Mass Transfer II

Mass Transfer II
Evaluation scheme
Lecture Lab
Marks Weightage Marks Weightage
Minor I Exam 100 5 Lab Report 1 10 3
Minor II Exam 100 5 Lab Report 2 10 3
Major Exam 100 10 Lab Report 3 10 3
Assignment 1 100 5 Lab Report 4 10 3
Assignment 2 100 5 Lab Report 5 10 3
Surprise Quiz 1 100 5 Lab Report 6 10 3
Surprise Quiz 4 100 5 Final Lab Exam 50 13
Viva voce 50 13
Total 50 50
Mass Transfer II
• What is Mass Transfer?
• How does it happen?
Diffusion
https://www.science-sparks.com/diffusion-demonstration
/
Diffusion
Natural process
Spontaneous
No energy input required
https://commons.wikimedia.org/wiki/File:Diffusion_microscopic_picture.gif
Diffusion in solids
https://en.wikipedia.org/wiki/Lattice_diffusion_coefficient
Mathematical approach
V ~ nm3
Number of molecules fluctuates
Random fluctuations
Density ill-defined
Concentration ill-defined
Functions are non-continuous,
non-differentiable
Continuum regime
Density, concentration
Continuous function
Differentiable function
https://www.sciencedirect.com/topics/engineering/continuum-hypothesis
•
Diffusive flux
Flux of orange
Flux of black
•
Convective flux (bulk flow)

Flux of white
https://physics.emory.edu/faculty/weeks/lab/flowing.html
Continuum domain
•
Flux of blue
https://www.science-sparks.com/diffusion-demonstration
/
Diffusion in solids
No bulk flow (assuming low concentration)

Convective flux = 0
Only diffusion
Negative sign: Direction of diffusive flux

opposite to concentration gradient
https://en.wikipedia.org/wiki/Lattice_diffusion_coefficient
Fick’s law
Steady state: Rectangular
z axis
0 L
High Low
concentration concentration
Diffusion
Steady state: Rectangular 3D
z axis
x axis
y axis
Steady state: Cylindrical
Diffusion from inside outwards

In cylindrical coordinates
z axis (axial)
𝜽a
xis
r axis (radial)
In our example:

z axis
𝜽a
xis
r axis
Mole balance inside cylindrical shell
r r+dr
Accumulation = Input – Output + Generation - Consumption

0
r r+dr
z
r r+dr
z
r r+dr
z
r r+dr
Diffusion from center outwards

z axis
𝜽a
xis
r axis

z axis
𝜽a
xis
r axis
Boundary conditions:
1. At r = r1, CA = CA1
2. At r = r2, CA = CA2

z axis
𝜽a
xis
r axis

z axis
𝜽a
xis
r axis

z axis
𝜽a
xis
r axis
z axis
𝜽a
xis Molar flux is given by
r axis
Total molar flux – inner surface:
z axis
𝜽a
xis
r axis
Compare with:
z axis
𝜽a
xis
r axis
Steady state: Spherical
• Diffusive Flux 𝐽𝐴 = −𝐷𝐴𝐵 𝛻𝑐𝐴
In spherical coordinates
𝑑 1 𝑑 1 𝑑
𝛻= 𝑟+ 𝜃+ 𝜑
𝑑𝑟 𝑟 𝑑𝜃 𝑟𝑠𝑖𝑛𝜃 𝑑𝜑
𝜽
r
In our example:
φ
𝑑𝑐𝐴 𝑑𝑐𝐴
=0 =0
𝑑𝜃 𝑑𝜑
In spherical coordinates
𝑑𝑐𝐴
𝐽𝐴 = −𝐷𝐴𝐵 𝛻𝑐𝐴 = −𝐷𝐴𝐵 𝑟
𝑑𝑟
𝜽
r
Mole balance inside spherical shell

Mole balance inside spherical shell
Accumulation = Input – Output + Generation - Consumption
0
𝜽
r 𝑑𝑛
= 𝑓𝑙𝑢𝑥 𝑖𝑛 ∗ 𝑎𝑟𝑒𝑎 𝑖𝑛 − 𝑓𝑙𝑢𝑥 𝑜𝑢𝑡 ∗ 𝑎𝑟𝑒𝑎 𝑜𝑢𝑡
𝑑𝑡
φ
𝑓𝑙𝑢𝑥 𝑖𝑛 ∗ 𝑎𝑟𝑒𝑎 𝑖𝑛 − 𝑓𝑙𝑢𝑥 𝑜𝑢𝑡 ∗ 𝑎𝑟𝑒𝑎 𝑜𝑢𝑡 = 0

𝑓𝑙𝑢𝑥 𝑖𝑛 ∗ 𝑎𝑟𝑒𝑎 𝑖𝑛 − 𝑓𝑙𝑢𝑥 𝑜𝑢𝑡 ∗ 𝑎𝑟𝑒𝑎 𝑜𝑢𝑡 = 0

𝐽𝐴𝑟 ∗ 4𝜋𝑟 2 − 𝐽𝐴 𝑟+𝑑𝑟 ∗ 4𝜋 𝑟 + 𝑑𝑟 2 =0
𝜽
r
𝑟 + 𝑑𝑟 2 𝐽𝐴 𝑟+𝑑𝑟 − 𝑟 2 𝐽𝐴𝑟
=0
φ 𝑑𝑟
𝑑 𝑟 2 𝐽𝐴𝑟
=0
𝑑𝑟
𝑑 𝑟 2 𝐽𝐴𝑟 𝑑𝑐𝐴
=0 𝐽𝐴 = −𝐷𝐴𝐵 𝑟
𝑑𝑟 𝑑𝑟
𝜽
2 𝑑𝑐𝐴
r 𝑑 𝑟 𝐷𝐴𝐵
𝑑𝑟
− =0
φ 𝑑𝑟
𝑑 2
𝑑𝑐𝐴
𝑟 =0
𝑑𝑟 𝑑𝑟
𝑑 2
𝑑𝑐𝐴
𝑟 =0
𝑑𝑟 𝑑𝑟
𝜽 𝑑𝑐𝐴
r 𝑟2 =𝐴
𝑑𝑟
φ 𝑑𝑐𝐴 𝐴
= 2
𝑑𝑟 𝑟
𝐴
𝑐𝐴 = − + 𝐵
𝑟
𝐴
𝑐𝐴 = − + 𝐵
𝑟
Boundary conditions:
𝜽 1. At r = r1, CA = CA1
r 2. At r = r2, CA = CA2
φ 𝐴
𝑐𝐴1 =− +𝐵
𝑟1
𝐴
𝐵 = 𝑐𝐴1 +
𝑟1
𝐴
𝐵 = 𝑐𝐴1 +
𝑟1
𝐴
𝜽 𝑐𝐴2 =− +𝐵
r 𝑟2
𝐴 𝐴
φ 𝑐𝐴2 = − + 𝑐𝐴1 +
𝑟2 𝑟1
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2
𝐴=
𝑟1 − 𝑟2
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2
𝐴=
𝑟1 − 𝑟2
𝐴
𝜽 𝐵 = 𝑐𝐴1 +
𝑟1
r
𝑟1 𝑐𝐴1 − 𝑟2 𝑐𝐴2
φ 𝐵=
𝑟1 − 𝑟2
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2 1 𝑟1 𝑐𝐴1 − 𝑟2 𝑐𝐴2

𝑐𝐴 = − +
𝑟1 − 𝑟2 𝑟 𝑟1 − 𝑟2
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2 1 𝑟1 𝑐𝐴1 − 𝑟2 𝑐𝐴2
𝑐𝐴 = − +
𝑟1 − 𝑟2 𝑟 𝑟1 − 𝑟2
𝜽 Molar flux is given by
r
𝑑𝑐𝐴
𝑁𝐴 = 𝐽𝐴 = −𝐷𝐴𝐵
φ 𝑑𝑟
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2 1
𝑁𝐴 = −𝐷𝐴𝐵
𝑟1 − 𝑟2 𝑟2
Molar flux is given by
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2 1
𝑁𝐴 = −𝐷𝐴𝐵
𝑟1 − 𝑟2 𝑟2
𝜽
r
φ Total molar flux – inner surface:
𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2 1 2
𝑤 = 𝑁𝐴 𝑆𝑎𝑣 = −𝐷𝐴𝐵 ∗ 4𝜋𝑟1
𝑟1 − 𝑟2 𝑟12
Total molar flux – inner surface:
4𝜋𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2
𝑤 = 𝐷𝐴𝐵
𝜽 𝑟2 − 𝑟1
r
Compare with:
φ 𝑆𝑎𝑣 𝐷𝐴𝐵 𝑐𝐴1 − 𝑐𝐴2
𝑤 = 𝑁𝐴 𝑆𝑎𝑣 =
(𝑟2 − 𝑟1 )
𝑆𝑎𝑣 = 4𝜋𝑟1 𝑟2
Unsteady state: Rectangular 3D
𝑑𝑐𝐴 𝑑𝑐𝐴 𝑑𝑐𝐴
• Diffusive Flux 𝐽𝐴 = −𝐷𝐴𝐵 𝑖 + 𝑗 + 𝑘
𝑑𝑥 𝑑𝑦 𝑑𝑧
𝐽𝐴(𝑧+𝑑𝑧) 𝑑𝑥𝑑𝑦 𝐽𝐴𝑦 𝑑𝑥𝑑𝑧
z axis 𝑑 𝑑 𝑑
𝑑𝑐𝐴 𝛻= 𝑖+ 𝑗+ 𝑘
𝐽𝐴𝑧 = −𝐷𝐴𝐵 𝑑𝑥 𝑑𝑦 𝑑𝑧
𝑑𝑧
dy 𝐽𝐴 = −𝐷𝐴𝐵 𝛻𝑐𝐴
dx
𝐽𝐴𝑥 𝑑𝑦𝑑𝑧 𝐽𝐴(𝑥+𝑑𝑥) 𝑑𝑦𝑑𝑧
dz
x axis
𝐽𝐴(𝑦+𝑑𝑦) 𝑑𝑥𝑑𝑧 𝑑𝑐𝐴
𝐽𝐴𝑥 = −𝐷𝐴𝐵
𝑑𝑥
𝑑𝑐𝐴
𝐽𝐴𝑦 = −𝐷𝐴𝐵 𝐽𝐴𝑧 𝑑𝑥𝑑𝑦
y axis 𝑑𝑦
• Mass balance:
𝜕𝑁𝐴
= 𝐽𝐴𝑥 𝑑𝑦𝑑𝑧 − 𝐽𝐴 𝑥+𝑑𝑥 𝑑𝑦𝑑𝑧 + 𝐽𝐴𝑦 𝑑𝑥𝑑𝑧 − 𝐽𝐴 𝑦+𝑑𝑦 𝑑𝑥𝑑𝑧 + 𝐽𝐴𝑧 𝑑𝑥𝑑𝑦 − 𝐽𝐴 𝑧+𝑑𝑧 𝑑𝑥𝑑𝑦
𝜕𝑡
𝐽𝐴(𝑧+𝑑𝑧) 𝑑𝑥𝑑𝑦 𝐽𝐴𝑦 𝑑𝑥𝑑𝑧

z axis
dy
dx
𝐽𝐴𝑥 𝑑𝑦𝑑𝑧 𝐽𝐴(𝑥+𝑑𝑥) 𝑑𝑦𝑑𝑧
dz
x axis
𝐽𝐴(𝑦+𝑑𝑦) 𝑑𝑥𝑑𝑧
𝐽𝐴𝑧 𝑑𝑥𝑑𝑦
y axis
• Mass balance:
𝜕𝑁𝐴
= (𝐽𝐴𝑥 − 𝐽𝐴 𝑥+𝑑𝑥 )𝑑𝑦𝑑𝑧 + (𝐽𝐴𝑦 − 𝐽𝐴 𝑦+𝑑𝑦 )𝑑𝑥𝑑𝑧 + (𝐽𝐴𝑧 − 𝐽𝐴 𝑧+𝑑𝑧 )𝑑𝑥𝑑𝑦
𝜕𝑡
𝜕𝑁𝐴 𝜕𝐽𝐴𝑥 𝜕𝐽𝐴𝑦 𝜕𝐽𝐴𝑧
=− 𝑑𝑥𝑑𝑦𝑑𝑧 − 𝑑𝑥𝑑𝑦𝑑𝑧 − 𝑑𝑥𝑑𝑦𝑑𝑧
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧
𝜕𝑁𝐴 𝜕𝐽𝐴𝑥 𝜕𝐽𝐴𝑦 𝜕𝐽𝐴𝑧

