO: 180 at 500 K
Cl2: 710 at 500 K
(2-dimensional!)

Transition
State
Theory

CHads Cads + Hads

on noble metals, e.g. Rh(100)

CHads

Eb

E
CHads

Cads+Hads

reaction coordinate

CHads

Transition state

Cads + Hads

Paco Ample, Dani Curulla, TU/e, 2004

Transition State Theory

R#
K#

Henry Eyring
1901 - 1981

M.G. Evans
& M. Polanyi

kBT
h

kBT #
K
kTST =
h
#

kB T q
-E
=
e
h
q

/kB T

Transition State Theory: The Assumptions

R#
K#
Eb

passage over barrier only in

forward direction

kB T

equilibrium between reactants

and products for all degrees of
freedom, except for reaction
coordinate

passage over barrier is classical

event, described by one
reaction coordinate only

P
reaction coordinate

d [P]
dt

K#

R#

kB T
h

k BT
h

K#[R]
#

k BT q
h

- Eb / kBT

[R]

How to Compare
Transition State Theory
Expressions
with the
Arrhenius Equation?

How to Compare
Transition State Theory Expression
with Arrhenius Equation?

Key:

Eact

ln k
= kT
TST
T
2

Eact = Eb + m k BT

in transition state theory the activation energy is not precisely

equal to the barrier energy

= e

kBT q
h q

m: number of times T appears in the rate expression

The meaning of

Preexponential
Factors

Meaning of Preexponentials

= e
Standard case:
q# q; m = 1

kBT q
h q

=e

kB T
h

1013 s-1

transition state and reactants have same degrees of freedom and similar entropy

Loose TST:
q# >> q; m 1

Tight TST:
q# << q; m 1

1013 << < 1017 s-1

109 <

< 1013

s-1

Loose TST:

Tight TST:

q# >> q

q# << q

R#

R#
Eb

Eb

S# < 0

S# > 0

reaction coordinate
10

<

<

10

13

-1

reaction coordinate
10

13

<

<

10

17

-1

Application to
Surface Reactions:

Adsorption

Adsorption
direct:
(low sticking probability)

or
precursor mediated (trapping mediated):
(high sticking probability)

Adsorption in TST
precursor mediated (trapping mediated):
mobile transition state

rad s =

k BT q
h

- Eb / kBT

[AB]

Collision frequency
gas - surface

#
)2
k B T (qtrans

(qtrans)

#
#
qvib
qrot
qvib qrot

[AB]

Sticking
coefficient

direct adsorption
kads

kBT
h

qtrans2

kBT
h
qtrans3
Collision
frequency

# ads
qvib

qtrans3 qrot qvib

#
qvib

qrot qvib qtrans2

sticking
coefficient

extremely small rate of adsorption

due to lack of mobility in the transition state

precursor mediated adsorption

kads

qtrans2

kBT
h qtrans3

qrot qvib

collision
frequency

sticking
coefficient

qrot qvib

largest possible rate of adsorption:

mobility and free rotation in the precursor state

Adsorption
direct: immobile transition state
low sticking probability: << 10 -4

s=

#
#
qvib
qrot
qvib qrot

1
qvibqrot

<< 1

precursor mediated (trapping mediated):

mobile transition state
high sticking probability: 10

-2

Application to
Surface Reactions:

Desorption

Desorption of Atoms and Molecules

Adsorbed
state

Transition
state

Desorbed
state

Preexponential
factor
15

13

mobile

10

immobile

10

mobile

immobile

10

-1

-1

14-17

13

-1

10

-1

Temperature Programmed Desorption

Temperature
Ultra High Vacuum

Controller

Quadrupole
Mass Analyzer
Rate of desorption

Heating
wires

Thermocouple

Temperature

Single
Crystal

To
Pumps

Thermal desorption of e.g. CO

CO /Rh (1 00 )

C O /R h(111)

T a ds< 2 00 K

=5 K/s

( =5K/s)

CO
0 .7 5 ML
0 .6 8 ML
0 .5 5 ML
0 .4 2 ML

CO desorption rate ( a.u.)

C O Desorption Rate (a.u.)

