Lecture 5.

Surface Reaction Kinetics

5-1. Mechanism of surface reactions

Macro-diffusion Mass transport (bulkmacropore)

Diffusion In
Micro-diffusion Mass transport(macromicropore)

Adsorption Boundary  Surface

5단계
Five
Reaction Surface Reaction
steps

Desorption Surface  Boundary

Micro-diffusion Micropore  Macropore

Diffusion Out
Macro-diffusion Macropore  bulk

Overall crystal growth rate ~ “rate limiting step”

Organometallic Metal Atom

precursor
Organic Ligand

Main flow

Boundary layer
① ② ④
③

Substrate

① Adsorption& dissociation ② Desorption

③ Surface diffusion ④ Incorporation

1
 A( g ) + B ( g ) → AB ( g )
Langmuir-Hinshelwood Eley-Rideal Precursor-mediated
A B B B
AB AB AB
diffuse rebound
Bad Aad AB Aad AB Bt Aad AB

CH4 heating
C2H4(ad)+2H(ad) C2H6(ad) CH3,g + As products COt + 2O(ad) CO2

/ Pt(110) / Pt(100)

Evidence: - chemisorbed CO
CVD diamonds
is unreactive,
(At extreme conditions)
TPD (temperature - Even at very small θ 0 ,
programmed desorption) reaction probability ~ 1

Pulsed Beam Technique

Most of organic molecules
on transition metal surfaces
No time delay Time delay between
Products & unreacted
Reactants ~ 100 µ sec
Dominate in UHV
(gas-phase collisions Gas/surface collision Residence time of
negligible) ~ picoseconds Precursor ~ 100 µ sec

Dominate

<

Plasma process,
highly excited species

2
5-2. Unimolecular reaction.

A(g)
KA

kr
A products

K A [ A]
kr ⋅ θ A
rate = then, θ A =
1 + K A [ A]

kr ⋅ K A [ A]
=
1 + K A [ A]

ex) NH3/W

rate=kr (zero-order kinetics)

high pressure limit
kapp
rate

rate=krKA[A] (first-order kinetics)

low pressure limit

If I (Inhibitor) is present, then

kr ⋅ K A [ A]
rate =
1 + K A [ A] + K I [ I ]

if K I [ I ] >>
1 + K A [ A]

kr ⋅ K A [ A]
Then rate ≅ NH 3 / Pt , H 2 inhibitor
KI [I ]

3
5-3. Bimolecular reaction.

A. Langmuir-Hinshelwood [L-H]

Competitive adsorption

rate = kr ⋅ θ A ⋅ θ B

kr ⋅ K A ⋅ K B [ A][ B]
=
(1 + K A [ A] + K B [ B])2
- If [A], [B] is very small, rate ≈ kr ⋅ K A ⋅ K B [ A][ B ]

kr ⋅ K A ⋅ K B [ A][ B ]
- If A is weakly adsorbed, rate 
(1 + K B [ B])2

kr ⋅ K A [ A]
and if B is strongly adsorbed, rate = ex) CO, O2 / Pt , Quartz
K B [ B]
[B] ~ [CO]

Non-competitive adsorption

kr ⋅ K A ⋅ K B [ A][ B ]
rate = ex) H2 , NO / Au
(1 + K A [ A])(1 + K B [ B])
H2 , CO2 / W

B. Eley-Rideal [E-R]

rate= kr ⋅ θ B [ A]

kr ⋅ K B [ A][ B ]
=
1 + K A [ A] + K B [ B ]

4
C. Inhibition [I]

K A [ A]
θA =
1 + K A [ A] + K B [ B ] + K I [ I ]

K B [ B]
θB =
1 + K A [ A] + K B [ B ] + K I [ I ]

kr ⋅ K A ⋅ K B [ A][ B ]
rate =
(1 + K A [ A] + K B [ B] + K I [ I ])2

If K I [ I ]  >>

kr ⋅ K A ⋅ K B [ A][ B ]
then rate = 2
K I ⋅ [ I ]2

5
5-4. If product coverage is considered, then

A(g) B(g)
KB C(g)
KA
A + B C
θ A ,θ B ,θ C

θ A = K A ⋅ PA (1 − θ A − θ B − θC )

θ B = K B ⋅ PB (1 − θ A − θ B − θC )

dθ C
= kr ⋅ θ A ⋅ θ B − kd ⋅ θC ≈ 0
dt

kr
⇒ θC = ⋅θ A ⋅θB
kd

kr
따라서, θ A = K A ⋅ PA (1 − θ A − θ B − ⋅θ A ⋅θB )
kd

kr
θ B = K B ⋅ PB (1 − θ A − θ B − ⋅θ A ⋅θB )
kd

coupled & non − linear

if θC → 0 ,

K A ⋅ PA
kd >> then, θ A =
1 + K A PA + K B PB

K B ⋅ PB
θB =
1 + K A PA + K B PB

⇒ Langmuir − Hinshelwood equation rate = kr ⋅ θ A ⋅ θ B

kr ⋅ K A ⋅ K B ⋅ PA ⋅ PB
=
(1 + K A ⋅ PA + K B ⋅ PB ) 2

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5-5. Example
2CO + O2 → 2CO2 / Pt , Pd , Rh

Mechanism

K

CO( g ) ← → CO(ad )


k1
O2  → 2O(ad )

k2
CO(ad ) + O (ad )  → CO2 (ad )

kd
CO2 (ad )  → CO2 ( g )

Assumptions: Desorption (CO2) fast, O2 adsorption slow, CO strongly adsorbs

θCO =⋅
K PCO (1 − θCO ) ⇐ θCO2 is also very low
θO is very low
K ⋅ PCO
θCO =
1 + K ⋅ PCO

steady state for O(ad )

dθ o
= 2k1 ⋅ PO2 (1 − θCO ) 2 − k2 ⋅ θCO ⋅ θO ≈ 0
dt
because θ o , θCO2 is low.

rate =k2 ⋅ θCO ⋅ θO

=2k1 ⋅ PO2 (1 − θCO ) 2

2k1 ⋅ PO2
= ⇐ CO is excessive
(1 + K ⋅ PCO ) 2
inhibition