Mass-transfer coefficients

CL 321
Kaustubh Rane

1
 Recap: Molecular diffusion
Gases
𝐴 through non-diffusing 𝐵 Equimolal counter-diffusion
𝑫𝑨𝑩 𝒑𝒕
• 𝑁𝐴 = (𝑝𝐴1 − 𝑝𝐴2 )
𝑹𝑻𝒛𝒑𝑩,𝑴 𝑫𝑨𝑩
• 𝑁𝐴 = (𝑝𝐴1 − 𝑝𝐴2 )
𝑹𝑻𝒛
𝑝𝐵2 −𝑝𝐵1
• 𝑝𝐵,𝑀 = 𝑝
ln(𝑝𝐵2 )
𝐵1

Liquids
𝐴 through non-diffusing 𝐵 Equimolal counter-diffusion
𝑫𝑨𝑩 𝝆
• 𝑁𝐴 = (𝑥 − 𝑥𝐴2 ) • 𝑁𝐴 =
𝑫𝑨𝑩 𝝆
(𝑥 − 𝑥𝐴2 )
𝒛𝒙𝑩,𝑴 𝑴 𝒂𝒗 𝐴1 𝒛 𝑴 𝒂𝒗 𝐴1

2
 Mass transfer coefficients
Gases
𝐴 through non-diffusing 𝐵 Equimolal counter-diffusion
• 𝑁𝐴 = 𝒌𝑮 (𝑝𝐴1 − 𝑝𝐴2 ) • 𝑁𝐴 = 𝒌′𝑮 (𝑝𝐴1 − 𝑝𝐴2 )

• 𝑁𝐴 = 𝒌𝒚 (𝑦𝐴1 − 𝑦𝐴2 ) • 𝑁𝐴 = 𝒌′𝒚 (𝑦𝐴1 − 𝑦𝐴2 )

• 𝑁𝐴 = 𝒌𝑪 (𝐶𝐴1 − 𝐶𝐴2 ) • 𝑁𝐴 = 𝒌′𝑪 (𝐶𝐴1 − 𝐶𝐴2 )

Liquids
𝐴 through non-diffusing 𝐵 Equimolal counter-diffusion

• 𝑁𝐴 = 𝒌𝑳 (𝐶𝐴1 − 𝐶𝐴2 ) • 𝑁𝐴 = 𝒌′𝑳 (𝐶𝐴1 − 𝐶𝐴2 )

• 𝑁𝐴 = 𝒌𝒙 (𝑥𝐴1 − 𝑥𝐴2 ) • 𝑁𝐴 = 𝒌′𝒙 (𝑥𝐴1 − 𝑥𝐴2 )

3
 Relating different transfer coefficients

Gases Liquids
𝑘𝑦
• 𝑘𝐺 =
𝑝𝑡 𝑘𝑥
• 𝑘𝐿 =
𝐶
𝑘𝐶
• 𝑘𝐺 =
𝑅𝑇

General mass-transfer coefficient

𝑭 = 𝑫𝑨𝑩 𝑪/𝒛
Gases
𝑝𝐵,𝑀
• 𝐹 = 𝑘𝐺 𝑝𝐵,𝑀 = 𝑘𝑦
𝑝𝑡
= Liquids
𝑝𝐵,𝑀 • 𝐹 = 𝑘𝐿 𝑥𝐵,𝑀 𝐶 = 𝑘𝑥 𝑥𝐵,𝑀
𝑘𝐶
𝑅𝑇
• 𝐹 = 𝑘′𝐿 𝐶 = 𝑘′𝑥
• 𝐹 = 𝑘𝐺 𝑝𝑡 = 𝑘′𝑦 = 𝑘′𝐶 𝐶
4
 Examples

Calculate 𝐹, 𝑘𝐺 , 𝑘𝑦 , 𝑘𝐶

Calculate 𝐹, 𝑘𝐿 , 𝑘𝑥

5
Adapted from “Mass transfer operations” by Treyball
 Interphase mass transfer

• A process is accompanied by a “driving force”

• For mass transfer in a single phase, driving forces are:

• Difference in concentrations, partial pressure etc.

