TWO FILM THEORY FOR INTERFACIAL MASS TRANSFER

Suggested first by Nernst (1904) and later worked on by Lewis and Whitman (1923)
Consider dissolution of ammonia from air into water

GAS FILM
𝑝1 LIQUID FILM
𝑐1𝑖
BULK GAS BULK LIQUID
water
𝑝1𝑖 𝑐1

Air bubble
containing 3% ammonia INTERFACE
𝑝1𝑖 : Pressure of ammonia on gas side at the interface
𝑐1𝑖 : Concentration of ammonia on liquid side at the interface
Interface in thin and equilibrium is attained across it instantaneously
This means 𝑝1𝑖 = 𝐻𝑐1𝑖

• All resistance to mass transfer on gas side is in the GAS FILM or unstirred layer; no resistance in bulk gas
• All resistance to mass transfer on liquid side is in the LIQUID FILM or unstirred layer; no resistance in bulk liquid
 DRAW PROFILES BASED ON TWO FILM THEORY
Chloroform is transferred from water to air. Concentration of chloroform in air is lower than its
concentration in water at equilibrium.
Benzoic acid is dissolving in water from a disk

GAS FILM LIQUID FILM

LIQUID FILM
𝑐1𝑖
𝑐1 Benzoic
BULK LIQUID
BULK GAS 𝑐1𝑖 BULK LIQUID acid
′
𝑐1𝑖 𝑐1

𝑐1′
Profiles for chloroform transfer Profiles for benzoic acid transfer
 DRAW PROFILES BASED ON TWO FILM THEORY

Penicillin is extracted from water phase into butyl acetate phase. Penicillin is ten times more soluble in
butyl acetate than in water.

Water is evaporating into air from a lake

ACETATE FILM AIR FILM

′ 𝑐1 𝑝1𝑖
𝑐1𝑖
LAKE
BULK BULK AIR
BULK WATER SIDE
ACETATE 𝑐1𝑖
𝑝1
𝑐1′ WATER FILM

Profiles for penicillin transfer Profiles for water vapour transfer

 TWO FILM THEORY FOR INTERFACIAL MASS TRANSFER
Consider dissolution of ammonia from air into water

GAS FILM
𝑝1 LIQUID FILM
𝑐1𝑖
BULK GAS BULK LIQUID
water
𝑝1𝑖 𝑐1

Air bubble
containing 3% ammonia The gas and liquid films are thin; steady state is expected across the film

𝐷
Apply Fick’s law of diffusion for liquid film and find flux across it; 𝑁1 = 𝑐1𝑖 − 𝑐1
Diffusivity of ammonia is 𝐷 and film thickness is 𝑙 𝑙 𝑙𝑖𝑞

Write flux in terms of mass transfer coefficient, 𝑘𝑐 𝑁1 = 𝑘𝑐 𝑐1𝑖 − 𝑐1

𝐷
Equating these fluxes, 𝑘𝑐 =
𝑙
 TWO FILM THEORY FOR INTERFACIAL MASS TRANSFER

• One could find a mass transfer coefficient in gas phase using a similar formula
• Film thickness, 𝑙, is unknown apriori
𝐷 • Even though diffusivity, 𝐷, can be estimated with reasonable accuracy, 𝑘𝑐 cannot be
𝑘𝑐 = calculated because 𝑙 is unknown
𝑙
• Film theory is easy to understand
• It is useful in effects of chemical reaction on mass transfer

Interpretation of effects of variables on mass transfer coefficients based on film theory

0.8
𝑘𝑑 𝑑𝑣 𝑜 𝜈 0.33
Turbulent flow through a tube = 0.026
𝐷 𝜈 𝐷
The effects of variables such as velocity, diffusivity are lumped in film thickness
What happens to film thickness if speed is doubled? Diffusivity is halved?
Speed doubles, 𝑘𝑐 rises by 74%, film becomes thinner by 43%
Diffusivity is halved, 𝑘𝑐 falls by 63%, film becomes thicker by 60%
Liquid film thickness around benzoic acid disk
𝑐𝑚 𝑐𝑚2
What is the unstirred layer thickness if 𝑘𝑐 = 9 × 10−4 and 𝐷 = 1 × 10−5 ?
𝑠 𝑠

𝑐𝑚2
𝐷 1×10−5
𝑠
Unstirred layer thickness = = 𝑐𝑚 = 111 𝑚𝑖𝑐𝑟𝑜𝑛𝑠
𝑘𝑐 9×10−4
𝑠

This means the concentration changes from 𝑐𝑠𝑎𝑡 to 𝑐𝑏𝑢𝑙𝑘 in a small film ~100 microns thick
This is THINNER than one strand of your hair!

