Mass Transfer

CHE304

Chapter 25
Unsteady-State Molecular Diffusion
Dr Mohammed Gamal Mohammed

1
Unsteady-State Mass Transfer
The general differential equation of diffusional mass transfer is:
𝜕𝑐𝐴
𝛁. 𝐍𝑨 + − 𝑅𝐴 = 0
𝜕𝑡
We will consider the case of no chemical reaction, and no bulk flow (static fluid) and constant
diffusivity in one dimension.
𝑅𝐴 = 0
𝜕𝑐𝐴
𝐍𝑨 = −𝐷𝐴𝐵
𝜕𝑧
The equation reduces to “Fick’s second law”:
𝝏𝒄𝑨 𝝏𝟐 𝒄𝑨
= 𝑫𝑨𝑩
𝝏𝒕 𝝏𝒛𝟐
Concentration is dependent on space and time. Therefore, we will deal with Partial Differential
Equations (PDE’s)
2
Partial Differential Equation
• Differential equations with more than one independent variables.

• They require initial condition (I.C.) in addition to the boundary

conditions (B.C.)

• Solution of PDE’s requires using different approaches depending on

the type of equation to be solved, one of them is using “Laplace
Transforms”.

3
Laplace Transform (ℒ)

4
Laplace Transform (ℒ)
• A mathematical method for converting differential equations into algebraic equations, and
converting partial differential equations into ordinary differential equations.
• The equation are commonly converted from functions of “t” in original equations to functions of
“s” in Laplace transform.
• In “s” domains, the equations are easier to solve, after solving it is transformed to “t domain” by
performing “inverse Laplace transformation (ℒ −1 )”
• Laplace transform formula:
+∞
ℒ 𝐹 𝑡 =𝐹 𝑠 =න 𝑒 −𝑠𝑡 𝑓 𝑡 𝑑𝑡
0

• There are standard tables for transforms from “s domain” to “t domain”

5
Laplace Transform Tables

6
Example 1
First put the notation:
Solve the following equation using Laplace 𝑦=𝐹 𝑡 , 𝑎𝑛𝑑 ℒ 𝑦 =ℒ 𝐹 𝑡 =𝑓 𝑠
transform
𝑑2 𝑦 For boundary conditions:
− 16𝑦 = 0
𝑑𝑡 2 𝐹 0 =1 𝑎𝑛𝑑 𝐹′ 0 = 1
With the boundary conditions
𝑑𝑦 Laplace transformation:
𝑦𝑡=0 = 1 𝑎𝑛𝑑 ቤ =1
𝑑𝑡 𝑡=0 ℒ 𝑓 ′′ 𝑡 − 16𝑓 𝑡 =0

𝑓 𝑠 𝑓 𝑡
𝑠 2 𝑓 𝑠 − 𝑠𝐹 0 − 𝐹 ′ 0 − 16𝑓(𝑠) = 0
1 𝑎𝑡 𝑠 2 𝑓 𝑠 − 𝑠 − 1 − 16𝑓(𝑠) = 0
𝑒
𝑠−𝑎
1 𝑠 2 − 16 𝑓 𝑠 − 𝑠 + 1 = 0
𝑒 −𝑎𝑡
𝑠+𝑎
𝑠+1 𝑠+1
𝑠𝑓 𝑠 − 𝐹 0 𝐹′ 𝑡 𝑓 𝑠 = 2 =
𝑠 − 16 𝑠+4 𝑠−4
𝑠 2 𝑓 𝑠 − 𝑠𝐹 0 − 𝐹 ′ 0 𝐹 ′′ 𝑡

7
Example 1
𝑠+1 𝑠+1 3Τ8 5Τ8
𝑓 𝑠 = = 𝑓 𝑠 = +
𝑠 2 − 16 𝑠+4 𝑠−4 𝑠+4 𝑠−4
𝑠+1 𝐴 𝐵 𝟑 𝟓
𝑓 𝑠 = = + 𝒚 = 𝓛−𝟏 𝒇 𝒔 = 𝒆−𝟒𝒕 + 𝒆𝟒𝒕
𝑠+4 𝑠−4 𝑠+4 𝑠−4 𝟖 𝟖
𝑠+1=𝐴 𝑠−4 +𝐵 𝑠+4
𝑠 + 1 = 𝑠 𝐴 + 𝐵 + 4 −𝐴 + 𝐵 𝑓 𝑠 𝑓 𝑡
𝐴+𝐵 =1 1
𝑒 𝑎𝑡
−𝐴 + 𝐵 = 1Τ4 𝑠−𝑎
1
Solving the two equations: 𝑒 −𝑎𝑡
𝑠+𝑎
𝐵 = 5Τ8 , 𝐴 = 3Τ8 𝑠𝑓 𝑠 − 𝐹 0 𝐹′ 𝑡
3Τ8 5Τ8 𝑠 2 𝑓 𝑠 − 𝑠𝐹 0 − 𝐹 ′ 0 𝐹 ′′ 𝑡
𝑓 𝑠 = +
𝑠+4 𝑠−4

