9/9/2015

Assembling Elementary Steps into 
Reaction Cycles
• An Ethane Pyrolysis Example
– Commercially important process for olefins 
production (ethylene)
– Main products are ethylene and hydrogen
– Modern models need to be able to predict BTX 
and other byproducts as well
– Classical illustration of Rice‐Herzfeld chain 
mechanism

Ethane Pyrolysis Mechanism

C2 H 6 
 2CH 3 
CH 3  C2 H 6 
CT
CH 4  C2 H 5 
C2 H 5  

1
H  C 2 H 4
C2 H 6 
K
H 2  C2 H 4
H  C2 H 6 
11
H 2  C2 H 5 
E* ~ 68kcal / mol 2C2 H 5  
 C4 H10
n  0.5  1.5 2H  
 H2

2CH 3  
 C2 H 6

C2 H 5   H  
 C2 H 6

CH 3   H  
 CH 4

CH 3  C2 H 5  
 C3 H 8

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Kinetics Analysis
rC2 H 6  C2 H 6  kCT CH 3  C2 H 6  k11 H  C2 H 6  H  C2 H 5 

The object is to obtain a rate law with only

observables (molecules) and parameters, using
kinetics tools to eliminate the unobservables
(radicals)

Kinetics Tools:
1. Steady state approximation
2. Comparison of predicted and observed products
3. Long-chain approximation

Kinetics Analysis
rC2 H 6  C2 H 6  kCT CH 3  C2 H 6  k11 H  C2 H 6  H  C2 H 5 

Kinetics Tools:

1. Steady state approximation dH  / dt  dC2 H 5  / dt  dCH 3  / dt  0

2. Comparison of predicted and observed products: CH4 minor

3. Long-chain approximation: H2 and C2H4 major products

rC2 H 6  C2 H 6  k11 H  C2 H 6  H  C2 H 5 

Suppose H + C2H5 is main termination step

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Kinetics Analysis
Suppose H + C2H5 is main termination step
H : 0  k1C2 H 5  k11 H  C2 H 6  H  C2 H 5  Substituti ng for H 
C 2 H 5  : 0  k1C2 H 5   k11 H  C2 H 6  H  C2 H 5   kCT CH 3  C2 H 6 ( /  )
C2 H 5   C2 H 6
CH 3  : 0  2C2 H 6  kCT CH 3  C2 H 6 H
0  k1C2 H 5   k11 H  C2 H 6  H  C2 H 5 
Therefore
becomes
C 2 H 5  : 0  k1C2 H 5   k11 H  C2 H 6  H  C2 H 5  2C2 H 6 ( /  ) ( /  )
0  k1 C2 H 6  k11 H  C2 H 6  H  C2 H 6
Adding H  and C 2 H 5  : H H
2C2 H 6  2H  C2 H 5  k11C2 H 6 H  C2 H 6 H   k1 ( /  )C2 H 6
2

This is the Steady State Approximation     2  4k11k1 / 

H 
The creation and destruction of radicals are balanced 2k11
rC2 H 6  C2 H 6  k11 H  C2 H 6

    2  4k11k1 / 
rC2 H 6  C2 H 6  k11 C2 H 6
2k11
 2  4k11k1 / 
   4k11k1 / 
rC2 H 6  C2 H 6  C2 H 6
2

C2 H 6  k11k1 /  C2 H 6
rC2 H 6 
2
  k11k1 / 
k  k11k1 /  , n  1

Long Chain Kinetics Analysis Substituting for H 

( /  )
C2 H 5   C2 H 6
H
0  k1C2 H 5   k11 H  C2 H 6
provides
k11 H 
C2 H 5   C2 H 6
k1
therefore
k1
H 2 
k11
k1k11
r  k11 H  C2 H 6  C2 H 6


• Repeat for H‐H termination
• Repeat for C2H5‐C2H5 termination

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Abstraction of Reaction Cycles:

Overall Reaction A B + C


Elementary Steps A  2


+ A   + B


  C+ 


2 , 2 ,  +   T.P.

 are "in situ" catalysts in this Rice-Herzfeld cycle.

Reactions 7 © Michael T. Klein

The Simplification of
Statistical Termination
A A
Cross Termination Twice as Likely
As Self Termination
B B

A    2       2

A   (  2  2   2 )   (    ) 2
LCA : k11 A  k1
2
2k11 A k11 A k A
A   2 (1  ( ))   2 (1  11 ) 2
k1 k1 k1
k11 A3 / 2 ( /  )1/ 2 k11 A3 / 2 ( /  )1/ 2
r  k11 A  1/ 2

 2k11 A k11 A 2  k A
1    1  11
 k1  k1
Reactions
 k1
8 © Michael T. Klein

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Ethane Pyrolysis and NetGen

Molecules as Graphs

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Reactions as Matrices

Generating Reactions on the 
Computer

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Machine Mimicking Human Logic

NetGen Output: The Ethane 
Pyrolysis Mechanism

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Light Gas Thermal Cracking Model Predictions

A Simple Approximation
• The LCA provides an analytically tractable 
solution
• All chain lengths may not be high (long)
• For short chains, fission step may control
• Investigate the approximation:

ri  rLCA  rexact

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RH Construct for Approximate Solution

Analysis
Full Solution with Statistical Termination:

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Full Solution

Long Chain Solution

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Approximate Solution

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