Gas film thickness around benzoic acid disk

𝑐𝑚 𝑐𝑚2
What is the unstirred layer thickness if 𝑘𝑐 = 0.47 and 𝐷 = 0.233 ?
𝑠 𝑠

𝑐𝑚2
𝐷 0.233
𝑠
Unstirred layer thickness = = 𝑐𝑚 = 500 𝑚𝑖𝑐𝑟𝑜𝑛𝑠
𝑘𝑐 0.47
𝑠

This means the concentration changes from 𝑐𝑠𝑎𝑡 to 𝑐𝑏𝑢𝑙𝑘 in a small film ~500 microns thick
For transfer of i-butanol from water to air, which film controls the mass transfer?
𝑐𝑚2
Data: Diffusivity of i-butanol in water is 6 × 10−6
𝑠
𝑐𝑚2
Diffusivity of i-butanol in air is 0.06
𝑠
Total pressure is 1 atm an temperature is 80 oC
Equilibrium relation is 𝑝 = 0.53𝑥
𝑐𝑚2
𝐷 6×10−6 𝑐𝑚
𝑠
Mass transfer coefficient of i-butanol in water is, 𝑘𝑐 = = = 6 × 10−4
𝑙 0.01 𝑐𝑚 𝑠
𝑐𝑚2
𝐷 0.06 𝑐𝑚
𝑠
Mass transfer coefficient of i-butanol in air is, 𝑘𝑐 = = = 1.2
𝑙 0.05 𝑐𝑚 𝑠

′ ′
Derive overall mass transfer coefficient: 𝑘 𝑐1 − 𝑐1𝑖 = 𝑘 ′ 𝑐1𝑖 − 𝑐1′ and 𝑐1𝑖 = 𝑚𝑐1𝑖

1 1 𝑚
Overall mass transfer coefficient based on water-side is: = +
𝐾 𝑘 𝑘′
′ ′ 𝑐1𝑖 𝑅𝑇𝑐𝑇 ′ 𝑅𝑇𝑐𝑇 𝑐𝑚
𝑝1𝑖= 0.53𝑥1𝑖 ⇒ 𝑐1𝑖 𝑅𝑇= 0.53 ⇒ 𝑐 ⇒𝑚= = 3007 𝐾 = 2.6 × 10−4
𝑐𝑇 0.53 1𝑖 0.53 𝑠
−4 𝑐𝑚
𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 − 𝑠𝑖𝑑𝑒 2.4 × 10 𝑠 = 40%
= 𝑐𝑚
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 6 × 10−4
𝑠
 FILM THEORY IS NOT REALISTIC IN MANY SITUATIONS
LIQUID FILM
Do you expect the unstirred film to retain its
𝑐1𝑖 identity in these situations?
BULK LIQUID
• Simplest of theories 𝑐1
of mass transfer
• Easy to understand gas
• Useful in analysis LIQUID FILM packing
of systems where 𝑐1𝑖 liquid
reactions occur BULK LIQUID

𝑐1

water LIQUID FILM

𝑐1𝑖 Air bubble
Air
with 3% BULK LIQUID Stirred tank
ammonia
𝑐1
 PHYSICS OF TURBULENT FLOWS GIVES A REALISTIC PICTURE OF MASS TRANSFER

Stirred tank Flow past a sphere

Air bubble Only one bubble

is shown for
simplicity

eddy • Turbulence creates eddies in flows

• Size of eddies is small, down to say tens of microns
• Velocity of eddies can be high
• Eddies could be in contact with gas bubbles for a small fraction
of a second to few seconds

Watch video of animation of flow in stirred tank Watch video of animation of flow past a sphere
https://www.youtube.com/watch?v=TUE1S7F4ooc https://www.youtube.com/watch?v=PEeOc_jq3Bw
 HIGBIE’S PENETRATION THEORY OF MASS TRANSFER (1935)
Analysis of diffusion through semi-infinite layer

Consider one bubble • Eddies are in contact with gas bubble for very short time
Eddies on it are shown as liquid elements • During such short contact times, eddy can be modeled as
semi-infinite layer
Gas dissolves
in an unstirred liquid
Gas-liquid
boundary

Goes to ∞ shell
𝜕𝑐 𝜕2𝑐
Mass balance across shell gives =𝐷 2 Initial condition: 𝑡 = 0, 𝑐 = 𝑐∞ Boundary conditions: 𝑧 = 0, 𝑐 = 𝑐𝑠𝑎𝑡
𝜕𝑡 𝜕𝑧
𝑧 = ∞, 𝑐 = 𝑐∞
𝑧
Solution to this equation is obtained by defining a new variable, 𝜂 =
4𝐷𝑡
𝑐𝑠𝑎𝑡 − 𝑐 𝑧 𝐷 𝐷
Solution is = 𝑒𝑟𝑓 Flux at 𝑧 = 0, 𝑁1 = 2 𝑐𝑠𝑎𝑡 − 𝑐∞ ⇒ 𝑘𝑐 = 2 𝑡 is contact time
𝑐𝑠𝑎𝑡 − 𝑐∞ 4𝐷𝑡 𝜋𝑡 𝜋𝑡