8
Example 1 – Analytical Solution
Solve the following equation using Laplace transform
𝑑2 𝑦
− 16𝑦 = 0 Differential Equation General Solution
𝑑𝑡 2
With the boundary conditions 𝑑𝑦 𝑓 𝑥
= න 𝑔𝑑𝑦 = න 𝑓𝑑𝑥 + 𝐶1
𝑑𝑦 𝑑𝑥 𝑓 𝑦
𝑦𝑡=0 = 1 𝑎𝑛𝑑 ቤ =1
𝑑𝑡 𝑡=0
𝑑𝑦
+𝑓 𝑥 𝑦=𝑔 𝑥 𝑦 = 𝑒 − ‫ 𝑥𝑑𝑓 ׬‬න 𝑒 ‫ 𝑥𝑑𝑔 𝑥𝑑𝑓 ׬‬+ 𝐶1
The general solution is: 𝑑𝑥
𝑦 = 𝐶3 e4t + 𝐶4 𝑒 −4𝑡
𝑑2𝑦 𝑦 = 𝐶1 𝑐𝑜𝑠 𝑎𝑥 + 𝐶2 𝑠𝑖𝑛 𝑎𝑥
B.C.1: 0
1 = 𝐶3 𝑒 + 𝐶4 𝑒 0
2
+ 𝑎2 𝑦 = 0
𝑑𝑥
𝐶3 + 𝐶4 = 1 𝑦 = 𝐶1 𝑐𝑜𝑠ℎ 𝑎𝑥 + 𝐶2 𝑠𝑖𝑛ℎ 𝑎𝑥
𝑑2𝑦 or
𝑑𝑦 − 𝑎2 𝑦 = 0
B.C.2: ቚ = 1 = 4𝐶3 𝑒 0 − 4𝐶4 𝑒 0 𝑑𝑥 2 𝑦 = 𝐶3 𝑒 𝑎𝑥 + 𝐶4 𝑒 −𝑎𝑥
𝑑𝑡 𝑡=0

𝐶3 − 𝐶4 = 1Τ4 1 𝑑 𝑑𝑦 𝐶1 𝐶2
𝑥2 + 𝑎2 𝑦 = 0 𝑦= 𝑐𝑜𝑠 𝑎𝑥 + 𝑠𝑖𝑛 𝑎𝑥
𝐶3 = 5Τ8 , 𝐶4 = 3Τ8 𝑥 𝑑𝑥 𝑑𝑥 𝑥 𝑥
𝟓 𝟒𝒕 𝟑 −𝟒𝒕
𝐲= 𝒆 + 𝒆
𝟖 𝟖𝟒
9
Integration Tables
Differential Equation General Solution

𝑑𝑦 𝑓 𝑥
= න 𝑔𝑑𝑦 = න 𝑓𝑑𝑥 + 𝐶1
𝑑𝑥 𝑓 𝑦

𝑑𝑦
+𝑓 𝑥 𝑦=𝑔 𝑥 𝑦 = 𝑒 − ‫ 𝑥𝑑𝑓 ׬‬න 𝑒 ‫ 𝑥𝑑𝑔 𝑥𝑑𝑓 ׬‬+ 𝐶1
𝑑𝑥

𝑑2𝑦 𝑦 = 𝐶1 𝑐𝑜𝑠 𝑎𝑥 + 𝐶2 𝑠𝑖𝑛 𝑎𝑥

2 + 𝑎2𝑦 = 0
𝑑𝑥
𝑦 = 𝐶1 𝑐𝑜𝑠ℎ 𝑎𝑥 + 𝐶2 𝑠𝑖𝑛ℎ 𝑎𝑥
𝑑2𝑦 or
2 − 𝑎2𝑦 = 0
𝑑𝑥 𝑦 = 𝐶3 𝑒 𝑎𝑥 + 𝐶4 𝑒 −𝑎𝑥
1 𝑑 𝑑𝑦 𝐶1 𝐶2
𝑥2 + 𝑎2𝑦 = 0 𝑦 = 𝑐𝑜𝑠 𝑎𝑥 + 𝑠𝑖𝑛 𝑎𝑥
𝑥 𝑑𝑥 𝑑𝑥 𝑥 𝑥
10
Example 2
Solve the following equation using Laplace transform First put the notation:
𝑑2 𝑦 𝑑𝑦 𝑦=𝐹 𝑡 , 𝑎𝑛𝑑 ℒ 𝑦 =ℒ 𝐹 𝑡 =𝑓 𝑠
+ 3 + 2𝑦 = 0
𝑑𝑡 2 𝑑𝑡
For boundary conditions:
Where
𝐹 0 =1 𝑎𝑛𝑑 𝐹′ 0 = 0
𝑑𝑦
𝑦𝑡=0 = 1 𝑎𝑛𝑑 ቤ =0
𝑑𝑡 𝑡=0 Laplace transformation:
ℒ 𝑓 ′′ 𝑡 + 3𝑓 ′ 𝑡 + 2𝑓 𝑡 =0
𝑓 𝑠 𝑓 𝑡
𝑠 2 𝑓 𝑠 − 𝑠𝐹 0 − 𝐹 ′ 0 + 3 𝑠𝑓 𝑠 − 𝐹 0 + 2𝑓(𝑠) = 0
1
𝑒 𝑎𝑡 𝑠 2 𝑓 𝑠 − 𝑠 + 3 𝑠𝑓 𝑠 − 1 + 2𝑓(𝑠) = 0
𝑠−𝑎
1 𝑠 2 + 3𝑠 + 2 𝑓 𝑠 = 𝑠 + 3 𝐹 0 = 𝑠 + 3
𝑒 −𝑎𝑡
𝑠+𝑎
𝑠𝑓 𝑠 − 𝐹 0 𝐹′ 𝑡
𝑠+3 𝑠+3
𝑓 𝑠 = =
𝑠 2 + 3𝑠 + 2 𝑠+2 𝑠+1
𝑠 2 𝑓 𝑠 − 𝑠𝐹 0 − 𝐹 ′ 0 𝐹 ′′ 𝑡

