Chemical reaction

engineering 2
Teknik Kimia Universitas Pertamina
Catia Angli Curie - 2019
4. Diffusion & Reaction – part 1

Content Objectives
 Effective diffusivity  Understand about internal
 Thiele Modulus diffusion in catalyst pellet

 For 1st order reaction in  Able to estimate Thiele Modulus &

spherical catalyst internal effectiveness factor
 Able to determine when the
 Internal Effectiveness Factor
reaction is limited by internal
 Weisz-Prater Criterion for Internal diffusion
Diffusion Limitations
Diffusion & Reaction in Spherical
Catalyst Pellet

𝐶𝐴𝑠 > 𝐶𝐴 (𝑟)

Reaction is on the surface of catalyst
The pores are of irregular shape
Effective Diffusivity (De)
 Effective diffusion coefficient / effective diffusivity (De)
 To describe the average diffusion in the catalyst, at any r within the pellet
 It considers only radial variation in concentration

 It accounts for the fact that:
• Radial flux (WAr) will be based on the total
area normal to the diffusion (ie. 4πr2) rather
than area of the void alone
• The paths are turtuous
• The pores are of varying cross-sectional area
Effective Diffusivity (De)
Typical value:

3.0

0.4

0.8

Accounts for the

variation of A
Thiele Modulus
Thiele Modulus (𝜙𝑛 )
 A ratio developed to describe the relationship between diffusion rate and
surface reaction rate in a catalyst pellet (in the absence of external mass
transfer limitation)
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝜙𝑛2 =
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛

depends on:
• the reaction order (n)
• the shape of the catalyst pellet

Developed based on mole balance (diffusion & catalytic reaction) in the catalyst particle

 When Thiele modulus is large → diffusion limits the overall rate of reaction
 When 𝜙𝑛 is small → surface reaction is usually the rate-limiting
Thiele Modulus (𝜙𝑛 ) for reaction in
spherical catalyst
 From shell balance in the spherical catalyst, we’ll obtain:

 For 1st order reaction,

Thiele Modulus (𝜙𝑛 ) for 1st order
reaction in spherical catalyst
 Solving the shell balance for concentration profile, we’ll obtain:

(Concentration profile for 1st order reaction)

 Plotting the profile at various 𝜙1

Concentration varied with catalyst’ radius

Rate of reaction will also vary (except for
0-order reaction)
Various Thiele Modulus formulation
 Thiele modulus for spherical particle in various reaction order:
Internal Effectiveness Factor
Internal Effectiveness Factor (η)
 Concentration varied with catalyst’ radius
Rate of reaction will also vary (except for 0-order reaction)

 Internal effectiveness factor is defined as:

A measure of how far the reactant diffuses into the pellet before reacting

−𝑟𝐴 −𝑟′𝐴 −𝑟"𝐴

𝜂= = =
−𝑟𝐴𝑠 −𝑟′𝐴𝑠 −𝑟"𝐴𝑠

−𝑟𝐴 −𝑟𝐴 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑀𝐴

𝜂= = =
−𝑟𝐴𝑠 −𝑟𝐴𝑠 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑀𝐴𝑠

𝑀𝐴 = Molar rates of A/time

Internal Effectiveness Factor (η)
For a reaction of A → B (1st order)
The denumerator (𝑀𝐴𝑠 )
 𝑀𝐴𝑠 = the rate if the concentration of A in the entire catalyst is equal to CAs
𝑀𝐴𝑠 = −𝑟𝐴𝑠 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒
4 3
𝑀𝐴𝑠 = −𝑟𝐴𝑠 × 𝜋𝑅
3
 At high T, adsorpsion <, the denominator in the catalytic rate law often
approaches 1, so we can take:
−𝑟𝐴 = 𝑘𝐶𝐴𝑛

 For 1st order reaction & for CA=CAs

−𝑟𝐴𝑠 = 𝑘𝐶𝐴𝑠

4 3
𝑀𝐴𝑠 = 𝑘𝐶𝐴𝑠 × 𝜋𝑅
3
Internal Effectiveness Factor (η)
For a reaction of A → B (1st order)
The numerator (𝑀𝐴 )
 Actual rate of reaction
 The rate of diffusion of A into the pellet at the outer surface
(all A reacts inside the catalyst & no A diffuses back out)