• Transfer continues till driving force exists

• Driving force = 0 ⇒ System has reached equilibrium

• What is the driving force for interphase mass transfer?

6
 Phase-equilibria
• Consider a closed system

• Pressure and temperature are specified

• Contains two phases 𝛼 and 𝛽

• n components in each phase. Eg. 𝑁1𝛼 , 𝑁2𝛼 , … , 𝑁𝑖𝛼 , … , 𝑁𝑛𝛼

• Characteristic free-energy: Gibbs free energy 𝐺(𝑃, 𝑇, 𝑵𝜶 , 𝑵𝜷 )

𝑵𝒂𝒓𝒃 ≡ Not stable

𝑮

𝑵𝒎𝒊𝒏 ≡ Stable

𝑵𝒎𝒊𝒏 𝑵𝒂𝒓𝒃
𝑵 7
 Phase-equilibria
• From the calculus of thermodynamics:
𝑛 𝑛
𝛽 𝛽
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + ෍ 𝜇𝑖𝛼 𝑑𝑁𝑖𝛼 + ෍ 𝜇𝑖 𝑑𝑁𝑖
𝑖=1 𝑖=1

• Minimum ⇒ 𝑑𝐺 = 0

𝑛 𝛼 𝛼 𝛽 𝛽
• 𝑃, 𝑇 ≡ constant ⇒ 𝑖=1 𝜇𝑖 𝑑𝑁𝑖 + 𝜇𝑖 𝑑𝑁𝑖 = 0
σ

𝛽
• Closed system ⇒ 𝑑𝑁𝑖𝛼 = −𝑑𝑁𝑖

𝑛
𝛽
෍(𝜇𝑖𝛼 − 𝜇𝑖 )𝑑𝑁𝑖𝛼 = 0
𝑖=1
𝛽
• Driving force: 𝜇𝑖𝛼 − 𝜇𝑖
8
 Driving force

• 𝛼 ≡ vapour and 𝛽 ≡ liquid

𝒗 𝒍
• Driving force:𝜇𝑖𝑣 − 𝜇𝑖𝑙
𝒑𝒊 𝒙𝒊
• But, chemical potentials are
difficult to work with

• Can we express 𝜇𝑖𝑣 − 𝜇𝑖𝑙 in terms of partial pressures or

compositions?

• 𝜇𝑖𝑣 = Λ𝑣𝑖 𝑇, 𝑃 + 𝑅𝑇𝑙𝑛𝑓𝑖 𝑓𝑖 = 𝜙𝑖 𝑝𝑖

• 𝜇𝑖𝑙 = Λ𝑙𝑖 𝑇, 𝑃 + 𝑅𝑇𝑙𝑛𝑎𝑖 𝑎𝑖 = 𝛾𝑖 𝑥𝑖

• Cannot directly compare 𝑓𝑖 and 𝑎𝑖 because of Λ𝑙𝑖 and Λ𝑣𝑖

9
 Driving force

• Think about the vapour

𝒗 𝒍 phase that is in equilibrium
with our liquid
𝒑𝒊 𝒙𝒊 • 𝜇𝑖∗𝑣 = 𝜇𝑖𝑙

• 𝜇𝑖∗𝑣 = Λ𝑣𝑖 𝑇, 𝑃 + 𝑅𝑇𝑙𝑛𝑓𝑖∗

• Now, we can compare 𝑓𝑖 and 𝑓𝑖∗

• For ideal gases, we will have 𝑝𝑖 and 𝑝𝑖∗

• Similarly, we can consider 𝜇𝑖∗𝑙 = 𝜇𝑖𝑣

• Then, we can compare 𝑎𝑖∗ and 𝑎𝑖

• Useful for employing overall mass-transfer coefficient 10

 Direction of mass transfer
𝛽
• From 𝛼 → 𝛽 if 𝜇𝑖𝛼 > 𝜇𝑖
• From concentration profiles near the interface
Case 1 Case 2 Case 3