11
Example 2
𝑓 𝑠 𝑓 𝑡
𝑠+3 𝐴 𝐵
𝑓 𝑠 = = + 1
𝑠+2 𝑠+1 𝑠+2 𝑠+1 𝑒 𝑎𝑡
𝑠−𝑎
1
𝐴 𝑠+1 +𝐵 𝑠+2 =𝑠+3 𝑒 −𝑎𝑡
𝑠+𝑎
𝑠𝑓 𝑠 − 𝐹 0 𝐹′ 𝑡
𝐴 + 𝐵 = 1 𝑎𝑛𝑑 𝐴 + 2𝐵 = 3
𝑠 2 𝑓 𝑠 − 𝑠𝐹 0 − 𝐹 ′ 0 𝐹 ′′ 𝑡
𝐵 = 2 𝑎𝑛𝑑 𝐴 = −1

−1 2
𝑓 𝑠 = +
𝑠+2 𝑠+1

−1 2
𝐹 𝑡 = ℒ −1 + = −𝑒 −2𝑡 + 2𝑒 −𝑡
𝑠+2 𝑠+1

12
Error Function
Error function (erf) a mathematical special
function that takes the form:
2 𝑧 −𝜉2
erf 𝑧 = න𝑒 𝑑𝜉
𝜋 0
The function output is in the range of -1 to 1
Complementary error function is defined as:
2 𝑧 −𝜉2
erfc 𝑧 = 1 − erf 𝑧 = 1 − න 𝑒 𝑑𝜉
𝜋 0
Error function is sometimes the output of inverse
Laplace transform

13
 erf 𝜙
𝝓 𝐞𝐫𝐟 𝝓 𝝓 𝐞𝐫𝐟 𝝓 𝝓 𝐞𝐫𝐟 𝝓 𝝓 𝐞𝐫𝐟 𝝓
0.00 0.0000 0.65 0.6420 1.35 0.9438 2.05 0.9963
0.025 0.0282 0.70 0.6778 1.40 0.9523 2.10 0.9970
0.05 0.0564 0.75 0.7112 1.45 0.9597 2.15 0.9976
0.10 0.1125 0.80 0.7421 1.50 0.9661 2.20 0.9981
0.15 0.1680 0.85 0.7707 1.55 0.9716 2.25 0.9985
0.20 0.2227 0.90 0.7969 1.60 0.9763 2.30 0.9989
0.25 0.2763 0.95 0.8209 1.65 0.9804 2.35 0.9991
0.30 0.3286 1.00 0.8427 1.70 0.9838 2.40 0.9993
0.35 0.3794 1.05 0.8624 1.75 0.9867 2.45 0.9995
0.40 0.4284 1.10 0.8802 1.80 0.9891 2.50 0.9996
0.45 0.4755 1.15 0.8961 1.85 0.9911 2.55 0.9997
0.50 0.5205 1.20 0.9103 1.90 0.9928 2.60 0.9998
0.55 0.5633 1.25 0.9229 1.95 0.9942 2.65 0.9998
0.60 0.6039 1.30 0.9340 2.00 0.9953 2.70 0.9999

14
Error Function
2 𝑧 −𝜉2
erf 𝑧 = න 𝑒 𝑑𝜉
𝜋 0

For 𝒛 ≤ 𝟎. 𝟓

𝟐 𝒛𝟑
𝐞𝐫𝐟 𝒛 = 𝒛−
𝝅 𝟑

For 𝒛 > 𝟏

𝟏
𝐞𝐫𝐟 𝒛 = 𝟏 − 𝐞𝐱𝐩 −𝒛𝟐
𝒛 𝝅

15
Useful References
• “Appendix C: Mathematical Topics” in Transport Phenomenon by R. B.
Bird, W. E. Stewart and E. N. Lightfoot

• M.R. Spiegel, S Lipschutz and J Liu, Mathematical Handbook of

Formulas and Tables, Third edition, 2009

16
Examples to be Covered

Unsteady State Molecular

Diffusion Systems

USS-MD into a finite medium

USS-MD into a semi-infinite
(Charts for simple geometric
medium (analytical solution)
shapes)

17
Examples to be Covered

Unsteady State Molecular

Diffusion Systems

USS-MD into a finite medium

USS-MD into a semi-infinite
(Charts for simple geometric
medium (analytical solution)
shapes)

18
“Semi Infinite” Medium

This is ACTUALLY not an infinite depth.

