CHEN4235

Surface Reactions and Kinetics

1:10 – 2:25pm, Tuesday and Thursday

Instructor: Jingguang Chen (jgchen@columbia.edu)

TA: Zhexi Lin (zl2453@columbia.edu)

- Textbook: Principles of Adsorption and Reaction on Solid

Surfaces, Richard I Masel, Wiley Series in Chemical
Engineering, 1996, Wiley and Sons;
- Class Handouts and Lecture Notes
 Syllabus
Jan. 12, 14 Nomenclature and definition of surface structures. Mathematical methods
in converting surface structures between real and reciprocal spaces.
Jan. 19, 21 Principles of experimental techniques in characterizing surface structures.
Jan. 26, 28 Kinetics and thermodynamics of adsorption on surfaces.
Feb. 2, 4, 9 Kinetics and thermodynamics of chemical reactions on surfaces;
Principles and application of experimental techniques in characterizing
surface reactions and intermediates
Feb. 11 Midterm 1
Feb. 16 Guest lecture: density functional theory (DFT).
Feb. 18, 23, 25 Kinetics and thermodynamics of desorption from surfaces. Temperature
programmed desorption.
Mar. 2, 4 No class; Spring Break
Mar. 9, 11 Surface kinetic modeling of adsorption, reaction, and desorption processes.
Mar. 16 Midterm 2
Mar. 18 Correlating kinetics and thermodynamics.
Mar. 23, 25, 30 Effect of surface electronic structures on kinetics.
April 1, 6, 8, 13 Transport effects on kinetics.
April 15 Class overview.
April ?? Final Exam
Overall Course Grade
HW: 10%; Midterm 1: 30%; Midterm 2: 30%; Final: 30%
 Review of Chemical Engineering Kinetics

- To increase the rate of desired reactions (rD)

- To decrease the rate of undesired reactions (rU)

Example:
A → D (desired reaction with rate constant kD)
A → U (undesired reaction with rate constant kU)

rD = kD CAa CDd
rU = kU CAb CUu

Question: why should the rate depend on the product, CDd

 Review of Chemical Engineering Kinetics
Examples of desired and undesired reactions:

A → D (desired reaction with rate constant kD)

C2H4 + ½ O2 → C2H4O (ethylene epoxide)

A → U (undesired reaction with rate constant kU)

C2H4 + 3O2 → 2CO2 + 2H2O (greenhouse gas CO2;
wasteful of hydrocarbon resources)
In some cases it is more important to decrease rU than to
increase rD:
- Pharmaceutical: undesired products cause side-effects
- Chemical: product separation is often costly
- Electrochemical: CO2 reduction instead of H2O reduction
 Review of Chemical Engineering Kinetics

There are two ways to increase the rate of desired reactions

(rD) or to decrease the rate of undesired reactions (rU)
rD = kD CAa CDd
rU = kU CAb CUu

1. Reactor design: Depending on whether a > b or a < b,

select different reactors (Batch, CSTR or PDF) and/or
reactor configurations (multiple reactors in series or
parallel)
- CSTR (continuous stirred tank reactor)
- PFR (plug flow reactor)
2. Utilization of catalysts (focus of current class)
 Effects of Catalysts on Kinetics

rD = kD CAa CDd
rU = kU CAb CUu

1. Modify (increase or decrease) rate constants: activation

barrier and entropy
2. Change the values of a, b, d, u in both magnitude (i.e.,
first-order, second-order, fractional order) and sign
(positive or negative): different rate-determining steps
3. Increase concentration of CA: higher local concentration of
reactant A

Definition of catalysts: Materials that modify the rate of a

reaction without being consumed/produced
 Definition of Rate Constant

rD = kD CAa CDd
rU = kU CAb CUu

k = A exp [-EA/RT]
Definition:
EA: Activation barrier of a reaction step (related to enthalpy)
A: Pre-exponential factor (related to entropy)
R: Gas constant
T: Absolute temperature (K)
Reaction rate (rate constant k) can be increased by
decreasing EA and/or increasing A
 Illustration of Catalytic Effects on Kinetics

- The presence of a catalyst decreases EA, and

consequently increases k and the rate of reaction
- However, a catalyst does not change the thermodynamical
values (DH, DG) of the overall reaction of A → D
 Illustration of Reaction Steps on Catalyst Surfaces

Catalysis involves several steps: transport/diffusion,

adsorption, surface reaction, and desorption. It is critical to
identify which one is the rate-determining step.
 Reaction Steps on Catalyst Surfaces

1. A (bulk) → A (near catalyst surface)

Transport: Concentration of CA (or PA) might be different from
experimentally-measured CAo (or PAo) if reaction is transport-limited
2. A + S → A-S
Adsorption: Rate of adsorption (kinetics) and equilibrium coverage
of adsorbates (thermodynamics – adsorption isotherm)
3. A-S → D-S
Surface reaction: Rate of reaction (kinetics)
4. D-S → D (near catalyst surface)
Desorption: Rate of desorption (kinetics) and binding energy of
adsorbates (thermodynamics)
5. D → D (bulk)
Transport: Concentration of CD (or PD) might be different from
experimentally-measured values if reaction is transport-limited
 Sequence of Lectures (Principles & Techniques)

1. Structures of catalyst surfaces

2. Adsorption kinetics and thermodynamics

3. Surface reaction kinetics and rate laws

4. Desorption kinetics and correlation with adsorption

5. Correlating kinetics (adsorption, surface reaction,

desorption) with thermodynamic properties of catalysts
(adsorption energy, surface structures, electronic
properties)

6. Effect of transport limitation on reaction kinetics (reaction

order, activation barrier, product selectivity)
 Objectives of CHEN4235

1. Understand how fundamental properties of catalysts

control the rates of adsorption, surface reaction and
desorption?

2. How to design catalysts to enhance reaction kinetics?

- Conversion of reactants (increasing k)
- Product selectivity (increasing kD/kD)
- Catalyst stability (decreasing k for deactivation reactions)
- Transition from “trial-and-error” to rational design of catalysts
based on fundamental understanding

3. Examples of fundamental properties:

- Electronic: Pt (d8) vs. Au (d10)
- Structural: Pt(100) surface (Pt cube) vs. Pt(111) surface (Pt
pyramid)
 Review of Ideal Reactors
- Batch Reactor:
- No inflow, no outflow
- Uniform CA and T throughout reactor
- dCA/dt = f(t)

- CSTR:
- Steady-state inflow and outflow
- Uniform CA and T throughout reactor
- dCA/dt = 0

- PFR:
- Steady-state inflow and outflow
- Non-uniform CA and T along direction of flow; uniform CA and T
normal to the direction of flow
- dCA/dt = 0; dCA/dt = f(t)
- t = VCAo/FAo (homogeneous); t = WCAo/FAo (heterogeneous);
Single and Multiple Reactors
Design Equations for Ideal Batch Reactors
Design Equations for Ideal CSTR
Design Equations for Ideal PFR