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Chemical Reaction Engineering (CRE) Is The

The document discusses chemical reaction engineering and covers several topics: 1. It introduces the pseudo steady state hypothesis (PSSH), which assumes the net rate of reaction of active intermediates is zero. 2. It uses the example reaction 2NO + O2 → 2NO2 to illustrate PSSH and how the rate law decreases with increasing temperature. 3. It provides a step-by-step derivation of the rate law rA = kCA2/(1 + k'CA) from a proposed reaction mechanism involving an active intermediate.

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Abhinav Shukla
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76 views21 pages

Chemical Reaction Engineering (CRE) Is The

The document discusses chemical reaction engineering and covers several topics: 1. It introduces the pseudo steady state hypothesis (PSSH), which assumes the net rate of reaction of active intermediates is zero. 2. It uses the example reaction 2NO + O2 → 2NO2 to illustrate PSSH and how the rate law decreases with increasing temperature. 3. It provides a step-by-step derivation of the rate law rA = kCA2/(1 + k'CA) from a proposed reaction mechanism involving an active intermediate.

Uploaded by

Abhinav Shukla
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
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 2/24/2011
 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
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
4
The rate law for the reaction

A  B C

is found from experiment to be


2
kC
 rA  A
1  k C A
How did this rate law come about? Suggest a mechanism
consistent with the rate law.

5
For reactions with active intermediates, the reaction
coordinated now has trough in it and the active intermediate,
A*, sits in this trough

6
1 A  A  A * A
k1
r1 A*  k1C A2

2 A * A  A  A
k2
r2 A*  k2CA*CA

3 A *  B  C
k3
r3 A*  k3C A*

7
k3 is defined w.r.t. A*
Reaction (1) r1 A*  k1C 2
A
(1)

Reaction (2) r2 A*  k2CACA* (2)

Reaction (3) r3 A*  k3C A* (3)

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


r1 A  r1 A* , r3B  r3 A*
8
Rate of Formation of Product

rB  r3B  r3 A*  k3C A* (4)

Pseudo Steady State Hypothesis r*A = 0

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

 k1C  k 2C AC A*  k3C A*  0
2
A (6)

Solving for C A*
k1C A2
C A* 
k3  k 2C A
9
Substituting for C A* in Equation (4) the rate of formation
of B is
k1k3C A2 (8)
rB 
 k3  k 2C A

Relative rates overall


A  B C
rA rB

1 1
k1k3C A2 (9)
rA  rB  
k3  k 2C A
10
For high concentrations of A, we can neglect k 3 with regard to
k2C A , i.e.,
k2C A  k3

and the rate law becomes

k1k3
rA   C A  kCA (10)
k2

Apparent first order.

11
For low concentrations of A, we can neglect k 2CA with regard
to k3, i.e.,
k3  k2C A
and the rate law becomes

rA  
k3k1 2
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 C A
12
Why 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
k1k3C A
- rA 
k 2  k 2C I
13
Hall of Fame Reaction
The reaction 2NO +O2 2NO2
has an elementary rate law
rNO2  kC CO2
2
NO
However… Look what happens to the rate as the temperature is
increased.
-rNO2

14 T
Why does the rate law decrease with increasing temperature?

:
(1)
NO  O 2  NO
k1 *
3

(2)
NO  NO  O 2
*
3
k2

(3)
NO  NO  2 NO2
*
3
k3

Write Rate of formation of Product rNO2


Note: k3 is defined w.r.t. NO2
15
NO3*
Assume that all reactions are elementary reactions, such
that:

r1NO3 = k1CNOCO2 = k1 [ NO][O2 ]

r2 NO* = -k2CNO* = k2 éë NO ùû *
3
3 3

r3NO* = -k3CNO* CNO = k3 ë NO3 ùû [ NO]


é *
3 3

rNO = 2 é -r3NO* ù
2 ë 3 û

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

r1NO* = r1 Þ r1NO* = k1[ NO] [O2 ]


3 3

-r2NO* = r2 Þ r2NO * = -k2 [ NO3* ]


3 3

r3
-r3NO = Þ r3NO = - k3 [ NO3* ] [ NO]
1
* *
2 3 2
3

rNO* = r1NO* + r2NO* + r3NO*


3 3 3 3

= k1[ NO] [O2 ] - k2 [ NO ] - k3 [ NO3* ] [ NO]


1
rNO* *
3
17
3 2
The PSSH assumes that the net rate of species A* (in this
case NO3*) is zero.
rNO *  0
3

0 = k1 [ NO] [O2 ] - k2 ë NO û - k3 ë NO3 ùû [ NO ]


1
é *
3 ù é *

2
0 = k1 [ NO] [O2 ] - éë NO3* ùû ( k2 + [ NO])

k1 [ NO ][O2 ]
éë NO ùû =
*

k2 + k3 [ NO ]
3
18
k1 NO O2 
NO *
3
k 2  NO 
k3
2
rNO2 = -2r3NO* = 2 éë NO3* ùû [ NO]
3

k1k3 [ NO ] [O2 ]
2

rNO2 =
k3
k2 + [NO]
2
19
k2 >> k3 [ NO]
E2   E1  E3 
rNO2 
k1k3
NO O2  
2 A1 A3
e RT
NO O2 
2

k2 A2
E2  E1  E3 
-rNO2

The result shows why the rate


decreases as temperature increases. T
20
21

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