For the swimmer it is way deeper than
what he can reach.
For him, it is infinite!
This is what we call “Semi-Infinite Depth” 19
Diffusion in a Semi-Infinite Medium
One-dimensional mass transfer of a solute into a semi-infinite
stationary liquid or solid medium where surface concentration of the
solute is fixed.
Examples:
- Absorption of oxygen gas into a deep tank of still water
- Doping of phosphorous into a silicon wafer

The concentration at the surface is always constant at CAs

The concentration in the bulk of the medium is always constant at CAo
Before diffusion starts the concentration everywhere was CAo

20
Diffusion in a Semi-Infinite Medium
Converting text into equations:
• Boundary conditions:
At 𝑧 = 0 𝑐𝐴 = 𝑐𝐴𝑠 for t>0 or 𝑐𝐴 0, 𝑡 = 𝑐𝐴𝑠
At 𝑧 = ∞ 𝑐𝐴 = 𝑐𝐴𝑜 for t>0 or 𝑐𝐴 ∞, 𝑡 = 𝑐𝐴𝑜
• Initial condition:
At 𝑡 = 0 𝑐𝐴 = 𝑐𝐴𝑜 for all z or 𝑐𝐴 𝑧, 0 = 𝑐𝐴𝑜
• Diffusion mass transfer equation
𝜕𝑐𝐴 𝜕 2 𝑐𝐴
= 𝐷𝐴𝐵
𝜕𝑡 𝜕𝑧 2

This equation with the given boundary conditions can be solved using Laplace
transform
BUT initial condition MUST BE HOMOGENOUS (i.e., 𝐹 0 = 0) and boundary
conditions are recommended to be homogeneous.
21
Solution Steps
Redefine
Partial Variable Partial 𝓛 Ordinary
Differential Differential Differential
Equation to adjust Equation Laplace Equation
𝒄′′ = 𝒇 𝒕, 𝒛 I.C. 𝜽′′ = 𝒇 𝒕, 𝒛 Transform 𝜃′ҧ = 𝑓 𝑠, 𝑧

𝐈𝐧𝐭𝐞𝐠𝐫𝐚𝐭𝐢𝐨𝐧

Algebraic Back to Algebraic 𝓛−𝟏 Algebraic

Equation Equation Equation
𝒄 = 𝒇 𝒕, 𝒛 Original 𝜽 = 𝒇 𝒕, 𝒛 Inverse 𝜃ҧ = 𝑓 𝑠, 𝑧
variable Laplace
Transform
22
 Diffusion in a Semi-Infinite Medium
Applying Laplace transform: Original Equations
Define 𝜽 = 𝒄𝑨 − 𝒄𝑨𝒐
• Boundary conditions:
• Boundary conditions: • Boundary conditions:
At 𝑧 = 0 𝑐𝐴 = 𝑐𝐴𝑠 for t>0
𝑐 −𝑐 At 𝑧 = ∞ 𝑐𝐴 = 𝑐𝐴𝑜 for t>0
At 𝑧 = 0 𝜃 = 𝑐𝐴𝑠 − 𝑐𝐴𝑜 for t>0 𝐴𝑡 𝑧 = 0 𝜃ҧ = 𝐴𝑠 𝐴𝑜 for t > 0
s
• Initial condition:
At 𝑧 = ∞ 𝜃 = 0 for t>0 𝐴𝑡 𝑧 = ∞ 𝜃ҧ = 0 for t > 0 At 𝑡 = 0 𝑐𝐴 = 𝑐𝐴𝑜 for all z

• Initial condition: • Diffusion mass transfer equation

Initial condition: 𝜕𝑐𝐴 𝜕 2 𝑐𝐴
= 𝐷𝐴𝐵
At 𝑡 = 0 𝜃 = 0 for all z 𝜕𝑡 𝜕𝑧 2
𝐴𝑡 𝑡 = 0 𝜃ҧ = 0 for all z

• Diffusion mass transfer equation • Diffusion mass transfer equation 𝒇 𝒔 𝒇 𝒕

𝜕𝜃 𝜕2𝜃 𝑑 2 𝜃ҧ 𝑎
= 𝐷𝐴𝐵 2 𝑠𝜃ҧ − 0 = 𝐷𝐴𝐵 2 𝑎
𝜕𝑡 𝜕𝑧 𝑑𝑧 𝑠
𝑠𝑓 𝑠 − 𝐹 0 𝐹′ 𝑡
𝑑 𝜃ҧ
2

Time Domain Laplace Domain 𝐷𝐴𝐵 − 𝑠𝜃ҧ = 0

𝜕𝑧 2
𝑓 𝑡 =𝜃 𝑓 𝑠 = 𝜃ҧ 23
 Diffusion in a Semi-Infinite Medium
𝑐𝐴𝑠 −𝑐𝐴𝑜
𝑑 2 𝜃ҧ 𝑠 Applying B.C. 1: 𝐶2 =
− 𝜃ҧ = 0 s Boundary conditions:
𝜕𝑧 2 𝐷𝐴𝐵 So,
𝑐𝐴𝑠 − 𝑐𝐴𝑜
1 𝐴𝑡 𝑧 = 0 → 𝜃ҧ = for t > 0
exp −𝑧 𝑠 s
ODE General Solution 𝐷𝐴𝐵
𝜃ҧ = 𝑐𝐴𝑠 − 𝑐𝐴𝑜 𝐴𝑡 𝑧 = ∞ → 𝜃ҧ = 0 for t > 0
𝑦 = 𝐶1 𝑐𝑜𝑠ℎ 𝑎𝑥 + 𝐶2 𝑠𝑖𝑛ℎ 𝑎𝑥 s
𝑑2𝑦 or
− 𝑎2 𝑦 = 0
𝑑𝑥 2 𝑦 = 𝐶3 𝑒 𝑎𝑥 + 𝐶4 𝑒 −𝑎𝑥 Applying inverse Laplace transform
𝑧
𝜃 = 𝑐𝐴 − 𝑐𝐴𝑜 = 𝑐𝐴𝑠 − 𝑐𝐴𝑜 erfc
𝑠 𝑠 2 𝐷𝐴𝐵 𝑡
𝜃ҧ = 𝐶1 exp 𝑧 + 𝐶2 exp − 𝑧 𝑐𝐴 − 𝑐𝐴𝑜 𝑧 𝑧 𝒇 𝒔 𝒇 𝒕
𝐷𝐴𝐵 𝐷𝐴𝐵 = erfc = 1 − erf
𝑐𝐴𝑠 − 𝑐𝐴𝑜 2 𝐷𝐴𝐵 𝑡 2 𝐷𝐴𝐵 𝑡 exp −𝑎 𝑠 𝑎
erfc
Applying B.C. 2: C1 must be zero, otherwise 𝑠 2 𝑡
𝜃ҧ = ∞ at 𝑧 = ∞ 𝑐𝐴𝑠 − 𝑐𝐴 𝑧
= erf
𝑐𝐴𝑠 − 𝑐𝐴𝑜 2 𝐷𝐴𝐵 𝑡
𝑠
𝜃ҧ = 𝐶2 exp − 𝑧
𝐷𝐴𝐵