 For 1st order reaction

𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1
Internal Effectiveness Factor (η)
For a reaction of A → B (1st order)
 We’ve had:
 𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1
4 3
 𝑀𝐴𝑠 = 𝑘𝐶𝐴𝑠 × 𝜋𝑅
3

𝑀𝐴 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1

 Hence: 𝜂= =
𝑀𝐴𝑠 4
𝑘𝐶𝐴𝑠 × 3 𝜋𝑅3

𝑀𝐴 𝐷𝑒
𝜂= = 3 2 ∅1 coth ∅1 − 1
𝑀𝐴𝑠 𝑘𝑅
1/Thiele modulus for 1st order reaction (1Τ∅12 )

3 Internal effectiveness factor for 1st order

𝜂= 2 ∅1 coth ∅1 − 1
∅1 reaction in a spherical catalsyt
Internal Effectiveness Factor (η)
 For 1st order reaction in a spherical particle:

3 𝑘𝑅 2
𝑘
𝜂 = 2 ∅1 coth ∅1 − 1 with ∅12 = or ∅1 = 𝑅
∅1 𝐷𝑒 𝐷𝑒

 As particle diameter << → ∅1 << → effectiveness factor approaches 1

The reaction is
surface-reaction
limited

 Note:
Internal Effectiveness Factor (η)
Side note:
3
 If ∅1 >2 → 𝜂 ≈ 2 ∅1 − 1
∅1

3
 If ∅1 >20 → 𝜂≈
∅1

 So, when Thiele modulus is large → 𝜂 become small

The reaction is
diffusion-limited
within the pellet
Internal effectiveness & Thiele Modulus

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝜙𝑛2 =
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛

In any case, changing factors that affect external mass transport rate
(eg. fluid velocity) won’t affect the overall rate of reaction
Internal Effectiveness Factor (η)
So, for 1st order reaction that is limited by internal diffusion in spherical catalyst
particles,
 The internal effectiveness factor can be written as

3 3 𝐷𝑒
𝜂≈ =
∅1 𝑅 𝑘

 And the actual rate can be written as:

= 𝜂𝑘𝐶𝐴𝑠
3 3 𝑆𝑎 = catalyst’ surface area/catalyst mass
−𝑟𝐴 = 𝐷𝑒 𝑘𝐶𝐴𝑠 −𝑟𝐴 = 𝐷𝑒 𝑆𝑎 𝜌𝑐 𝑘"𝐶𝐴𝑠
𝑅 𝑅 𝜌𝑐 = catalyst’ density
Increasing actual rate of reaction for
internal-diffusion limited
 The actual rate of reaction for 1st order reaction that is limited by internal
diffusion in spherical catalyst particles :

3 3
−𝑟𝐴 = 𝐷𝑒 𝑘𝐶𝐴𝑠 −𝑟𝐴 = 𝐷𝑒 𝑆𝑎 𝜌𝑐 𝑘"𝐶𝐴𝑠
𝑅 𝑅
 So, to increase the rate, we may:
 Decrease catalyst’ size
 Increase T
 Increase the concentration
 Increase internal surface area
Weisz-Prater Criterion
Weisz-Prater Criterion for Internal
Diffusion Limitations
 Uses measured values of reaction rate (-rA observed) to check whether the
reaction is limited by internal diffusion

(For 1st-order reaction in

spherical catalyst)

Weisz-Prater Criterion
Weisz-Prater Criterion for Internal
Diffusion Limitations

2
2
−𝑟𝐴𝑠 𝑅 −𝑟′𝐴𝑠 𝜌𝑐 𝑅2
𝜙𝑛 = =
𝐶𝐴𝑠 𝐷𝑒 𝐶𝐴𝑠 𝐷𝑒

Hence,

If CWP<<1 → no diffusion limitation

If CWP>>1 → strongly limited by diffusion
Exercise
Additional notes on internal
effectiveness
Internal Effectiveness Factor (η) for
Reaction with Volume Change
 Effectiveness factor ratios
for 1st order reaction on
spherical catalyst

Example:
 For a gas phase reaction
of A → 2B (𝜀=1)
 If the Thiele modulus =
10, the 𝜂′Τ𝜂=0.8
Internal Effectiveness Factor (η) for
Reaction Other Than 1st Order
 Thiele Modulus for spherical catalyst with n-th order of reaction:

 For large values of Thiele Modulus

 So, the effectiveness factor decrease with increasing CAs

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.