IS CONTACT TIME KNOWN? DETERMINED? No

 DANCKWERTS’ SURFACE RENEWAL THEORY OF MASS TRANSFER (1951)

• Higbie’s theory assumes all eddies have same contact time

• This assumption is not plausible
• P V Danckwerts suggested that eddies are replaced with fresh liquid surface continuously
• Implication of this suggestion is that there is a DISTRIBUTION OF CONTACT TIMES
• Few eddies are in contact for very short time and few for very long time;
mathematically stated from 𝑡 = 0 to 𝑡 = ∞
• Danckwerts called the time as surface renewal time

probability that a surface element

𝐸 𝑡 𝑑𝑡 =
is at the surface for time t

𝑡
−
𝑒 𝜏
𝐸 𝑡 = , 𝜏 is average residence time of an element at the surface
𝜏

∞
‫׬‬0 𝐸 𝑡 𝑑𝑡 = 1; sum of all probabilities equals ONE
 DANCKWERTS’ SURFACE RENEWAL THEORY OF MASS TRANSFER (1951)

𝐷
𝐹𝑙𝑢𝑥 = 𝑐 − 𝑐1
𝜋𝑡 1𝑖

∞ 𝐷 𝐷
If the residence time distribution is factored in, 𝐹𝑙𝑢𝑥 = ‫׬‬0 𝐸 𝑡 𝑐1𝑖 − 𝑐1 𝑑𝑡 = 𝑐1𝑖 − 𝑐1
𝜋𝑡 𝜏

𝐷
The mass transfer coefficient, 𝑘𝑐 =
𝜏

COMPARISON OF THEORIES OF MASS TRANSFER

• Film theory has an unknown film thickness, 𝑙

• Higbie’s penetration theory introduced a contact time, 𝑡
• Danckwerts’ theory replaced contact time with a surface renewal time, 𝜏

1Τ
Film theory: 𝑘𝑐 ∝ 𝐷; penetration and surface renewal theories, 𝑘𝑐 ∝ 𝐷; correlations suggest 𝑘𝑐 ∝ 𝐷 2 to 𝐷
Contact time and surface renewal time
Air is sparged through a fermenter to provide oxygen for microbes for their respiration.
Oxygen dissolves from air bubbles in the fermenter medium and from there to the microbes.
Calculations show that a 5000 liter fermenter operation needs an oxygen transfer rate of 7.2 moles per hour.
If the interfacial area for mass transfer of oxygen is 1 cm2/cm3, medium is 40% saturated with oxygen and
Henry’s law constant is 42,000 atm, find contact time and surface renewal time.

Write equation for mass transfer rate and determine mass transfer coefficient
𝑁1 𝑁1 𝑁1
𝑁1 = 𝑘𝑐 𝑎𝑉 𝑐1𝑖 − 𝑐1 ⇒ 𝑘𝑐 = = =
𝑎𝑉 𝑐1𝑖 − 𝑐1 0.6𝑎𝑉𝑐1𝑖 0.6𝑎𝑉 𝑝𝑐𝑇
𝐻
Substitute the numbers and find 𝑘𝑐

𝑚𝑜𝑙 1 ℎ
7.2 × 𝑐𝑚
ℎ 3600 𝑠
𝑘𝑐 = = 2.4 × 10−3 Find contact and renewal times
𝑚𝑜𝑙 𝑠
0.21 𝑎𝑡𝑚 × 0.055
𝑐𝑚2 𝑐𝑐
0.6 × 1 3 × 5 × 106 𝑐𝑚3 ×
𝑐𝑚 42000 𝑎𝑡𝑚

4𝐷 𝐷
Contact time is 𝑡 = =4𝑠 Surface renewal time is 𝑡 = = 3.1 𝑠
𝜋𝑘𝑐2 𝑘𝑐2
 TUTORIAL 3
A steroid present in an 1 liter of an aqueous phase is extracted into 15 liters of butyl acetate phase.
The two phases are mutually immiscible. Find the time taken to extract 99% of the
steroid from the former into the latter. Diffusion coefficients of the steroid in aqueous and acetate phases are
𝑐𝑚2 𝑐𝑚2
1.5 × 10−5 and 7 × 10−6 , respectively.
𝑠 𝑠
Assume that the unstirred film thickness in both phases is 100𝜇𝑚.
2
The interfacial area per volume of the mixture is 0.25 𝑐𝑚 ൗ𝑐𝑚3. Continuous
butyl acetate phase
The steroid is seven times more soluble in acetate phase than in aqueous phase.