=− + + 𝑑𝑥𝑑𝑦𝑑𝑧
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧
𝜕𝑁𝐴
= −(𝛻 ∙ 𝐽𝐴 )𝑑𝑥𝑑𝑦𝑑𝑧
𝜕𝑡
𝑑 𝑑 𝑑
𝛻= 𝑖+ 𝑗+ 𝑘 𝐽𝐴 = 𝐽𝐴𝑥 𝑖 + 𝐽𝐴𝑦 𝑗 + 𝐽𝐴𝑧 𝑘
𝑑𝑥 𝑑𝑦 𝑑𝑧
• Mass balance:
𝜕𝑁𝐴
= −(𝛻 ∙ 𝐽𝐴 )𝑑𝑥𝑑𝑦𝑑𝑧
𝜕𝑡
𝜕𝐶𝐴
𝑑𝑥𝑑𝑦𝑑𝑧 = −(𝛻 ∙ 𝐽𝐴 )𝑑𝑥𝑑𝑦𝑑𝑧
𝜕𝑡
𝜕𝐶𝐴
= −(𝛻 ∙ 𝐽𝐴 )
𝜕𝑡
𝐽𝐴 = −𝐷𝐴𝐵 𝛻𝐶𝐴
𝜕𝐶𝐴
= 𝛻 ∙ 𝐷𝐴𝐵 𝛻𝐶𝐴
𝜕𝑡
𝜕𝐶𝐴
= 𝐷𝐴𝐵 𝛻 ∙ 𝛻𝐶𝐴
𝜕𝑡
• Mass balance:
𝜕𝐶𝐴
= 𝐷𝐴𝐵 𝛻 ∙ 𝛻𝐶𝐴 Divergence of gradient of scalar
𝜕𝑡
𝜕 𝜕 𝜕
𝛻= 𝑖+ 𝑗+ 𝑘
𝜕𝑥 𝜕𝑦 𝜕𝑧
𝜕2 𝜕2 𝜕2
𝛻 ∙ 𝛻 = 2 + 2 + 2 = 𝛻2 Laplacian
𝜕𝑥 𝜕𝑦 𝜕𝑧
𝜕𝐶𝐴
= 𝐷𝐴𝐵 𝛻 2 𝐶𝐴
𝜕𝑡
What is the gradient of a scalar field? What is the divergence of a vector field?
𝜕𝐶𝐴
𝜕𝑡
Time t = 0 Time t > 0

y
𝜕𝐶𝐴
𝜕𝑡
x
No concentration gradient along y axis and z axis
𝜕𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵
𝜕𝑡 𝜕𝑥 2
z Let 𝐶𝐴 = 𝑇 𝑡 𝑋(𝑥)
𝜕 𝑇 𝑡 𝑋 𝑥 𝜕2 𝑇 𝑡 𝑋 𝑥
= 𝐷𝐴𝐵
𝜕𝑡 𝜕𝑥 2
𝜕𝑇 𝑡 𝜕2𝑋 𝑥
𝑋 𝑥 = 𝐷𝐴𝐵 𝑇 𝑡
𝜕𝑡 𝜕𝑥 2
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
𝜕𝑇 𝑡 𝜕2𝑋 𝑥
𝑋 𝑥 = 𝐷𝐴𝐵 𝑇 𝑡
𝜕𝑡 𝜕𝑥 2
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
=
𝐷𝐴𝐵 𝑇 𝑡 𝜕𝑡 𝑋 𝑥 𝜕𝑥 2
LHS is a function of t only

z RHS is a function of x only
Therefore,
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
= = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = −𝑣𝑒, 𝑜𝑟 0, 𝑜𝑟 + 𝑣𝑒
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = −𝑣𝑒, 0, +𝑣𝑒
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
= 2
= +𝑣𝑒 = 𝜆2
z 𝐷𝐴𝐵 𝑇 𝑡 𝜕𝑡 𝑋 𝑥 𝜕𝑥
1 𝜕𝑇 𝑡
= 𝜆2
𝐷𝐴𝐵 𝑇 𝑡 𝜕𝑡
2𝐷
𝑇 𝑡 = 𝐴𝑒 𝜆 𝐴𝐵 𝑡
At 𝑡 → ∞, 𝑇(𝑡) → ∞
Time t > 0 Not a physically acceptable solution
y
𝜕𝐶𝐴
𝜕𝑡
x
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
= =0
z 𝐷𝐴𝐵 𝑇 𝑡 𝜕𝑡 𝑋 𝑥 𝜕𝑥 2
1 𝜕2𝑋 𝑥
=0
𝑋 𝑥 𝜕𝑥 2
𝜕2𝑋 𝑥
=0
𝜕𝑥 2
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
𝜕2𝑋 𝑥
=0
𝜕𝑥 2
𝑋 𝑥 = 𝐴𝑥 + 𝐵
1 𝜕𝑇 𝑡
=0
z
𝜕𝑇 𝑡
=0
𝜕𝑡
𝑇 𝑡 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐶𝐴 = 𝑇 𝑡 𝑋(𝑥) = 𝐴′𝑥 + 𝐵′
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
1 𝜕𝑇 𝑡 1 𝜕2𝑋 𝑥
= 2
= −𝜆2
z 𝐷𝐴𝐵 𝑇 𝑡 𝜕𝑡 𝑋 𝑥 𝜕𝑥
1 𝜕𝑇 𝑡
= −𝜆2
2𝐷
𝑇 𝑡 = 𝐴𝑒 −𝜆 𝐴𝐵 𝑡
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
1 𝜕2𝑋 𝑥
2
= −𝜆2
𝑋 𝑥 𝜕𝑥
1 𝜕2𝑋 𝑥 2
= −𝜆
𝑋 𝑥 𝜕𝑥 2
z 𝑋 𝑥 = 𝐴′ sin 𝜆𝑥 + 𝐵′ cos 𝜆𝑥
𝐶𝐴 = 𝑇 𝑡 𝑋(𝑥)
2𝐷
𝐶𝐴 = 𝑒 −𝜆 𝐴𝐵 𝑡 𝐴′′ sin 𝜆𝑥 + 𝐵′′ cos 𝜆𝑥
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
The generalized solution is:
𝐶𝐴
= 𝐴′ 𝑥 + 𝐵′
∞
2𝐷
+ 𝑒 −𝜆 𝐴𝐵 𝑡 𝐴𝜆′′ 𝑠𝑖𝑛 𝜆𝑥 + 𝐵𝜆′′ cos 𝜆𝑥
z 𝜆=−∞
Boundary conditions: at t = 0
x = 0, 𝐶𝐴 = 𝐶𝐴0
x = a, 𝐶𝐴 = 𝐶𝐴∞
At t  ∞, 𝐶𝐴 = 𝐶𝐴∞
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x At t  ∞, 𝑥 = 0, 𝐶𝐴 = 𝐶𝐴∞
𝐶𝐴∞ = 𝐵′
At t  ∞, 𝑥 = 𝑎, 𝐶𝐴 = 𝐶𝐴∞
𝐶𝐴∞ = 𝐴′ 𝑎 + 𝐵′
z
𝐶𝐴∞ = 𝐴′ 𝑎 + 𝐶𝐴∞
𝐴′ = 0
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
The generalized solution is:
∞
2𝐷
𝐶𝐴 = 𝐶𝐴∞ + 𝑒 −𝜆 𝐴𝐵 𝑡 𝐴𝜆′′ sin 𝜆𝑥 + 𝐵𝜆′′ cos 𝜆𝑥
𝜆=−∞
z
We know that CA is a symmetric function
𝐴𝜆′′ = 0
∞
2𝐷
𝐶𝐴 = 𝐶𝐴∞ + 𝐵𝜆′′ 𝑒 −𝜆 𝐴𝐵 𝑡 cos 𝜆𝑥
𝜆=−∞
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
∞
2𝐷
𝐶𝐴 = 𝐶𝐴∞ + 𝐵𝜆′′ 𝑒 −𝜆 𝐴𝐵 𝑡 cos 𝜆𝑥
𝜆=−∞
At t = 0, x = a, 𝐶𝐴 = 𝐶𝐴∞
z
∞
𝐶𝐴∞ = 𝐶𝐴∞ + 𝐵𝜆′′ cos 𝜆𝑎

𝜆=−∞
𝐵𝜆′′ cos 𝜆𝑎 = 0
𝜆=−∞
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
∞
𝐵𝜆′′ cos 𝜆𝑎 = 0
𝜆=−∞
Since cos 𝜆𝑎 are linearly independent functions,
𝐵𝜆′′ = 0 or cos 𝜆𝑎 = 0
z 𝐵𝜆′′ = 0 gives a trivial solution
cos 𝜆𝑎 = 0
2n + 1 π
𝜆𝑎 = ,𝑛 ∈ ℵ
2
2n + 1 π
Time t > 0 𝜆=
2𝑎
y
𝜕𝐶𝐴
𝜕𝑡
x
𝐶𝐴
∞ 2
2n+1 π 2n + 1 π
′′ − 𝐷𝐴𝐵 𝑡
= 𝐶𝐴∞ + 𝐵𝑛 𝑒 2𝑎 cos 𝑥
2𝑎
𝑛=0
To evaluate 𝐵𝑛′′ :
z at t = 0, x = 0, 𝐶𝐴 = 𝐶𝐴0
∞
𝐶𝐴0 = 𝐶𝐴∞ + 𝐵𝑛′′

𝑛=0
What should we do next?

Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
𝐶𝐴
∞ 2
2n+1 π 2n + 1 π
′′ − 𝐷𝐴𝐵 𝑡
= 𝐶𝐴∞ + 𝐵𝑛 𝑒 2𝑎 cos 𝑥
2𝑎
𝑛=0
To evaluate 𝐵𝑛′′ :
z at t = 0, 𝐶𝐴 = 𝐶𝐴0 𝑓𝑜𝑟 − 𝑎 < 𝑥 < 𝑎

