ChBE 6260 Topic 4

Steady State Analysis

We will move onto chapter 3 in Hines & Maddox, which focuses on developing macroscopic and
microscopic continuity equations. We will consider these as well, but also focus on several
“complicated” cases involving reactions.
Before going into the details, it is useful to provide some terms and terminology.
The first is the concept of a mass transfer coefficient, which is an approximate engineering idea
that simplifies the description of certain mass transfer processes.
To use this concept, assume that changes in concentration are limited to a small part of the
system’s volume near its boundary.
➢ 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝛼 (𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑖𝑎𝑙 𝑎𝑟𝑒𝑎 )(𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒)

For instance “𝑘𝑐 ” relates to 𝐽𝐴 = 𝑘𝑐 [𝐶𝐴𝑜 − 𝐶𝐴𝜕 ] or 𝐽𝐴 = 𝑘𝑐 [𝐶𝐴𝜕 − 𝐶𝐴𝑜 ]

➢ Must pay attention to coordinate origin and detailed physical situation

“kx” is related to “kc”, since 𝐽𝐴 = 𝑘𝑥 [𝑥𝐴𝑜 − 𝑥𝐴𝜕 ] 𝑜𝑟 𝐽𝐴 = 𝑘𝑥 [𝑥𝐴𝜕 − 𝑥𝐴𝑜 ]

Similarly 𝐽𝐴 = 𝑘𝑦 [[𝑦𝐴𝑜 − 𝑦𝐴𝜕 ]]

1. Homogeneous reactions: 𝑅𝐴𝜈 = ±𝑘𝐴 𝐶𝐴 = ±𝑘𝐴𝜈 𝐶𝐴 where CA= local homogeneous

concentration of reactant A.
2. Heterogeneous (surface) reaction: 𝑅𝐴𝑠 = ±𝑘𝐴𝑠𝑠 𝐶𝐴𝑠𝑠 = 𝑘𝐴𝑠 𝐶𝐴𝑠 = [𝑘𝐴𝑠𝑠 𝐾]𝐶𝐴𝑠
𝑚𝑜𝑙 𝐴
a. 𝐶𝐴𝑠𝑠 is the local surface concentration of reactant A [=]
𝑐𝑚2
b. 𝐶𝐴𝑠 is the local homogeneous concentration of A in contact with the surface that
𝑚𝑜𝑙 𝐴
has 𝐶𝐴𝑠𝑠 on it [=]
𝑐𝑚3
𝐶𝐴𝑠 𝑠 𝐴 𝐴𝑠
c. 𝐾 = [ ] [ 𝑆] , = 𝑎 → partition coefficient relating surface concentration to the
𝐶𝐴𝑠 𝑉 𝑉
local homogeneous concentration in equilibrium with it. The surface area to
volume ratio accounts for the difference in a surface concentration and a “3D”
concentration.
3. “Effective homogeneous reaction in a porous medium
𝜈
𝑅𝐴,𝑒 = [𝑘𝐴𝑠 ∗ 𝑎]𝐶𝐴𝑠 = [𝑘𝐴𝑠𝑠 𝐾]𝐶𝐴𝑠 = 𝑘𝐴,𝑒𝜈
𝐶𝐴𝑠

Formulation of Diffusion Models

Shell balance method
Important nots:
1. Reactions that occur within the shell are “sources” or sinks for component “A”
[𝑅𝐴 = ±𝑘𝑁 𝐶𝐴𝑁 ] (Usually N=1 for our simple cases)

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ChBE 6260 Topic 4

2. Reactions that occur at a boundary of the volume for which the shell balance applies are
not sources or sinks. They enter only as boundary conditions. For example:
a. 𝑁𝐴 |𝑠𝑢𝑟𝑓𝑎𝑐𝑒 = ±𝑘𝑁,𝑠 𝐶𝐴𝑁 |𝑠𝑢𝑟𝑓𝑎𝑐𝑒
3. We will use 𝑁𝐴 = −𝐶𝐷𝐴𝐵 ∇𝑥𝐴 + 𝑥𝐴 (𝑁𝐴 + 𝑁𝐵 ) for the flux rate in and out of the volume
of the shell. Several examples of relationships between 𝑁𝐴 & 𝑁𝐵 :
a. 𝑁𝐵 = 0 (no net movement of B)
b. 𝑁𝐴 = −𝑁𝐵 (equimolar counter diffusion)
1 1
c. 𝑁𝐴 = − 𝑁𝐵 ( 𝐴 ⇌ 𝐵 𝑜𝑐𝑐𝑢𝑟𝑖𝑛𝑔 𝑎𝑡 𝑎 𝑠𝑢𝑟𝑓𝑎𝑐𝑒)
2 2
d. 𝑥𝐴 (𝑁𝐴 + 𝑁𝐵 ) = 0, 𝑥𝐴 ≪ 1
4. Common boundary conditions:
a. Concentration, CA, fixed at some surface
b. Flux, NA, fixed at some surface (e.g., NA=0)
c. Mass transfer analogy to Newton’s Law of Cooling -- 𝑁𝐴𝑜 = 𝑘𝑐 (𝐶𝐴𝑜 − 𝐶𝐴𝜕 ) at
some surface
d. Chemical reaction occurs at a surface, 𝑁𝐴𝜕 = 𝑘𝑠 𝐶𝐴𝑠