24
Concentration Profile
𝑐𝐴𝑠 − 𝑐𝐴 𝑧
= erf
𝑐𝐴𝑠 − 𝑐𝐴𝑜 2 𝐷𝐴𝐵 𝑡

The profile is for 𝐷𝐴𝐵 = 10−6 𝑐𝑚2 Τ𝑠, 𝑐𝐴𝑜 = 0 𝑚𝑜𝑙𝑒𝑠Τ𝑚3 ,

𝑐𝐴𝑠 = 0.1 𝑚𝑜𝑙𝑒𝑠Τ𝑚3

For the semi-infinite medium assumption to be valid, the

following condition must be fulfilled:
𝐿> 𝐷𝐴𝐵 𝑡

Where L is the actual thickness of the medium where diffusion

takes place.

If the condition is not fulfilled, the boundary conditions will not

be satisfied

25
Flux at the Surface
𝑧
𝑐𝐴 = 𝑐𝐴𝑠 − 𝑐𝐴𝑠 − 𝑐𝐴𝑜 erf
2 𝐷𝐴𝐵 𝑡 𝒅
𝟐
𝟐𝒆−𝒙
2 𝒆𝒓𝒇 𝒙 =
𝜕𝑐𝐴 2 −
𝑧
1 𝒅𝒙 𝝅
2 𝐷𝐴𝐵 𝑡
= − 𝑐𝐴𝑠 − 𝑐𝐴𝑜 × 𝑒 ×
𝜕𝑧 𝜋 2 𝐷𝐴𝐵 𝑡

At z=0
𝜕𝑐𝐴 𝑐𝐴𝑠 − 𝑐𝐴𝑜
ቤ =−
𝜕𝑧 𝑧=0 𝜋𝐷𝐴𝐵 𝑡

Hence,
𝜕𝑐𝐴 𝐷𝐴𝐵 𝑐𝐴𝑠 − 𝑐𝐴𝑜
𝑁𝐴 ቚ = −𝐷𝐴𝐵 ቤ =
𝑧=0 𝜕𝑧 𝑧=0 𝜋𝐷𝐴𝐵 𝑡

𝑫𝑨𝑩
𝑵𝑨 ቚ = 𝒄 − 𝒄𝑨𝒐
𝒛=𝟎 𝝅𝒕 𝑨𝒔

26
Amount Transferred of A within Time t
The total amount of species A transferred with time t can be
calculated as follows:
𝑡
𝑚𝐴 𝑡 − 𝑚𝐴 𝑡𝑜 = 𝑆 න 𝑁𝐴 ቚ 𝑑𝑡
𝑡𝑜 𝑧=0