∞
2n + 1 π
𝐶𝐴0 = 𝐶𝐴∞ + 𝐵𝑛′′ cos 𝑥
2𝑎
𝑛=0
2m+1 π
Multiplying both sides with cos 𝑥
2𝑎
and integrating from –a to +a
Time t > 0
Orthonormality of functions
y
𝜕𝐶𝐴
𝜕𝑡
x
2m + 1 π
𝐶𝐴0 − 𝐶𝐴∞ cos 𝑥
2𝑎
∞
2n + 1 π 2m + 1 π
= 𝐵𝑛′′ cos 𝑥 cos 𝑥
2𝑎 2𝑎
𝑛=0
z 𝑎
2m + 1 π
𝐶𝐴0 − 𝐶𝐴∞ cos 𝑥 𝑑𝑥
2𝑎
−𝑎
∞ 𝑎
2n + 1 π 2m + 1 π
= 𝐵𝑛′′ cos 𝑥 cos 𝑥 𝑑𝑥
2𝑎 2𝑎
𝑛=0 −𝑎
Time t > 0
𝜕𝐶𝐴
𝜕𝑡
1
cos 𝑎𝑥 cos(𝑏𝑥) = cos 𝑎 − 𝑏 𝑥 + cos 𝑎 + 𝑏 𝑥
2
𝑎
2n + 1 π 2m + 1 π
cos 𝑥 cos 𝑥 𝑑𝑥
2𝑎 2𝑎
−𝑎
𝑎
1 n−m n+m+1
= cos 𝜋 𝑥 + cos 𝜋 𝑥 𝑑𝑥
2 𝑎 𝑎
−𝑎
𝑎 n−m n−m
= sin 𝜋 𝑎 − sin −𝜋 𝑎
2𝜋(𝑛 − 𝑚) 𝑎 𝑎
𝑎 n+m+1 n+m+1
+ sin 𝜋 𝑎 − sin −𝜋 𝑎
2𝜋(𝑛 + 𝑚 + 1) 𝑎 𝑎
𝑎
= sin 𝜋 n − m − sin −𝜋 n − m
2𝜋(𝑛 − 𝑚)
𝑎
+ sin 𝜋 n + m + 1 − sin −𝜋 n + m + 1
2𝜋(𝑛 + 𝑚 + 1)
y
𝜕𝐶𝐴
𝜕𝑡
x 𝑎
2n + 1 π 2m + 1 π
cos 𝑥 cos 𝑥 𝑑𝑥
2𝑎 2𝑎
−𝑎
𝑎
= sin 𝜋 n − m
𝜋(𝑛 − 𝑚)
𝑎
+ sin 𝜋 n + m + 1
𝜋(𝑛 + 𝑚 + 1)
For 𝑛 ≠ 𝑚
z 𝑎
2n + 1 π 2m + 1 π
cos 𝑥 cos 𝑥 𝑑𝑥 = 0
2𝑎 2𝑎
−𝑎
For 𝑛 = 𝑚
𝑎
2n + 1 π 2m + 1 π
cos 𝑥 cos 𝑥 𝑑𝑥 = a
Time t > 0 2𝑎 2𝑎
−𝑎
y
𝜕𝐶𝐴
𝜕𝑡
x
𝑎
2m + 1 π
𝐶𝐴0 − 𝐶𝐴∞ cos 𝑥 𝑑𝑥
2𝑎
−𝑎
∞ 𝑎
2n + 1 π 2m + 1 π
= 𝐵𝑛′′ cos 𝑥 cos 𝑥 𝑑𝑥
2𝑎 2𝑎
𝑛=0 −𝑎
z 𝑎
2m + 1 π ′′ 𝑎
𝐶𝐴0 − 𝐶𝐴∞ cos 𝑥 𝑑𝑥 = 𝐵𝑚
2𝑎
−𝑎
2 𝐶𝐴0 − 𝐶𝐴∞ 𝑎 2m + 1 π 2m + 1 π
sin 𝑎 − sin − 𝑎
2m + 1 𝜋 2𝑎 2𝑎
= 𝐵𝑚′′ 𝑎
Time t > 0
y
𝜕𝐶𝐴
𝜕𝑡
x
′′
4 𝐶𝐴0 − 𝐶𝐴∞ 2m + 1 π
𝐵𝑚 = sin
2m + 1 𝜋 2
′′ =
4 𝐶𝐴0 − 𝐶𝐴∞
𝐵𝑚 (−1)𝑚
2m + 1 𝜋
Time t > 0
∞ 2
4 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π
− 𝐷𝐴𝐵 𝑡
𝐶𝐴 = 𝐶𝐴∞ + (−1)𝑛 𝑒 2𝑎 cos 𝑥
2n + 1 𝜋 2𝑎
𝑛=0
𝜕𝐶𝐴
𝜕𝑡
Average concentration:
𝑎 𝑎
𝐶 𝑑𝑥
−𝑎 𝐴
𝐶 𝑑𝑥
−𝑎 𝐴
𝐶𝐴𝜃 = 𝑎 =
𝑑𝑥 2𝑎
−𝑎
𝑎 ∞ 2
1 4 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π
𝐶𝐴𝜃 = 𝐶𝐴∞ + −1 𝑛𝑒− 2𝑎
𝐷𝐴𝐵 𝑡
cos 𝑥 𝑑𝑥
2𝑎 2n + 1 𝜋 2𝑎
−𝑎 𝑛=0
𝑎 𝑎 ∞ 2
1 1 4 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π
𝑛𝑒− 2𝑎 𝐷𝐴𝐵 𝑡
𝐶𝐴𝜃 = 𝐶𝐴∞ 𝑑𝑥 + −1 cos 𝑥 𝑑𝑥
2𝑎 2𝑎 2n + 1 𝜋 2𝑎
−𝑎 −𝑎 𝑛=0
∞ 2 𝑎
2 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π
𝐶𝐴𝜃 = 𝐶𝐴∞ + −1 𝑛𝑒− 2𝑎 𝐷𝐴𝐵 𝑡
cos 𝑥 𝑑𝑥
𝑎 2n + 1 𝜋 2𝑎
𝑛=0 −𝑎
𝜕𝐶𝐴
𝜕𝑡
∞ 2 𝑎
2 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π
𝐶𝐴𝜃 = 𝐶𝐴∞ + −1 𝑛𝑒− 2𝑎 𝐷𝐴𝐵 𝑡
cos 𝑥 𝑑𝑥
𝑎 2n + 1 𝜋 2𝑎
𝑛=0 −𝑎
𝐶𝐴𝜃
= 𝐶𝐴∞
∞ 2
4𝑎 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π 2n + 1 π
𝑛𝑒− 2𝑎 𝐷𝐴𝐵 𝑡
+ −1 sin 𝑎 − sin − 𝑎
𝑎 2n + 1 2 𝜋 2 2𝑎 2𝑎
𝑛=0
∞ 2
8𝑎 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π 2n + 1 π
𝑛𝑒− 2𝑎
𝐷𝐴𝐵 𝑡
𝐶𝐴𝜃 = 𝐶𝐴∞ + −1 sin
𝑎 2n + 1 2 𝜋 2 2
𝑛=0
∞ 2
8𝑎 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π
𝑛𝑒− 2𝑎 𝐷𝐴𝐵 𝑡 𝑛
𝐶𝐴𝜃 = 𝐶𝐴∞ + −1 −1
𝑎 2n + 1 2 𝜋 2
𝑛=0
𝜕𝐶𝐴
𝜕𝑡
∞ 2
8𝑎 𝐶𝐴0 − 𝐶𝐴∞ 2n+1 π
𝑛 − 2𝑎
𝐷𝐴𝐵 𝑡 𝑛
𝐶𝐴𝜃 = 𝐶𝐴∞ + −1 𝑒 −1
𝑎 2n + 1 2 𝜋 2
𝑛=0
∞ 2
8 𝐶𝐴0 − 𝐶𝐴∞ − 2n+1 π
𝐷𝐴𝐵 𝑡
𝐶𝐴𝜃 = 𝐶𝐴∞ + 𝑒 2𝑎
2n + 1 2 𝜋 2
𝑛=0
Fraction unremoved E:
∞ 2
(𝐶𝐴𝜃 − 𝐶𝐴∞ ) 8 2n+1 π
− 2𝑎 𝐷𝐴𝐵 𝑡
𝐸𝑎 = = 𝑒
𝐶𝐴0 − 𝐶𝐴∞ 2n + 1 2 𝜋 2
𝑛=0
∞ 2
8 𝜋2 𝐷𝐴𝐵 𝑡 8 3π 2 8 5π 2 8 −
2n+1 π
𝐷𝐴𝐵 𝑡
− − 2𝑎 𝐷𝐴𝐵 𝑡 − 2𝑎 𝐷𝐴𝐵 𝑡 2𝑎
𝐸𝑎 = 2 𝑒 4𝑎2 + 2 𝑒 + 𝑒 + 𝑒
𝜋 9𝜋 25𝜋 2 2n + 1 2 𝜋 2
𝑛=3
𝜕𝐶𝐴
𝜕𝑡
∞ 2
(𝐶𝐴𝜃 − 𝐶𝐴∞ ) 8 2n+1 π
− 2𝑎 𝐷𝐴𝐵 𝑡
𝐸𝑎 = = 𝑒
𝐶𝐴0 − 𝐶𝐴∞ 2n + 1 2 𝜋 2
𝑛=0
∞ 2
8 𝜋2 𝐷𝐴𝐵 𝑡 2
1 −9𝜋 𝐷2𝐴𝐵𝑡 1 25𝜋2 𝐷𝐴𝐵 𝑡 1 2n+1 π
− − − 2𝑎 𝐷𝐴𝐵 𝑡
𝐸𝑎 = 2 𝑒 4𝑎2 + 𝑒 4𝑎 + 𝑒 4𝑎2 + 2𝑒
𝜋 9 25 2n + 1
𝑛=3
𝜕𝐶𝐴
𝜕𝑡
Time t = 0 Time t > 0

𝜕𝐶𝐴
𝜕𝑡
y
No concentration gradient along y axis
x
𝜕𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵 +
𝜕𝑡 𝜕𝑥 2 𝜕𝑧 2
Let 𝐶𝐴 = 𝑇 𝑡 𝑋 𝑥 𝑍(𝑧)
z
Solve at home
Time t > 0
𝜕𝐶𝐴
𝜕𝑡
y
x
𝜕𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵 +
𝜕𝑡 𝜕𝑥 2 𝜕𝑧 2
(𝐶𝐴𝜃 − 𝐶𝐴∞ )
𝐸= = 𝐸𝑎 𝐸𝑏
𝐶𝐴0 − 𝐶𝐴∞
z
Time t > 0
𝜕𝐶𝐴
𝜕𝑡
y
x
𝜕𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵 + +
𝜕𝑡 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
Let 𝐶𝐴 = 𝑇 𝑡 𝑋 𝑥 𝑌(𝑦)𝑍(𝑧)
z
(𝐶𝐴𝜃 − 𝐶𝐴∞ )
𝐸= = 𝐸𝑎 𝐸𝑏 𝐸𝑐
𝐶𝐴0 − 𝐶𝐴∞
Solve at home
Time t > 0
Unsteady state diffusion
𝜕𝐶𝐴
𝜕𝑡
Similar equations can be derived for cylindrical and spherical geometries
Important note:
At x = a, 𝐶𝐴 = 𝐶𝐴∞ implies that –
1. There is no resistance to diffusion in the surrounding fluid (Diffusivity = infinity)
2. Concentration within surrounding fluid does not change (infinitely large fluid)
3. Fluid is well mixed – molecules diffusing out are continuously removed
Types of solid diffusion
• Diffusion through polymers
• Example: diffusion through polymer membranes
• Gas molecules can “dissolve” into the polymer
• Gas molecules diffuse through polymer
• Diffusivity is a function of temperature – activated
diffusion
• 𝐷𝐴 = 𝐷0 𝑒 −𝐻𝐷/𝑅𝑇
• Diffusion through crystalline solids
• Mechanism of diffusion varies with lattice structure
• Isotropic – does not depend on direction (uniform in all
directions)
• Cubic lattice – isotropic diffusivity
• Mechanism of diffusion varies with lattice structure
• Isotropic – does not depend on direction (uniform in all
directions)
• Cubic lattice – isotropic diffusivity
• Important mechanisms of diffusion –
• Interstitial mechanism: lattice atoms move temporarily to allow
solute molecules to move and diffuse from one interstitial
space to another
• Vacancy mechanism: movement into unoccupied lattice sites
• Interstitialcy mechanism: large solute in an interstitial site
pushes lattice atom into interstitial site, and occupies vacancy
• Important mechanisms of diffusion –
• Crowd-ion mechanism: lattice atoms are closely atoms. Solute
atom displaces several atoms at once to create a flux
• Diffusion along grain boundaries: 2 or more crystals interface at
a grain boundary. Diffusivity is higher in these regions
• Diffusion in porous solids
• Surface diffusion: diffusion along the surface of
adsorbent – activated diffusion, surface analog of Fick’s
law
• Pores have varying lengths, varying cross-sectional
areas, are not straight
• Pores can be modeled as straight, cylindrical structures
having constant length – effective diffusivity is lower to
account for reality
• For gases diffusing into pores of a solid
• Pore diameter d, and mean free path of gas λ
• d/λ >20 – ordinary molecular diffusion
• d/λ < 0.2 – Knudsen’s law
• Rate of diffusion depends on collision of molecules with pore
walls, not with other gas molecules
• Each gas diffuses independently
• For gases diffusing into pores of a solid
• Pore diameter d, and mean free path of gas λ
• d/λ >20 – ordinary molecular diffusion
𝑑𝑢𝐴
𝑁𝐴 = (𝑝 − 𝑝𝐴2 )
3𝑅𝑇𝑙 𝐴1
• 𝑢𝐴 is the average molecular velocity of A, given by

1
8𝑔𝑐 𝑅𝑇 2
𝑢𝐴 =
𝜋𝑀𝐴
𝐷𝐾,𝐴
𝑁𝐴 = (𝑝 − 𝑝𝐴2 )
𝑅𝑇𝑙 𝐴1
1
𝑑 8𝑔𝑐 𝑅𝑇 2
𝐷𝐾,𝐴 =
3 𝜋𝑀𝐴
• 𝐷𝐾,𝐴 is the Knudsen diffusion coefficient

• 0.2 < d/λ < 20 – Knudsen diffusion + normal diffusion
𝑁𝐴 𝐷𝐴𝐵,𝑒𝑓𝑓
𝑁𝐴 𝐷𝐴𝐵,𝑒𝑓𝑓 𝑝𝑡 𝑁𝐴 + 𝑁𝐵 1 + 𝐷𝐾,𝐴,𝑒𝑓𝑓 − 𝑦𝐴2
𝑁𝐴 = ln
𝑁𝐴 + 𝑁𝐵 𝑅𝑇𝑧 𝑁𝐴 𝐷𝐴𝐵,𝑒𝑓𝑓
1 +
𝑁𝐴 + 𝑁𝐵 𝐷𝐾,𝐴,𝑒𝑓𝑓 − 𝑦𝐴1
• Knudsen diffusion is not known for liquids

Gas absorption
• Gas molecules dissolve into liquid phase
• Removing pollutants: H2S, NOx, SOx, etc.
• Recovering valuable chemicals from vapour phase
• Stripping – liquid molecules move into gas phase
What is a phase?
Thermodynamics
• Equilibrium distribution of chemical components
• Maximum extent of separation
Pure gas Pure gas
Pure liquid Liquid + dissolved gas
Equilibrium state
What is equilibrium? What is steady state?
Thermodynamics
• Equilibrium solubility of gas
A
A: Relatively insoluble gas
Partial pressure of solute in gas
B: Highly soluble gas
Any concentration of gaseous solute

can be achieved inside liquid, if
sufficiently high pressure is applied
Liquefied solute should be miscible

B in liquid solvent
Mole fraction of solute in liquid

Thermodynamics
• Equilibrium solubility of gas
NH3 (30°C)
Usually dissolution of gas inside

liquid is exothermic
As temperature increases, solubility

NH3 (10°C) will
• Decrease (exothermic)
• Increase (endothermic)
van’t Hoff’s law of mobile

equilibrium

Thermodynamics
• Multicomponent mixtures
1 2
For ideal solutions, component

solubilities are independent (not
influenced by each other)

Thermodynamics
• Multicomponent mixtures: ideal liquid solutions
• Average intermolecular forces of attraction and
repulsion in solution are unchanged upon mixing
constituents
• Volume of solution changes linearly with composition
• Mixing is neither endothermic nor exothermic (for gas
mixing into liquid, heat of condensation is not included)
• Total vapour pressure is linear function of liquid mole
fractions
Ideal solutions do not exist in reality!

Thermodynamics
• Chemically similar compounds  nearly ideal solutions
• Benzene in toluene
• Ethyl and propyl alcohol
• Hydrocarbon gases into hydrocarbon liquids
Thermodynamics
• Partial pressure of component in gas = vapour pressure
of pure liquid component*mole fraction inside liquid
• 𝑝𝑖∗ = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
• Liquid phase = ideal solution

• Gas phase = ideal gas
What is an ideal gas? What is pressure?