Let’s work a shell balance for the case of a heterogeneous chemical reaction
➔ We can apply the exact same approach used for the problem involving diffusion through
a stagnant film. In fact, the exact same shell balance applies in this case because there is
no homogeneous reaction occurring. Thus we can still assume steady state and 𝑁𝐴𝑥 =
𝑁𝐴𝑦 = 0
Boundary Conditions: Schematic of heterogeneous catalytic reactor
1) 𝑎𝑡 𝑧 = 0, 𝑥𝐴 = 𝑥𝐴,𝑜 surface of length x, for which 𝑥𝐴𝑜 & 𝑥𝐴𝜕 are
2) 𝑎𝑡 𝑧 = 𝜕, 𝑥𝐴 = 𝑥𝐴𝜕 constant.
In general this surface concentration will not be
known, but we put it in here as a parameter to be
evaluated. We will return to this later and relate
𝑥𝐴𝜕 to the flux to the surface, 𝑁𝐴 |𝜕 =
𝐶𝑥𝐴𝑠,𝜕 𝑘𝑠 , 𝑙𝑎𝑡𝑒𝑟

At steady state, there is a simple relationship between NA & NB, since at any z plane we choose,
1
we know that 𝑁𝐴 = −2𝑁𝐵 . Thus to prevent accumulation or depletion, 𝑁𝐵 = − 𝑁𝐴 , so,
2

𝑑𝑥𝐴 1 𝐶𝐷𝐴𝐵 𝑑𝑥𝐴

𝑁𝑍 = −𝐶𝐷𝐴𝐵 + 𝑥𝐴 𝑁𝐴 → 𝑁𝐴 = − 𝑥 𝐸𝑞. 𝐴
𝑑𝑧 2 1 − 𝐴 𝑑𝑧
2
Separate variables, integrate, and apply boundary conditions:

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ChBE 6260 Topic 4

𝑥𝐴
2𝐶𝐷𝐴𝐵 (1 − 𝛿 )
𝑁𝐴 = ln [ 2 ] 𝐸𝑞. 𝐵
𝛿 𝑥𝐴
(1 − 𝑜 )
2
𝑥𝐴 𝛿
For 𝑥𝐴 ≪ 1, we can expand equation B in a series and retain only one term: ln (1 − )≈
2
𝑥𝐴 𝛿 𝑥𝐴 𝑜 𝑥𝐴 𝑜
− & ln (1 − )≈−
2 2 2

2𝐶𝐷𝐴𝐵 𝑥𝐴 𝑜 𝑥𝐴 𝛿 𝐶𝐷𝐴𝐵
Thus, 𝑁𝐴 = [ − ]= [𝑥𝐴 𝑜 − 𝑥𝐴 𝛿 ] = 𝐽𝐴∗ 𝐸𝑞. 𝐶
𝛿 2 2 𝛿

We can get rid of 𝑥𝐴 𝛿 by using the condition, 𝑎𝑡 𝑧 = 𝛿, 𝑁𝐴 |𝛿 = 𝐶𝐴 𝑠 𝑘𝑠 = 𝐶𝑥𝐴 𝛿 𝑘𝑠 . To allow an

analytical solution, let’s use equation C as a limiting case for 𝑁𝐴 , which is a constant.
𝑥𝐴 𝑜
𝐶𝑘𝑠 𝑥𝐴 𝛿 = 𝐶𝐷𝐴𝐵 [𝑥𝐴 𝑜 − 𝑥𝐴 𝛿 ] → 𝑥𝐴 𝛿 = 𝛿𝑘
substitute this into equation C
[1+𝐷 𝑠 ]
𝐴𝐵

𝛿𝑘𝑠
𝐶𝐷𝐴𝐵 𝑥𝐴𝑜 𝐷𝐴𝐵
𝑁𝐴 = [ ] 𝐸𝑞. 𝐷
𝛿 𝛿𝑘
1+ 𝑠
𝐷𝐴𝐵
𝛿𝑘𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝛿𝑘𝑠
≈ 𝐷𝑎𝑚𝑘𝑜ℎ𝑙𝑒𝑟 𝑁𝑢𝑚𝑏𝑒𝑟 = 𝐴𝑠 ↑↑, we end up with a diffusion
𝐷𝐴𝐵 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝐷𝐴𝐵
controlled case.

Example:
A reduction reaction takes place between hydrogen gas (𝑥𝐴,𝑏𝑢𝑙𝑘 ) and a nonporous manganese
oxide plate,
𝑀𝑛3 𝑂4 (𝑠) + 4𝐻2 (𝑔) → 3𝑀𝑛(𝑠) + 4𝐻2 𝑂(𝑔)
The reaction can be considered to be instantaneous
What’s the expression for steady state molar flux of H2? What is 𝑥𝐻2 (𝑧)?

