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First Order Reaction: The Equation Becomes (1) - Transformation of Y, Produces

The document discusses first order reaction kinetics and how internal diffusion limitations can lead to apparent or measured kinetics that differ from the true kinetics. It shows that for a first order reaction, the internal effectiveness factor depends on the Thiele modulus. It also demonstrates that if internal diffusion limitations are significant, the measured reaction order will be (n+1)/2 where n is the true reaction order, and the measured activation energy will be twice the true activation energy.

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Aravind kugan
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20 views

First Order Reaction: The Equation Becomes (1) - Transformation of Y, Produces

The document discusses first order reaction kinetics and how internal diffusion limitations can lead to apparent or measured kinetics that differ from the true kinetics. It shows that for a first order reaction, the internal effectiveness factor depends on the Thiele modulus. It also demonstrates that if internal diffusion limitations are significant, the measured reaction order will be (n+1)/2 where n is the true reaction order, and the measured activation energy will be twice the true activation energy.

Uploaded by

Aravind kugan
Copyright
© © All Rights Reserved
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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First Order Reaction

• The equation becomes


d 2 2  d  2
    1   0 (1)
d   d 
2

•Transformation of y =  , produces

d 1  dy  y d 2 1  d 2 y  2  dy  2 y
   2   2   2    3
d   d   d 2
  d    d  
First Order Reaction
• Insert into Equation (1) , produces
2
d y
 1 y 0
2

d2

• Differentiation equation has the following


solution
y  A1 cosh 1  B1 sinh 1
• In terms of 
A1 B1
y  cosh 1  sinh 1
 
First Order Reaction
• Boundary Conditions,
when λ=0, cosh 1  1
when 1/λ→∞, sinh 1  0
• Because  is finite at the centre, the term A1
is zero
• The constant B is evaluated using boundary
conditions λ=1 and  = 1
• Dimensionless concentration profile is,
CA 1  sinh 1 
   
C AS   sinh 1 

Concentration Profile

Small values of Thiele modulus implies that surface reaction controls and significant
amount of reactant diffuses well into the pellet interior without reacting.

Large values of Thiele modulus indicates that surface reaction is rapid and reactant is
consumed very close to the external surface pellet
Internal Effectiveness Factor
• Magnitude of importance between diffusion
and reaction (value between 0-1)
• η = (actual overall rate of reaction)/ (rate of
reaction that would result if entire interior is
exposed to external surface conditions CAS,TS)
• In terms of symbol, it is defined as
η = -rA/-rAS = -r’A/-r’AS = –r”A/-r”AS
Internal Effectiveness Factor
• Define MA, moles per unit time
η = -r’A/-r’AS = (-r’A/-r’AS ) x mass of catalyst
= MA /MAS
• MAS = (rate per unit surface area) x (surface
area/mass of catalyst) x (mass of catalyst)
= (k1CAS) x Sa x (4/3)(πρcR3)
= -r’AS x (4/3)(πρcR3)
Internal Effectiveness Factor
d
Recall that MA = 4πRDeCAS d (at λ =1)
• Differentiate the above equation and evaluate
the result at λ = 1,
d  1 cosh 1 1 sinh 1 
   2 
d   sinh 1  sinh 1  1
 1 coth 1 1

• MA = 4πRDeCAS 1 coth 1 1


Internal Effectiveness Factor
• Insert the terms MAS and MA into the
definition of η
η = MA/MAS
= 4πRDeCAS 1 coth 1 1 / -r’AS x (4/3)(πρcR3)
= 3  coth   1
 2 1 1
1

k S  R 2
Recall that for first 12  1 a c
order reaction, De
Internal Effectiveness Factor
Internal Effectiveness Factor
• As diameter particle decreases, Thiele
modulus decreases as well and effectiveness
factor reaches 1 (surface reaction limited)
• When Thiele modulus is large (>30), internal
effectiveness factor is small and the reaction is
diffusion limited
3 3 De
 
1 R k1S a  c
Internal Effectiveness Factor
• Define overall rate of reaction in terms of
Thiele modulus, we define rate law for first
order reaction,
-r’A = (Actual reaction/Reaction at surface) x
Reaction at surface
= η x –r’AS
= η x (k1CAS) (Sa)
Insert into the equation,
-r’A = (3/R) (DeSak1/ρc)1/2 x CAS
Internal Effectiveness Factor
• Therefore to increase the overall reaction rate,
1. Decrease radius
2. Increase T
3. Increase concentration
4. Increase internal surface area
Internal Effectiveness Factor
• For large Thiele modulus factor and nth order
of reaction, the effectiveness factor is given as
1/ 2 1/ 2
 2  3  2  3 De
    
(1 n ) / 2
C AS
 n 1 n  n 1 R kn S a c
Falsified Kinetics
• Measured reaction order and activation
energy are not the true values
• E.g. for differential reactor of nth order
reaction, -r’A= k’n x Cn’AS (Measured Rate)
• Construct a log-log plot to find the order of
reaction
True Reaction Rate
• Definition of internal effectiveness factor,
-r’A = η x (-r’AS) = η x (knSaCnAS)
• For large Thiele modulus,
-r’A =η x (knSaCnAS)
=  2  3 x (knSaCnAS)
1/ 2

 n 1 n

3 2 De
= n
k n S a C AS
R n 1 c S a kn

= 3 2 De S a 1/ 2 ( n 1) / 2
kn C AS
R c (n  1)
Falsified Kinetics
• By equating true reaction rate and measured
reaction rate, we find that apparent
(measured) reaction order is related to true
reaction order by
n’ = (n+1)/2
• Similarly, for Activation Energy, it is related by
ETrue = 2 Eapparent

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