Thermodynamics
Pure gas at T, Psat
Pure liquid at T
By author of the original work: Cmglee - Own work, CC BY-SA 3.0,

https://commons.wikimedia.org/w/index.php?curid=34865054
Thermodynamics
• Raoult’s law
Pure gas at T, Psat Pure gas at T, x1Psat
Mixed liquid at T
Pure liquid at T
(volatile 1, nonvolatile 2)
Thermodynamics
• Raoult’s law
Pure gas at T, x1Psat Mixed gas at T,

(x1P1sat+x2P2sat)
Mixed liquid at T Mixed liquid at T

(volatile 1, nonvolatile 2) (volatile 1, volatile 2)
Raoult’s law example
Total pressure = 14.7 psi 𝑝𝑖∗ = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
Temperature = 75 °F
Component Vapour mole Partial Vapour Liquid mole

fraction (yi) pressure (psi) pressure (psi) fraction (xi)
Propane 0.2
i-Butane 0.2
n-Butane 0.2
i-Pentane 0.2
n-Pentane 0.2
Solvent 0
Thermodynamics
• Multicomponent mixtures: non-ideal liquid
solutions
Non-ideal Ideal
𝑝𝑖∗
= 𝑦𝑖∗ = 𝑚𝑥𝑖 𝑝𝑖∗ = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
𝑝𝑡
𝑝𝑖∗ 𝑃𝑖
𝑠𝑎𝑡
1 2 = 𝑦𝑖∗ = 𝑥𝑖
Partial pressure of
𝑝𝑡 𝑝𝑡
solute in gas
Mole fraction of
solute in liquid
Thermodynamics
• Multicomponent mixtures: non-ideal liquid
solutions
• Henry’s law
Deviation from Henry’s law:
𝑝𝑖∗ • Chemical reaction with solvent
= 𝑦𝑖∗ = 𝑚𝑥𝑖 • Electrolytic dissociation (ammonia-water)
𝑝𝑡
• Non-ideal gas
1 2
Partial pressure of
solute in gas
Mole fraction of
solute in liquid
Choice of solvent for absorption
• High gas solubility
• Chemically similar: miscible liquids
• For ideal liquid solutions, solubility is independent of
solvent liquid
• For absorption with chemical reaction, reaction should
be reversible for recovery of solute (example: hydrogen
sulfide + ethanolamine)
• Low volatility
• Non-corrosive
• Inexpensive
Choice of solvent for absorption
• Low viscosity – higher heat transfer and mass
transfer
• Non-toxic, non-flammable, chemically stable, low
freezing point
Material balance: countercurrent
Gas out
Total gas flux (mol/area.time) = G
• Insoluble gas flux = GS
Liquid in • Solute A flux = yG = YGS
As y decreases, G also decreases

GS remains constant
𝑝𝐴
𝑦=
(𝑝𝐴 + 𝑝𝐺𝑠 )
1−𝑦
Liquid out 𝑝𝐺𝑠 = 𝑝𝐴
𝑦
𝑝𝐺𝑠 𝑣 𝑝𝐴 𝑣 1 − 𝑦
Gas in =
𝑅𝑇 𝑅𝑇 𝑦
Gas out
𝑝𝐺𝑠 𝑣 𝑝𝐴 𝑣 1 − 𝑦
=
𝑅𝑇 𝑅𝑇 𝑦
1−𝑦
𝐺𝑆 = 𝑦𝐺
𝑦
𝑦
Liquid out 𝐺𝑆 = 𝑌𝐺𝑆 = 𝑦𝐺
1−𝑦
𝑦
Gas in 𝑌=
1−𝑦
Gas out
𝑦 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴
𝑌= =
1−𝑦 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐺𝑆
Y = Mole ratio
𝑌
Liquid out 𝑦=
(1 + Y)
Gas in 𝑌𝐺 𝐺
𝑌𝐺𝑆 = 𝑦𝐺 = 𝐺𝑆 =
(1 + Y) (1 + Y)
Gas out
Total liquid flux (mol/area.time) = L
• Nonvolatile solvent flux = LS
Liquid in • Solute A flux = xL = XLS
𝑥 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴
𝑋= =
1−𝑥 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐿𝑆
X = Mole ratio
𝑋
Liquid out 𝑥=
(1 + X)
Gas in 𝑋𝐿 𝐿
𝑋𝐿𝑆 = 𝑥𝐿 = 𝐿𝑆 =
(1 + X) (1 + X)
Gas out
G2, GS, Y2, y2
Mass balance on solute A
Liquid in
L2, LS, X2, x2 𝑋𝐿𝑆 + 𝑌1 𝐺𝑆 = 𝑋1 𝐿𝑆 + 𝑌𝐺𝑆
𝐺𝑆 (𝑌1 − 𝑌) = 𝐿𝑆 (𝑋1 − 𝑋)
Liquid: L, LS, X, x
Gas: G, GS, Y, y Straight line between (X1, Y1) and (X2, Y2)
Liquid out
L1, LS, X1, x1
Gas in
G1, GS, Y1, y1
Gas out Mass balance on solute A
G2, GS, Y2, y2
𝐺𝑆 (𝑌1 − 𝑌) = 𝐿𝑆 (𝑋1 − 𝑋)
Liquid in
L2, LS, X2, x2 Straight line between (X1, Y1) and (X2, Y2)
Bottom
Y1
Liquid: L, LS, X, x
Gas: G, GS, Y, y
Y
Liquid out
L1, LS, X1, x1 Top
Y2
Gas in
G1, GS, Y1, y1
X2 X1 X
Why is operating line above equilibrium curve?
G2, GS, Y2, y2
𝐺𝑆 (𝑌1 − 𝑌) = 𝐿𝑆 (𝑋1 − 𝑋)
Liquid in
L2, LS, X2, x2 Straight line between (X1, Y1) and (X2, Y2)
Top
Y2
Liquid: L, LS, X, x
Gas: G, GS, Y, y
Y
Liquid out
L1, LS, X1, x1
Y1 Bottom
Gas in
G1, GS, Y1, y1 X X1 X2
Stripper
G2, GS, Y2, y2 𝑦 𝑥
𝐺𝑆 𝑌1 − = 𝐿𝑆 𝑋1 −
1−𝑦 1−𝑥
Liquid in
L2, LS, X2, x2 Curve between (x1, y1) and (x2, y2)
Bottom
y1
Liquid: L, LS, X, x
Gas: G, GS, Y, y
y
Liquid out
L1, LS, X1, x1 Top
y2
Gas in
G1, GS, Y1, y1
x2 x1 x
Gas out Minimum liquid/gas ratio
G2, GS, Y2, y2 𝐿𝑆
(𝑌1 − 𝑌) = (𝑋 − 𝑋)
𝐺𝑆 1
Liquid in
L2, LS, X2, x2 Y1, Y2, X2, GS are fixed. Choose LS
Bottom
Y1
Liquid: L, LS, X, x
Gas: G, GS, Y, y
Y
Liquid out
L1, LS, X1, x1 Top
Y2
Gas in
G1, GS, Y1, y1
X2 X1 X
Minimum liquid/gas ratio
Bottom
𝐿𝑆
Y1
(𝑌1 − 𝑌) = (𝑋 − 𝑋)
𝐺𝑆 1
Y
Y1, Y2, X2, GS are fixed. Choose LS
Top
Less LS:
Y2
• Less cost
• Closer to equilibrium curve
• Less driving force for mass transfer
X2 X1 X • Slower kinetics
• More residence time
• Bigger equipment
Material balance: cocurrent

G1, GS, Y1, y1
Liquid in 𝑋𝐿𝑆 + 𝑌𝐺𝑆 = 𝑋1 𝐿𝑆 + 𝑌1 𝐺𝑆
L2 , L S , X 2 , x 2
𝐺𝑆 𝑌 − 𝑌1 = −𝐿𝑆 (𝑋 − 𝑋1 )
Liquid out
L1, LS, X1, x1
Gas in Liquid: L, LS, X, x
G2, GS, Y2, y2 Gas: G, GS, Y, y
Straight line between (X1, Y1) and (X2, Y2)
with negative slope
Gas out 𝐺𝑆 𝑌 − 𝑌1 = −𝐿𝑆 (𝑋 − 𝑋1 )

G1, GS, Y1, y1
Liquid in
L2 , L S , X 2 , x 2 Inlet
Y2
Y1
Liquid out Exit
L1, LS, X1, x1
Gas in Liquid: L, LS, X, x Y
G2, GS, Y2, y2 Gas: G, GS, Y, y
X2 X1 X
Inlet
Y2
𝐺𝑆 𝑌 − 𝑌1 = −𝐿𝑆 (𝑋 − 𝑋1 )
• Very tall tower built in two parts –

Y1
second column run in cocurrent mode

Exit
to save pipeline costs for gas (large
Y
diameter)
Liquid
X2 X1 X
Gas
• Pure gas absorption into liquid
• No difference between countercurrent and cocurrent
• Rapid irreversible chemical reaction inside liquid
• Only 1 theoretical stage needed
Countercurrent multistage
Gas out
G1, GS, Y1, y1
Liquid in Y1
L0 , L S , X 0 , x 0 X1
Y2
X2
Y3
X3
Y4
X4
YN-2
XN-2
YN-1
XN-1
YN
Gas in XN
GN+1, GS, YN+1, yN+1 Liquid out
LN, LS, XN, xN
Gas out
G1, GS, Y1, y1
Liquid in Y1
L0, LS, X0, x0 X1
Y2
X2 YN+1, XN
Y3
X3
Y4 YN, XN-1
X4 YN, XN
Y
YN-2
XN-2
YN-1
Y1, X0
XN-1
YN Y1, X1
Gas in XN
LN, LS, XN, xN X
Dilute gas mixtures:
Gas out • Henry’s law
G1, GS, Y1, y1 • Mole fractions
Liquid in • Kremser equations
L0, LS, X0, x0
yN+1, xN Operating line
Equilibrium curve
Henry’s law
yN, xN-1
yN , xN
y
Gas in
GN+1, GS, YN+1, yN+1 Liquid out y 1 , x0
y1, x1
LN, LS, XN, xN
x
Gas out Dilute gas mixtures:
G1, GS, Y1, y1 • Henry’s law
Liquid in • Mole fractions
L0, LS, X0, x0 • Kremser equations
𝑌𝑁+1 − 𝑌1 𝐴𝑁+1 − 𝐴
=
𝑌𝑁+1 − 𝑚𝑋0 𝐴𝑁+1 − 1
𝐿
𝐴=
𝑚𝐺
For A < 1, operating line and equilibrium

curve approach each other  limited
Gas in absorption even for infinite trays
LN, LS, XN, xN 𝐿
𝐿
<1 <𝑚
𝑚𝐺 𝐺
Gas out Dilute gas mixtures:
G1, GS, Y1, y1 • Henry’s law
Liquid in • Mole fractions
L0, LS, X0, x0 • Kremser equations
𝑌𝑁+1 − 𝑌1 𝐴𝑁+1 − 𝐴
=
𝑌𝑁+1 − 𝑚𝑋0 𝐴𝑁+1 − 1
𝐿
𝐴=
𝑚𝐺
For A > 1, operating line and equilibrium

curve move away from each other  any
Gas in separation possible
LN, LS, XN, xN 𝐿
𝐿
>1 >𝑚
𝑚𝐺 𝐺
Gas out Non-isothermal operation
G1, GS, Y1, y1, HG1 • Absorption is usually exothermic
Liquid in • Temperature increases
L0, LS, X0, x0, HL0 • Absorption decreases
• Colling may be required
• Enthalpy balance
Overall enthalpy balance:
𝐿0 𝐻𝐿0 + 𝐺𝑁+1 𝐻𝐺𝑁+1 = 𝐿𝑁 𝐻𝐿𝑁 + 𝐺1 𝐻𝐺1 + 𝑄𝑇
Gas in
GN+1, GS, YN+1, Liquid out QT is the heat removed from the column
yN+1, HGN+1 LN, LS, XN, xN, HLN
G1, GS, Y1, y1, HG1
Liquid in
L0, LS, X0, x0, HL0
Reference: Enthalpies of pure liquid solvent, pure gas

solvent, and pure solute at reference temperature t0 and 1
atm = 0
𝐻𝐿 = 𝐶𝐿 𝑡𝐿 − 𝑡0 + ∆𝐻𝑆
Molar enthalpy of mixing
Gas in
GN+1, GS, YN+1, Liquid out If solute is gas at t0, only sensible heat
yN+1, HGN+1 LN, LS, XN, xN, HLN If solute is liquid at t0, latent heat of
vaporization also included
G1, GS, Y1, y1, HG1
Liquid in
L0, LS, X0, x0, HL0
If liquid = ideal liquid solution, enthalpy of mixing = 0

If solute is gas, heat evolved = latent heat of condensation
If adiabatic absorber, QT = 0
Enthalpy balance for each tray is to be solved separately
Gas in
GN+1, GS, YN+1, Liquid out
Gas out Tray efficiency
G1, GS, Y1, y1, HG1
Liquid in
L0, LS, X0, x0, HL0
Murphree tray efficiency:
𝑦𝑛 − 𝑦𝑛+1 ,n
𝐸𝑀𝐺 = ∗
𝑦𝑛 − 𝑦𝑛+1
Gas in
GN+1, GS, YN+1, Liquid out
Tray efficiency
Murphree tray efficiency:

𝑦𝑛 − 𝑦𝑛+1 yN+1, xN
𝐸𝑀𝐺 = ∗ Murphree efficiency
𝑦𝑛 − 𝑦𝑛+1
Operating line Equilibrium curve
,n
yN, xN-1
y yN , xN
y1, x0
y1 , x 1
x
Tray efficiency
Overall efficiency:
yN+1, xN
𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑡𝑟𝑎𝑦𝑠 Murphree efficiency
𝐸𝑂 =
𝑅𝑒𝑎𝑙 𝑡𝑟𝑎𝑦𝑠 Equilibrium curve
Operating line
Assuming tray efficiencies are
same for all trays yN, xN-1
• Operating curve = straight yN , xN
line (dilute solutions) y
• Equilibrium curve = straight
line (Henry’s law)
• Isothermal operation (dilute y1, x0
solutions) y1 , x 1
x
Countercurrent packed absorber
• Liquid and gas contact throughout the equipment,
not intermittently
• Concentrations change continuously throughout
length
• Every point on operating line physically exists
• Height equivalent to an equilibrium stage (HETP)
• Theoretical plate
• Number of plates calculated similar to plate absorber
• Height of packing corresponding to each theoretical
plate calculated
• Multiply to give total height of absorber
• Method no longer used
• Mass balance
Liquid in:
• Interfacial area/unit L0, LS, X0, x0
Gas out:
volume = a G1, GS, Y1, y1
• Interfacial area inside dz

𝑑𝑆 = 𝑎𝑑𝑉
• Net flow of A inside gas Liquid: L, LS, X, x
Gas: G, GS, Y, y dV, dz
= 𝐺𝑦𝐴𝑐 𝑎𝑡 𝑉 − 𝐺𝑦𝐴𝑐 𝑎𝑡 𝑉 + 𝑑𝑉
𝑑(𝐺𝑦)
= 𝐴𝑐 𝑑𝑉
𝑑𝑉
AC = cross sectional area of absorber Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
• Net flow of A out of gas L0, LS, X0, x0
Gas out:
into liquid G1, GS, Y1, y1
= 𝑁𝐴 𝑑𝑆
𝑁𝐴
𝑁𝐴 𝑁𝐴 + 𝑁𝐵 − 𝑦𝐴,𝑖 Liquid: L, LS, X, x
𝑁𝐴 = 𝐹 ln
𝑁𝐴 + 𝑁𝐵 𝐺 𝑁𝐴 dV, dz
𝑁𝐴 + 𝑁𝐵 − 𝑦𝐴,𝐺 Gas: G, GS, Y, y
𝑁𝐵 = 0
1 − 𝑦𝐴,𝑖
𝑁𝐴 𝑑𝑆 = 𝑎𝑑𝑉𝐹𝐺 ln
1 − 𝑦𝐴,𝐺
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
• At steady state L0, LS, X0, x0
Gas out:
G1, GS, Y1, y1
1 − 𝑦𝐴,𝑖 𝑑(𝐺𝑦)
𝑎𝑑𝑉𝐹𝐺 ln = 𝐴𝑐 𝑑𝑉
1 − 𝑦𝐴,𝐺 𝑑𝑉
1 − 𝑦𝑖 𝑑(𝐺𝑦)
𝑎𝐹𝐺 ln = Liquid: L, LS, X, x
1−𝑦 𝑑𝑧 dV, dz
Gas: G, GS, Y, y
𝑑(𝐺𝑦) 𝑑 𝐺𝑆 𝑦 𝐺𝑆 𝑑𝑦 𝐺 𝑑𝑦
= = =
𝑑𝑧 𝑑𝑧 1 − 𝑦 (1 − 𝑦)2 𝑑𝑧 1 − 𝑦 𝑑𝑧
1 − 𝑦𝑖 𝐺 𝑑𝑦
𝑎𝐹𝐺 ln =
1−𝑦 1 − 𝑦 𝑑𝑧
Liquid out: Gas in:
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
Gas out:
G1, GS, Y1, y1
1 − 𝑦𝑖 𝐺 𝑑𝑦
𝑎𝐹𝐺 ln =
1−𝑦 1 − 𝑦 𝑑𝑧
𝐺𝑑𝑦 Liquid: L, LS, X, x

𝑑𝑧 = dV, dz
1−𝑦 Gas: G, GS, Y, y
𝐹𝐺 𝑎(1 − 𝑦) ln 1 − 𝑦𝑖
𝑧 𝑦1
𝐺𝑑𝑦
𝑑𝑧 =
1−𝑦
0 𝑦2 𝐹𝐺 𝑎(1 − 𝑦) ln 1 − 𝑦𝑖
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
Gas out:
G1, GS, Y1, y1
𝑧 𝑦1
𝐺𝑑𝑦
𝑑𝑧 =
1−𝑦
0 𝑦2 𝐹𝐺 𝑎(1 − 𝑦) ln 1 − 𝑦𝑖
Liquid: L, LS, X, x
To determine yi Gas: G, GS, Y, y dV, dz
𝐹𝐿 𝑎
1 − 𝑦𝑖 1−𝑥 𝐹𝐺 𝑎
=
1−𝑦 1 − 𝑥𝑖
For every point (x, y) on the operating
curve, yi vs xi given by above equation
is plotted
Intersection with equilibrium curve Liquid out: Gas in:
gives local (xi, yi) L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
Kremser equations
L0, LS, X0, x0 L1, LS, X1, x1 L2, LS, X2, x2 L3, LS, X3, x3 LN , L S , X N , x N
1 2 3 N
G1, GS, Y1, y1 G2, GS, Y2, y2 G3, GS, Y3, y3 G N , G S , Y N , yN GN+1, GS,
YN+1, yN+1
Mass balance from stage 1 till n
𝐺𝑆 𝑌𝑛+1 + 𝐿𝑆 𝑋0 = 𝐺𝑆 𝑌1 + 𝐿𝑆 𝑋𝑛
Assuming Y = mX
𝐺𝑆 (𝑌𝑛+1 − 𝑌1 ) = 𝐿𝑆 (𝑋𝑛 − 𝑋0 )
𝐿𝑆
𝑌𝑛+1 − 𝑌1 = (𝑌 − 𝑚𝑋0 )
𝑚𝐺𝑆 𝑛
𝐿𝑆
𝑌𝑛+1 − 𝑌1 = (𝑋 − 𝑋0 )
𝐺𝑆 𝑛 𝑌𝑛+1 = 𝐴 𝑌𝑛 − 𝑚𝑋0 + 𝑌1
Kremser equations
L0, LS, X0, x0 L1 , L S , X 1 , x 1 L2, LS, X2, x2 L3, LS, X3, x3 LN , L S , X N , x N
1 2 3 N
G1, GS, Y1, y1 G2, GS, Y2, y2 G3, GS, Y3, y3 G N , G S, YN , y N GN+1, GS,
YN+1, yN+1
𝑌𝑛+1 = 𝐴 𝑌𝑛 − 𝑚𝑋0 + 𝑌1
Recursive formula
For n = 1
𝑌2 = 𝐴 𝑌1 − 𝑚𝑋0 + 𝑌1
Kremser equations
1 2 3 N
YN+1, yN+1
𝑌𝑛+1 = 𝐴 𝑌𝑛 − 𝑚𝑋0 + 𝑌1
For n = 2
𝑌3 = 𝐴 𝑌2 − 𝑚𝑋0 + 𝑌1 = 𝐴 𝐴 𝑌1 − 𝑚𝑋0 + 𝑌1 − 𝑚𝑋0 + 𝑌1
𝑌3 = (𝐴2 + 𝐴) 𝑌1 − 𝑚𝑋0 + 𝑌1
Kremser equations
1 2 3 N
YN+1, yN+1
𝑌𝑛+1 = 𝐴 𝑌𝑛 − 𝑚𝑋0 + 𝑌1
For n = 3
𝑌4 = 𝐴 𝐴2 + 𝐴 + 1 (𝑌1 − 𝑚𝑋0 ) + 𝑌1
Kremser equations
1 2 3 N
YN+1, yN+1
𝑌𝑛+1 = 𝐴 𝑌𝑛 − 𝑚𝑋0 + 𝑌1
For n = 4
𝑌5 = 𝐴 𝐴3 + 𝐴2 + 𝐴 + 1 (𝑌1 − 𝑚𝑋0 ) + 𝑌1
𝑌𝑛+1 = 𝐴 𝐴𝑛−1 + 𝐴𝑛−2 + ⋯ + 𝐴 + 1 (𝑌1 − 𝑚𝑋0 ) + 𝑌1

Kremser equations
1 2 3 N
YN+1, yN+1
𝑌𝑛+1 = 𝐴 𝐴𝑛−1 + 𝐴𝑛−2 + ⋯ + 𝐴 + 1 (𝑌1 − 𝑚𝑋0 ) + 𝑌1
𝐴 𝐴𝑛 − 1
𝑌𝑛+1 = (𝑌1 − 𝑚𝑋0 ) + 𝑌1
𝐴−1
𝐴𝑛+1 − 𝐴
𝑌𝑛+1 = (𝑌1 − 𝑚𝑋0 ) + 𝑌1
𝐴−1
Kremser equations
1 2 3 N
YN+1, yN+1
𝐴𝑛+1 − 𝐴
𝑌𝑛+1 = (𝑌1 − 𝑚𝑋0 ) + 𝑌1
𝐴−1
𝑌𝑛+1 − 𝑌1 𝐴𝑛+1 − 𝐴
=
𝑌1 − 𝑚𝑋0 𝐴−1
For n = N 𝑌𝑁+1 − 𝑌1 𝐴𝑁+1 − 𝐴

=
𝑌1 − 𝑚𝑋0 𝐴−1
Kremser equations
1 2 3 N
YN+1, yN+1
𝑌𝑁+1 − 𝑌1 𝐴𝑁+1 − 𝐴
=
𝑌1 − 𝑚𝑋0 𝐴−1
𝑌𝑁+1 − 𝑌1 + 𝑌1 − 𝑚𝑋0 𝐴𝑁+1 − 𝐴 + 𝐴 − 1

=
𝑌1 − 𝑚𝑋0 𝐴−1
𝑌𝑁+1 − 𝑌1 𝐴𝑁+1 − 𝐴
=
𝑌𝑁+1 − 𝑚𝑋0 𝐴𝑁+1 − 1 𝑌𝑁+1 − 𝑚𝑋0 𝐴𝑁+1 − 1
=
𝑌1 − 𝑚𝑋0 𝐴−1
• Mass balance
Liquid in:
Gas out:
G1, GS, Y1, y1
𝑧 𝑦1
𝐺𝑑𝑦
𝑑𝑧 =
1−𝑦
0 𝑦2 𝐹𝐺 𝑎(1 − 𝑦) ln 1 − 𝑦𝑖
Liquid: L, LS, X, x
To determine yi Gas: G, GS, Y, y dV, dz
𝐹𝐿 𝑎
1 − 𝑦𝑖 1−𝑥 𝐹𝐺 𝑎
=
1−𝑦 1 − 𝑥𝑖
For every point (x, y) on the operating
curve, yi vs xi given by above equation
is plotted
Intersection with equilibrium curve Liquid out: Gas in:
gives local (xi, yi) L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
𝑁𝐴
𝑁𝐴 𝑁𝐴 + 𝑁𝐵 − 𝑦𝐴,𝑖
𝑁𝐴 = 𝐹 ln Liquid in:
𝑁𝐴 + 𝑁𝐵 𝐺 𝑁𝐴
L0, LS, X0, x0
Gas out:
𝑁𝐴 + 𝑁𝐵 − 𝑦𝐴,𝐺 G1, GS, Y1, y1
𝑁𝐴
𝑁𝐴 𝑁𝐴 + 𝑁𝐶 − 𝑥𝐴,𝐿
𝑁𝐴 = 𝐹 ln
𝑁𝐴 + 𝑁𝐶 𝐿 𝑁𝐴
𝑁𝐴 + 𝑁𝐶 − 𝑥𝐴,𝑖 Liquid: L, LS, X, x
𝑁𝐵 = 0 𝑁𝐶 = 0
1 − 𝑦𝐴,𝑖 1 − 𝑥𝐴,𝐿
𝐹𝐺 ln = 𝐹𝐿 ln
1 − 𝑦𝐴,𝐺 1 − 𝑥𝐴,𝑖
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
1 − 𝑦𝐴,𝑖 1 − 𝑥𝐴,𝐿
𝐹𝐺 ln = 𝐹𝐿 ln Liquid in:
1 − 𝑦𝐴,𝐺 1 − 𝑥𝐴,𝑖 Gas out:
L0, LS, X0, x0
G1, GS, Y1, y1
𝐹𝐺 𝐹𝐿
1 − 𝑦𝐴,𝑖 1 − 𝑥𝐴,𝐿
ln = ln
1 − 𝑦𝐴,𝐺 1 − 𝑥𝐴,𝑖
𝐹𝐺 𝐹𝐿 Liquid: L, LS, X, x
1 − 𝑦𝐴,𝑖 1 − 𝑥𝐴,𝐿 dV, dz
= Gas: G, GS, Y, y
1 − 𝑦𝐴,𝐺 1 − 𝑥𝐴,𝑖
𝐹𝐺 𝐹𝐿
1 − 𝑦𝐴,𝑖 1 − 𝑥𝐴,𝐿
=
1 − 𝑦𝐴,𝐺 1 − 𝑥𝐴,𝑖
𝐹𝐿
1 − 𝑦𝐴,𝑖 1 − 𝑥𝐴,𝐿 𝐹𝐺
=
1 − 𝑦𝐴,𝐺 1 − 𝑥𝐴,𝑖 Liquid out: Gas in:
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
Gas out:
𝑧 𝑦1 G1, GS, Y1, y1
𝐺𝑑𝑦
𝑑𝑧 =
1−𝑦
0 𝑦2 𝐹𝐺 𝑎(1 − 𝑦) ln 1 − 𝑦𝑖
Since, Liquid: L, LS, X, x