𝑑𝑥𝐻2
𝑁𝐻2 = −𝐶𝐷𝐴𝐵 + 𝑥𝐻2 Σ𝑁𝑖
𝑥𝑧

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ChBE 6260 Topic 4

Only H2 and H2O are diffusing in the boundary layer and 𝑁𝐻2 = −𝑁𝐻2 𝑂 (equimolar counter
diffusion)
Thus, Σ𝑁𝑖 = 0, and,
𝑑𝑥𝐻2 𝐶𝐷𝐴𝐵
𝑁𝐻2 = −𝐶𝐷𝐴𝐵 → 𝑁𝐻2 = (𝑥𝐻2 ,𝐵𝑢𝑙𝑘 − 𝑥𝐻2 ,𝑠𝑢𝑟𝑓𝑎𝑐𝑒 )
𝑑𝑧 𝛿
𝑑𝑁𝐴 𝑑 𝑑𝑥𝐴
At steady state, = 0, 𝑠𝑜 ( ) = 0 → 𝑥𝐴 (𝑧) = 𝐶1 𝑧 + 𝐶2
𝑑𝑧 𝑑𝑧 𝑑𝑧

Equation above assumes constant 𝐷𝐴𝐵 𝑎𝑛𝑑 𝐶

The “shell balance” approach can be generalized by using 3D “equations of change” and
discarding unnecessary terms:

[𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴] = [𝑅𝑎𝑡𝑒 𝑜𝑓 𝐴 𝑖𝑛] − [𝑅𝑎𝑡𝑒 𝑜𝑓 𝐴 𝑜𝑢𝑡] + [𝑅𝑎𝑡𝑒 𝑜𝑓 𝐴 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 ]

Expressing the above terms using:

𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴
𝜌𝐴 = 𝑎𝑛𝑑 𝑛𝐴 = 𝑚𝑎𝑠𝑠 𝑓𝑙𝑢𝑥 𝑜𝑓 𝐴 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑡𝑜 𝑓𝑖𝑥𝑒𝑑 𝑐𝑜𝑜𝑟𝑑𝑖𝑛𝑎𝑡𝑒𝑠 = 𝜌𝐴 𝑣𝐴
𝑐𝑚3
𝜕𝜌𝐴
[∆𝑥∆𝑦∆𝑧] = ∆𝑦∆𝑧[𝑛𝐴𝑥 |𝑥 − 𝑛𝐴 𝑥 |𝑥+∆𝑥 ] + 𝑥𝑦∆𝑧 [𝑛𝐴𝑦 |𝑦 − 𝑛𝐴 𝑦 |𝑦+∆𝑦 ] + ∆𝑥∆𝑦[𝑛𝐴𝑧 |𝑧 −
𝜕𝑡
𝑛𝐴 𝑧 |𝑧+∆𝑧 ] + ∆𝑥∆𝑦∆𝑧𝑟𝐴

After dividing by [∆𝑥∆𝑦∆𝑧]:

𝜕𝜌𝐴 𝜕𝑛𝐴𝑥 𝜕𝑛𝐴 𝑦 𝜕𝑛𝐴 𝑧 𝜕𝜌𝐴

= −[ + + ] + 𝑟𝐴 𝑜𝑟 + (∇ ∙ 𝑛𝐴 ) = 𝑟𝐴
𝜕𝑡 𝑑𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡
𝜕𝜌𝐵
Similar process can be done for B to get + (∇ ∙ 𝑛𝐵 ) = 𝑟𝐵
𝜕𝑡
𝜕𝜌
For the total mass we get + (∇ ∙ 𝜌𝑣) = 0
𝜕𝑡

𝜕𝐶𝐴 𝜕𝐶𝐵
In molar units: + (∇ ∙ 𝑁𝐴 ) = 𝑅𝐴 𝑎𝑛𝑑 + (∇ ∙ 𝑁𝐵 ) = 𝑅𝐵
𝜕𝑡 𝜕𝑡

𝜕𝐶
+ (∇ ∙ 𝐶𝑉 ∗ ) = 𝑅𝐴 + 𝑅𝐵
𝜕𝑡

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ChBE 6260 Topic 4

We can insert the mass or molar fluxes;

𝑛𝐴 = 𝜔𝐴 (𝑛𝐴 + 𝑛𝐵 ) − 𝜌𝐷𝐴𝐵 𝑣𝜔𝐴 = 𝜌𝐴 𝑣 − 𝜌𝐷𝐴𝐵 ∇𝜔𝐴
Lastly:
𝜕𝜌𝐴
+ (∇ ∙ 𝜌𝐴 𝑣) = (∇ ∙ 𝜌𝐷𝐴𝐵 ∇𝜔𝐴 ) + 𝑟𝐴 ∗∗∗
𝜕𝑡
BSL Tables

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ChBE 6260 Topic 4

Diffusion with homogeneous chemical reaction:

A homogeneous rxn of 𝐴 + 𝐵 → 𝐴𝐵 occurs

throughout the liquid and the “generation rate”
of A is given by:
𝑅𝐴 = −𝑘𝐴𝑣 𝐶𝐴
(actually a consumption of A)

In reality, a ternary situation exists (A,B & AB), but the amount of A & AB are so low that A
“thinks” it is only diffusing in B (i.e., 𝑥𝐴 ≪ 1)
Assumptions: Boundary conditions:

1. Steady state ( CB doesn’t change measurably) 1. 𝑎𝑡 𝑧 = 0, 𝐶𝐴 = 𝐶𝐴𝑜

2. 𝜌, 𝐷𝐴𝐵 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑑𝐶𝐴
2. 𝑎𝑡 𝑧 = 𝐿, 𝑁𝐴𝑧 = 0 → =0
𝜕𝐶𝐴 𝜕𝐶𝐴 𝑑𝑧
3. = =0
𝜕𝑦 𝜕𝑥
(No flux through bottom of container)
4. 𝑉𝑋 = 𝑉𝑦 = 𝑉𝑧 = 0

From the BSL table:

Rectangular Coordinates:
𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴
+ (𝑣𝑥 + 𝑣𝑦 +𝑣𝑧 ) = 𝐷𝐴𝐵 ( 2 + + ) + 𝑅𝐴
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑥 𝜕𝑦 2 𝜕𝑧 2

(1) (4) (3)

The final differential equation to solve is:
𝑑 2 𝐶𝐴 𝑑 2 𝐶𝐴
0 = 𝐷𝐴𝐵 → 0 = 𝐷𝐴𝐵 − 𝑘𝐴𝑣 𝐶𝐴
𝑑𝑧 2 𝑑𝑧 2
We can also arrive at this result via a shell balance

𝑑2 𝐶𝐴 2
𝑘𝐴𝑣
→ − 𝑎 𝐶𝐴 = 0, 𝐶𝐴 = 𝐴𝑠𝑖𝑛ℎ(𝑎𝑧) + 𝐵𝑐𝑜𝑠ℎ(𝑎𝑧), 𝑤ℎ𝑒𝑟𝑒 𝑎 = √
𝑑𝑧 2 𝐷𝐴𝐵

Boundary Conditions:
1. 𝐶𝐴 = 𝐶𝐴𝑜 𝑎𝑡 𝑧 = 0 → 𝐵 = 𝐶𝐴𝑜
𝑑𝐶𝐴
2. |𝐿 = 0 = 𝑎𝐴𝑐𝑜𝑠ℎ(𝑎𝐿) + 𝐵𝑎𝑠𝑖𝑛ℎ(𝑎𝐿)
𝑑𝑧

𝐶𝐴𝑜 sinh(𝑎𝐿)
So, 𝐴 = −
cosh(𝑎𝐿)

𝐶𝐴𝑜 sinh(𝑎𝐿)
Thus, 𝐶𝐴 = 𝐶𝐴𝑜 cosh(𝑎𝑧) − sinh(𝑎𝑧)
cosh(𝑎𝐿)

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ChBE 6260 Topic 4

𝑧
cosh [𝑎𝐿 (1 − )]
𝐶𝐴 = 𝐶𝐴𝑜 𝐿
cosh(𝑎𝐿)
We can also easily find the flux of A at the surface of the liquid.
𝑑𝐶𝐴 𝐷𝐴𝐵 𝐶𝐴𝑜 1 𝑧
𝑁𝐴 |𝑧=0 = −𝐷𝐴𝐵 |𝑧=0 = − [𝑏1 (− sinh (𝑏1 (1 − )))]
𝑑𝑧 cosh(𝑏1 ) 𝐿 𝐿 𝑧=0
𝐷𝐴𝐵 𝐶𝐴𝑜 𝑏1
So, 𝑁𝐴𝑧 |𝑧=0 = tanh(𝑏1 ) or,
𝐿

𝑘𝐴𝑣 𝐿2
𝑁𝐴 |𝑧=0 = 𝐶𝐴𝑜 √𝐷𝐴𝐵 𝑘𝐴𝑣 tanh [√ ]
𝐷𝐴𝐵

𝑣 𝐿2
𝑘𝐴
In cases where √ > 1.5, one can approximate 𝑁𝐴 |𝑧=0 well by:
𝐷𝐴𝐵

𝑁𝐴 |𝑧=0 ≈ 𝐶𝐴𝑜 √𝐷𝐴𝐵 𝑘𝐴𝑣 = 𝐶𝐴𝑜 𝑘𝑎𝑝𝑝𝑎𝑟𝑒𝑛𝑡

Above equation represents cases with serious diffusional limitations

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ChBE 6260 Topic 4

Example Degradation of toxic organic solutes via biofilms

𝐴 = 𝑃ℎ𝑒𝑛𝑜𝑙
𝐵 = 𝐵𝑖𝑜𝑓𝑖𝑙𝑚 (ℎ𝑜𝑚𝑜𝑔𝑒𝑛𝑒𝑜𝑢𝑠)
Rate of Degradation:
𝑅𝐴,𝑚𝑎𝑥 𝐶𝐴
𝑅𝐴 =
𝐾𝐴 + 𝐶𝐴
𝑅𝐴,𝑚𝑎𝑥 = 𝑀𝑎𝑥 𝑑𝑒𝑔𝑟𝑎𝑑𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒

𝐾𝐴 = 𝑀𝑖𝑐ℎ𝑎𝑒𝑙𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Biofilm is rich in peroxidase, which oxidatively degrades phenol

𝐶𝐴∞ is constant at steady state since the tank is well-mixed

𝐶𝐴 (𝑧) in the biofilm will decrease as A is degraded

There is no convective mass transfer limitations, 𝐶𝐴𝑠 = 𝐶𝐴∞ , 𝜌 is constant

Goal: Treat 0.1 𝑚3 /ℎ𝑟 of wastewater containing 0.1 𝑚𝑜𝑙/𝑚3 toxic A

If biofilm thickness is 2.0 mm, what is the required surface area of biofilm necessary to achieve
𝐶𝐴∞ = 0.02 𝑚𝑜𝑙/𝑚3 ?

−3
𝑚𝑜𝑙 −10
𝑚2 𝑚𝑜𝑙
𝑅𝐴,𝑚𝑎𝑥 = 5.7 ∗ 10 𝐷𝐴𝐵 = 2.0 ∗ 10 𝐾𝐴 = 0.3 3 𝑇 = 25°𝐶
𝑚3 𝑠 𝑠 𝑚
First, we need to express the degradation rate of A in terms of a surface area:
(𝑅𝑎𝑡𝑒 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑑𝑒𝑔𝑟𝑎𝑑𝑒𝑑 ) = (𝑅𝑎𝑡𝑒 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑎𝑑𝑑𝑒𝑑 𝑡𝑜 𝑡𝑎𝑛𝑘) − (𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑒𝑥𝑖𝑡𝑖𝑛𝑔 𝑡𝑎𝑛𝑘 )

𝑚3 𝑚𝑜𝑙 𝑚𝑜𝑙
𝜔𝐴 = 𝑣𝐶𝐴𝑜 − 𝑣𝐶𝐴∞ = 𝑣(𝐶𝐴𝑜 − 𝐶𝐴∞ ) = 0.1 (0.1 − 0.02) 3 = 8.0 ∗ 10−3
ℎ𝑟 𝑚 ℎ𝑟
This degradation rate is proportional to the flux of A into the biofilm multiplied by biofilm
surface area.
𝜔𝐴 = 𝐴𝑠 𝑁𝐴 |𝑧
We have a homogeneous reaction within the biofilm with this reaction rate
𝑅𝐴,𝑚𝑎𝑥 𝐶𝐴
𝑅𝐴 = − in this case, 𝐾𝐴 ≫ 𝐶𝐴 , so,
𝐾𝐴 +𝐶𝐴

𝑅𝐴,𝑚𝑎𝑥
𝑅𝐴 = − 𝐶𝐴 = −𝑘1 𝐶𝐴 𝑎𝑛𝑑 𝑘1 = 1.9 ∗ 10−2 𝑠 −1
𝐾𝐴

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ChBE 6260 Topic 4

This simplifies to our previous result:

𝑑 2 𝐶𝐴
𝐷𝐴𝐵 − 𝑘1 𝐶𝐴 = 0
𝑑𝑧 2

𝑘𝑎𝑣 𝛿 2
𝑁𝐴 |𝑧=0 = 𝐶𝐴∞ √𝐷𝐴𝐵 𝑘𝑎𝑣 tanh ( √ )
𝐷𝐴𝐵

𝑚𝑜𝑙
𝑁𝐴 |𝑧=0 = 2.9 ∗ 10−8
𝑚2 𝑠
𝜔𝐴
𝐴𝑠 = = 57 𝑚2
𝑁𝐴 |𝑧=0

Page 9 of 17
ChBE 6260 Topic 4

Diffusion and Reaction Inside a Porous Catalyst Particle

Assumptions: Using spherical coordinates “equation of change”:

1. Steady State 𝜕𝐶𝐴 𝜕𝐶𝐴 1 𝜕𝐶𝐴 1 𝜕𝐶𝐴

+ (𝑣𝑟 + 𝑣𝜃 + 𝑣𝜙 )
2. No 𝜃 𝑜𝑟 𝜙 dependence 1 𝜕𝑡 𝜕𝑟 𝑟 𝜕𝜃 𝑟𝑠𝑖𝑛(𝜃) 𝜕𝜙
5 5 5
3. 𝑥𝐴 ≪ 1, 𝐶 ≈ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 1 𝜕 𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴 1 𝜕 2 𝐶𝐴
4. 𝐷𝐴 =constant effective = 𝐷𝐴 ( 2 (𝑟 2 )+ 2 (𝑠𝑖𝑛𝜃 )+ 2 2 ) + 𝑅𝐴
𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 sin 𝜃 𝜕𝜙 2
diffusivity
2 2
5. No bulk flow, 𝑣 = 0
6. Constant T,P 𝑑 2 𝑑𝐶𝐴
𝑆𝑜, 𝐷𝐴 (𝑟 ) = 𝑟 2 𝑘1𝑣 𝐶𝐴
𝑑𝑟 𝑑𝑟
Boundary Conditions:
∗
1. 𝐶𝐴 = 𝐶𝐴,𝑠 𝑎𝑡 𝑟 = 𝑅
2. 𝐶𝐴 = 𝑓𝑖𝑛𝑖𝑡𝑒 𝑎𝑡 𝑟 = 0