𝜶 𝜷 𝜶 𝒙𝒊 𝜷 𝜶 𝒙𝒊 𝜷
𝒙𝒊
𝒙
𝒚 𝒚𝒊 𝒙 𝒚𝒊
𝒙
𝒚 𝒚
𝒚𝒊

𝒚 𝒚𝒊 𝒚𝒊

𝒚𝒊 𝒚 𝒚
𝒙𝒊 𝒙𝒊 𝒙𝒊
𝒙 𝒙 𝒙
11
 Direction of mass transfer

Case 4 Case 5
𝜶 𝒙𝒊 𝜷 𝜶 𝒙𝒊 𝜷
𝒚
𝒚𝒊 𝒙 𝒙
𝒚
𝒚𝒊

𝒚𝒊 𝒚

𝒚 𝒚𝒊
𝒙𝒊 𝒙𝒊
𝒙 𝒙

For steady state: 𝑁𝐴 = 𝒌𝒚 𝑦 − 𝑦𝑖 = 𝒌𝒙 (𝑥 − 𝑥𝑖 ) 12

 Overall mass transfer coefficient

• Convenient to work with mole fractions

• Let 𝐾𝑥 , 𝐾𝑦 be the overall mass transfer coefficients

• Driving force: 𝑦 − 𝑦 ∗ or 𝑥 ∗ − 𝑥
𝜶 𝒙𝒊 𝜷
• 𝑦 ∗ ≡ equilibrium with 𝑥
𝒚
𝒙
• 𝑥 ∗ ≡ equilibrium with 𝑦
𝒚𝒊
• 𝑁𝐴 = 𝐾𝑦 𝑦 − 𝑦 ∗ = 𝐾𝑥 (𝑥 ∗ − 𝑥)

How to relate 𝑲𝒙 , 𝑲𝒚 to 𝒌𝒙 and 𝒌𝒚 ?

13
 Overall mass transfer coefficient : 𝐾𝑦

𝜶 𝒙𝒊 𝜷
• Steady state: 𝑁𝐴 = 𝑘𝑦 𝑦 − 𝑦𝑖 =
𝒚
𝒙 𝑘𝑥 (𝑥𝑖 − 𝑥)

𝒚𝒊 • 𝑦 − 𝑦 ∗ = 𝑦 − 𝑦𝑖 + 𝑦𝑖 − 𝑦 ∗

• Let 𝑦𝑖 = 𝑚′ 𝑥𝑖 and 𝑦 ∗ = 𝑚′ 𝑥 𝒚
• 𝑦 − 𝑦 ∗ = 𝑦 − 𝑦𝑖 + 𝑚′ 𝑥𝑖 − 𝑥 ∗
𝒚𝒊
𝑁𝐴 𝑁𝐴 𝑚′ 𝑁𝐴
• = + 𝒚∗ 𝒎′
𝐾𝑦 𝑘𝑦 𝑘𝑥

•
1
=
1
+
𝑚′ 𝒙 𝒙𝒊 𝒙∗
𝐾𝑦 𝑘𝑦 𝑘𝑥
14
 Overall mass transfer coefficient : 𝐾𝑥
𝜶 𝒙𝒊 𝜷
• Steady state: 𝑁𝐴 = 𝑘𝑦 𝑦 − 𝑦𝑖 =
𝒚 𝑘𝑥 (𝑥𝑖 − 𝑥)
𝒙
• 𝑥 ∗ − 𝑥 = 𝑥 − 𝑥𝑖 + 𝑥𝑖 − 𝑥 ∗
𝒚𝒊

• Let 𝑦𝑖 = 𝑚"𝑥𝑖 and 𝑦 = 𝑚"𝑥 ∗ 𝒚

• 𝑦 − 𝑦 ∗ = 𝑦 − 𝑦𝑖 /𝑚" +
𝑥𝑖 − 𝑥 ∗ 𝒚𝒊 𝒎"
𝑁𝐴 𝑁𝐴 𝑁𝐴 𝒚∗
• = +
𝐾𝑥 𝑚"𝑘𝑦 𝑘𝑥
1 1 1
•
𝐾𝑥
=
𝑚"𝑘𝑦
+
𝑘𝑥
𝒙 𝒙𝒊 𝒙∗
15
 Approximations to 𝐾𝑦
• If the solute is highly soluble in
the 𝛽 phase