𝑦 − 𝑦𝑖 = 1 − 𝑦𝑖 − (1 − 𝑦) Gas: G, GS, Y, y dV, dz
And,
1 − 𝑦𝑖 − (1 − 𝑦)
(1 − 𝑦)𝐿𝑀 =
1−𝑦
ln 1 − 𝑦𝑖
𝑦1
(1 − 𝑦)𝐿𝑀 𝐺𝑑𝑦
𝑧=
𝐹𝐺 𝑎(1 − 𝑦)(𝑦 − 𝑦𝑖 ) Liquid out: Gas in:
𝑦2
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
Gas out:
𝑦1
G1, GS, Y1, y1
(1 − 𝑦)𝐿𝑀 𝐺𝑑𝑦
𝑧=
𝐹𝐺 𝑎(1 − 𝑦)(𝑦 − 𝑦𝑖 )
𝑦2
𝐻𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑔𝑎𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑢𝑛𝑖𝑡: 𝐻𝑡𝐺 Liquid: L, LS, X, x

𝐺
𝐻𝑡𝐺 =
𝐹𝐺 𝑎
𝑦1
(1 − 𝑦)𝐿𝑀 𝑑𝑦
𝑧= 𝐻𝑡𝐺
(1 − 𝑦)(𝑦 − 𝑦𝑖 )
𝑦2
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
Gas out:
𝑦1 G1, GS, Y1, y1
𝑧= 𝐻𝑡𝐺
(1 − 𝑦)(𝑦 − 𝑦𝑖 )
𝑦2
If HtG is constant, Liquid: L, LS, X, x

𝑦1
𝑧 = 𝐻𝑡𝐺 = 𝐻𝑡𝐺 𝑁𝑡𝐺
(1 − 𝑦)(𝑦 − 𝑦𝑖 )
𝑦2
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑎𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑢𝑛𝑖𝑡𝑠: 𝑁𝑡𝐺
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
Liquid in:
• For liquid L0, LS, X0, x0
Gas out:
𝑥1 G1, GS, Y1, y1
(1 − 𝑥)𝐿𝑀 𝑑𝑥
𝑧= 𝐻𝑡𝐿
(1 − 𝑥)(𝑥 − 𝑥𝑖 )
𝑥2
𝑧 = 𝐻𝑡𝐿 𝑁𝑡𝐿 Liquid: L, LS, X, x

𝐿
𝐻𝑡𝐿 =
𝐹𝐿 𝑎
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑢𝑛𝑖𝑡𝑠: 𝑁𝑡𝐿
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• When equilibrium curve
Liquid in:
is straight, slope = m L0, LS, X0, x0
Gas out:
G1, GS, Y1, y1
• Overall mass transfer
coefficient
• If most mass transfer
resistance is within gas Liquid: L, LS, X, x
phase Gas: G, GS, Y, y dV, dz
𝑧 = 𝐻𝑡𝑂𝐺 𝑁𝑡𝑂𝐺
𝐺
𝐻𝑡𝑂𝐺 =
𝐹𝑂𝐺 𝑎
𝑦1
𝑁𝑡𝑂𝐺 =
(1 − 𝑦)(𝑦 − 𝑦𝑖 ) Liquid out: Gas in:
𝑦2
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
• Mass balance
• At steady state
1
𝒚𝟏 y2 , x 2
(𝟏 − 𝒚)𝑳𝑴 𝒅𝒚
𝑵𝒕𝑮 =
(𝟏 − 𝒚)(𝒚 − 𝒚𝒊 )
𝒚𝟐 yi, xi
y
1 − 𝑦𝑖 − (1 − 𝑦) y1 , x 1
(1 − 𝑦)𝐿𝑀 =
1−𝑦 yi, xi
ln 1 − 𝑦𝑖
0
x
• Mass balance
• At steady state
1
𝒚𝟏 y2 , x 2
𝑵𝒕𝑮 =
(𝟏 − 𝒚)(𝒚 − 𝒚𝒊 )
𝒚𝟐 yi, xi
y
1 − 𝑦𝑖 − (1 − 𝑦)
(1 − 𝑦)𝐿𝑀 = y1 , x 1
1−𝑦
ln 1 − 𝑦𝑖
0 yi, xi
𝐺
𝐻𝑡𝐺 = x
𝐹𝐺 𝑎
• Mass balance
• At steady state
1
𝒚𝟏 y2 , x 2
𝑵𝒕𝑮 =
(𝟏 − 𝒚)(𝒚 − 𝒚𝒊 )
𝒚𝟐 yi, xi
y
𝐻𝑡𝐺 =
𝐹𝐺 𝑎
y1 , x 1
0 yi, xi
x
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
𝑧 = 𝐻𝑡𝑂𝐺 𝑁𝑡𝑂𝐺
𝑦1
𝐺 (1 − 𝑦)𝐿𝑀 𝑑𝑦
𝐻𝑡𝑂𝐺 = 𝑁𝑡𝑂𝐺 =
𝐹𝑂𝐺 𝑎 (1 − 𝑦)(𝑦 − 𝑦𝑖 )
𝑦2
𝑦1
(1 − 𝑦)∗𝐿𝑀 𝑑𝑦
𝑁𝑡𝑂𝐺 = Liquid out: Gas in:
(1 − 𝑦)(𝑦 − 𝑦 ∗ )
𝑦2 L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
resistance is within liquid Liquid: L, LS, X, x
𝑧 = 𝐻𝑡𝑂𝐿 𝑁𝑡𝑂𝐿
𝑥1
𝐿 (1 − 𝑥)𝐿𝑀 𝑑𝑥
𝐻𝑡𝑂𝐿 = 𝑁𝑡𝑂𝐿 =
𝐹𝑂𝐿 𝑎 (1 − 𝑥)(𝑥 − 𝑥𝑖 )
𝑥2
𝑥1
(1 − 𝑥)∗𝐿𝑀 𝑑𝑥
𝑁𝑡𝑂𝐿 = Liquid out: Gas in:
(1 − 𝑥)(𝑥 − 𝑥 ∗ )
𝑥2 L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
Two phase mass transfer
𝑁𝐴
𝑁𝐴 − 𝑦𝐴,𝑖
𝑁
𝑁𝐴 = 𝐹 ln
𝑁 𝐺 𝑁𝐴
− 𝑦𝐴
𝑁
Phase I Phase II
𝑁𝐴
𝑁𝐴 − 𝑥𝐴
𝑁 xA xA,i yA,i yA
𝑁𝐴 = 𝐹 ln
𝑁 𝐿 𝑁𝐴
− 𝑥𝐴,𝑖
𝑁 y*A x*A
𝑁𝐴
𝑁𝐴 − 𝑦𝐴∗
𝑁
𝑁𝐴 = 𝐹 ln
𝑁 𝑂𝐺 𝑁𝐴
− 𝑦𝐴
𝑁
𝑁𝐴
𝑁
𝑁𝐴 = 𝐹 ln
𝑁 𝑂𝐿 𝑁𝐴
− 𝑥𝐴∗
𝑁
𝑁𝐴
𝑁
𝑁𝐴 = 𝐹 ln
− 𝑦𝐴
𝑁 Phase I Phase II
𝑁𝐴 𝑁𝐴
𝑁 − 𝑦𝐴∗ xA xA,i yA,i yA
𝐹𝑂𝐺 𝐴
𝑁
𝑁
𝑒 =
𝑁𝐴
− 𝑦𝐴 y*A x*A
𝑁
𝑁𝐴
𝑁
𝑁𝐴 = 𝐹 ln
𝑁 𝐺 𝑁𝐴
− 𝑦𝐴
𝑁
𝑁𝐴 𝑁𝐴
𝑁 − 𝑦𝐴,𝑖
𝐹𝐺 𝐴
𝑁
𝑁
𝑒 =
𝑁𝐴
− 𝑦𝐴
𝑁
𝑁𝐴 𝑁𝐴
𝑁𝐴 𝑁𝐴
− 𝑦𝐴∗ 𝑁 − 𝑦𝐴,𝑖
𝑁
𝐹𝑂𝐺 𝐴 𝑁 𝐹𝐺 𝐴
𝑁
𝑒 𝑁 = 𝑒 =
𝑁𝐴 𝑁𝐴
− 𝑦𝐴 − 𝑦𝐴
𝑁 𝑁 xA xA,i yA,i yA
𝑁𝐴 y*A x*A
𝑁
𝑁𝐴 = 𝐹 ln
𝑁 𝐿 𝑁𝐴
− 𝑥𝐴,𝑖
𝑁
𝑁𝐴 yA
𝑁𝐴 𝑁𝐴 𝑁𝐴
− 𝑁
𝑁 − 𝑥𝐴 − 𝑥𝐴,𝑖
𝐹𝐿 𝐴
𝑁
𝑁 𝐹𝐿 𝐴
𝑁
𝑁 m‘’
𝑒 = 𝑒 =
𝑁𝐴 𝑁𝐴
− 𝑥𝐴,𝑖 − 𝑥𝐴
𝑁 𝑁 yA,i
m'
y*A
𝑦𝐴,𝑖 −𝑦𝐴∗ ′′
𝑦𝐴 − 𝑦𝐴,𝑖
𝑚′ = 𝑚 = ∗
xA xA,i x*A
𝑥𝐴,𝑖 − 𝑥𝐴 𝑥𝐴 − 𝑥𝐴,𝑖
𝑁𝐴
− 𝑁
𝑁𝐴
− 𝑥𝐴,𝑖 𝑦𝐴,𝑖 − 𝑦𝐴∗ Phase I Phase II
𝐹𝐿 𝐴 𝑁 ′
𝑒 𝑁 = 𝑚 =
𝑁𝐴 𝑥𝐴,𝑖 − 𝑥𝐴
− 𝑥𝐴 xA xA,i yA,i yA
𝑁
𝑁𝐴
− 𝑁 y*A x*A
𝐹𝐿 𝐴
𝑁
𝑥𝐴 − 𝑥𝐴,𝑖
𝑒 −1=
𝑁𝐴
− 𝑥𝐴
𝑁
𝑁𝐴 yA
− 𝑁
𝐹𝐿 𝐴 𝑦𝐴,𝑖 − 𝑦𝐴∗
𝑚′ 1 − 𝑒 𝑁 = m‘’
𝑁𝐴
− 𝑥𝐴
𝑁 yA,i
m'
𝑁𝐴 𝑁𝐴
− 𝑁
− 𝑥𝐴 𝑦𝐴,𝑖 − 𝑦𝐴∗ y*A
𝑁 𝐹𝐿 𝐴
𝑚′ 1−𝑒 𝑁 =
𝑁𝐴 𝑁𝐴
− 𝑦𝐴 − 𝑦𝐴 xA xA,i x*A
𝑁 𝑁
𝑁𝐴 𝑁𝐴
𝑁𝐴 𝑁𝐴
− 𝑦𝐴∗ 𝑁 − 𝑦𝐴,𝑖
𝑁
𝐹𝑂𝐺 𝐴 𝑁 𝐹𝐺 𝐴
𝑁
𝑒 𝑁 = 𝑒 =
𝑁𝐴 𝑁𝐴
𝑁 𝑁 xA xA,i yA,i yA
y*A x*A
𝑁𝐴 𝑁𝐴
− 𝑁
− 𝑥𝐴 𝑦𝐴,𝑖 − 𝑦𝐴∗
𝑁 𝐹𝐿 𝐴
𝑚′ 1−𝑒 𝑁 =
𝑁𝐴 𝑁𝐴
𝑁 𝑁
yA
𝑁𝐴 𝑁𝐴 𝑁𝐴 𝑁𝐴 m‘’
𝑁 𝑁 − 𝑥𝐴 − 𝑁
𝐹𝑂𝐺 𝐴 𝐹𝐺 𝐴 𝑁 𝐹𝐿 𝐴
𝑒 𝑁 =𝑒 𝑁 + 𝑚′ 1−𝑒 𝑁 yA,i
𝑁𝐴 m'
− 𝑦𝐴
𝑁
y*A
xA xA,i x*A
Phase I Phase II
Similarly,
xA xA,i yA,i yA
−
𝑁𝐴 𝑁𝐴
− 𝑁
𝑁𝐴 𝑁𝐴
𝑁 1 − 𝑦𝐴 𝑁
𝐹𝑂𝐿 𝐴
𝑁
𝐹𝐿 𝐴
𝑁
𝑁 𝐹𝐺 𝐴
𝑁 y*A x*A
𝑒 =𝑒 + ′′ 1−𝑒
𝑚 𝑁𝐴
− 𝑥𝐴
𝑁
yA
m‘’
yA,i
m'
y*A
xA xA,i x*A
𝑁𝐴
𝑁𝐴 = 𝐹 ln
− 𝑦𝐴
𝑁𝐴 1 − 𝑦𝐴∗
= ln y*A x*A
𝐹𝑂𝐺 1 − 𝑦𝐴
1 − 𝑦𝐴∗ − (1 − 𝑦𝐴 )
(1 − 𝑦𝐴 )∗𝐿𝑀 =
1 − 𝑦𝐴∗
ln 1 − 𝑦 yA
𝐴
m‘’
𝑁𝐴 𝑦𝐴 − 𝑦𝐴∗
= yA,i
𝐹𝑂𝐺 (1 − 𝑦𝐴 )∗𝐿𝑀
m'
y*A
xA xA,i x*A
𝑁𝐴
𝑁𝐴 = 𝐹 ln
𝑁 𝐺 𝑁𝐴
− 𝑦𝐴
𝑁
xA xA,i yA,i yA
𝑁𝐴 1 − 𝑦𝐴,𝑖
= ln y*A x*A
𝐹𝐺 1 − 𝑦𝐴
1 − 𝑦𝐴,𝑖 − (1 − 𝑦𝐴 )
(1 − 𝑦𝐴 )𝑖𝐿𝑀 =
1−𝑦
ln 1 − 𝑦𝐴,𝑖 yA
𝐴
m‘’
𝑁𝐴 𝑦𝐴 − 𝑦𝐴,𝑖
= yA,i
𝐹𝐺 (1 − 𝑦𝐴 )𝑖𝐿𝑀
m'
y*A
xA xA,i x*A
𝑁𝐴
𝑁𝐴 = 𝐹 ln
𝑁 𝐿 𝑁𝐴
− 𝑥𝐴,𝑖
𝑁𝐴 1 − 𝑥𝐴
= ln y*A x*A
𝐹𝐿 1 − 𝑥𝐴,𝑖
1 − 𝑥𝐴,𝑖 − (1 − 𝑥𝐴 )
(1 − 𝑥𝐴 )𝑖𝐿𝑀 =
1−𝑥
ln 1 − 𝑥𝐴,𝑖 yA
𝐴
m‘’
𝑁𝐴 𝑥𝐴,𝑖 − 𝑥𝐴
=
𝐹𝐿 (1 − 𝑥𝐴 )𝑖𝐿𝑀 yA,i
m'
𝑚′ = 𝑚′′ = 𝑚 y*A
𝑁𝐴 𝑦𝐴,𝑖 − 𝑦𝐴∗ xA xA,i x*A
=
𝐹𝐿 𝑚(1 − 𝑥𝐴 )𝑖𝐿𝑀
𝑁𝐴 𝑦𝐴 − 𝑦𝐴∗ 𝑁𝐴 𝑦𝐴 − 𝑦𝐴,𝑖
= = Phase I Phase II
𝐹𝑂𝐺 (1 − 𝑦𝐴 )∗𝐿𝑀 𝐹𝐺 (1 − 𝑦𝐴 )𝑖𝐿𝑀
xA xA,i yA,i yA
𝑁𝐴 𝑦𝐴,𝑖 − 𝑦𝐴∗
=
𝐹𝐿 𝑚(1 − 𝑥𝐴 )𝑖𝐿𝑀 y*A x*A
𝑁𝐴
(1 − 𝑦𝐴 )∗𝐿𝑀 = 𝑦𝐴 − 𝑦𝐴∗
𝐹𝑂𝐺
𝑁𝐴 yA
(1 − 𝑦𝐴 )𝑖𝐿𝑀 = 𝑦𝐴 − 𝑦𝐴,𝑖
𝐹𝐺
m‘’
𝑁𝐴
𝑚(1 − 𝑥𝐴 )𝑖𝐿𝑀 = 𝑦𝐴,𝑖 − 𝑦𝐴∗ yA,i
𝐹𝐿
m'
y*A
(1 − 𝑦𝐴 )∗𝐿𝑀 = (1 − 𝑦𝐴 )𝑖𝐿𝑀 + 𝑚(1 − 𝑥𝐴 )𝑖𝐿𝑀 xA xA,i x*A
𝐹𝑂𝐺 𝐹𝐺 𝐹𝐿
(1 − 𝑦𝐴 )∗𝐿𝑀 = (1 − 𝑦𝐴 )𝑖𝐿𝑀 + 𝑚(1 − 𝑥𝐴 )𝑖𝐿𝑀 Phase I Phase II
𝐹𝑂𝐺 𝐹𝐺 𝐹𝐿
xA xA,i yA,i yA
1 1 1 − 𝑦𝐴 𝑖𝐿𝑀 𝑚 1 − 𝑥𝐴 𝑖𝐿𝑀
= + y*A x*A
𝐹𝑂𝐺 𝐹𝐺 (1 − 𝑦𝐴 )∗𝐿𝑀 𝐹𝐿 (1 − 𝑦𝐴 )∗𝐿𝑀
Similarly, yA
1 1 1 − 𝑦𝐴 𝑖𝐿𝑀 1 1 − 𝑥𝐴 𝑖𝐿𝑀 m‘’