𝑡
𝐷𝐴𝐵
𝑚𝐴 𝑡 − 𝑚𝐴 𝑡𝑜 = 𝑆 න 𝑐 − 𝑐𝐴𝑜 𝑑𝑡
𝑡𝑜 𝜋𝑡 𝐴𝑠

𝐷𝐴𝐵 𝑡 1
𝑚𝐴 𝑡 − 𝑚𝐴 𝑡𝑜 = 𝑆 𝑐𝐴𝑠 − 𝑐𝐴𝑜 න 𝑑𝑡
𝜋 𝑡𝑜 𝑡

𝐷𝐴𝐵
𝑚𝐴 𝑡 − 𝑚𝐴 𝑡𝑜 = 2𝑆 𝑐𝐴𝑠 − 𝑐𝐴𝑜 𝑡 − 𝑡𝑜
𝜋

27
Example 2
In one typical process, phosphorous oxychloride, POCl3, which has a normal boiling point of 105 oC is
vaporized. The POCl3 vapors are fed into a chemical vapor deposition (CVD) reactor at elevated temperature
and reduced system pressure (e.g., 0.10 atm), where POCl3 decomposes on the silicon surface according to
the reaction
𝑆𝑖(𝑠) + 2𝑃𝑂𝐶𝑙3 → 𝑆𝑖𝑂2(𝑠) + 3𝐶𝑙2 + 2𝑃(𝑠)
A SiO2 coating rich in molecular phosphorous (P) is formed over the crystalline-silicon surface. The molecular
phosphorous then diffuses through the crystalline silicon to form the Si–P thin film. So the coating is the
source for mass transfer of phosphorous, and the silicon wafer is the sink for mass transfer of phosphorous.
Consider a simplified case where the P-atom concentration is constant at the interface. As the diffusion
coefficient of P atoms in crystalline silicon is very low, and only a thin film of Si–P is desired, phosphorous
atoms do not penetrate very far into the silicon. Therefore, the phosphorous atoms cannot “see” through
the entire thickness of the wafer, and the Si solid serves as a semi-infinite sink for the diffusion process.
It is desirable to predict the properties of the Si–P thin film as a function of doping conditions. The
concentration profile of the doped phosphorous atoms is particularly important for controlling the electrical
conductivity of the semiconducting thin film.
Consider the phosphorous doping of crystalline silicon at 1100 oC, a temperature high enough to promote
phosphorous diffusion. The surface concentration of phosphorous (cAs) is 2.5×1020 atoms P/cm3 solid Si,
which is relatively diluted. The diffusivity of P in Si is 6.5×10-13 cm2/sec. Furthermore, the phosphorous-rich
coating is considered as an infinite source relative to the amount of P atoms transferred, so that cAs is
constant.
Predict the depth of the Si–P thin film after 1 h, if the target concentration is 1% of the surface value
(2.5×1018 atoms P/cm3 solid Si), and the concentration profile of P atoms after 1 h.

28
List of Assumptions

• Unsteady state

• Semi infinite medium

• One-dimensional diffusion in z-direction

• Constant boundary conditions (𝑐𝐴𝑜 and 𝑐𝐴𝑠 )

• No homogeneous reaction

• Constant T and P, and constant diffusivity.

29
I.C., B.C. and Solution
Initial condition: The analytical solution to the differential equation with the
At t = 0, 𝑐𝐴 = 𝑐𝐴𝑜 boundary conditions takes the form:
𝑐𝐴𝑠 − 𝑐𝐴 𝑧
= erf
𝑐𝐴𝑠 − 𝑐𝐴𝑜 2 𝐷𝐴𝐵 𝑡
Boundary Conditions:
Given the value of 𝑐𝐴 = 2.5 × 1018 𝑎𝑡𝑜𝑚𝑠 𝑃/𝑐𝑚3 𝑠𝑜𝑙𝑖𝑑 𝑆𝑖
At 𝑧 = 0, 𝑐𝐴 = 𝑐𝐴𝑠 = 2.5 × 1020 𝑎𝑡𝑜𝑚𝑠 𝑃/𝑐𝑚3 𝑠𝑜𝑙𝑖𝑑
𝑐𝐴𝑠 − 𝑐𝐴 2.5 × 1020 − 2.5 × 1018
At 𝑧 = ∞, 𝑐𝐴 = 𝑐𝐴𝑜 = 0 = = 0.99
𝑐𝐴𝑠 − 𝑐𝐴𝑜 2.5 × 1020 − 0
𝑧
erf = 0.99
Continuity equation reduces to: 2 𝐷𝐴𝐵 𝑡

𝜕𝑐𝐴 𝜕 2 𝑐𝐴 𝑧
= 𝐷𝐴𝐵 = 1.82
𝜕𝑡 𝜕𝑧 2 2 𝐷𝐴𝐵 𝑡

30
Calculating the depth
𝑧
= 1.82
2 𝐷𝐴𝐵 𝑡
𝑧 = 1.82 × 2 𝐷𝐴𝐵 𝑡
Time=1 hour=3600 sec
𝐷𝐴𝐵 = 6.5 × 10−13 𝑐𝑚2 /𝑠

𝑧 = 1.82 × 2 𝐷𝐴𝐵 𝑡
𝑧 = 1.82 × 2 × 6.5 × 10−13 × 3600
𝑧 = 1.76 × 10−4 𝑐𝑚 = 1.76 𝜇𝑚

31
Log Scale vs Linear Scale

32
Examples to be Covered

Unsteady State Molecular

Diffusion Systems

USS-MD into a finite medium

USS-MD into a semi-infinite
(Charts for simple geometric
medium (analytical solution)
shapes)

33
Strategy of Solution
• Analytical solution of Fick’s second law for finite medium is long and includes a
lot of mathematical steps.
• The mathematical solution for the unsteady-state mass transfer with certain
restrictive boundary conditions, has been presented in a wide variety of charts to
facilitate the solution for several simple shapes
• Flat plate/slab
• Sphere
• Long cylinder

• The charts give the dimensionless concentration as a function of dimensionless

time and dimensionless position for unsteady state molecular diffusion.
34
Remember Fick’s Second Law
A special case of general continuity equation Continuity equation reduces to:
where: 𝜕𝜌𝐴
= 𝐷𝐴𝐵 𝛁2 𝜌𝐴
𝜕𝑡
• 𝐷𝐴𝐵 = 𝑐𝑜𝑛𝑠𝑡
Similarly in molar units:
• 𝜌 = 𝑐𝑜𝑛𝑠𝑡 (incompressible fluid)
𝜕𝑐𝐴
• 𝑟𝐴 = 0 = 𝐷𝐴𝐵 𝛁2 𝑐𝐴
𝜕𝑡
• Fluid is static (no bulk flow)

35
Conditions to Use the Charts
• Fick’s second law applies

• The body has an initial uniform

concentration 𝑐𝐴𝑜

• The boundary is subject to a new

condition that is constant with time.

