Catalytic Mechanisms

Data Analysis
Chemical Vapor Deposition (CVD)

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors
in which they take place.
 Catalytic Mechanisms

B  C
2A 
 cat

(a)  The initial rate of reaction is shown below

       (A)                         (B)


                            (C)

2
 Catalytic Mechanisms

 B  C
A 

(A) (B)
kPA kPA
rA  rA 
1 K APA  K BPB 1 K APA  KC PC 
(A) (B)

 A S
A  S  
 A S
A  S 
 
A S 
 BS  C A S 
 B  C S

 B  S
BS  
 C  S
C S 
 

3
 Catalytic Mechanisms

 B  C
2A 

(C) (D)
kPA2 kPA2
rA  2
rA 
1 K APA  KCPC  1 K APA  KCPC 2
(C) (D)

 A S
A  S  
 A S
A  S 
 
A S  Ag 
 B  C S A S  A S 
 B  S  C S

 C  S
C S  
 C  S
C S 
 

4
 Catalytic Mechanisms
2A 
 B  C


 A S
A  S 


A S  A S 
 B  C S


 C  S
C S 


kPA2
rA  2
1 K APA  KCPC 
5
 Catalytic Mechanisms

2
4PA
 
 rA0
1  4PA0  K C PC 0
mol
  0.0138
For PC 0  2 atm and PA0  1 atm, then  rA0
kgcat  s
4
 
 rA0 2
 0.0138
1  4  2KC 
One equation and one unknown
K C  6 atm1
2
4PA
6  
 rA0
1  4PA  6PC 2
 Catalytic Mechanisms

 B  C
2A 


 A S  C AS 
A  S 
 rA  rA0  k A PAC V   C AS  K APAC V
 K A 


 B  S  C S
A S  A S  rA  rS  k SC 2AS



 C  S
C S  rA  rDC  k DC CCS  PC C V KC   CCS  KC PC C V


Where KA = 4 atm–1 and KC = 6 atm–1

1) At what is the ratio of sites with A adsorbed to those sites with C
adsorbed when the conversion is 50%?
2) What is the conversion when the sites with A adsorbed are equal
to those with C adsorbed?
7
 Catalytic Mechanisms
2A 
 B  C
B C
A 
 
2 2
K A  4 and KC  6
Ratio of site concentrations
C AS K A PA C V K A PA
 
CCS KC PC C V KC PC
PA  PA0 1 X 1 X
X
PC  PA0
21 X
1 X  P
K A PA0  
C AS 1 X P0 K A 1 X
 2
CCS  X2 P  KC X
KC PA0  
8 1 X P0
 Catalytic Mechanisms
1) At X = 0.5

C AS
~
24 1 0.5
 1.33
CCS 60.5

2) At an equal concentrations of A and C sites, the conversion will be

C AS 2K A 1 X 2K A 24  8

1 , then X   
CCS KC X KC  2K A 6  24  14

X  0.57
9
 Dimethyl Either

2CH 3OH 

 CH 3 – O  CH 3  H 2O
2ME 
 DME  W



Initially water does not exit the reactor the same as DME because
Which of the following best describes the data
A There is more DME than water.
B Steady state has been reached.
C Water reacts with ME.
10 D Water is adsorbed on the surface.
Chemical Reaction Engineering in the Electronics Industry
Chemical Reaction Engineering in the Electronics Industry
ChE 342
Czochralski Crystal Growth – Heat Transfer
Doping of n/p junction – Diffusion
ChE 344
Chemical Vapor Deposition (Catalysis Analogy)
Photo Resist Formation
Photo Resist Dissolution
Etching
The 5 steps
1. Postulate Mechanism
(sometimes first includes a gas phase reaction (then
adsorption, surface reaction and desorption)
2. Postulate Rate Limiting Step
3. Evaluate Parameters in Terms of Measured Variables
4. Surface Area Balance
5. Evaluate Rate Law Parameters
 Chemical Reaction Engineering in the Electronics Industry

13
 Chemical Vapor Deposition

14
 Chemical Vapor Deposition

15
 Chemical Vapor Deposition
1) Mechanism
Gas Phase
Homogeneous

 SiH  H  PH 2 PSiH 2 
SiH 4 
 2 2 rSiH 4  k SiH 4 PSiH 4  
 K P 
Heterogeneous
 fSiH 2 

 SiH  S˜
SiH 2  S˜  rAD  k APSiH 2 f V  
  2
KSiH 2 

 

SiH 2  S˜ 
 S˜  H 2 rDep  rS  k SfSiH 2

16
f V = fraction of surface that is vacant
 Chemical Vapor Deposition
2) Rate Limiting Step
rDep  rS  k SfSiH 2

3) Express fi in terms of Pi
 rAD
0
kA
fSiH 2  KSiH 2 f V PSiH 2

4) Area Balance
 1  fV  fSiH 2  fV  KSiH 2 PSiH 2 f V

17
 Chemical Vapor Deposition
4) Area Balance
1  fV  fSiH 2  fV  KSiH 2 PSiH 2 f V

1
fV 
1 K SiH 2 PSiH 2

5) Combine
 k SKSiH 2 PSiH 2
rDep 
1 KSiH 2 PSiH 2


18
 Homogeneous Reaction

 SiH  H  PH 2 PSiH 2 
SiH 4 
 2 2 rSiH 4  k SiH 4 PSiH 4  
 K P 

rSiH 4 K P PSiH 2
 0  PSiH 2 
 k SiH 4 PH 2

k SK P KSiH 2 PSiH 4 k 1PSiH 4

rDep  
PH 2  KSiH 2 K P PSiH 4 PH 2  K1PSiH 4


19