T ads = 140 K

CO
0 .8 2 ML
0 .8 0 ML
0 .7 7 ML
0 .7 0 ML
0 .6 8 ML
0 .6 2 ML
0 .5 9 ML
0 .4 7 ML
0 .4 3 ML
0 .3 3 ML
0 .2 5 ML
0 .1 7 ML
0 .1 1 ML
0 .0 8 ML
0 .0 4 ML

0 .2 7 ML
0 .1 9 ML
0 .1 2 ML

2 00

3 00

4 00

5 00

6 00

7 00

3 00

Temperatur e (K)

4 00

5 00

6 00

Temperature (K)

Kinetic parameters: Edes = 130 -150 kJ/mol

= 1013 - 1016 s-1

Preexponential Factors

for Desorption at Low Coverages

CO
CO

Co(0001)
Ni(111)

CO
CO
CO
CO
CO
CO
CO
CO
CO
CO

Ni(100)
Cu(100)
Ru(0001)
Rh(111)
Pd(111)

from

Pd(100)
Pd(211)
Ir(110)
Pt(111)

28 kcal/mol
31
37
30
31
16
38
32
34
35
38
35
37
32

1015 s-1
1015
1017
1015
1014
1014
1016
1014
1014
1015
1016
1014
1013
1014

V.P. Zhdanov, Elementary Physicochemical Processes at Surfaces,

Plenum, New York, 1991

LEED of Rh (111)

0.25 ML NH3

Peculiar TPD patterns

NH3 Desorption Rate [a.u.]

Ammonia on Rh(111):

(2x2) NH3

Rh atom
NH3
Rh (111) - (2x2) NH3

100

200

300

400

500

Temperature [K]

Lateral Interactions?
Preexponential Factor?

R. M. van Hardeveld, R.A. van Santen and J.W. Niemantsverdriet

Surface Sci. 369 (1996) 23

NH3 on Rhodium, TPD and Calculations

NH3 on

coverage

Eads (kJ/mol)
TPD

Rh(111)

Rh(100)

0
0.11
0.25

81.53.0

0
0.11
0.25

90.04.0

Calculated

82
70
91
81

F. Frechard, R.A. van Santen, A. Siokou, J.W. Niemantsverdriet and J. Hafner

J. Chem. Phys., 111 (1999) 8124

Lateral Interactions cannot explain the large shift in TPD !

Better explanation: mobile adsorption state, which becomes
hindered at higher coverage

Dissociation:

The CO molecule dissociates in the transition state:

optimal overlap between d- and 2*-orbitals
De Koster and Van Santen

Dissociation of Adsorbed Molecules

O2

Ag(110)
Ag(111)

7.8 kcal/mol
8.3

1.7 109 s-1

1.7 107

O2

Pt(111)

2.5

9.0 1011

N2

Fe(111)

4.3

7.0 107

C2H6

Pt(111)

16.4

8.0 109

C2H2

Pt(111)

13.2

3.0 1012

CH4

Rh film

11

2.

from

1010

C T Campbell, Y K Sun and W H Weinberg,

Chem. Phys. Lett. 179 (1991) 53

Dissociation proceeds through tight transition states

with prefactors smaller than for desorption

Application to
Surface Reactions:

CO Oxidation
LH or ER?

CO oxidation (surface-mediated)
O2
CO2

CO
+

catalyst
adsorption

adsorption

reaction

reaction desorption

desorption

reaction coordinate

Eley - Rideal Mechanism

direct reaction between gas phase
and adsorbed species

How likely is an
E-R event ???

Eley-Rideal or
Langmuir-Hinshelwood
+

CO + 1/2 O2

CO + Oads = CO2
on Rhodium (111)

E
- 42.5

CO + Oads

26.8
kcal/mol

- 74.1

COads + Oads

CO2
CO2,ads

- 67.9

- 73.3

reaction coordinate

in the most favorable case for ER (Eact = 0): kER / kLH = 7 x 10

-6

W H Weinberg, in Dynamics of Gas-Surface Interactions,

(C.T. Rettner and M.N.R. Ashfold, eds.) Royal Society of Chemistry, Cambridge,1991

Fundamental & Applied Catalysis

Knowledge

How much do we know?

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syn

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Acknowledgements
Schuit Institute of Catalysis

TPD-TPSIMS-HREELS
Marco Hopstaken (now Philips)
Martijn van Hardeveld (now Shell)
Herman Borg (now Philips)
Wouter van Gennip (now Philips)
Davy Nieskens
Sander van Bavel
DFT Calculations
Dr Daniel Curulla
Paco Ample (Univ Tarragona)
Tracy Bromfield (Sasol)

Collaborations
TU/e:
Prof Rutger van Santen
Prof Peter Hilbers
Dr Johan Lukkien
Univ Tarragona
Prof Josep Ricart
Funding

NWO, NCF,
Spanish Ministerio de Eduacion
Catalan Government
Eindhoven University of Technology

Concepts of Modern Catalysis and Kinetics

I. Chorkendorff & J.W. Niemantsverdriet
Copyright 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30574-2
Price: 69 Euro