Dispersed
Identify control volume and write mass balance equation over this volume water phase

Control volume is aqueous phase

Mass balance equation: Accumulation = rate at which steroid is transferred to butyl acetate phase
Write the mass balance equation in mathematically using overall mass transfer coefficient based on aqueous side
𝑉 is volume, 𝐾 is mass transfer coefficient, 𝑐 is concentration
prime over variables represent acetate phase
 TUTORIAL 3
A steroid present in an 1 liter of an aqueous phase is extracted into 15 liters of butyl acetate phase.
The two phases are mutually immiscible. Find the time taken to extract 99% of the
steroid from the former into the latter. Diffusion coefficients of the steroid in aqueous and acetate phases are
𝑐𝑚2 𝑐𝑚2
1.5 × 10−5 and 7 × 10−6 , respectively.
𝑠 𝑠
Assume that the unstirred film thickness in both phases is 100𝜇𝑚.
2
The interfacial area per volume of the mixture is 0.75 𝑐𝑚 ൗ𝑐𝑚3. Continuous
butyl acetate phase
The steroid is seven times more soluble in acetate phase than in aqueous phase.

Dispersed
Identify control volume and write mass balance equation over this volume water phase

Control volume is aqueous phase

Mass balance equation: Accumulation = rate at which steroid is transferred to butyl acetate phase
Write the mass balance equation in mathematically using overall mass transfer coefficient based on aqueous side
𝑑𝑐1
𝑉 = 𝐾𝐴 𝑐1 − 𝑚𝑐1′ How to find 𝐾? Individual mass transfer coefficients are needed. How to find these?
𝑑𝑡
𝑐𝑚2 𝑐𝑚2
𝐷 1.5 × 10−5 𝑐𝑚 𝐷 ′ 7 × 10−6 𝑐𝑚
𝑠 −3 ′ 𝑠 −4 Find 𝐾
𝑘= = = 1.5 × 10 𝑘 = ′ = = 7 × 10
𝑙 0.01 𝑐𝑚 𝑠 𝑙 0.01 𝑐𝑚 𝑠
 TUTORIAL 3
′ ′
Equate the fluxes, 𝑘 𝑐1 − 𝑐1𝑖 = 𝑘 ′ 𝑐1𝑖 − 𝑐1′ and 𝑐1𝑖 = 𝑚𝑐1𝑖

𝑐1−𝑚𝑐1′ 1 𝑐𝑚
Mass transfer flux, 𝑁1 = 1 𝑚 Overall mass transfer coefficient, 𝐾 = 1 𝑚 = 4.5 × 10−4
+ + ′ 𝑠
𝑘 𝑘′ 𝑘 𝑘
1ൗ
𝑊𝑎𝑡𝑒𝑟 𝑝ℎ𝑎𝑠𝑒 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 −3 Water phase offers large resistance even though
= 1.5 × 10 = 80%
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 1ൗ mass transfer coefficient is higher in this phase!
1.2 × 10−3
𝑑𝑐1 ′
Let’s return to 𝑉 = 𝐾𝐴 𝑐1 − 𝑚𝑐1′ Overall mass balance at all times, 𝑉 𝑐10 − 𝑐1 = 𝑉 ′ 𝑐1′ − 𝑐10
𝑑𝑡

𝑉 ′ 𝑑𝑐1
𝑐1′ = 𝑐10 − 𝑐1 as 𝑐10 =0 Integrate this equation now, 𝑉 = 𝐾𝐴 𝑐1 − 𝑚𝑐1′ by writing 𝑐1′ in terms of 𝑐1
𝑉′ 𝑑𝑡

𝑉 1 1
𝑡= 𝑙𝑛 CHECK! Substituting the given values, 𝑡 = 9 𝑚𝑖𝑛
𝐾𝐴 1 + 𝑚𝑉 ′ 1+
𝑚𝑉 ′ 𝑐1 𝑚𝑉 ′
−
′𝑉 ′𝑉 𝑐10 ′𝑉
 CHECK YOUR UNDERSTANDING

• Explain two-film, penetration and surface renewal theories in your own words
• What are the drawbacks of these theories? What purpose they serve?
• What is the typical liquid film thickness? Gas film thickness? How and when do we use these?
• For flow through a packed tower, how can we interpret dependence of mass transfer
coefficient on velocity of liquid in the tower?