= +
𝐹𝑂𝐿 𝑚𝐹𝐺 (1 − 𝑥𝐴 )∗𝐿𝑀 𝐹𝐿 (1 − 𝑥𝐴 )∗𝐿𝑀 yA,i
m'
y*A
xA xA,i x*A
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
𝐺
𝐻𝑡𝑂𝐺 =
𝐹𝑂𝐺 𝑎
𝐺 𝐺 1 − 𝑦𝐴 𝑖𝐿𝑀 𝑚𝐺 𝐿 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐺 = = +
𝐹𝑂𝐺 𝑎 𝐹𝐺 𝑎 (1 − 𝑦𝐴 )∗𝐿𝑀 𝐿 𝐹𝐿 𝑎 (1 − 𝑦𝐴 )∗𝐿𝑀
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
𝐺 1 − 𝑦𝐴 𝑖𝐿𝑀 𝑚𝐺 𝐿 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐺 = +
𝐹𝐺 𝑎 (1 − 𝑦𝐴 )∗𝐿𝑀 𝐿 𝐹𝐿 𝑎 (1 − 𝑦𝐴 )∗𝐿𝑀
1 − 𝑦𝐴 𝑖𝐿𝑀 𝑚𝐺 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐺 = 𝐻𝑡𝐺 + 𝐻𝑡𝐿
(1 − 𝑦𝐴 )∗𝐿𝑀 𝐿 (1 − 𝑦𝐴 )∗𝐿𝑀
Liquid out: Gas in:

L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
is straight, slope = m yA
• Overall mass transfer m‘’

coefficient yA,i
• If most mass transfer m'
resistance is within gas y*A
phase xA xA,i x*A
1 − 𝑦𝐴 𝑖𝐿𝑀 𝑚𝐺 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐺 = 𝐻𝑡𝐺 + 𝐻𝑡𝐿
(1 − 𝑦𝐴 )∗𝐿𝑀 𝐿 (1 − 𝑦𝐴 )∗𝐿𝑀
𝑦𝐴,𝑖 ≈ 𝑦𝐴∗
𝑚𝐺 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐺 = 𝐻𝑡𝐺 + 𝐻
𝐿 𝑡𝐿 (1 − 𝑦𝐴 )∗𝐿𝑀
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
𝑧 = 𝐻𝑡𝑂𝐿 𝑁𝑡𝑂𝐿
𝑥1
𝐿 (1 − 𝑥)∗𝐿𝑀 𝑑𝑥
𝐻𝑡𝑂𝐿 = 𝑁𝑡𝑂𝐿 =
𝐹𝑂𝐿 𝑎 (1 − 𝑥)(𝑥 − 𝑥 ∗ )
𝑥2
1 1 1 − 𝑦𝐴 𝑖𝐿𝑀 1 1 − 𝑥𝐴 𝑖𝐿𝑀
= + Liquid out: Gas in:
𝐹𝑂𝐿 𝑚𝐹𝐺 (1 − 𝑥𝐴 )∗𝐿𝑀 𝐹𝐿 (1 − 𝑥𝐴 )∗𝐿𝑀
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
𝐿
𝐻𝑡𝑂𝐿 =
𝐹𝑂𝐿 𝑎
1 1 1 − 𝑦𝐴 𝑖𝐿𝑀 1 1 − 𝑥𝐴 𝑖𝐿𝑀
= +
𝐹𝑂𝐿 𝑚𝐹𝐺 (1 − 𝑥𝐴 )∗𝐿𝑀 𝐹𝐿 (1 − 𝑥𝐴 )∗𝐿𝑀
𝐿 𝐺 1 − 𝑦𝐴 𝑖𝐿𝑀 𝐿 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐿 = +
𝑚𝐺 𝐹𝐺 𝑎 (1 − 𝑥𝐴 )∗𝐿𝑀 𝐹𝐿 𝑎 (1 − 𝑥𝐴 )∗𝐿𝑀 Liquid out: Gas in:
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
Liquid in:
Gas out:
G1, GS, Y1, y1
coefficient
𝐿 𝐺 1 − 𝑦𝐴 𝑖𝐿𝑀 𝐿 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐿 = +
𝑚𝐺 𝐹𝐺 𝑎 (1 − 𝑥𝐴 )∗𝐿𝑀 𝐹𝐿 𝑎 (1 − 𝑥𝐴 )∗𝐿𝑀
𝐿 1 − 𝑦𝐴 𝑖𝐿𝑀 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐿 = 𝐻 + 𝐻𝑡𝐿
𝑚𝐺 𝑡𝐺 (1 − 𝑥𝐴 )∗𝐿𝑀 (1 − 𝑥𝐴 )∗𝐿𝑀
Liquid out: Gas in:
L0, LS, X0, x0 G 1 , G S, Y 1 , y 1
is straight, slope = m yA
• Overall mass transfer m‘’

coefficient yA,i
• If most mass transfer m'
resistance is within liquid y*A
phase xA xA,i x*A
𝐿 1 − 𝑦𝐴 𝑖𝐿𝑀 1 − 𝑥𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐿 = 𝐻 + 𝐻𝑡𝐿
𝑚𝐺 𝑡𝐺 (1 − 𝑥𝐴 )∗𝐿𝑀 (1 − 𝑥𝐴 )∗𝐿𝑀
𝐿 1 − 𝑦𝐴 𝑖𝐿𝑀
𝐻𝑡𝑂𝐿 = 𝐻𝑡𝐿 + 𝐻𝑡𝐺
𝑚𝐺 (1 − 𝑥𝐴 )∗𝐿𝑀
Non-isothermal packed absorber
• When heat is liberated upon absorption
• Temperature increases
• Solubility decreases
• Mass transfer driving force decreases
• Absorption of HCl, NOX into water, etc
• Evaporation of solvent
Multicomponent systems
• More than one component in gas phase dissolves
into liquid phase
• Solubility data exists for ideal solutions
(hydrocarbon mixtures, etc.)
• Mass balances and enthalpy balances solved
simultaneously, for plate absorbers
• Computer programs are used
Multicomponent systems
• For absorber design:
• Input gas flow rate, composition, temperature
• Input liquid composition, temperature
• Pressure
• Heat exchange
• Parameters needed:
• Input liquid flow rate
• Number of trays
• Absorption of any one component
• Any two can be independently fixed
Absorption with chemical reaction
• CO2 in alkaline solutions
• SO2 in limestone
• Absorbed solute converts into another chemical
compound
• High concentration driving force
• High mass transfer
• High liquid phase mass transfer
Distillation
• Separation based on difference in volatility
• Many components volatile
• More volatile separated from less volatile
• Heat input
Distillation
• Different from other methods
• New substance is not added (such as in absorption,
adsorption, liquid-liquid extraction, leaching, etc.)
• Many components are volatile (unlike evaporation,
crystallization, drying, etc.)
Distillation
• Restricted to work with given components
• Components may have similar volatilities
• Distillation may be impractical in many cases
Thermodynamics
• Vapour liquid equilibrium: Raoult’s law
P1sat
𝑃 = 𝑝1 + 𝑝2 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡
𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡 + (1 − 𝑥1 )𝑃2𝑠𝑎𝑡
P
𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡 + 𝑃2𝑠𝑎𝑡

P2sat
Straight line
x1  Which component is more volatile?

