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Falsified Kinetics:: K C C KC

The reaction is limited by internal (pore) diffusion in the catalyst particles. This results in "falsified kinetics" where the apparent activation energy and reaction order are incorrect if analyzed assuming kinetic control. For 5 mm particles, the apparent activation energy is 50 kJ/mol instead of the true kinetic value of 83 kJ/mol. Smaller 2 mm particles would show an apparent activation energy of 60 kJ/mol due to the diffusion limitation being less pronounced.

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358 views3 pages

Falsified Kinetics:: K C C KC

The reaction is limited by internal (pore) diffusion in the catalyst particles. This results in "falsified kinetics" where the apparent activation energy and reaction order are incorrect if analyzed assuming kinetic control. For 5 mm particles, the apparent activation energy is 50 kJ/mol instead of the true kinetic value of 83 kJ/mol. Smaller 2 mm particles would show an apparent activation energy of 60 kJ/mol due to the diffusion limitation being less pronounced.

Uploaded by

edelmandala
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 PDF, TXT or read online on Scribd

Falsified Kinetics:

Consider a reaction limited by External mass transfer, i.e. in the fluid phase. The mass transfer
km d p
coefficient is given by Sh  2 and km ~ T . The rate is given by
DA

km CAbulk  CAsurface  kmCAbulk . It will weakly depend on temperature. The order will appear to

be 1, regardless of actual kinetics.

If the reaction is limited by internal (i.e. pore) diffusion, then CAsurface CAbulk and the rate is

given by kC Anbulk . Since it is limited by internal diffusion, we can assume that Th is large and

2 3 2 DA
hence the rate approaches kr CAn bulk ~  3  kr CAn bulk
n  1 Th n 1 kr S A  B R 2CAn1bulk
 n 1 
 
 2 
~ kr C Abulk

 n 1
Now, this will appear as a reaction with order   and activation energy of E/2. This is
 2 
sometimes referred to as ‘falsified kinetics’. If data were acquired in a porous catalyst when
diffusion in the pores is rate limiting, and if the data were analyzed assuming that it is kinetic
limited, then the model will fit the data well, but we will get incorrect estimate of activation energy
and order (and the pre-exponent). If the experiments are conducted with smaller (or larger) catalyst
particles, then this ‘kinetic’ model will not predict the results correctly.

If the reaction is limited by kinetics, of course we will get the correct kinetics i.e. correct estimate
of order (n), pre-exponent (k0) and activation energy (E).
Example:
A fluid ‘A’ reacts on a porous catalyst (B) surface to form a product ‘C’. The bulk A concentration
is 100 mM. The reaction is first order. The effective diffusivity of A in B is De= 5×10-3 mm2/s.
10000

The kinetic rate constant (accounting for surface area and density of the catalyst) is 1012 e T
s 1
The catalyst particles diameter is 5 mm. Determine the rates if the reactions are conducted at 300,
320, 340 and 360 K. What can we learn from the data? If we use particles of 2 mm diameter, what
results would we get?

Solution:

T(K) k (s-1) Th  Apparent rate


(mol/lit/s)
300 0.003338 2.04 0.8 2.67E-04
320 0.02681 5.79 0.43 1.15E-03
340 0.1685 14.51 0.19 3.24E-03
360 0.8635 32.85 0.0885 7.64E-03

Apparent k (s-1) 1/T (K-1) ln(apparent-k)


0.00267 0.003333 -5.92557
0.011494 0.003125 -4.46594
0.032432 0.002941 -3.4286
0.076449 0.002778 -2.57113

ln(apparent k)
0
0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034
-1

-2
y = -6020.8x + 14.231
-3 R² = 0.9952

-4

-5

-6

-7
The apparent activation energy is 50 kJ/mol, while the actual activation energy is 83 kJ/mol.

If we assume that kinetics are rate limiting, we will wrongly conclude that the activation energy is
50 kJ/mol.

For 2 mm particles

Apparent rate
T(K) k(s-1) Th  (mol/lit/s)
300 0.003338 0.817097 0.958143 3.20E-04
320 0.02681 2.315601 0.761562 2.04E-03
340 0.168513 5.805391 0.427756 7.21E-03
360 0.863504 13.14157 0.210912 1.82E-02

Apparent k (s-1) 1/T (K-1) ln(apparent-k)


0.003199 0.003333 -5.74507
0.020418 0.003125 -3.89136
0.072082 0.002941 -2.62994
0.182124 0.002778 -1.70307

The apparent activation energy would be 60 kJ/mol

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