𝒚𝒊 • Small change in equilibrium

𝒚∗ y ⇒ large change in
𝒙 𝒙𝒊 corresponding 𝑥

• Slope 𝑚′ → 0

• 1/𝐾𝑦 → 1/𝑘𝑦

• 𝛼 phase controls the rate of mass transfer

16
 Approximations to 𝐾𝑥

• If the solute is less soluble in the 𝛽

phase
𝒚𝒊
𝒚∗ • Small change in equilibrium 𝑥 require
large change in corresponding 𝑦
𝒙 𝒙𝒊

• Slope 𝑚" → ∞

• 1/𝐾𝑥 → 1/𝑘𝑥

• 𝛽 phase controls the rate of mass transfer

17
 Significance for the design of equipment

• Consider a component being transferred from 𝛼 to 𝛽

• Let 𝛼 be of lower density Near top

𝜶, 𝒚𝟐 𝜷, 𝒙𝟏 𝒚𝒊∗
𝒚
𝒙𝟏 𝒙𝒊
Near bottom
𝒚

𝒙 𝒚𝒊
𝒚𝟏
𝜶, 𝒚𝟏 𝜷, 𝒙𝟐
𝒙∗ 𝒙𝒊
𝜶 controlled at top, 𝜷 controlled at bottom 18
 Estimation of mass-transfer coefficients
𝐶𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑣𝑒 𝑚𝑎𝑠𝑠 (𝑚𝑜𝑙𝑎𝑟) 𝑓𝑙𝑢𝑥
• Sherwood number 𝑆ℎ =
𝑀𝑎𝑠𝑠 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑢𝑥 𝑏𝑦 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛

𝑘𝐿𝑐𝑜𝑛𝑣 𝐿
• 𝑆ℎ = 𝐿: Characteristic length scale
𝐷𝐴𝐵

• 𝑆ℎ analogous to the Nusselt’s number in heat transfer

𝑀𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦
• Schmidt number 𝑆𝑐 =
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦

𝜇
• 𝑆𝑐 =
𝜌𝐷𝐴𝐵

• 𝑆𝑐 analogous to the Prandtl number in heat transfer

𝜌𝑣𝐿
• 𝑅𝑒 =
𝜇 19
 Estimation of mass-transfer coefficients
• Empirical relations between 𝑆ℎ, 𝑆𝑐 𝑎𝑛𝑑 𝑅𝑒 are used for different
systems

• 𝑆ℎ = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × 𝑆𝑐 𝑎 × 𝑅𝑒 𝑏

• Laminar flow through a circular tube (𝑅𝑒 ≤ 2100):

𝐷 1/3
• 𝑆ℎ = 1.62 1.62𝑅𝑒 𝑆𝑐
𝐿

• Turbulent flow through a tube (4000 ≤ 𝑅𝑒 ≤ 60000; 0.6 ≤ 𝑆𝑐 ≤

3000):

• 𝑆ℎ = 0.023 𝑅𝑒 0.83 𝑆𝑐 0.33

Self-study: Other empirical relations

20
 Theories for mass-transfer coefficients
• Provides insights into the physical mechanism

• Rationalize the values of different parameters

• Potential for rationally manipulating the system

• Empirical relations may not be available always

• Can aid in the development of empirical relations

• Theories consider a simplified analogue of the real system (physical

model)

• Physical model: Has characteristics of the real system, but easier to

analyse theoretically
• 1) Film theory, 2) penetration theory, 3) surface renewal theory and
21
3) boundary layer theory
 Film theory
• Simplest (and least realistic). Given by Whitman in 1923

• Relates mass transfer coefficients to the molecular diffusivities

Assumptions
𝑪𝑨𝒊
• Mass-transfer by
molecular diffusion in the
film

𝑪𝑨𝒃 • Steady state

• Composition is uniform
𝜹 outside the film
𝒛 22
 Film theory
• Steady state ⇒ 𝑁𝐴,𝑧 𝑧
= 𝑁𝐴,𝑧 𝑧+Δ𝑧