36
Parameters
• Actual Parameters • Dimensionless Parameters
• 𝑡 time 𝑐𝐴𝑠 − 𝑐𝐴 Unaccomplished concentration
𝑌=
• 𝑥 actual position 𝑐𝐴𝑠 − 𝑐𝐴0 change

• 𝑥1 Characteristic length 𝐷𝐴𝐵 𝑡

𝑋𝐷 = Relative time
• 𝑐𝐴0 Initial concentration (at t=0) 𝑥12
• 𝑐𝐴𝑠 Concentration at the surface at 𝑥
𝑛= Relative position
any time t>0 𝑥1
• 𝑐𝐴 Concentration at any point at
𝐷𝐴𝐵
any time t>0 𝑚= Relative resistance
𝑘𝑐 𝑥1

Depend on Geometry … 37
Geometry-Related Parameters
• The characteristic length, x1, is the
distance from the point of symmetry
• For shapes where the transport takes
place from two opposite faces, x1 is the
distance from the midpoint to the
surfaces from which the transfer occurs
• For shapes where the transport takes
place from only one of the faces, the x1
value is calculated as if the thickness
were twice the true value

38
 Relative Resistance (𝑚)
1
𝐷𝐴𝐵 𝑘 𝐸𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒
𝑚= = 𝑥𝑐 =
𝑘𝑐 𝑥1 1 𝐵𝑜𝑑𝑦 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒
𝐷𝐴𝐵

• Relative resistance represent the ratio of diffusional

mass transfer to the convection mass transfer

• This term takes into account the convective mass-transfer processes at the boundary.

• In case of negligible convective mass-transfer resistance:

• 𝑘𝑐 ≫ 𝐷𝐴𝐵 , so 𝑚 will be zero. Molecular diffusion controls the flux of the diffusing species.

• The concentration of the species A at the surface, will be equal to the concentration in the bulk fluid → 𝒄𝑨𝒔 = 𝒄𝑨∞

39
Relative Resistance and 𝑌
• If 𝑚 = 0 (no convection resistance), 𝑐𝐴𝑠 = 𝑐𝐴∞
𝑐𝐴𝑠 − 𝑐𝐴 𝑐𝐴∞ − 𝑐𝐴
𝑌= =
𝑐𝐴𝑠 − 𝑐𝐴0 𝑐𝐴∞ − 𝑐𝐴0

• If 𝑚 > 0, 𝑐𝐴𝑠 ≠ 𝑐𝐴∞ , 𝑐𝐴𝑠 is not known

Y is calculated using the bulk concentration:
𝑐𝐴∞ − 𝑐𝐴
𝑌=
𝑐𝐴∞ − 𝑐𝐴0

40
Biot Number (𝐵𝑖)

𝑇ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑜 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛𝑎𝑙 𝑀. 𝑇.

𝐵𝑖𝑜𝑡 𝑁𝑢𝑚𝑏𝑒𝑟 =
𝑇ℎ𝑒 𝑒𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑜 𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛 𝑀. 𝑇.

𝐿
1 𝑘𝑐 𝐿 𝐷𝐴𝐵
𝐵𝑖𝑜𝑡 𝑁𝑢𝑚𝑏𝑒𝑟 = = =
𝑚 𝐷𝐴𝐵 1
𝑘𝑐

41
Summary of Symbols

42
Unst. St. Transport Charts for Different Geometries

43
Example 3
A drug capsule consists of a 0.652-cm-diameter spherical bead and is loaded
with a uniform initial concentration of 68.9 mg/cm3 of Dramamine (the
active ingredient). The drug diffuses through the bead to the body where it
is quickly swept by the body fluids. The convective mass-transfer resistance
is negligible.
The diffusion coefficient of Dramamine (species A) in the gel matrix (species
B) is 3×10-7 cm2/s at a body temperature of 37 C.
Considering this unsteady state diffusion, what is the residual concentration
of Dramamine at the center of the spherical bead after 48 h?

44
Spherical Bead
𝑐𝐴0 = 68.9 𝑚𝑔/𝑐𝑚3
𝑐𝐴𝑠 = 0 𝑚𝑔/𝑐𝑚3

𝐷 0.562
𝑥1 = 𝑅 = = = 0.326 𝑐𝑚
2 2
𝐷𝐴𝐵 = 3 × 10−7 𝑐𝑚2 /𝑠
𝑡 = 48 ℎ𝑟 = 48 × 60 × 60 = 172800 𝑠

Negligible convection mass transfer resistance:

𝑘𝑐 ≫ 𝐷𝐴𝐵 , 𝑖. 𝑒. 𝐷𝐴𝐵 Τ𝑘𝑐 ~0

𝐷𝐴𝐵 𝑡 3 × 10−7 × 172800

𝑋𝐷 = 2 =
𝑥1 0.3262
𝑋𝐷 = 0.488

𝑥 0 𝑐𝐴𝑠 − 𝑐𝐴
𝑛= = =0 𝑌=
𝑥1 0.326 𝑐𝐴𝑠 − 𝑐𝐴0
0 − 𝑐𝐴
𝐷𝐴𝐵 0.018 =
𝑚= =0 0 − 68.9
𝑘𝑐 𝑥1
𝑐𝐴 0,48 ℎ𝑟 = 1.24 𝑚𝑔/𝑐𝑚3
45
Unsteady State Diffusion in 3D Shapes
The charts can be used for cases of diffusion in 3D shapes such as cubes and
cylinders.
The same procedure is used with only one difference: Calculation of 𝑌.
Individual 𝑌’s are calculated, each based on the direction of diffusion, and the
resultant 𝑌 is their product of them.

