Chemical reaction

engineering 2
Teknik Kimia Universitas Pertamina
Catia Angli Curie - 2019
4. Diffusion & Reaction – part 2

Content Objectives
 Falsified kinetics  Understand about internal
 Overall effectiveness factor diffusion in catalyst pellet

 Mears Criterion  Able to estimate & differentiate

internal & overall effectiveness
factor
 Able to determine when the
reaction is not limited by external
diffusion
Falsified Kinetics
In Internal Diffusion Limited Reaction
Falsified Kinetics
 When the overall reaction is limited by internal diffusion
 The measured kinetics (reaction order & activation energy) might not be
the true value → falsified/disguised kinetics

Obtaining apparent reaction order (n’) Obtaining apparent activation energy (Eapp)

Log-log plot of measured reaction rate Plot of ln (–rA’) vs 1/T

(–rA’) vs bulk concentration of A (CAs)
Falsified Kinetics - Reaction order
 The experiment is set so that the
external mass transfer is not rate-
limiting
𝐶𝐴𝑠 = 𝐶𝐴𝑏

 Measured rate: Apparent reaction order

 In the discussion of internal

effectiveness factor we’ve had:
True reaction order

Actual rate

 For large values of Thiele Modulus (internal mass transfer is limiting) :

Falsified Kinetics - Reaction order

 Equating the true reaction rate with the measured (apparent) rate:

 Thus
 So the true & apparent reaction order is related by:

Apparent reaction order

or
Falsified Kinetics – Activation Energy
 Measured activation energy :

 True activation energy :

 Based on:
Falsified Kinetics – Activation Energy

 Taking the natural log for both sides:

 Gives:

True activation energy

Falsified Kinetics
When limited by internal diffusion:

 Does it matter?
 The effect would be significant
 If particle (catalyst) size were decreased so that the overall rate is no
longer limited by internal diffusion
 Semilog plot of k vs 1/T Reminder from CRE 1 course

Arrhenius
equation
• High slope → high E &
Plot of ln k vs 1/T
vice versa
• Higher E → more sensitive
to T change
• Reaction is more T-
sensitive at low T than at
high T
Falsified Kinetics
When limited by internal diffusion:

 Does it matter?
 The effect would be significant
 If particle (catalyst) size were decreased so that the overall rate is no
longer limited by internal diffusion
This may lead to

Runaway Reaction
 A thermally unstable reaction system which exhibits an uncontrolled
accelerating rate of reaction leading to rapid increases in temperature and May cause explosion
pressure.

https://www.aiche.org/ccps/resources/glossary/process-safety-glossary/runaway-reactions
Overall Effectiveness Factor
Overall Effectiveness Factor
 Internal effectiveness factor → relates actual rate with rate at CAs
 Overall effectiveness factor → relates actual rate with rate at CAb

Defining overall effectiveness factor

 When both external & internal diffusion are important,
Rate of transport of A from bulk fluid
= net rate of reaction on & within the catalyst
to the external surface of catalyst

𝐶𝐴𝑏 ≠ 𝐶𝐴𝑠 ≠ 𝐶𝐴
 Overall Effectiveness Factor
Rate of transport of A from bulk fluid
= net rate of reaction on & within the catalyst
to the external surface of catalyst

Molar rate of A (MA) to all of the external surface area:

(Reactor volume)

(External surface area/Volume)

(catalyst’ surface area/catalyst mass)

Catalyst mass/catalyst volume

Catalyst volume/reactor volume

Overall Effectiveness Factor

 Dividing with ΔV:

 For most catalyst, internal surface area >> external surface area

𝑊𝐴𝑟 𝑎𝑐 = −𝑟𝐴

 For 1st order reaction:

Overall Effectiveness Factor

 The actual rate of reaction become:

 Dividing with kcac gives

Ω = overall effectiveness factor

Overall Effectiveness Factor
 If the rate is in fact not limited by external mass transfer (high kc)

can be neglected

 The overall effectiveness factor ≈ internal effectiveness factor

Ω≈𝜂
Mears Criterion
Mears Criterion (MR)
 Similar with Weisz-Prater Criterion
 Uses measured rate of reaction to check if external mass transfer can be
neglected
 Mears number:

measured

calculated

Then calculate MR
 If MR < 0.15 → external mass transfer can be neglected
Mears Criterion (MR)
 Mears also proposed that when

 Bulk temperature will be = T at the external surface of the catalyst

References

 Fogler, H. S. 2009. “Elements of Chemical Reaction Engineering”, 4th Ed.

Prentice-Hall.
 Levenspiel, O. 1999. “Chemical Reaction Engineering”, 3rd Ed. John Wiley &
Sons.