Thermodynamics
• Vapour liquid equilibrium: Raoult’s law
𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡 + 𝑃2𝑠𝑎𝑡

P1sat
𝑥1 𝑃1𝑠𝑎𝑡 = 𝑝1 = 𝑦1 𝑃
𝑦1 𝑃
𝑥1 =
𝑃1𝑠𝑎𝑡
P
𝑦1 𝑃 𝑠𝑎𝑡
𝑃= 𝑠𝑎𝑡 𝑃1 − 𝑃2𝑠𝑎𝑡 + 𝑃2𝑠𝑎𝑡
𝑃1
P2sat
𝑦1 𝑠𝑎𝑡 𝑠𝑎𝑡
𝑃2𝑠𝑎𝑡
1 = 𝑠𝑎𝑡 𝑃1 − 𝑃2 +
𝑃1 𝑃
x1 
Raoult’s law
Thermodynamics 𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡 + 𝑃2𝑠𝑎𝑡
𝑃2𝑠𝑎𝑡
• Vapour liquid equilibrium 𝑦1 𝑠𝑎𝑡 𝑠𝑎𝑡
1 = 𝑠𝑎𝑡 𝑃1 − 𝑃2 +
𝑃1 𝑃
𝑦1 𝑠𝑎𝑡 𝑠𝑎𝑡
𝑃2𝑠𝑎𝑡
1 − 𝑠𝑎𝑡 𝑃1 − 𝑃2 =
𝑃1 𝑃
P1sat
𝑃1𝑠𝑎𝑡 − 𝑦1 𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡 𝑃2𝑠𝑎𝑡
=
𝑃1𝑠𝑎𝑡 𝑃
P
𝑃1𝑠𝑎𝑡 𝑃2𝑠𝑎𝑡
𝑃 = 𝑠𝑎𝑡
𝑃1 − 𝑦1 𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡
P2sat
Not a straight line
x1,y1
Thermodynamics
• Vapour liquid equilibrium: in general
Constant temperature
P1sat
All liquid
P
y1
P2sat x1
All vapour
Equilibrium
x1,y1
Thermodynamics
Constant pressure
All vapour
T2sat
T
y1
T1sat x1
All liquid
Equilibrium
x1,y1
Thermodynamics Equilibrium
y1
• Vapour liquid equilibrium: in general D
x1
y1
C
T2sat x1
D y1
C
T
B x1
B
A T1sat
y1
A
x1,y1
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 1 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑌𝑍
=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 1 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑋𝑌
T2sat
T
X Y Z
T1sat y1
x1
x1,y1
y1
• Vapour liquid equilibrium: in general D
x1
y1
C
x1
y1
y1
B x1
y1
A
x1 
Thermodynamics
Relative volatility:
𝐾𝐴
𝛼𝐴𝐵 =
𝐾𝐵
𝑦𝐴 𝑦𝐵
𝐾𝐴 = 𝐾𝐵 =
𝑥𝐴 𝑥𝐵
y1
𝑦𝐴
𝑥
𝛼𝐴𝐵 = 𝑦𝐴
𝐵
𝑥𝐵
x1 
Relative volatility:
Thermodynamics 𝑦𝐴
𝑥
𝛼𝐴𝐵 = 𝑦𝐴
𝐵
• Vapour liquid equilibrium: in general 𝑥𝐵
For binary mixture,

𝑦𝐴
𝑥𝐴 𝑦𝐴 1 − 𝑥𝐴
𝛼𝐴𝐵 = =
1 − 𝑦𝐴 𝑥𝐴 (1 − 𝑦𝐴 )
1 − 𝑥𝐴
Measure of separability of A and B

y1
• For α = 1, no separation is possible

• Higher α = easier separation
• α changes with xA
x1 
Thermodynamics
• Pure substance: critical temperature
Tc = critical temperature
Gas does not liquefy, no matter how

high the pressure
Liquid
P
Tc
Solid
Vapour Gas
T
Thermodynamics
• Vapour liquid equilibrium
P1
TC2 P2
P4
T
P3
y1 
P3
T2sat P2
TC1 P4
P1
T1sat
x1,y1 x1
y1
• Vapour liquid equilibrium D
x1
y1
C
P1sat x1
A
y1
B
B
P
x1
C
D
P2sat y1
A
x1,y1
Thermodynamics
Raoult’s law
• Vapour liquid equilibrium
𝑃 = 𝑝1 + 𝑝2 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡
P1sat
P
P2sat
x1 
Thermodynamics
• Positive deviation from Raoult’s law
𝑃 > 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡
P1sat
P
P2sat
x1 
Thermodynamics
• Positive deviation from Raoult’s law
P1sat
Henry’s law limit
Raoult’s law limit
P
𝑝𝑖
𝛾= >1
𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
P2sat
x1 
Thermodynamics
• Positive deviation from Raoult’s law: minimum
boiling azeotrope
x1
x1 y1 P1sat
y1
Maxima in P vs x diagram
P
P2sat
x1 , y 1 
Thermodynamics
boiling azeotrope
T2sat
Minima in T vs x diagram
T
y1
x1 y1
T1sat
x1
x1 , y 1 
Thermodynamics
boiling azeotrope
Azeotrope may be broken for
some mixtures by changing the
pressure
y<x
y1 
Example: ethanol-water at
y>x
pressure below 70 mmHg
x1 
Thermodynamics
• Extreme positive deviation from Raoult’s law:
immiscibility
T2sat Isobutanol-water
Vapour
y1 Heteroazeotrope
T
x1 T1sat
y1
x1
Liquid Liquid
x1 , y 1 
Thermodynamics
immiscibility
Isobutanol-water
Heteroazeotrope
y1
x1 
Thermodynamics
complete immiscibility
Insoluble liquids
Each liquid is practically pure,

and independent
𝑃 = 𝑝1 + 𝑝2
y1
Raoult’s law: 𝑝1 = 𝑥1 𝑃1𝑠𝑎𝑡
How is 𝑃1𝑠𝑎𝑡 calculated?
x1 
Thermodynamics
complete immiscibility
Insoluble liquids
Each liquid is practically pure,

and independent
𝑃 = 𝑝1 + 𝑝2
y1
Raoult’s law: 𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡
𝑃 = 𝑃1𝑠𝑎𝑡 + 𝑃2𝑠𝑎𝑡
x1 
Example
• Water and hexane are taken at room temperature
and 1 atm pressure, in an equimolar ratio, mixed,
and heated. Find the two boiling points.
Example
• Water and hexane are taken at room temperature
in an equimolar ratio, mixed, and heated. Find the
two boiling points.
• At room temperature (77°F),
𝑠𝑎𝑡 𝑠𝑎𝑡
𝑃 = 𝑃𝑤𝑎𝑡𝑒𝑟 + 𝑃ℎ𝑒𝑥𝑎𝑛𝑒
Example
• Water and octane are taken at room temperature
and 1 atm pressure, in an equimolar ratio, mixed,
and heated. Find the two boiling points.
Steam distillation
• As long as liquid water is present, the organic
compound can be made to vaporize at a
temperature < boiling point
• No vacuum required
• High temperatures not required
• Avoid thermal degradation of chemical
• High amount of heat flux to vaporize water
Steam distillation
• Optimum pressure for better vapour mole fraction
of organic compound
• Sparge superheated vapour of insoluble chemical
to saturate it with organic compound
Thermodynamics
• Negative deviation from Raoult’s law
𝑃 < 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡
P1sat
P
P2sat
x1 
Thermodynamics
• Negative deviation from Raoult’s law: maximum
boiling azeotrope
𝑃 < 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡
P1sat
x1
y1 Minima in P vs x diagram
x1
P2sat
y1
P
x1 , y 1 
Thermodynamics
boiling azeotrope
y1
T1sat
y1 x1 Maxima in T vs x diagram
x1
T
T2sat
x1 , y 1 
Thermodynamics
boiling azeotrope
y>x
Hydrochloric acid-water
y1 
y<x
x1 
Thermodynamics
Ethanol-water Hydrochloric acid-water
y>x
y<x
y1 
y1 
y>x
y<x
x1  x1
Thermodynamics
Ethanol-water Hydrochloric acid-water
y>x
y<x
y1 
y1 
y>x
y<x
x1  x1
Enthalpy-concentration diagram
• Liquid enthalpy: sensible heat + enthalpy of mixing
• 𝐻𝐿 = 𝑀𝐶𝐿 𝑡𝐿 − 𝑡0 + ∆𝐻𝑆
• If mixing is exothermic, ∆𝐻𝑆 < 0
• For ideal liquid mixture ∆𝐻𝑆 = 0
• 𝐻𝐺 =?
Relative enthalpy
Enthalpy-temperature diagram
tG
𝐻𝐺,𝐴 = 𝑀𝐴 𝐶𝐿,𝐴 𝑡𝐺 − 𝑡0 + 𝜆𝐴 𝑀𝐴
𝐻𝐺,𝐵 = 𝑀𝐵 𝐶𝐿,𝐵 𝑡𝐺 − 𝑡0 + 𝜆𝐵 𝑀𝐵
Temperature
• Gas enthalpy:
𝐻𝐺 = 𝑦𝐴 𝑀𝐴 𝐶𝐿,𝐴 𝑡𝐺 − 𝑡0 + 𝜆𝐴 𝑀𝐴 + 1 − 𝑦𝐴 𝑀𝐵 𝐶𝐿,𝐵 𝑡𝐺 − 𝑡0 + 𝜆𝐵 𝑀𝐵
Gas enthalpy
𝐻𝐺 = 𝑦𝐴 𝑀𝐴 𝐶𝐿,𝐴 𝑡𝐺 − 𝑡0 + 𝜆𝐴 𝑀𝐴 + 1 − 𝑦𝐴 𝑀𝐵 𝐶𝐿,𝐵 𝑡𝐺 − 𝑡0 + 𝜆𝐵 𝑀𝐵
Liquid enthalpy 𝐻𝐿 = 𝑀𝐶𝐿 𝑡𝐿 − 𝑡0 + ∆𝐻𝑆
𝜆𝐵
Enthalpy
𝜆𝐴
xA, yA 
𝜆𝐵
Enthalpy
𝜆𝐴
xA, yA 
yA 
xA

Mass Transfer II

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Mass Transfer II

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Mass Transfer II

No energy input required

Number of molecules fluctuates

Convective flux (bulk flow)

No bulk flow (assuming low concentration)

Negative sign: Direction of diffusive flux

Diffusion from inside outwards

Diffusion from inside outwards

Mole balance inside cylindrical shell

Mole balance inside cylindrical shell

Accumulation = Input – Output + Generation - Consumption

Mole balance inside cylindrical shell

Mole balance inside cylindrical shell

Mole balance inside cylindrical shell

Mole balance inside cylindrical shell

Mole balance inside cylindrical shell

Mole balance inside spherical shell

𝑓𝑙𝑢𝑥 𝑖𝑛 ∗ 𝑎𝑟𝑒𝑎 𝑖𝑛 − 𝑓𝑙𝑢𝑥 𝑜𝑢𝑡 ∗ 𝑎𝑟𝑒𝑎 𝑜𝑢𝑡 = 0

𝑓𝑙𝑢𝑥 𝑖𝑛 ∗ 𝑎𝑟𝑒𝑎 𝑖𝑛 − 𝑓𝑙𝑢𝑥 𝑜𝑢𝑡 ∗ 𝑎𝑟𝑒𝑎 𝑜𝑢𝑡 = 0

𝑟1 𝑟2 𝑐𝐴1 − 𝑐𝐴2 1 𝑟1 𝑐𝐴1 − 𝑟2 𝑐𝐴2

φ Total molar flux – inner surface:

𝐽𝐴(𝑧+𝑑𝑧) 𝑑𝑥𝑑𝑦 𝐽𝐴𝑦 𝑑𝑥𝑑𝑧

𝜕𝑁𝐴 𝜕𝐽𝐴𝑥 𝜕𝐽𝐴𝑦 𝜕𝐽𝐴𝑧

Time t = 0 Time t > 0

No concentration gradient along y axis and z axis

LHS is a function of t only

𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = −𝑣𝑒, 0, +𝑣𝑒

𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = −𝑣𝑒, 0, +𝑣𝑒

𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = −𝑣𝑒, 0, +𝑣𝑒

𝐶𝐴∞ = 𝐶𝐴∞ + 𝐵𝜆′′ cos 𝜆𝑎

Since cos 𝜆𝑎 are linearly independent functions,

𝐶𝐴0 = 𝐶𝐴∞ + 𝐵𝑛′′

What should we do next?

z at t = 0, 𝐶𝐴 = 𝐶𝐴0 𝑓𝑜𝑟 − 𝑎 < 𝑥 < 𝑎

Time t = 0 Time t > 0

Similar equations can be derived for cylindrical and spherical geometries

• 𝑢𝐴 is the average molecular velocity of A, given by

• 𝐷𝐾,𝐴 is the Knudsen diffusion coefficient

• Knudsen diffusion is not known for liquids

Pure gas Pure gas

Pure liquid Liquid + dissolved gas

B: Highly soluble gas

Any concentration of gaseous solute

Liquefied solute should be miscible

Mole fraction of solute in liquid

Usually dissolution of gas inside

As temperature increases, solubility

van’t Hoff’s law of mobile

Mole fraction of solute in liquid

For ideal solutions, component

Mole fraction of solute in liquid

Ideal solutions do not exist in reality!

• Liquid phase = ideal solution

What is an ideal gas? What is pressure?

Pure gas at T, Psat

By author of the original work: Cmglee - Own work, CC BY-SA 3.0,

Pure gas at T, Psat Pure gas at T, x1Psat

Pure gas at T, x1Psat Mixed gas at T,

Mixed liquid at T Mixed liquid at T

Component Vapour mole Partial Vapour Liquid mole

As y decreases, G also decreases

Y1, Y2, X2, GS are fixed. Choose LS

Gas out Mass balance on solute A