46
 Unsteady State Diffusion in 3D Shapes
Diffusion in 2 dimensions: Cuboid
• Calculate Y twice, once per dimension.
• The resultant Y is calculated as follows:
𝑌 = 𝑌𝑎 𝑌𝑏
Diffusion in 3 dimensions: Cuboid
• Calculate Y three times.
• The resultant Y is calculated as follows:
𝑌 = 𝑌𝑎 𝑌𝑏 𝑌𝑐
47
 Unsteady State Diffusion in 3D Shapes
Diffusion in 2 dimensions: Cylinder

• Calculate Y twice, once per dimension.

• The resultant Y is calculated as follows:

𝑌 = 𝑌𝑎 𝑌𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟

48
Example 3 - Continued
Consider the spherical capsule is now a cube 0.652 cm on a side. Recalculate the
residual concentration of Dramamine at the center of the cube after 48 h?
Consider that the capsule is now a cylindrical tablet of diameter 0.652 cm and
thickness 0.3 cm. Recalculate the concentration at the same conditions.

49
 Cube Capsule
𝑎
𝑥1 = = 0.326 𝑐𝑚
Givens: 2
𝑐𝐴0 = 68.9 𝑚𝑔/𝑐𝑚3
𝐷𝐴𝐵 𝑡 3 × 10−7 × 172800
𝑐𝐴𝑠 = 0 𝑚𝑔/𝑐𝑚3 𝑋𝐷 = 2 =
𝑥1 0.3262
𝐷𝐴𝐵 = 3 × 10−7 𝑐𝑚2 /𝑠
𝑋𝐷 = 0.488
𝑡 = 48 ℎ𝑟 = 172800 𝑠
𝑥 0
Negligible convection 𝑛= = =0
𝑥1 0.326
mass transfer resistance:
From chart: 𝑌𝑎 = 0.4
𝑘𝑐 ≫ 𝐷𝐴𝐵
𝑌𝑎 = 𝑌𝑏 = 𝑌𝑐 = 0.4
So 𝐷𝐴𝐵 Τ𝑘𝑐 ~0
𝑌 = 𝑌𝑎 𝑌𝑏 𝑌𝑐 = 0.43 = 0.064
𝐷𝐴𝐵
𝑚= =0 𝑐𝐴𝑠 − 𝑐𝐴 0 − 𝑐𝐴
𝑘𝑐 𝑥1 𝑌= = = 0.064
𝑐𝐴𝑠 − 𝑐𝐴0 0 − 68.9
𝑐𝐴 = 0.064 × 68.9 = 4.41 𝑚𝑔/𝑐𝑚3
50
 Cylindrical Capsule
Radial Direction
Givens:
𝑥1 = 𝑅 = 0.326 𝑐𝑚
3
𝑐𝐴0 = 68.9 𝑚𝑔/𝑐𝑚
𝑚=0
3
𝑐𝐴𝑠 = 0 𝑚𝑔/𝑐𝑚
𝐷𝐴𝐵 𝑡 3 × 10−7 × 172800
𝐷𝐴𝐵 = 3 × 10−7 𝑐𝑚2 /𝑠 𝑋𝐷 = 2 =
𝑥1 0.3262
𝑡 = 48 ℎ𝑟 = 172800 𝑠
𝑋𝐷 = 0.488
Negligible convection
𝑥 0
mass transfer resistance: 𝑛= = =0
𝑥1 0.326
𝑘𝑐 ≫ 𝐷𝐴𝐵
From chart: 𝑌𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟 = 0.1
So 𝐷𝐴𝐵 Τ𝑘𝑐 ~0

𝐷𝐴𝐵
𝑚= =0
𝑘𝑐 𝑥1

51
 Cylindrical Capsule
Axial Direction
Givens: 𝑥1 = 𝑅 = 0.15 𝑐𝑚
𝑐𝐴0 = 68.9 𝑚𝑔/𝑐𝑚3
Negligible convection mass transfer resistance:
3
𝑐𝐴𝑠 = 0 𝑚𝑔/𝑐𝑚
𝐷𝐴𝐵 = 3 × 10−7 𝑐𝑚2 /𝑠 𝐷𝐴𝐵 𝑡 3 × 10−7 × 172800
𝑋𝐷 = 2 = = 2.304
𝑥1 0.152
𝑡 = 48 ℎ𝑟 = 172800 𝑠
𝑥 0
Negligible convection 𝑛= = =0
𝑥1 0.326
mass transfer resistance:
𝑘𝑐 ≫ 𝐷𝐴𝐵
From chart: 𝑌𝑎 = 0.005
So 𝐷𝐴𝐵 Τ𝑘𝑐 ~0
𝑌 = 𝑌𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟 𝑌𝑎 = 0.1 × 0.005
𝐷𝐴𝐵
𝑚= =0
𝑘𝑐 𝑥1 𝑐𝐴𝑠 − 𝑐𝐴 0 − 𝑐𝐴
𝑌 = 0.5 × 10−3 = =
𝑐𝐴𝑠 − 𝑐𝐴0 0 − 68.9
𝑐𝐴 = 0.5 × 10−3 × 68.9 = 0.03445 𝑚𝑔/𝑐𝑚3
52
End of Chapter 25

53