Professional Documents
Culture Documents
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
Obtaining apparent reaction order (n’) Obtaining apparent activation energy (Eapp)
Actual rate
Equating the true reaction rate with the measured (apparent) rate:
Thus
So the true & apparent reaction order is related by:
or
Falsified Kinetics – Activation Energy
Measured activation energy :
Based on:
Falsified Kinetics – Activation Energy
Gives:
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
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
(Reactor volume)
For most catalyst, internal surface area >> external surface area
𝑊𝐴𝑟 𝑎𝑐 = −𝑟𝐴
can be neglected
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