𝑑𝑁𝐴
• Δ𝑧 → 0 ⇒ =0
𝑑𝑧

𝐶𝐴 𝜕𝑐𝐴
• 𝑁𝐴 = 𝑁𝐴 + 𝑁𝐵 − 𝐷𝐴𝐵
𝐶 𝜕𝑧
Equimolal counterdiffusion

𝑑𝑁𝐴 𝑑2 𝐶𝐴
= 0 ⇒ 𝐷𝐴𝐵 2
=0
𝑑𝑧 𝑑𝑧

Boundary conditions: 𝑧 = 0 𝐶𝐴 = 𝐶𝐴𝑖

𝑧 = 𝛿 𝐶𝐴 = 𝐶𝐴𝑏

𝐶𝐴𝑖 − 𝐶𝐴𝑏 𝑫𝑨𝑩

𝐶𝐴 = 𝐶𝐴𝑖 − 𝑧 ⇒ 𝑁𝐴 = 𝐶𝐴𝑖 − 𝐶𝐴𝑏
𝛿 𝜹
𝒌𝑳 23
 Penetration theory
• Given by Higbie in 1935

• Unsteady state mass-transfer at the interface

𝜷 𝜶

𝜶 𝜷

• Time of exposure is constant for all eddies

• Equilibrium exists at the interface

24
Adapted from “Mass transfer operations” by Treyball
 Penetration theory

𝜶 • Material balance on the

single element

𝜷 • Fick’s second law:

𝜕𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵
𝜕𝑡 𝜕𝑧 2
• Initial condition (𝑡 = 0, 𝑧 ≥ 0) 𝐶𝐴 = 𝐶𝐴𝑏

• Boundary conditions:
• 𝑡 > 0, 𝑧 = 0 𝐶𝐴 = 𝐶𝐴𝑖
• 𝑡 > 0, 𝑧 → ∞ 𝐶𝐴 = 𝐶𝐴𝑏
𝑫𝑨𝑩
𝑁𝐴 = 𝟐 𝐶𝐴𝑖 − 𝐶𝐴𝑏
𝝅𝒕𝒄
Self-study: Derivation
25
Adapted from “Mass transfer operations” by Treyball
 Penetration theory

𝐶𝐴
𝑪𝑨𝒊 𝒕
→∞
= 𝐶𝐴𝑏 + 𝐶𝐴𝑖 − 𝐶𝐴𝑏 1 − erfc 𝜂
𝒕𝟐
𝑧
𝜂= 𝑪𝑨𝒃 𝒕𝟏
2 𝐷𝐴𝐵 𝑡

𝒛
• Useful when droplets of one phase move in another phase

• When phases flow over random packings

• 𝑡𝑐 can be estimated in different ways

• For rising bubble: Ratio of diameter to the rise velocity

26
 Surface-renewal theory

• Given by Danckwert in 1951

• Time of exposure is not constant for all eddies

• 𝑡𝑐 for different elements vary

• Depends on the rate of production of fresh surface area.

𝜶
𝑁𝐴 = 𝐷𝐴𝐵 𝑠 𝐶𝐴𝑖 − 𝐶𝐴𝑏

𝑘𝐿 = 𝐷𝐴𝐵 𝑠 𝜷

27
 Boundary Layer theory

• Considers fluid mechanics explicitly

Velocity
𝒗∞ boundary • Velocity boundary
layer layer ≡ 0.99𝑣∞
Mass
𝒚
𝜹(𝒙) boundary • Mass boundary layer ≡
layer 0.01𝐶𝑖
𝜹𝒄 (𝒙)
𝑪𝒊
𝒙

𝜇
• 𝑆𝑐 = governs the relative thickness
𝜌𝐷𝐴𝐵

• 𝑆𝑐 > 1 ⇒ 𝛿 𝑥 > 𝛿𝐶 𝑥

• 𝑆𝑐 < 1 ⇒ 𝛿 𝑥 < 𝛿𝐶 𝑥 28
 Boundary Layer theory
• Let 𝐶 = 𝑎0 + 𝑎1 𝑦 + 𝑎2 𝑦 2 + 𝑎3 𝑦 3