A useful trick allows us to simplify solutions in spherical coordinates:

∗
𝐶𝐴,𝑠 𝑓(𝑟)
Assume 𝐶𝐴 = , still general, since f(r) hasn’t been specified yet
𝑟

We then see that:

𝑑𝐶𝐴 𝑓′ 𝑓 𝑑𝐶𝐴
= 𝐶𝐴∗ [ − ] → 𝑟2 ∗ [𝑟𝑓 ′
= 𝐶𝐴,𝑠 − 𝑓]
𝑑𝑟 𝑟 𝑟2 𝑑𝑟

𝑑 𝑑𝐶𝐴 ∗ [𝑓 ′ ∗
So, [𝑟 2 ] = 𝐶𝐴,𝑠 + 𝑟𝑓 ′′ = 𝑓 ′ ] = 𝐶𝐴,𝑠 𝑟𝑓 ′′
𝑑𝑟 𝑑𝑟

𝑘𝑖𝑣 𝑓 𝑑2𝑓 𝑘𝑖𝑣

Thus, 𝑓 ′′ = = 𝛼2𝑓 → = 𝛼 2 𝑓 ∗∗ 𝛼 = √ (homogeneous reaction)
𝐷𝐴 𝑑𝑟 2 𝐷𝐴

𝑑 2 𝐶𝐴
This is mathematically identical to: 𝐷𝐴𝐵 = 𝑘𝐴𝑣 𝐶𝐴
𝑑𝑧 2

Page 10 of 17
ChBE 6260 Topic 4

So we already know the solution to **:

𝑓(𝑟) = 𝐴𝑠𝑖𝑛ℎ(𝛼𝑟) + 𝐵𝑐𝑜𝑠ℎ(𝛼𝑟)
We also need to transform our boundary conditions in terms of 𝑓(𝑟):
∗
∗
𝐶𝐴,𝑠 𝑓(𝑟) ∗
𝐵𝐶 1: 𝐶𝐴 = 𝐶𝐴,𝑠 𝑎𝑡 𝑟 = 𝑅 → 𝐶𝐴 = |𝑅 = 𝐶𝐴,𝑠
𝑟
𝐵𝐶 1′ : 𝑓(𝑟) = 𝑅 𝑎𝑡 𝑟 = 𝑅
∗
𝐶𝐴,𝑠 𝑓(𝑟)
𝐵𝐶 2: 𝐶𝐴 = 𝑓𝑖𝑛𝑖𝑡𝑒 𝑎𝑡 𝑟 = 0 → 𝐶𝐴 = ≠ ∞ 𝑎𝑡 𝑟 → 0
𝑟
𝐵𝐶 2′ : 𝑓(𝑟) = 0 𝑎𝑡 𝑟 = 0
𝑅
Thus, 𝐵 = 0 𝑠𝑖𝑛𝑐𝑒 cosh(0) = 1 (𝐵𝐶 2′ ) 𝑎𝑛𝑑 𝐴 = 𝑠𝑖𝑛𝑐𝑒 𝑓(𝑅) = 𝑅
sinh(𝛼𝑟)

𝑅𝑠𝑖𝑛ℎ(𝛼𝑟) ∗ 𝑅 sinh(𝛼𝑟)
So, 𝑓(𝑟) = → 𝐶𝐴 (𝑟) = 𝐶𝐴,𝑠 [ ]
sinh(𝛼𝑅) 𝑟 sinh(𝛼𝑅)

The molar flow of A at the surface at r=R, 𝜔𝐴𝑠 , 𝑖𝑠:

𝑑𝐶𝐴
𝜔𝐴𝑠 = 4𝜋𝑅2 𝑁𝐴𝑠 = −4𝜋𝑅2 𝐷𝐴 |
𝑑𝑟 𝑟=𝑅
∗ [1
𝜔𝐴𝑠 = 4𝜋𝑅𝐷𝐴 𝐶𝐴,𝑠 − 𝛼𝑅𝑐𝑜𝑡ℎ(𝛼𝑅)]

Imagine that all diffusional resistance is eliminated by powdering the pellet. If the orginal pellet
contains â 𝑐𝑚2 𝑎𝑟𝑒𝑎 𝑝𝑒𝑟 𝑐𝑚3 of pellet, we see that the total area that becomes available is:
4
𝐴𝑡𝑜𝑡 = 𝜋𝑅3 𝑎̂
3
Such that the maximum flow to the surface would be:
4 ∗
𝜔𝐴𝑜 = 𝜋𝑅3 𝑎̂[−𝑘𝐴𝑠 𝐶𝐴,𝑠 ]
3
Thus, 𝑘𝐴𝑠 is the “real” surface rate constant, but using 𝑘𝑖𝑣 = 𝑎̂𝑘𝐴𝑠 as an effectiver parameter
works as well

