Surface Kinetics

(Unimolecular Reactions)
Lecture 07

John Andrew Kane P. Jovellana

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Outline
Introduction
Unimolecular reactions
Langmuir-Hinshelwood approach
Decomposition reactions
Overview of bimolecular reactions
Eley-Rideal mechanism
Case studies for the cases

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 What do we know so far?
Seven-step model
Catalyst surfaces are not uniform
Adsorption isotherms

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Other Issues
Details still debatable
Lack of accurate knowledge of the structured
chemisorbed particles
Non-uniformity of catalyst surface

Too detailed
Solve this problem
Simple approach
 empirical in nature
 use power law form

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Approach
Model reactions on
uniform (ideal) surfaces
Concept of rate
determining step
GOAL:
Propose a rate
law (for steps 3-5)

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Different Approaches
1. Langmuir-Hinshelwood (L-H)
 Surface reaction is RDS
 Adsorption and desorption: quasi-equilibrium
 Langmuir isotherm

2. Hougen-Watson (H-W)
 Adsorption or desorption is RDS
 Langmuir isotherm

3. Steady-State Approximations (SSA)

 No RDS
 Most abundant reaction intermediate (MARI)

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Active Sites of Catalysts
Reactions are not catalyzed over the entire
surface but only at certain active sites or
centers that result from unsaturated atoms
in the surface.
An active site is a point on the catalyst
surface that can form strong chemical
bonds with an adsorbed atom or molecule.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Recall: Definitions
r a: rate of adsorption
rc: rate of collisions
F: fraction of colliding molecules that
adhere to the surface
p: pressure of the gas
θ: fraction of surface that is covered by
adsorbed molecules (surface coverage)

Note:
ra is proportional to p and (1- θ). But rd is
proportional to θ. Why?
ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018
 Recall: Thus,
ra = rcF
ra = kp(1- θ)
rd = k’ θ

Note:
θ is proportional to the volume of adsorbed
molecules, v. Why?
The adsorption is less than a
monomolecular layer
Note that v is directly measurable; θ is not.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Langmuir Adsorption Isotherms

Associative adsorption

Dissociative adsorption

Competitive adsorption

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Ethylene Hydrogenation on Platinum

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular Reaction: Single-Site
 Example: reversible isomerization of A to B on an
active site, S
 What is the rate law?

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular: Single-Site; Reaction RDS

r=
(
L kK A PA - kK B PB )
 What happens if:
 Reaction is irreversible? 1+ K A PA + K B PB
 Reaction takes places in a differential reactor?
 B is readily desorbed?
ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018
 Differential Reactors for Kinetic Studies
 Differential reactors are running in a very low
conversion mode. They are ‘appropriate' reactors
for kinetic measurements.
 When the conversion is infinitesimally small, the
conversion represents directly the reaction rate.
 It will gain data that may be used to calculate the
rate constant (k), energy of activation (EA) , and
the preexponential factor (A).
 Typical differential reactors are fixed bed reactors
with very low fixed bed heights.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular: Single-Site; Reaction RDS

r=
(
L kK A PA - kK B PB )
1+ K A PA + K B PB

LkK A PA kapp PA
r= =
1+ K A PA 1+ K A PA
ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018
 Unimolecular: Single-Site; Reaction RDS

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular Decomposition;
No additional sites required

What is the rate law?

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular Reactions

If the site balance is not

affected, the rate law (for the
same specializations) will
still be the same.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Case Studies (Single Site)
If chemisorption of A is very strong and A nearly
saturates the surface, then

θA >>> θB, θC, θV and r = kPA0 = k

and the reaction is zero order with respect to A

This was found for the decomposition of ammonia

on W between 973 and 1573 K.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Case Studies (Single Site)
If the surface coverage of all species is low, then

θV >>> θB, θC, θA and r = kPA

This was observed for phosphine decomposition on

Mo near 900 K

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Case Studies (Single Site)
If chemisorption of B is more pronounced than that
of A and C, then

θB >> θA, θC and product inhibition occurs

the rate becomes r = kPA/(1 + KBPB).

This was observed for O2 inhibition during nitrous

oxide decomposition on Pt at about 900 K.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Case Studies (Single Site)
If chemisorption of B is especially strong so that it
nearly saturates the surface, then

θB >> θA, θC , θV and inverse 1st order

dependence on B can occur i.e., r = kPA/PB

This was observed during ammonia decomposition

over Pt between 1273 and 1773 K.

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular decomposition with at least 1
additional site in the RDS (or any step preceding it)

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular decomposition with at least 1
additional site in the RDS (or any step preceding it)

Why not L2?

r=
(
L kK A PA - kK B PB KC PC )
(1+ K A PA + K B PB + KC PC )
2

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Why not L2?

This reaction step requires that [A-S] and [S] are

nearest neighbor sites on the surface
The probability of that to happen is ½(Z/L)
Where Z is the number of nearest neighbor
sites around the site of a surface
Hence, ½(Z/L)(L2) = ½(ZL), and
The rate is always proportional to site density L
(in the regime of kinetic control)

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Unimolecular decomposition with
at least 1 additional site in the RDS

For an irreversible reaction,


Lk K A PA
r
1  K A PA  K B PB  K C PC 2

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Illustration: N2O Decomposition on Mn2O3
Yamashita and Vannice (1996)

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Illustration: N2O Decomposition on Mn2O3

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Illustration: N2O Decomposition on Mn2O3
Model Parameters (from Optimization) for N2O
Decomposition over Mn2O3

At 623 K:

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Eley-Rideal Mechanism
 Reaction is assumed irreversible:

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Eley-Rideal Mechanism
 Reaction is assumed irreversible:

r = kPB [ A - S ] = kLq A PB
LkK A PA PB
r=
1+ K A PA + KC PC
 If B could be adsorbed, but becomes inactive as an
adsorbed species, what happens to the rate law?

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

 Summary
 By now, you should have learned:
 The different approaches in modeling
reactions on surfaces
 How unimolecular reactions are modeled
 The implication of each species on the
site balance
 How certain restrictions affect the
effective rate equations

ChE 126: Chemical Reaction Engineering II A.Y. 2017-2018

Questions?