• Boundary conditions:
𝜕2 𝐶
• At 𝑦 = 0, 𝐶 = 𝐶𝑖 and 2 = 0 (Fick’s second law)
𝜕𝑦
𝜕𝐶
• At 𝑦 = 𝛿𝑐 , 𝐶 = 0 and = 0
𝜕𝑦

3
𝐶 3 𝑦 1 𝑦
• =1− +
𝐶𝑖 2 𝛿𝐶 2 𝛿𝐶

𝜕𝐶 𝟑 𝑫𝑨𝑩
• 𝑁𝐴 = −𝐷𝐴𝐵 = (𝐶𝑖 − 0)
𝜕𝑦 𝑦=0 𝟐 𝜹𝑪
−0.5
𝛿 𝛿 𝑣𝑥𝜌
• Empirical relationships: = 𝑆𝑐 −1/3 and = 4.64
𝛿𝐶 𝑥 𝜇

𝑘𝐿𝑎𝑣𝑔 𝐿 𝟐/𝟑
• = 𝑆ℎ𝑎𝑣𝑔 = 0.646𝑅𝑒 0.5 𝑆𝑐1/3 𝒌𝑳𝒂𝒗𝒈 ∝ 𝑫𝑨𝑩
𝐷𝐴𝐵 29
 Examples

30
Adapted from “Mass transfer operations” by Treyball
 Examples: Determination of mass transfer coeff from experiments

Air at 347K and 1 atm is blown at high speed around single naphthalene sphere, which
sublimates partially. When the experiment begins, the diameter of the sphere is 2.0 cm.
After 14.32 minutes, the diameter of the sphere is 1.85cm. Estimate 𝑘𝐶 for the gas
phase. The density of naphthalene is 1.145 g/cc and its vapour pressure at 347 K is 670
Pa.

31
Adapted from “Mass transfer operations” by Treyball
 Examples: Overall mass transfer coef

32
Adapted from “Mass transfer operations” by Treyball
 Examples: From empirical relations

A naphthalene sphere with the diameter equal to 1.5 cm is placed into a pure stream of
𝐶𝑂2 at 1atm and 100𝑜 𝐶. The vapour pressure of naphthalene at the surface temperature
is 10mmHg and the diffusivity in 𝐶𝑂2 is 5.15 × 10−6 𝑚2 /𝑠. Estimate the rate of
sublimation of naphthalene and the change in the sphere diameter after 60𝑠 of the
exposure to 𝐶𝑂2 stream for the following two scenarios:

(a) when 𝐶𝑂2 flows past the sphere at a velocity of 6𝑚/𝑠

(b) When 𝐶𝑂2 environment around the sphere is stagnant

For gases, 𝑆ℎ = 2 + 0.0552𝑅𝑒 0.5 𝑆𝑐1/3 when 𝑆𝑐 = 0.6 𝑡𝑜 2.7 and 𝑅𝑒 = 1 𝑡𝑜 48000

𝜇𝐶𝑂2 = 1.8 × 10−5 𝑃𝑎. 𝑠 𝜌 = 1.145𝑔/𝑐𝑐

33
Adapted from the assignment of CL 303 in 2010
 Examples: From empirical relations
Water containing 0.1𝑀 benzoic acid flows at the speed of 0.1 cm/s through a 1 cm rigid
tube of cellulose acetate, the walls of which are permeable to small electrolytes. These
walls are 0.01 cm thick; solutes within the walls diffuse as through water. The tube is
immersed in a large well-stirred water bath. The mass-transfer coefficient of benzoic
acid from bulk to the walls is described by the following correlation:

1/3
𝑘𝑑 𝑑2 𝑣
= 1.62
𝐷𝐴𝐵 𝐷𝐴𝐵 𝐿

Where 𝐿 is the pipe length 𝑣 is the average velocity in the pipe.

After 50 cm of tube, what fraction of 0.1𝑀 benzoic acid solution has been removed?

𝐷𝐴𝐵 = 7.97 × 10−10 𝑚2 /𝑠

34
Adapted from the assignment of CL 303 in 2010
 Examples: Boundary layer theory

35
Adapted from “Mass transfer operations” by Treyball