It is common to rank diffeerent catalysts according to their freedom from diffusional control
using a parameter 𝜂𝐴 , which is defined as the ratio of the actual 𝜔𝐴𝑠 to that of the maximum
possible 𝜔𝐴𝑜 consumption rate of A:
𝜔𝐴𝑠 4𝜋𝑅𝐷𝐴 𝐶𝐴∗𝑠
𝜂𝐴 = = [1 − 𝛼𝑅𝑐𝑜𝑡ℎ(𝛼𝑅)]
𝜔𝐴𝑜 4/3𝜋𝑅3 𝑎̂(−𝑘𝐴𝑠 𝐶𝐴∗𝑠 )

Page 11 of 17
ChBE 6260 Topic 4

3 𝑘𝑖𝑣
𝜂𝐴 = [𝐾𝑐𝑜𝑡ℎ(𝐾) − 1] 𝐾 = 𝑅 √
𝐾2 𝐷𝐴

The above expression for the spherical geometry can be generalized to treat porous plate and
cylinder catalysts by defining a more general version of “K” in terms of external surface area, Sx
and particle volume, Vp.

𝑉𝑝 𝑘𝑖𝑣 𝑉𝑝 𝑘𝐴𝑠 𝑎̂
Let 𝜙 = √ = √ “Thiele Modulus”
𝑆𝑥 𝐷𝐴 𝑆𝑥 𝐷𝐴

𝑉𝑝 𝑅 𝑉𝑝 𝑅 𝑉𝑝
( ) = → 𝐾 = 3𝜙 ( ) = ( ) =𝑑
𝑆𝑥 𝑠𝑝ℎ𝑒𝑟𝑒 3 𝑆𝑥 𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟 2 𝑆𝑥 𝑝𝑙𝑎𝑡𝑒

Page 12 of 17
ChBE 6260 Topic 4

Continuous fermentation via immobilized yeast cells

Conversion of glucose via yeast cells – biofuels from cellulosic sources
Nonviable yeast cells are immobilized in alginate beads. The beads are stirred in a glucose
medium under anaerobic conditions.
The effective diffusivity in the beads depends on the cell density according to the relationship:
𝑚2
𝐷𝐴,𝑒𝑓𝑓 = (6.33 − 7.17𝑥𝑐𝑒𝑙𝑙𝑠 ) ∗ 10−10
𝑠
𝑥𝑐𝑒𝑙𝑙𝑠 = 𝑤𝑡. 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑦𝑒𝑎𝑠𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑔𝑒𝑙
Glucose consumption can be assumed to be zero-order; the reaction rate constant at a yeast
density in the beads of 15 wt% is 0.5 g/min*L
The concentration of glucose should remain above zero at all points in the bead.
For a medium containing 30 g/L glucose, find the maximum radius of the beads as a function of
cell loading between 10 and 45 wt%

Spherical Equation of change

𝑑 2 𝐶𝐴 𝑑𝐶𝐴
𝐷𝐴,𝑒 ( 2 𝑟 2 + 2𝑟 ) − 𝑘𝑜 𝑟 2 = 0
𝑑𝑟 𝑑𝑟

𝐵𝐶 1: 𝐶𝐴 = 𝐶𝐴𝑠 𝑎𝑡 𝑟 = 𝑅

𝑑𝐶𝐴
𝐵𝐶 2: = 0 𝑎𝑡 𝑟 = 𝑅𝑜 = 0
𝑑𝑟

Solution:
𝑘𝑜 𝑅2 𝑟 2 2𝑅𝑜3 2𝑅𝑜3
𝐶𝐴 = 𝐶𝐴𝑠 + ( 2−1+ 3 − 3 )
6𝐷𝐴,𝑒 𝑅 𝑅 𝑅

𝑘𝑜 𝑅2 𝑟 2
𝐶𝐴 = 𝐶𝐴𝑠 + ( − 1)
6𝐷𝐴,𝑒 𝑅2

For zero order reaction kinetics in spherical coordinates,

𝑅 𝑘𝑜
𝜙𝑜 = √
3√2 𝐷𝐴,𝑒 𝐶𝐴𝑠

𝐶𝐴 𝑘𝑜 𝑅2 𝑟2 𝜙𝑜2 𝑟 2
=1+ ( 2 − 1) = 1 + ( − 1) ∗∗∗
𝐶𝐴𝑠 6𝐷𝐴,𝑒 𝐶𝐴𝑠 𝑅 3 𝑅2

First we need the reate constante in more useful units:

Page 13 of 17
ChBE 6260 Topic 4

𝑔 𝑘𝑔
𝑘𝑜 = 0.5 = 8.33 ∗ 10−5 3
𝑚𝑖𝑛 ∗ 𝐿 𝑚 ∗𝑠
Evaluate *** at CA=0 at r=0

6𝐷𝐴,𝑒 𝐶𝐴𝑠
𝑅𝑀𝑎𝑥 = √
𝑘𝑜

Xcell 𝐷𝐴,𝑒 (𝑚2 /𝑠 ∗ 10−10 ) 𝑘𝑜 (𝑘𝑔 ∗ 𝑚−3 ∗ 𝑠 −1 ∗ 10−3 ) 𝑅𝑀𝑎𝑥 (𝑚𝑚)

0.1 5.61 5.56 4.26
0.2 4.9 11.1 2.82
0.3 4.18 16.7 2.12
0.4 3.46 22.2 1.67
0.45 3.1 25.0 1.49

Page 14 of 17
ChBE 6260 Topic 4

Shrinking Core Problem:

Imagine a catalyst particle that has deactivated via coking, and we are trying to regenerate that
particle with hot O2
The following reaction occurs:
𝐶 + 𝑂2 → 𝐶𝑂2
The sketch of the system:

Let’s apply a shell balance to solve this. Although the core is shrinking with time, we assume
that the concentration profiles in any instant in time to be steady state over the Ro-R distance.
This is known as the quasi-steady state assumption (QSSA).
Shell Balance:
𝑁𝐴𝑟 4𝜋𝑟 2 |𝑟 − 𝑁𝐴𝑟 4𝜋𝑟 2 |𝑟+∆𝑟 + 0𝑔𝑒𝑛 = 0𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

𝑑𝑁𝐴𝑟 𝑟 2
= 0 𝐸𝑞. 𝐴
𝑑𝑟
Next, we note that for every mole of O2 in, we have 1 mole CO2 out,
𝑁𝐶𝑂2 = −𝑁𝑂2
𝑑𝐶𝐴
𝑁𝐴𝑟 = −𝐷𝐴,𝑒𝑓𝑓 𝐸𝑞. 𝐵
𝑑𝑟
𝑑 𝑑𝐶𝐴 2 𝑑 2 𝑑𝐶𝐴
𝐸𝑞. 𝐴 𝑎𝑛𝑑 𝐸𝑞. 𝐵 (−𝐷𝐴,𝑒𝑓𝑓 𝑟 )=0 → (𝑟 )=0
𝑑𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟
Now the important part: Boundary Conditions
At outer surface of particle: 𝑟 = 𝑅𝑜 , 𝐶𝐴 = 𝐶𝐴𝑜

At fresh carbon/gas interface: 𝑟 = 𝑅(𝑡), 𝐶𝐴 = 0 (rapid reaction)

Page 15 of 17
ChBE 6260 Topic 4

Integrate and apply BC

1 1
𝐶𝐴 ( − )
𝑅(𝑡) 𝑟
=
𝐶𝐴𝑜 1 1
−
𝑅(𝑡) 𝑅𝑜
Insert above equations in to flux equations
𝑑𝐶𝑂2
𝑁𝑂2𝑟 = −𝐷𝑂2,𝑒𝑓𝑓
𝑑𝑟
𝐷𝑂2,𝑒𝑓𝑓 𝐶𝑂2 ,𝑜
=−
1 1
( − ) 𝑟2
𝑅(𝑡) 𝑅𝑜
Overall Mass Balance on carbon
[Rate In] – [Rate Out] + [Rate of Generation] – [Rate of Consumption] = [Rate of Accumulation]
𝑑 4 3
𝑟𝑐′ 4𝜋𝑅2 = ( 𝜋𝑅 𝜌𝑐 𝜙𝑐 )
𝑑𝑡 3
𝜙𝑐 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛 𝑖𝑛 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
𝑑𝑅 𝑟𝑐′
= 𝐸𝑞. 𝐶
𝑑𝑡 𝜙𝑐 𝜌𝑐
Finally the rate of disappearance of carbon is equal to the flux of O2 to the gas carbon interface:
𝐷𝐴,𝑒𝑓𝑓 𝐶𝐴,𝑜
−𝑟𝑐′ = −𝑁𝐴,𝑟 |𝑟=𝑅 = 𝐸𝑞. 𝐷
𝑅2
𝑅−
𝑅𝑜
Put equation D into equation C and then integrate with R=Ro at t=0, the time required for the
carbon to recede to a radius R is:

𝜌𝑐 𝑅𝑜2 𝜙𝑐 𝑅 2 𝑅 3
𝑡= [1 − 3 ( ) + 2 ( ) ]
6𝐷𝐴,𝑒𝑓𝑓 𝐶𝐴𝑜 𝑅𝑜 𝑅𝑜

Complete time for consumption

𝜌𝑐 𝑅𝑜2 𝜙𝑐
𝑡=
6𝐷𝐴,𝑒𝑓𝑓 𝐶𝐴𝑜

This approach can be modified (and made more complex) for situations other than equimolar
counter diffusion and instantaneous surface reactions.

Page 16 of 17
ChBE 6260 Topic 4

Page 17 of 17