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Chemical Reaction Engineering (CRE) Is The

Lecture 14 covered the pseudo steady state hypothesis (PSSH) and its application to reaction mechanisms involving active intermediates. [1] The PSSH assumes the net rate of reaction of active intermediates is zero. [2] It was applied to explain the mechanism and temperature dependence of the rate law for the reaction of 2NO + O2 → 2NO2, which involves the short-lived intermediate NO3*. [3] The PSSH allows derivation of the overall rate law from the elementary reaction steps and concentrations of stable species, without having to measure intermediate concentrations.

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56 views21 pages

Chemical Reaction Engineering (CRE) Is The

Lecture 14 covered the pseudo steady state hypothesis (PSSH) and its application to reaction mechanisms involving active intermediates. [1] The PSSH assumes the net rate of reaction of active intermediates is zero. [2] It was applied to explain the mechanism and temperature dependence of the rate law for the reaction of 2NO + O2 → 2NO2, which involves the short-lived intermediate NO3*. [3] The PSSH allows derivation of the overall rate law from the elementary reaction steps and concentrations of stable species, without having to measure intermediate concentrations.

Uploaded by

Mita Agustina
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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Lecture 14

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.
Lecture 14 – Thursday 2/28/2013
 Pseudo Steady State Hypothesis (PSSH)
 Net rate of reaction of active intermediates is zero
 Hall of Fame Reaction: 2NO +O2 2NO2
 Introduction to Enzyme Kinetics
 Begin non-Isothermal reactor design

2
Active Intermediates and PSSH
An active intermediate is a molecule that is in a
highly energetic and reactive state It is short
lived as it disappears virtually as fast as it is
formed. That is, the net rate of reaction of an
active intermediate, A*, is zero.

The assumption that the net rate of reaction is


zero is called the Pseudo Steady State
Hypothesis (PSSH)

3
Active Intermediates and PSSH

4
Example
The rate law for the reaction
A  B C

is found from experiment to be


2
 rA A
kC
1 kCA

How did this rate law come about? Suggest a


mechanism consistent with the rate law.
5
Example
For reactions with active intermediates, the reaction
coordinated now has trough in it and the active
intermediate, A*, sits in this trough

6
Example - Solution
1 A  A  A * A
k1
r1A*  k1C A2

2 A*A 
k2
AA r2 A*  k 2 C A* C A

3 A *  B  C
k3
r3 A*  k3C A*

7
Rate Laws:
k3 is defined w.r.t. A*

Reaction (1) r1A*  k1C 2A (1)

Reaction (2) r2 A*  k2CACA* (2)

Reaction (3) r3 A*  k3CA* (3)

But C*A cannot be measured since it is so small


Relative Rates: r1A  r1A* , r3B  r3 A*
8
Net Rates: Rate of Formation of Product

rB  r3B  r3 A*  k3CA* (4)

Pseudo Steady State Hypothesis r*A = 0

rA*   rA*  r1A*  r2 A*  r3 A* (5)

 k C2  k C C  k C 0 (6)
1 A 2 A A* 3 A*

Solving for CA* 2


CA* 1 A
k C
k3 k 2 C A
9
Substituting for CA* in Equation (4) the rate of
formation of B is
2
rB 1 3 A
k k C (8)
k3 k 2 C A

Relative rates overall


A  B C
rA rB

1 1
2
k k C
rA  rB  1 3 A (9)
k3 k 2 C A
10
For high concentrations of A, we can neglect k3 in
the denominator with respect to k2CA
k2CA  k3
and the rate law becomes
k1k 3
rA   CA  kCA (10)
k2
(apparent first order)

11
For low concentrations of A, we can neglect k2CA in
the denominator with respect to k3.
k3 k2CA
and the rate law becomes
k3k1 2
rA   C A  k1C A2 (11)
k3
(apparent second order)
Dividing by k3 and letting k’=k2/k3 and k=k1 we have
the rate law we were asked to derive
kCA2
 rA   (12)
1 kCA
Active Intermediates
Why do so many reactions follow elementary rate laws?

What about  rA  kCA


kCA
rA  (I  Inert)
1 k'C I
(1) A  I 
k1
 A* I
(2) A* I 
k2
 A I
(3) A 
k3
BC
k1k3CA
- rA 
k2 k2CI
13
Active Intermediates/Free Radicals
and PSSH
Hall of Fame Reaction
The reaction: 2NO +O2 2NO2
has an elementary rate law
rNO2  kCNO
2
CO2
However… Look what happens to the rate as the
temperature increases:

-rNO2

14
T
Why does the rate law decrease with increasing
temperature?
Mechanism:
NO  O2 
 NO3*
k1
(1)

NO NO  O2
*
3
k2
(2)

NO3*  NO 2NO
k3
2
(3)

Write rate of formation of product rNO2


Note: k3 is defined w.r.t. NO3*

15
Define k with respect to NO3 *
Assume that all reactions are elementary
reactions, such that:

r1NO3  k1CNOCO2  k1 NOO2 


r  k C  k NO* 
*
2NO
3
2 NO
*
3
2 3

r3NO  k3CNO CNO  k3  NO3*  NO


* *
3 3

rNO  2 r3NO* 
2  3

16
The net reaction rate for NO3* is the sum of the
individual reaction rates for NO3*:

r1NO*  r1 r1NO*  k1NOO2 


3 3

r2NO*  r2  r2NO*  k2 NO *


3
3 3

r3NO*  r3  r3NO*  k3  NO3*  NO


3 3

rNO*  r1NO*  r2NO*  r3NO*


3 3 3 3

rNO*  k1 NO O2  k2  NO   k3  NO  NO


*
3
*
3
3
17
Pseudo Steady State Hypothesis (PSSH)
The PSSH assumes that the net rate of species A*
(in this case NO3*) is zero.

rNO*  0
3

0  k1 NO O2  k2  NO3*   k3  NO3*  NO

0  k1 NO O2   NO3*  k2  NO

k1 NOO2 
 NO  
*
 3
k2  k3 NO
18
Pseudo Steady State Hypothesis (PSSH)

𝑘1 𝑁𝑂 𝑂2
[𝑁𝑂3∗ ] =
𝑘2 + 𝑘3 𝑁𝑂

3
 
rNO2  2r3NO*  2 NO NO
*
3

k1 k3 NO 2 O2
𝑟𝑁𝑂2 = 2
k2 + k3 NO

19
Pseudo Steady State Hypothesis (PSSH)
k2  k3 NO
E2 E1 E3 

rNO2 2
k1k3
NO O2  2
2 A1A3
e RT
NO O2 
2

k2 A2
E2  E1  E3 

This result shows why the -rNO2


rate decreases as
temperature increases.
T
20
End Lecture 14

21

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